CN110404538B - Use of waste agents - Google Patents
Use of waste agents Download PDFInfo
- Publication number
- CN110404538B CN110404538B CN201910332501.2A CN201910332501A CN110404538B CN 110404538 B CN110404538 B CN 110404538B CN 201910332501 A CN201910332501 A CN 201910332501A CN 110404538 B CN110404538 B CN 110404538B
- Authority
- CN
- China
- Prior art keywords
- waste
- desulfurizer
- agent
- feooh
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002699 waste material Substances 0.000 title claims abstract description 931
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 705
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 459
- 229910002588 FeOOH Inorganic materials 0.000 claims abstract description 390
- 239000003054 catalyst Substances 0.000 claims abstract description 365
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 247
- 238000000034 method Methods 0.000 claims abstract description 196
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 171
- 230000008569 process Effects 0.000 claims abstract description 129
- 239000005416 organic matter Substances 0.000 claims abstract description 61
- 230000009466 transformation Effects 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims description 280
- 239000007789 gas Substances 0.000 claims description 273
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 218
- 239000002028 Biomass Substances 0.000 claims description 213
- 239000002002 slurry Substances 0.000 claims description 175
- 239000011593 sulfur Substances 0.000 claims description 163
- 229910052717 sulfur Inorganic materials 0.000 claims description 163
- 238000006477 desulfuration reaction Methods 0.000 claims description 127
- 230000023556 desulfurization Effects 0.000 claims description 126
- 239000012492 regenerant Substances 0.000 claims description 118
- 239000007787 solid Substances 0.000 claims description 89
- 239000007788 liquid Substances 0.000 claims description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 83
- 239000000047 product Substances 0.000 claims description 79
- 230000003009 desulfurizing effect Effects 0.000 claims description 78
- 238000007254 oxidation reaction Methods 0.000 claims description 73
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 73
- 238000011069 regeneration method Methods 0.000 claims description 67
- 239000002245 particle Substances 0.000 claims description 62
- 239000000843 powder Substances 0.000 claims description 58
- 239000003245 coal Substances 0.000 claims description 48
- 239000000571 coke Substances 0.000 claims description 47
- 238000000197 pyrolysis Methods 0.000 claims description 47
- 239000004480 active ingredient Substances 0.000 claims description 41
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 40
- 239000011343 solid material Substances 0.000 claims description 39
- 230000008929 regeneration Effects 0.000 claims description 38
- 238000010438 heat treatment Methods 0.000 claims description 37
- 239000006185 dispersion Substances 0.000 claims description 36
- 239000007800 oxidant agent Substances 0.000 claims description 35
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 claims description 34
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 claims description 34
- 230000001590 oxidative effect Effects 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 31
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 30
- 230000001172 regenerating effect Effects 0.000 claims description 30
- 239000000725 suspension Substances 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 29
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 28
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 28
- 239000002351 wastewater Substances 0.000 claims description 27
- 239000005997 Calcium carbide Substances 0.000 claims description 26
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 23
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 21
- 239000011787 zinc oxide Substances 0.000 claims description 20
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 238000004073 vulcanization Methods 0.000 claims description 15
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 14
- 239000005751 Copper oxide Substances 0.000 claims description 14
- 229910000431 copper oxide Inorganic materials 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 238000005987 sulfurization reaction Methods 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910000464 lead oxide Inorganic materials 0.000 claims description 8
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 8
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 8
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 8
- 238000007613 slurry method Methods 0.000 claims description 5
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical group O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 claims 2
- 230000002829 reductive effect Effects 0.000 abstract description 105
- 238000004519 manufacturing process Methods 0.000 abstract description 33
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 abstract description 22
- 229910003296 Ni-Mo Inorganic materials 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 239000003921 oil Substances 0.000 description 89
- 235000019198 oils Nutrition 0.000 description 89
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 57
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 51
- 230000000694 effects Effects 0.000 description 48
- 239000000203 mixture Substances 0.000 description 40
- 239000003208 petroleum Substances 0.000 description 37
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 32
- 230000009286 beneficial effect Effects 0.000 description 30
- 229910052739 hydrogen Inorganic materials 0.000 description 27
- 239000000243 solution Substances 0.000 description 23
- 239000003502 gasoline Substances 0.000 description 22
- 239000001257 hydrogen Substances 0.000 description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 239000003034 coal gas Substances 0.000 description 20
- 238000001514 detection method Methods 0.000 description 19
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 18
- 239000000295 fuel oil Substances 0.000 description 18
- 150000002506 iron compounds Chemical class 0.000 description 18
- 229910000480 nickel oxide Inorganic materials 0.000 description 17
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 17
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 16
- 229940116318 copper carbonate Drugs 0.000 description 16
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 16
- 238000005810 carbonylation reaction Methods 0.000 description 15
- 230000005484 gravity Effects 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 14
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 14
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 14
- 230000007062 hydrolysis Effects 0.000 description 14
- 238000006460 hydrolysis reaction Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 239000006227 byproduct Substances 0.000 description 13
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon disulfide Substances S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 13
- 229910000428 cobalt oxide Inorganic materials 0.000 description 13
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 13
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 13
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 13
- 229910006299 γ-FeOOH Inorganic materials 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 241000219782 Sesbania Species 0.000 description 12
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 12
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 12
- 230000006315 carbonylation Effects 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 238000005336 cracking Methods 0.000 description 12
- 239000003672 gas field water Substances 0.000 description 12
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 12
- 238000000746 purification Methods 0.000 description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 12
- 229910006540 α-FeOOH Inorganic materials 0.000 description 12
- 229910003153 β-FeOOH Inorganic materials 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 239000003546 flue gas Substances 0.000 description 11
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 11
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 11
- 239000000956 alloy Substances 0.000 description 10
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 10
- 239000002910 solid waste Substances 0.000 description 10
- 239000002912 waste gas Substances 0.000 description 10
- 238000007906 compression Methods 0.000 description 9
- 230000006835 compression Effects 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000005054 agglomeration Methods 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- -1 alkali metal formates Chemical class 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 229930192474 thiophene Natural products 0.000 description 8
- 230000009471 action Effects 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 240000008042 Zea mays Species 0.000 description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000007900 aqueous suspension Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000001728 carbonyl compounds Chemical class 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 235000005822 corn Nutrition 0.000 description 6
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 230000003301 hydrolyzing effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000004537 pulping Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 6
- 239000010902 straw Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910000859 α-Fe Inorganic materials 0.000 description 6
- 229910017135 Fe—O Inorganic materials 0.000 description 5
- 102000005298 Iron-Sulfur Proteins Human genes 0.000 description 5
- 108010081409 Iron-Sulfur Proteins Proteins 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000008602 contraction Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 238000007689 inspection Methods 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000012075 bio-oil Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005188 flotation Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 239000010806 kitchen waste Substances 0.000 description 3
- 239000011344 liquid material Substances 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052952 pyrrhotite Inorganic materials 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000658 coextraction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical compound [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 239000004058 oil shale Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a new application of a waste agent. The new application relates to FeOOH waste agent and Fe21.333O32Waste agent, waste iron oxide agent,The waste Ni-Mo agent is used as hydrogenating and liquefying catalyst, CO converting catalyst and organic matter converting process. The waste agent is used as an idle resource, the price of the waste agent is far lower than that of a fresh catalyst, so that the production cost is reduced, but the catalytic effect of the waste agent as a hydrogenation liquefaction catalyst or a CO transformation catalyst is equivalent to that of a conventional catalyst.
Description
Technical Field
The invention belongs to the field of catalyst application, and particularly relates to a new application of a waste agent, in particular to an application of the waste agent as a hydrogenation liquefaction catalyst, as a CO transformation catalyst and in an organic matter transformation process.
Background
CO shift is a common industrial production process that utilizes the reaction of CO and steam to produce CO2And hydrogen gas. At present, the process is widely applied to the processing of hydrogen production, ammonia synthesis, methanol synthesis, methanation, synthetic oil and the like, and the hydrogen-carbon ratio in a reaction system can be adjusted through CO conversion so as to meet the requirement of a target product on raw materials.
In the CO shift reaction, a catalyst is an essential element in the reaction system. Common CO shift catalysts include high temperature catalysts, medium and high temperature catalysts, and low temperature catalysts, as follows:
(1) In the high temperature catalyst, Fe is contained in large amount2O3And/or Cr2O3As a main active component, taking MgO as a structural auxiliary agent;
(2) in the medium-high temperature catalyst, CoO and/or MoO are mostly used2MgO and Al are used as main active components2O3As a structural aid;
(3) in the low-temperature catalyst, copper and zinc are mostly used as main active components, the copper and the zinc are dissolved by nitric acid, the dissolved solution is mixed and added with soda ash solution for coprecipitation, and then Al (OH) is added into the solution3Or amorphous Al2O3Forming a supported catalyst.
In industrial production, desulfurization is also a common treatment process, a lot of desulfurization waste agents are generated after desulfurization treatment, the desulfurization waste agents need to be subjected to subsequent treatment, soil landfill is generally adopted, the landfill treatment not only occupies the land, but also has great harm to the residual of the soil, and the environment is also influenced. In consideration of recycling of the spent desulfurization agent, the spent desulfurization agent is generally regenerated by a specific regeneration process to restore the activity of the active material to a certain extent, thereby achieving recycling. However, the activity of the regenerated catalyst waste agent is reduced, and the desulfurization effect of the original desulfurizer cannot be achieved, so that the large-range reuse of the catalyst waste agent is limited. For example, the sulfur capacity of the desulfurizer using iron oxide as the main active component is reduced by at least 3 percent after regeneration, so that the desulfurizer after multiple regeneration can not meet the use requirement and still needs to be subjected to landfill treatment.
Meanwhile, the hydroliquefaction is a technology for partially or completely converting biomass, coal, etc. into liquid fuels by thermochemical or biochemical methods. Generally, the technology is divided into direct liquefaction of biomass, coal and the like and indirect liquefaction of biomass, coal and the like. The direct hydrogenation liquefaction technology is a technology of introducing H2, CO or inert gas into a reactor filled with biomass, coal and the like, a catalyst and using water or organic matters as a solvent, and thermally decomposing the biomass, the coal and the like at proper temperature and pressure to obtain liquid oil, namely a thermochemical reaction process for directly converting solid biomass into a liquid mixture. The indirect liquefaction is to gasify biomass, coal and the like and then further synthesize liquid products, or to convert cellulose and hemicellulose in the biomass into polysaccharide by a hydrolysis method and then to generate ethanol by a biomass fermentation technology.
In the hydrogenation liquefaction process, the catalyst is an essential element in a reaction system, which is beneficial to inhibiting side reactions such as polycondensation, heavy polymerization and the like and reducing the generation amount of macromolecular solid residues. Common hydrogenation and liquefaction catalysts can be classified into homogeneous catalysts and heterogeneous catalysts, and the specific points are as follows:
(1) homogeneous catalyst: acids, bases, alkali metal (bi) carbonates, alkali metal formates;
(2) Heterogeneous catalyst: metal catalyst, supported catalyst such as Co-Mo, Ni-Mo series hydrogenation catalyst.
In industrial production, desulfurization is also a common treatment process, a lot of desulfurization waste agents are generated after desulfurization treatment, the desulfurization waste agents need to be subjected to subsequent treatment, soil landfill is generally adopted, the landfill treatment not only occupies the land, but also has great harm to the residual of the soil, and the environment is also influenced. If the recycling of the desulfurization waste agent is further considered, the desulfurization waste agent is generally regenerated by adopting a specific regeneration process, so that the activity of active substances is recovered to a certain extent, thereby realizing recycling, however, the activity of the regenerated catalyst waste agent is reduced, the desulfurization effect of the original desulfurizer cannot be achieved, and the large-scale recycling is limited. For example, the sulfur capacity of the waste iron oxide desulfurizer is reduced after regeneration, so that the desulfurizer after multiple regeneration cannot meet the use requirement, and still needs to be subjected to landfill treatment.
Meanwhile, with the rapid development of social economy, stone non-renewable energy sources such as coal, crude oil, natural gas, oil shale and the like are gradually exhausted, and meanwhile, CO generated after the stone non-renewable energy sources are combusted 2、SO2、NOxThe environmental pollution caused by these pollutants is also becoming serious, which forces human beings to think about new ways of obtaining energy and methods for improving the environment.
At present, a biomass liquefaction technology becomes a new means for obtaining energy, the technology is an important component in biomass resource utilization, and the liquefaction mechanism is as follows: biomass is first cracked into oligomers, which are then dehydrated, dehydroxylated, dehydrogenated, deoxygenated and decarboxylated to form small molecule compounds, which are then reacted via condensation, cyclization, polymerization, etc. to produce new compounds. At present, the technology mainly comprises two major categories of indirect liquefaction and direct liquefaction, wherein the biomass direct liquefaction technology is to directly liquefy biomass from solid to liquid at proper temperature and pressure by adopting hydrolysis and supercritical liquefaction or introducing hydrogen and inert gas under the action of a solvent or a catalyst. In the whole process, the method mainly relates to pyrolysis liquefaction, catalytic liquefaction, pressurized hydrogenation liquefaction and the like.
In the above biomass liquefaction process, before liquefaction, dehydration treatment is required for the biomass raw material, which increases drying cost. Furthermore, the liquefaction must be carried out using a pure hydrogen atmosphere and expensive noble metal catalysts applied to the process, making the liquefaction process less economical. In addition, the whole process also generates a large amount of waste water which pollutes the environment, and the environmental benefit of the liquefaction process is poor. Therefore, the fact that the economic benefit and the environmental benefit of the existing biomass liquefaction process are both low becomes a main obstacle limiting the popularization and the application of the biomass liquefaction process. Theoretically, no matter the liquefaction atmosphere is changed, the raw material treatment cost is reduced or a cheap catalyst is selected, the further development of the biomass liquefaction process is facilitated, so that at present, researchers try to adopt a non-hydrogen environment to carry out biomass liquefaction conversion, but the catalytic efficiency of the adopted catalyst is low, and industrial popularization and application cannot be realized.
Therefore, how to recycle a large amount of waste agents to reduce the harm to the environment caused by landfill treatment is of great significance.
Disclosure of Invention
Therefore, the invention aims to solve the problems that the existing waste agent causes harm to the environment due to landfill treatment and the biomass liquefaction process in the prior art has low economic benefit and environmental benefit, thereby providing the FeOOH waste agent and Fe21.333O32The waste agent, the waste iron oxide agent and the waste Ni-Mo agent are used as hydrogenation and liquefaction catalysts, CO transformation catalysts and in organic matter transformation processes.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the invention provides FeOOH waste agent and Fe21.333O32The waste agent, the waste iron oxide agent and the waste Ni-Mo agent are used as hydrogenation and liquefaction catalysts, CO transformation catalysts and in organic matter transformation processes;
the FeOOH waste agent is waste FeOOH desulfurizer, waste desulfurizer which takes FeOOH as a main active component, and regenerated substance generated after regeneration of the waste desulfurizer containing FeOOH;
said Fe21.333O32The waste agent is Fe21.333O32The waste desulfurizing agent of (1), with Fe21.333O32As the main active ingredientWaste desulfurizer containing Fe21.333O32The regenerated regenerant of the desulfurizing agent waste agent;
The waste iron oxide agent is waste iron oxide desulfurizer, waste iron oxide desulfurizer containing iron oxide as a main active component, and regenerated product obtained by regenerating waste iron oxide desulfurizer;
the Ni-Mo waste agent is a waste agent of a hydrogenation catalyst which takes Ni-Mo as a main active component.
Further, the FeOOH desulfurizer waste agent is used as a biomass hydrogenation liquefaction catalyst.
The waste FeOOH desulfurizer is used as a biomass hydrogenation liquefaction catalyst, and the FeOOH is one or more of alpha-FeOOH, beta-FeOOH, gamma-FeOOH, delta-FeOOH, theta-FeOOH and amorphous FeOOH.
The waste FeOOH desulfurizer is used as a biomass hydrogenation liquefaction catalyst, and the waste FeOOH desulfurizer is generated after the FeOOH desulfurizer removes H2S in gas.
The FeOOH desulfurizer waste agent is used as a biomass hydrogenation liquefaction catalyst, and is generated after sulfur-containing components in coke oven gas are removed by the FeOOH desulfurizer.
The FeOOH desulfurizer waste agent is used as a biomass hydrogenation liquefaction catalyst, and is generated after sulfur-containing components in wastewater are removed by the FeOOH desulfurizer.
The waste FeOOH desulfurizer is used as a biomass hydrogenation liquefaction catalyst, and the waste FeOOH desulfurizer is waste gas generated by removing sulfur components in coal pyrolysis gas and/or calcium carbide furnace tail gas by using the FeOOH desulfurizer.
Compared with the prior art, the invention has the following beneficial effects:
(1) the waste FeOOH desulfurizer provided by the embodiment of the invention is used as a biomass hydrogenation liquefaction catalyst, the waste agent formed after desulfurization treatment of the existing FeOOH desulfurizer can be directly used as the biomass hydrogenation liquefaction catalyst, the application field of the waste FeOOH desulfurizer is expanded, the regeneration cost of the waste FeOOH desulfurizer is reduced, the landfill amount of the waste FeOOH desulfurizer is reduced, the harm to the environment is reduced, and meanwhile, the price of the waste FeOOH desulfurizer is far lower than that of the biomass hydrogenation liquefaction catalyst because the waste FeOOH desulfurizer is used as an idle resource, so that the production cost of the biomass liquefaction industry is reduced.
(2) According to the application of the FeOOH desulfurizer waste agent provided by the embodiment of the invention as the biomass hydrogenation liquefaction catalyst, through detection, the existing FeOOH desulfurizer waste agent is used as the biomass hydrogenation liquefaction catalyst, and the effect of the catalyst is equivalent to that of the conventional biomass hydrogenation liquefaction catalyst.
Further, the waste desulfurizer using FeOOH as a main active component is used as a biomass hydrogenation liquefaction catalyst.
The desulfurizer taking FeOOH as the main active component also comprises one or more of iron salt chromium mixture, polymeric ferric sulfate, basic copper carbonate, calcium bicarbonate, zinc oxide, calcium sulfate dihydrate, nickel oxide, cobalt oxide and nickel oxide.
The FeOOH is one or more of alpha-FeOOH, beta-FeOOH, gamma-FeOOH, delta-FeOOH, theta-FeOOH and amorphous FeOOH.
The waste agent of the desulfurizer using FeOOH as the main active component is the waste agent generated after the desulfurizer removes H2S in gas.
The waste agent of the desulfurizer which takes FeOOH as the main active component is the waste agent generated after the sulfur-containing component in the coke oven gas is removed by the desulfurizer.
The waste agent of the desulfurizer which takes FeOOH as the main active component is the waste agent generated after the desulfurizer removes sulfur-containing components in gasoline.
The waste agent of the desulfurizer which takes FeOOH as the main active component is the waste agent generated after the desulfurizer removes sulfur-containing components in petroleum or petroleum byproducts.
The waste agent of the desulfurizer which takes FeOOH as the main active component is the waste agent generated after the sulfur-containing component in the wastewater is removed by the desulfurizer.
The waste agent of the desulfurizer using FeOOH as the main active component is waste gas generated by removing sulfur-containing components in coal pyrolysis gas and/or calcium carbide furnace tail gas by using the desulfurizer.
Compared with the prior art, the invention has the following beneficial effects:
(1) the waste desulfurizer using FeOOH as the main active component provided by the embodiment of the invention is used as the biomass hydrogenation liquefaction catalyst, the waste desulfurizer formed after desulfurization treatment of the existing FeOOH desulfurizer can be directly used as the biomass hydrogenation liquefaction catalyst, the application field of the waste desulfurizer of FeOOH is expanded, the regeneration cost of the waste desulfurizer of FeOOH is reduced, the landfill quantity of the waste desulfurizer of FeOOH is reduced, the harm to the environment is reduced, and meanwhile, the price of the waste desulfurizer of FeOOH is far lower than the price of the biomass hydrogenation liquefaction catalyst because the waste desulfurizer of FeOOH is used as an idle resource, so that the production cost of the biomass hydrogenation liquefaction industry is reduced.
(2) According to the application of the waste desulfurizer using FeOOH as the main active component as the biomass hydrogenation liquefaction catalyst, the detection shows that the existing waste desulfurizer using FeOOH has the effect equivalent to that of the conventional biomass hydrogenation liquefaction catalyst.
Further, the waste desulfurizer containing FeOOH is regenerated and then used as a biomass hydrogenation liquefaction catalyst.
The waste desulfurizer containing FeOOH is regenerated and then used as a biomass hydrogenation liquefaction catalyst, and the FeOOH is one or more of alpha-FeOOH, beta-FeOOH, gamma-FeOOH, delta-FeOOH, theta-FeOOH and amorphous FeOOH.
The waste desulfurizer containing FeOOH is regenerated and then used as a biomass hydrogenation liquefaction catalyst, and the desulfurizer containing FeOOH also comprises one or more of iron salt chromium mixture, polymeric ferric sulfate, basic copper carbonate, calcium bicarbonate, zinc oxide, calcium sulfate dihydrate, nickel oxide, cobalt oxide and molybdenum oxide.
The waste desulfurizer containing FeOOH is regenerated and then used as a biomass hydrogenation liquefaction catalyst, and the waste desulfurizer containing FeOOH is generated after H2S in gas is removed by the desulfurizer containing FeOOH; or the like, or a combination thereof,
the waste desulfurizer containing FeOOH is generated after sulfur-containing components in the coke oven gas are removed by the FeOOH-containing desulfurizer; or the like, or a combination thereof,
the waste desulfurizer containing FeOOH is generated after the FeOOH-containing desulfurizer removes sulfur-containing components in the wastewater; or,
The waste desulfurizer containing FeOOH is waste gas generated by removing sulfur-containing components in coal pyrolysis gas and/or calcium carbide furnace tail gas by using the FeOOH-containing desulfurizer.
The waste desulfurizer containing FeOOH is regenerated and then used as a biomass hydrogenation liquefaction catalyst, and the regeneration method of the waste desulfurizer containing FeOOH comprises the following steps,
(1) grinding the waste desulfurizer containing FeOOH into particles to obtain waste agent powder;
(2) preparing the waste agent powder into suspension, introducing oxygen-containing gas for oxidation to convert iron sulfide in the suspension to form slurry containing amorphous FeOOH and elemental sulfur;
(3) and filtering the slurry to obtain a solid material, extracting elemental sulfur in the solid material by using a solvent, wherein the residual solid after extraction is the regenerated product containing the FeOOH desulfurizer waste agent.
The waste desulfurizer containing FeOOH is regenerated and then used as a biomass hydrogenation liquefaction catalyst, and the regeneration method of the waste desulfurizer containing FeOOH comprises the following steps,
(1) grinding the waste desulfurizer containing FeOOH into particles to obtain waste agent powder;
(2) preparing the waste agent powder into suspension, introducing oxygen-containing gas for oxidation to convert iron sulfide in the suspension to form slurry containing amorphous iron oxyhydroxide and elemental sulfur;
(3) And (3) placing the slurry or a solid material obtained after filtering the slurry into a container, introducing air to enable the elemental sulfur to float upwards, and obtaining a precipitate at the lower part of the container, namely the regenerated substance containing the FeOOH desulfurizer waste agent.
The regeneration method of the waste desulfurizer containing FeOOH used as the biomass hydrogenation liquefaction catalyst after regeneration also comprises the step of mixing the regenerated product containing the waste desulfurizer containing FeOOH with an organic binder.
The waste desulfurizer containing FeOOH is regenerated and then used as a biomass hydrogenation liquefaction catalyst, and the regeneration method of the waste desulfurizer containing FeOOH comprises the following steps,
(1) dispersing the waste desulfurizer containing FeOOH with weak acid water to form dispersion liquid;
(2) heating the dispersion liquid, adding an oxidant into the heated dispersion liquid for reaction, and rapidly transferring generated sulfur dioxide gas during the reaction;
(3) and after the reaction is finished, filtering the reaction solution, washing and drying the obtained precipitate to obtain the regenerated product containing the FeOOH desulfurizer waste agent.
Compared with the prior art, the invention has the following beneficial effects:
(1) the waste desulfurizer containing FeOOH provided by the embodiment of the invention can be used as a biomass hydrogenation liquefaction catalyst after being regenerated, the waste desulfurizer formed by the desulfurization treatment of the existing FeOOH-containing desulfurizer can be directly used as a biomass hydrogenation liquefaction catalyst, the application field of the regenerated waste desulfurizer containing FeOOH is developed, the landfill amount of the waste desulfurizer containing FeOOH is reduced, the harm to the environment is reduced, and meanwhile, the price of the waste desulfurizer containing FeOOH is far lower than that of the biomass hydrogenation liquefaction catalyst because the waste desulfurizer containing FeOOH is used as an idle resource, so that the production cost of the CO conversion industry is reduced.
(2) According to the application of the regenerated waste desulfurizer containing FeOOH in the embodiment of the invention as a biomass hydrogenation liquefaction catalyst, through detection, the regenerated waste desulfurizer containing FeOOH is used as a biomass hydrogenation liquefaction catalyst, and the effect of the regenerated waste desulfurizer containing FeOOH is equivalent to that of a conventional biomass hydrogenation liquefaction catalyst.
Further, the application of the waste FeOOH desulfurizer as a CO shift catalyst.
Preferably, the waste desulfurizer of FeOOH is used as a CO conversion catalyst, and the FeOOH is one or more of alpha-FeOOH, beta-FeOOH, gamma-FeOOH, delta-FeOOH, theta-FeOOH and amorphous FeOOH.
Preferably, the waste FeOOH desulfurizer is used as a CO shift catalyst, and the waste FeOOH desulfurizer is generated after the FeOOH desulfurizer removes H2S in gas.
Preferably, the waste FeOOH desulfurizer is used as a CO conversion catalyst, and the waste FeOOH desulfurizer is a waste generated after sulfur-containing components in the coke oven gas are removed by the FeOOH desulfurizer.
Preferably, the waste FeOOH desulfurizer is used as a CO conversion catalyst, and the waste FeOOH desulfurizer is waste gas generated by removing sulfur-containing components in coal pyrolysis gas and/or calcium carbide furnace tail gas by using the FeOOH desulfurizer.
Compared with the prior art, the invention has the following beneficial effects:
(1) the waste FeOOH desulfurizer provided by the embodiment of the invention can be used as a CO conversion catalyst, the waste generated after desulfurization treatment of the existing FeOOH desulfurizer can be directly used as the CO conversion catalyst, the application field of the waste FeOOH desulfurizer is expanded, the regeneration cost of the waste FeOOH desulfurizer is reduced, the landfill amount of the waste FeOOH desulfurizer is reduced, the harm to the environment is reduced, and meanwhile, the price of the waste FeOOH desulfurizer is far lower than that of the CO conversion catalyst because the waste FeOOH desulfurizer is used as an idle resource, so that the production cost of the CO conversion industry is reduced.
(2) The FeOOH desulfurizer waste agent provided by the embodiment of the invention is used as a CO conversion catalyst, and the detection shows that the existing FeOOH desulfurizer waste agent is used as a CO conversion catalyst, and the effect of the waste agent is equivalent to that of the conventional CO conversion catalyst.
Furthermore, the waste desulfurizer using FeOOH as the main active component is used as a CO conversion catalyst.
Preferably, the waste desulfurizer using FeOOH as a main active component is used as a CO shift catalyst, and the desulfurizer using FeOOH as a main active component further comprises one or more of iron salt chromium mixture, polymeric ferric sulfate, basic copper carbonate, calcium bicarbonate, zinc oxide, calcium sulfate dihydrate, nickel oxide, cobalt oxide and nickel oxide.
Preferably, the waste desulfurizer using FeOOH as the main active component is used as a CO conversion catalyst, and the FeOOH is one or more of alpha-FeOOH, beta-FeOOH, gamma-FeOOH, delta-FeOOH, theta-FeOOH and amorphous FeOOH.
Preferably, the waste agent of the desulfurizing agent with FeOOH as the main active component is used as a CO transformation catalyst, and the waste agent of the desulfurizing agent with FeOOH as the main active component is the waste agent generated after the desulfurizing agent removes H2S in the gas.
Preferably, the waste agent of the desulfurizing agent with FeOOH as the main active component is used as a CO conversion catalyst, and the waste agent of the desulfurizing agent with FeOOH as the main active component is a waste agent generated after the desulfurizing agent removes sulfur-containing components in the coke oven gas.
Preferably, the waste agent of the desulfurizing agent with FeOOH as the main active component is used as a CO conversion catalyst, and the waste agent of the desulfurizing agent with FeOOH as the main active component is a waste agent generated after the desulfurizing agent removes sulfur components in wastewater.
Preferably, the waste agent of the desulfurizing agent with FeOOH as the main active component is used as a CO conversion catalyst, and the waste agent of the desulfurizing agent with FeOOH as the main active component is waste gas generated by removing sulfur-containing components in coal pyrolysis gas and/or calcium carbide furnace tail gas by the desulfurizing agent.
Compared with the prior art, the invention has the following beneficial effects:
(1) the waste desulfurizer using FeOOH as the main active component provided by the embodiment of the invention is used as a CO conversion catalyst, the waste desulfurizer formed after desulfurization treatment of the existing FeOOH desulfurizer can be directly used as the CO conversion catalyst, the application field of the waste desulfurizer of FeOOH is expanded, the regeneration cost of the waste desulfurizer of FeOOH is reduced, the landfill quantity of the waste desulfurizer of FeOOH is reduced, the harm to the environment is reduced, and meanwhile, the price of the waste desulfurizer of FeOOH is far lower than that of the CO conversion catalyst because the waste desulfurizer of FeOOH is used as an idle resource, so that the production cost of the CO conversion industry is reduced.
(2) According to the application of the waste desulfurizer using FeOOH as the main active component as the CO shift catalyst, the detection shows that the effect of the existing waste desulfurizer using FeOOH is equivalent to that of the conventional CO shift catalyst.
Further, the waste desulfurizer containing FeOOH is regenerated and then used as a CO shift catalyst.
Preferably, the waste desulfurizer containing FeOOH is regenerated and used as a CO shift catalyst, and the FeOOH is one or more of alpha-FeOOH, beta-FeOOH, gamma-FeOOH, delta-FeOOH, theta-FeOOH and amorphous FeOOH.
Preferably, the waste desulfurizer containing FeOOH is regenerated and then used as a CO shift catalyst, and the desulfurizer containing FeOOH also comprises one or more of iron salt chromium mixture, polymeric ferric sulfate, basic copper carbonate, calcium bicarbonate, zinc oxide, calcium sulfate dihydrate, nickel oxide, cobalt oxide and molybdenum oxide.
Preferably, the waste desulfurizer containing FeOOH is regenerated and then used as a CO shift catalyst, and the waste desulfurizer containing FeOOH is generated after the desulfurizer containing FeOOH removes H2S in gas; or the like, or a combination thereof,
the waste desulfurizer containing FeOOH is generated after sulfur-containing components in the coke oven gas are removed by the FeOOH-containing desulfurizer; or,
the waste desulfurizer containing FeOOH is generated after the sulfur-containing components in the wastewater are removed by the FeOOH-containing desulfurizer; or,
the waste desulfurizer containing FeOOH is waste gas generated by removing sulfur-containing components in coal pyrolysis gas and/or calcium carbide furnace tail gas by using the FeOOH-containing desulfurizer.
Preferably, the waste desulfurizer containing FeOOH is regenerated and used as a CO shift catalyst, and the regeneration method of the waste desulfurizer containing FeOOH is,
(1) Grinding the desulfurizer waste agent containing FeOOH into particles to obtain waste agent powder;
(2) preparing the waste agent powder into suspension, introducing oxygen-containing gas for oxidation to convert iron sulfide in the suspension to form slurry containing amorphous FeOOH and elemental sulfur;
(3) and filtering the slurry to obtain a solid material, extracting elemental sulfur in the solid material by using a solvent, wherein the residual solid after extraction is the regenerated product containing the FeOOH desulfurizer waste agent.
Preferably, the waste desulfurizer containing FeOOH is regenerated and used as a CO shift catalyst, and the regeneration method of the waste desulfurizer containing FeOOH is,
(1) grinding the waste desulfurizer containing FeOOH into particles to obtain waste agent powder;
(2) preparing the waste agent powder into suspension, introducing oxygen-containing gas for oxidation to convert iron sulfide in the suspension to form slurry containing amorphous iron oxyhydroxide and elemental sulfur;
(3) and placing the slurry or a solid material obtained after filtering the slurry into a container, introducing air to enable the elemental sulfur to float upwards, wherein the precipitate at the lower part of the container is the regenerated substance containing the waste FeOOH desulfurizer.
Preferably, the regenerated waste desulfurizer containing FeOOH is used as a CO shift catalyst, and the method further comprises the step of mixing the regenerated waste desulfurizer containing FeOOH with an organic binder.
Preferably, the waste desulfurizer containing FeOOH is regenerated and used as a CO shift catalyst, and the regeneration method of the waste desulfurizer containing FeOOH is,
(1) dispersing the waste desulfurizer containing FeOOH with weak acid water to form dispersion liquid;
(2) heating the dispersion liquid, adding an oxidant into the heated dispersion liquid for reaction, and rapidly transferring generated sulfur dioxide gas during the reaction;
(3) and after the reaction is finished, filtering the reaction solution, washing and drying the obtained precipitate to obtain the regenerated product containing the FeOOH desulfurizer waste agent.
Compared with the prior art, the invention has the following beneficial effects:
(1) the waste desulfurizer containing FeOOH provided by the embodiment of the invention can be used as a CO conversion catalyst after being regenerated, the waste desulfurizer formed after the desulfurization treatment of the existing FeOOH-containing desulfurizer can be directly used as the CO conversion catalyst, the application field after the regeneration of the waste desulfurizer containing FeOOH is developed, the landfill amount of the waste desulfurizer containing FeOOH is reduced, the harm to the environment is reduced, and meanwhile, the price of the waste desulfurizer containing FeOOH is far lower than that of the CO conversion catalyst because the waste desulfurizer containing FeOOH is used as an idle resource, so that the production cost of the CO conversion industry is reduced.
(2) The waste desulfurizer containing FeOOH provided by the embodiment of the invention is regenerated and then used as a CO shift catalyst, and the detection shows that the existing waste desulfurizer containing FeOOH is regenerated and then used as a CO shift catalyst, and the effect of the waste desulfurizer is equivalent to that of the conventional CO shift catalyst.
Further, the application of the waste agent or waste agent regenerant of the desulfurizer containing FeOOH in the organic matter conversion process.
In the application of the waste agent or waste agent regenerant of the desulfurizer containing FeOOH in the organic matter conversion process, the FeOOH is one or more of alpha-FeOOH, beta-FeOOH, gamma-FeOOH, delta-FeOOH, theta-FeOOH and amorphous FeOOH.
In the application of the waste agent or the waste agent regenerant of the FeOOH-containing desulfurizer in the organic matter conversion process, the FeOOH-containing desulfurizer also comprises one or more of iron salt chromium mixture, polymeric ferric sulfate, basic copper carbonate, calcium bicarbonate, zinc oxide, calcium sulfate dihydrate, nickel oxide, cobalt oxide and molybdenum oxide.
In the application of the waste agent or waste agent regenerant of the FeOOH-containing desulfurizer in the organic matter conversion process, the waste agent of the FeOOH-containing desulfurizer is a waste agent generated after the FeOOH-containing desulfurizer removes H2S in gas, a waste agent generated after the FeOOH-containing desulfurizer removes sulfur-containing components in coke oven gas, a waste agent generated after the FeOOH-containing desulfurizer removes sulfur-containing components in wastewater, or a waste agent generated after the FeOOH-containing desulfurizer removes sulfur-containing components in coal pyrolysis gas and/or calcium carbide furnace tail gas.
In the application of the waste agent or the waste agent regenerant of the FeOOH-containing desulfurizing agent in the organic matter conversion process, the method for preparing the waste agent regenerant by regenerating the waste agent of the FeOOH-containing desulfurizing agent comprises but is not limited to the following steps, and the method for preparing the waste agent regenerant comprises the following steps of A1, grinding the waste agent of the FeOOH-containing desulfurizing agent into particles to obtain waste agent powder; a2, preparing the waste agent powder into suspension, introducing oxygen-containing gas for oxidation to convert iron sulfide in the suspension, and forming slurry containing amorphous iron oxyhydroxide and elemental sulfur; a3, filtering the slurry to obtain a solid material, extracting elemental sulfur in the solid material by using a solvent, wherein the residual solid after extraction is the regenerant of the waste agent containing the FeOOH desulfurizer. B1, grinding the waste agent of the desulfurizer containing FeOOH into particles to obtain waste agent powder; b2, preparing the waste agent powder into a suspension, introducing oxygen-containing gas for oxidation to convert iron sulfide in the suspension, and forming slurry containing amorphous iron oxyhydroxide and elemental sulfur; and B3, placing the slurry or the solid material obtained by filtering the slurry into a container, introducing air to enable the elemental sulfur to float upwards, and obtaining a precipitate at the lower part of the container, namely the regenerant containing the waste FeOOH desulfurizer. C1, dispersing the waste desulfurizer containing FeOOH in weak acid water to form a dispersion liquid; c2, heating the dispersion liquid, adding an oxidant into the heated dispersion liquid for reaction, and rapidly transferring generated sulfur dioxide gas during the reaction; and C3, after the reaction is finished, filtering the reaction solution, washing and drying the obtained precipitate to obtain the regenerant containing the FeOOH desulfurizer waste agent. The method for preparing the regenerant of the waste agent is characterized in that the regenerant of the waste agent of the desulfurizer containing FeOOH is obtained by oxidizing, vulcanizing and oxidizing the waste agent of the desulfurizer containing FeOOH by a slurry method. The waste agent of the desulfurizer containing FeOOH is mixed with water or alkali solution to prepare slurry; adding an oxidant into the slurry to perform primary oxidation reaction; adding a vulcanizing agent into the slurry after the oxidation reaction to perform a vulcanization reaction; adding an oxidant into the slurry after the vulcanization reaction to perform secondary oxidation reaction; circularly carrying out the sulfuration reaction and the secondary oxidation reaction; and carrying out solid-liquid separation on the slurry after the secondary oxidation reaction to obtain the regenerant of the waste desulfurizer containing FeOOH.
In the application of the waste agent or the waste agent regenerant of the FeOOH-containing desulfurizing agent in the organic matter conversion process, the waste agent and/or the waste agent regenerant of the FeOOH-containing desulfurizing agent and organic matters are prepared into slurry, and the slurry is mixed with pure CO or CO-containing gas for conversion reaction. Preferably, the method also comprises a step of adding a sulfur-containing compound, so that the molar ratio of the iron element to the sulfur element in the slurry is 1 (0.5-5).
In the application of the waste agent or the waste agent regenerant of the desulfurizer containing FeOOH in the organic matter conversion process, the reaction pressure of the conversion reaction is 5-22MPa, and the reaction temperature is 200-470 ℃.
In the application of the waste agent or waste agent regenerant of the FeOOH-containing desulfurizer in the organic matter conversion process, the content of the waste agent and/or waste agent regenerant of the FeOOH-containing desulfurizer in the slurry is 0.1-10 wt%, and the average particle size of the slurry is 0.1 mu m-5 mm.
In the application of the waste agent or waste agent regenerant of the desulfurizer containing FeOOH in the organic matter conversion process, the volume content of CO in the CO-containing gas is not less than 15%, preferably not less than 50%, and most preferably not less than 90%.
Compared with the prior art, the invention has the following beneficial effects:
(1) The waste agent of the desulfurizer containing FeOOH or the regenerant of the waste agent provided by the embodiment of the invention is used as a catalyst of an organic matter conversion process, so that the application field of the waste agent of the desulfurizer containing FeOOH or the regenerant of the waste agent of the desulfurizer containing FeOOH is expanded, the landfill quantity of the waste agent of the desulfurizer containing FeOOH is reduced, the harm to the environment is reduced, and meanwhile, the waste agent of the desulfurizer containing FeOOH is an idle resource and is low in price, so that the cost of the organic matter conversion process is reduced.
(2) The waste agent of the desulfurizer containing FeOOH or the regenerant of the waste agent provided by the embodiment of the invention can be suitable for liquefying biomass in an impure hydrogen atmosphere, so that the limitation that pure hydrogen must be used for liquefying and converting biomass is avoided, the cost is reduced, the process path of biomass conversion is expanded, and the large-scale quantitative production of a biomass conversion process in industry is realized.
(3) The waste agent of the desulfurizer containing FeOOH or the regenerant of the waste agent provided by the embodiment of the invention is used as a catalyst of an organic matter conversion process, can effectively utilize carbonylation to block free radical polycondensation of organic matters in a cracking process in the presence of CO, and realize conversion active hydrogen hydrogenation of CO and water.
(4) The waste agent of the desulfurizer containing FeOOH or the regenerant of the waste agent provided by the embodiment of the invention is used as a catalyst of an organic matter conversion process, a proper amount of sulfur and organic matter are added to form slurry, under the atmosphere of CO, the catalysts are firstly combined with CO to form a carbonyl compound, then carbon atoms are grafted on small molecular active sites formed after thermal cracking of organic matter (such as biomass and the like) through the carbonyl compound, and meanwhile, the effects of CO conversion in-situ hydrogen production and catalytic hydrodeoxygenation are realized under the catalytic action of iron and sulfur elements, the oxygen content of oil products is reduced, and the liquefaction yield of solid organic matter and the oil product yield of long molecular chain conversion to small molecules are greatly improved;
preferably, the regenerant is obtained by alternately carrying out vulcanization and oxidation regeneration on the waste desulfurizer by a slurry method, and further, an iron oxide compound and an iron sulfur compound crystal phase undergo reconstruction and transformation in the process through multiple vulcanization-oxidation reactions, and S is added2-Radius of ion(0.18nm) greater than O2-The ionic radius (0.14nm), so with the transformation between Fe-O bond and Fe-S bond, the unit cell of the ferrite compound also undergoes contraction and expansion, and further the crystal particles of the ferrite compound with stable structure become loose and crack, and a large amount of nano iron compound is generated. Meanwhile, the surface of the nano iron compound is covered with a non-polar elemental sulfur layer, the elemental sulfur layer can not only prevent the agglomeration and growth among the nano iron compound particles and greatly improve the dispersibility of the nano iron compound, but also can highly disperse the nano iron compound in a non-polar oil product by utilizing the similar compatibility characteristics existing among substances; moreover, because of the close sulfur-iron connection and the small particle size of the nano-iron compound, the sulfur and the nano-iron compound can react at low temperature to generate pyrrhotite (Fe) with poor heavy oil hydrogenation activity 1-xS), finally, the regenerated substance obtained by the method has small particle size and good lipophilicity, the structure of the regenerated substance is a flaky nano structure, and the adsorbed sulfur blocks the chips, thereby avoiding the agglomeration of the chips, greatly improving the adsorption capacity of CO, and enhancing the carbonylation, hydrogen production conversion and hydrogenation catalytic capacity.
(5) The waste agent of the FeOOH-containing desulfurizer or the regenerant of the waste agent provided by the embodiment of the invention is used as a catalyst of an organic matter conversion process, the organic matter conversion process comprises the steps of sequentially carrying out primary crushing, compression and secondary crushing on biomass solids, then mixing the biomass solids with the catalyst to obtain a mixture, adding the mixture into a solvent, grinding and pulping to obtain the slurry with the biomass content of 10-60 wt%, the invention initiatively adopts a treatment process of firstly compressing and then carrying out secondary crushing on the biomass solids, and the biomass solids are compressed to enable loose biomass solids to sequentially undergo the stages of rearrangement, position closing and the like and mechanical deformation, so that the volume of the biomass solids is greatly reduced, the porosity of the biomass can be reduced, the density and the specific gravity of the biomass can be increased, the waste agent of the FeOOH-containing desulfurizer is beneficial to being dispersed in oil products, and the content of the biomass solids in the oil products can be increased, the concentration of reaction materials is increased, the solid content in the slurry can reach 10-60 wt%, and meanwhile, the concentration of biomass solid in the slurry is increased The increase of the pressure difference also inevitably increases the conveying capacity of the pump to the biomass solid in unit time, thereby improving the efficiency of the whole liquefaction process and reducing the industrial cost and energy consumption; in addition, the increase of the specific gravity of the biomass solid is also beneficial to the suspension and dispersion of the biomass solid in the slurry, so that the viscosity of the slurry can be reduced, the smooth flowing of the slurry in a pipeline is realized, the pipeline is prevented from being blocked, the stable running and conveying of a pump are realized, and meanwhile, high-viscosity waste oil which cannot be used as a liquefying solvent in the prior art, such as waste engine oil, kitchen waste oil, rancidity oil and the like, can also be utilized. Further, the bulk density of the biomass after primary crushing and compression is regulated and controlled to be not less than 0.4 g/cm3Regulating and controlling the average particle size of the biomass subjected to secondary crushing to be less than 5mm, and adding the biomass into a solvent for grinding and pulping conveniently by the regulation and control mode so as to improve the solid content of the biomass in the slurry; the compression temperature is controlled to be 30-60 ℃, and the biomass is compressed at the temperature, so that the rheological property of biomass solid can be obviously enhanced, the viscosity of slurry is reduced, smooth flowing of the slurry in a pipeline is realized, the pipeline is prevented from being blocked, and the stable running and conveying of a pump are realized.
(6) The waste agent of the desulfurizer containing FeOOH or the regenerant of the waste agent provided by the embodiment of the invention is used as a catalyst of an organic matter conversion process, and a catalytic reaction raw material and CO-containing gas are subjected to reactions such as cracking, carbonylation, transformation, hydrogenation and the like in a reactor; further, by adopting a slurry bed reactor, firstly, reaction raw materials are fed into the slurry bed reactor from the bottom of the reactor to react, and simultaneously, gas containing CO is injected into the reactor, so that the difference control of the flow rate of each phase state can be realized in the reactor by depending on the different specific gravities of the gas, liquid and solid materials and matching with the change of the specific gravity difference caused by the yield of the light oil product after the reaction, the cracking, the carbonylation, the transformation, the hydrogenation and the reaction of the biomass solid raw materials are carried out in the reactor from bottom to top, even if the biomass solid with large specific gravity and the catalyst solid particles rise along with the gas and the light oil product in the process, the biomass solid and the catalyst solid particles return to the bottom to participate in the reaction again under the action of the gas containing CO at the upper part, and the injection quantity of the gas containing CO in the slurry entering the reactor are properly adjusted according to the material densities at the upper part, the middle part and the lower part of the reactor, thereby realizing the circulation of unconverted organic matters in the reactor and the balanced discharge of the catalyst, ensuring the full progress of various reactions, and being beneficial to improving the conversion rate of the organic matters and the yield of the bio-oil
(7) The waste agent of the desulfurizer containing FeOOH or the regenerant of the waste agent provided by the embodiment of the invention is used as a catalyst of an organic matter conversion process, and in the organic matter conversion process, organic matters do not need to be dehydrated, so that the drying cost is reduced; the gas containing CO is used in the reaction process, the gas containing CO can be pure CO or impure, for example, the gas contains CO, hydrogen sulfide, methane and the like, and can also be synthesis gas generated by gasifying coal, biomass, natural gas and mineral oil, the rest gas except CO in the synthesis gas can be a mixture containing hydrogen, carbon dioxide or methane and ethane, and the gas manufacturing cost is greatly reduced; in the reaction process, the combined processes of cracking reaction, carbonylation reaction, shift reaction, hydrogenation reaction and the like are realized by using CO-containing gas and adopting the action of a cheap iron-based catalyst or a waste agent, sufficient free radicals are easily provided, carbonization and coking of organic matters are avoided, the conversion rate of the organic matters and the liquid yield are high, and the reaction temperature and the pressure are reduced; the oil produced by the liquefaction process can also be used in a preceding process to formulate a slurry.
(8) The desulfurizer containing FeOOH mentioned in the application is a desulfurizer directly formed by FeOOH, or a desulfurizer formed by loading FeOOH as a main active component on a carrier, or a desulfurizer formed by mixing FeOOH with an organic binder or other additives and loading FeOOH on a carrier, and the like. In a word, the FeOOH-containing desulfurizer is applicable to desulfurizer prepared by all FeOOH-containing desulfurizer preparation methods in the prior art, the waste agent is waste agent generated by applying the FeOOH-containing desulfurizer to various desulfurization methods in the prior art, and is particularly applicable to FeOOH desulfurizer waste agent generated after desulfurization of biogas, liquid, coal gas, flue gas, petroleum and gasoline, and the waste agent regenerant obtained by the waste agent regeneration method can adopt all existing regeneration methods.
Further, a Fe21.333O32The waste desulfurizer is used as a biomass hydrogenation liquefaction catalyst.
Fe as mentioned above21.333O32Use of a spent desulphurizing agent as a catalyst for the hydroliquefaction of biomass, said Fe21.333O32The waste desulfurizer is Fe21.333O32Desulfurizing agent for removing H from gas2Waste agent generated after S.
Fe as described above21.333O32Use of a waste desulfurizer as a catalyst for biomass hydrogenation liquefaction, and Fe21.333O32The waste desulfurizer is Fe21.333O32The desulfurizer generates waste agent after removing sulfur-containing components in the coke oven gas.
Fe as described above21.333O32Use of a waste desulfurizer as a catalyst for biomass hydrogenation liquefaction, and Fe21.333O32The waste desulfurizer is Fe21.333O32The desulfurizer generates a waste agent after removing sulfur-containing components in the wastewater.
Fe as described above21.333O32Use of a waste desulfurizer as a catalyst for biomass hydrogenation liquefaction, and Fe21.333O32The waste desulfurizer is Fe21.333O32The desulfurizer removes waste gas generated by sulfur-containing components in coal pyrolysis gas and/or calcium carbide furnace tail gas.
Compared with the prior art, the invention has the following beneficial effects:
(1) fe provided by the embodiment of the invention21.333O32The waste desulfurizer is used as a biomass hydrogenation liquefaction catalyst, and the existing Fe is used21.333O32The waste agent formed after the desulfurization treatment of the desulfurizer can be directly used as a biomass hydrogenation liquefaction catalyst, and Fe is exploited 21.333O32The application field of the waste desulfurizer reduces Fe21.333O32The regeneration cost of the waste desulfurizer is reduced, and Fe is reduced21.333O32The landfill quantity of the desulfurizer reduces the harm to the environment, and simultaneously, the magnetic iron oxide red Fe21.333O32The waste desulfurizer is used as an idle resource, and the price of the waste desulfurizer is far lower than that of a biomass hydrogenation liquefaction catalyst, so that the production components of the hydrogenation industry are reduced.
(2) Fe provided by the embodiment of the invention21.333O32The detection shows that the existing magnetic iron oxide red Fe is used as the waste desulfurizer as the catalyst for biomass hydrogenation liquefaction21.333O32The waste desulfurizer is used as a biomass hydrogenation liquefaction catalyst, and the effect of the waste desulfurizer is equivalent to that of a conventional biomass hydrogenation liquefaction catalyst.
Further, a method using Fe21.333O32The waste desulfurizer is used as a biomass hydrogenation liquefaction catalyst.
Above with Fe21.333O32Use of a spent agent of a desulfurizing agent as a main active ingredient as a biomass hydro-liquefaction catalyst, the spent agent being made of Fe21.333O32The desulfurizer used as the main active component also comprises potassium oxide and anatase type Ti02One or more of copper oxide, lead oxide, zinc oxide and manganese dioxide.
Above with Fe21.333O32Use of a spent agent of a desulfurizing agent as a main active ingredient as a biomass hydro-liquefaction catalyst, the spent agent being made of Fe 21.333O32Waste agent of desulfurizing agent as main active component for removing H from gas by said desulfurizing agent2Waste agent generated after S.
Above with Fe21.333O32Use of a spent agent of a desulfurizing agent as a main active ingredient as a biomass hydro-liquefaction catalyst, the spent agent being made of Fe21.333O32The waste agent of the desulfurizer which is the main active component is the waste agent generated after the sulfur-containing component in the coke oven gas is removed by the desulfurizer.
Above with Fe21.333O32Use of a spent agent of a desulfurizing agent as a main active ingredient as a biomass hydro-liquefaction catalyst, the spent agent being made of Fe21.333O32Is mainly composed ofThe waste agent of the desulfurizer of the active component is generated after the desulfurizer removes sulfur-containing components in wastewater.
Above with Fe21.333O32Use of a spent agent of a desulfurizing agent as a main active ingredient as a biomass hydro-liquefaction catalyst, the spent agent being made of Fe21.333O32The waste agent of the desulfurizer which is the main active component is waste gas generated by removing sulfur-containing components in coal pyrolysis gas and/or calcium carbide furnace tail gas by the desulfurizer.
Compared with the prior art, the invention has the following beneficial effects:
(1) the Fe provided by the embodiment of the invention21.333O32The application of the desulfurizer waste agent as the main active component as a biomass hydrogenation liquefaction catalyst uses the existing Fe21.333O32The waste agent formed after the desulfurization treatment of the desulfurizer can be directly used as a biomass hydrogenation liquefaction catalyst, and Fe is exploited 21.333O32The application field of the waste desulfurizer reduces Fe21.333O32The cost of the waste desulfurizer regeneration is reduced, and Fe is reduced21.333O32The landfill amount of the waste desulfurizer reduces the harm to the environment, and simultaneously, the waste desulfurizer is Fe21.333O32The waste desulfurizer is used as an idle resource, and the price of the waste desulfurizer is far lower than that of a biomass hydrogenation liquefaction catalyst, so that the production cost of the hydrogenation industry is reduced.
(2) The Fe provided by the embodiment of the invention21.333O32The application of the desulfurizer waste agent as the main active component as the biomass hydrogenation liquefaction catalyst is detected, and the existing Fe21.333O32The waste desulfurizer is used as a biomass hydrogenation liquefaction catalyst, and the effect of the waste desulfurizer is equivalent to that of a conventional biomass hydrogenation liquefaction catalyst.
Further, a composition containing Fe21.333O32The waste desulfurizer is regenerated and then used as a biomass hydrogenation liquefaction catalyst.
Above-mentioned Fe-containing21.333O32The use of the regenerated waste desulfurizer as a biomass hydrogenation liquefaction catalyst, wherein the catalyst contains Fe21.333O32The desulfurizing agent also comprises potassium oxide and anatase type Ti02One or more of copper oxide, lead oxide, zinc oxide or manganese dioxide.
Above-mentioned Fe-containing21.333O32The use of the regenerated waste desulfurizer as a biomass hydrogenation liquefaction catalyst, wherein the catalyst contains Fe 21.333O32The waste desulfurizer contains Fe21.333O32Desulfurizing agent for removing H from gas2(iv) a waste agent produced after S; or alternatively
Said Fe-containing21.333O32The waste desulfurizer contains Fe21.333O32The desulfurizer generates waste agent after removing sulfur-containing components in the coke oven gas; or alternatively
Said Fe-containing21.333O32The waste desulfurizer contains Fe21.333O32The desulfurizer generates a waste agent after removing sulfur-containing components in the wastewater; or
Said Fe-containing21.333O32The waste desulfurizer contains Fe21.333O32The desulfurizer removes waste gas generated by sulfur-containing components in coal pyrolysis gas and/or calcium carbide furnace tail gas.
Above-mentioned Fe-containing21.333O32The waste desulfurizer is regenerated and then used as a biomass hydrogenation liquefaction catalyst, and the catalyst contains Fe21.333O32The regeneration method of the waste desulfurizer comprises the following steps,
(1) the Fe is added21.333O32The waste desulfurizer is dispersed by using weak acid aqueous solution to form dispersion liquid;
(2) heating the dispersion liquid, adding an oxidant into the dispersion liquid for reaction, and rapidly transferring generated sulfur dioxide gas during the reaction;
(3) after the reaction is finished, filtering the reaction solution, washing and drying the obtained precipitate to obtain the Fe-containing iron oxide21.333O32The regenerant of the waste desulfurizer.
Above-mentioned Fe-containing21.333O32The waste desulfurizer is regenerated and then used as biomass hydrogenation liquefaction catalyst Use of agents containing Fe21.333O32The regeneration method of the waste desulfurizer comprises the following steps,
said Fe is added21.333O32The waste desulfurizer has the temperature of 800 ℃ and the space velocity of 3000h-1Regeneration is carried out in a regeneration atmosphere consisting of O2/SO215-28 mol% O with a volume ratio of 1:1002/SO2And 72-85 mol% of N2 to obtain the Fe-containing alloy21.333O32The regenerant of the waste desulfurizer.
Above-mentioned Fe-containing21.333O32The waste desulfurizer is regenerated and then used as a biomass hydrogenation liquefaction catalyst, and the catalyst contains Fe21.333O32The regeneration method of the waste desulfurizer comprises the following steps,
(1) introducing superheated steam into the Fe-containing mixture21.333O32Blowing and heating the waste desulfurizer, and collecting the solid waste;
(2) introducing reducing gas to reduce the solid waste agent to obtain the Fe-containing iron21.333O32The regenerant of the waste desulfurizer.
Compared with the prior art, the invention has the following beneficial effects:
(1) the Fe-containing alloy provided by the embodiment of the invention21.333O32The waste desulfurizer is used as a biomass hydrogenation liquefaction catalyst, and the existing Fe is used21.333O32The waste agent formed after the desulfurization treatment of the desulfurizer can be directly used as a biomass hydrogenation liquefaction catalyst, and Fe is exploited21.333O32The application field of the waste desulfurizer reduces Fe 21.333O32The regeneration cost of the waste desulfurizer is reduced, and Fe is reduced21.333O32The landfill quantity of the desulfurizer reduces the harm to the environment, and simultaneously, the Fe causes21.333O32The waste desulfurizer is used as an idle resource, and the price of the waste desulfurizer is far lower than that of a biomass hydrogenation liquefaction catalyst, so that the production cost of the hydrogenation industry is reduced.
(2) The invention provides a composition containingWith Fe21.333O32The purpose of the waste desulfurizer is used as a biomass hydrogenation liquefaction catalyst, and the detection shows that the existing Fe21.333O32The waste desulfurizer is used as a biomass hydrogenation liquefaction catalyst, and the effect of the waste desulfurizer is equivalent to that of a conventional biomass hydrogenation liquefaction catalyst.
Further, the present invention provides Fe21.333O32The use of the spent desulfurizing agent as a CO shift catalyst.
Further, said Fe21.333O32The waste desulfurizer is Fe21.333O32The desulfurizer removes sulfur-containing components in the sulfur-containing gas to produce a waste agent.
Further, the sulfur-containing gas is at least one of tail gas, coke oven gas, pyrolysis coal gas and calcium carbide furnace tail gas generated after oil products are subjected to hydrogenation and quality improvement.
Further, said Fe21.333O32The waste desulfurizer is Fe21.333O32The desulfurizer removes sulfur-containing components in the sulfur-containing wastewater to produce a waste agent.
Further, said Fe21.333O32The waste desulfurizer is Fe 21.333O32The desulfurizer removes sulfur-containing components in the oil product to produce waste agent.
Further, the sulfur-containing component includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum by-products, gasoline, heavy oil and residual oil.
Compared with the prior art, the invention has the following beneficial effects:
(1) fe provided by the embodiment of the invention21.333O32The waste desulfurizer is used as a CO transformation catalyst, and the existing Fe is used21.333O32The waste agent formed after the desulfurization treatment of the desulfurizer can be directly used as a CO conversion catalyst, and the development of Fe21.333O32The application field of the waste desulfurizer reduces Fe21.333O32The regeneration cost of the waste desulfurizer is reduced, and Fe is reduced21.333O32The landfill quantity of the desulfurizer reduces the harm to the environment, and simultaneously, the Fe causes21.333O32The waste desulfurizer is used as an idle resource, and the price of the waste desulfurizer is far lower than that of a CO conversion catalyst, so that the production cost of the CO conversion industry is reduced.
(2) Fe provided by the embodiment of the invention21.333O32The waste desulfurizer is used as a CO transformation catalyst, and the detection shows that the existing Fe21.333O32The waste desulfurizer is used as a CO shift catalyst, and the effect of the waste desulfurizer is equivalent to that of the conventional CO shift catalyst.
Further, contains Fe 21.333O32The use of the waste agent of a desulfurizing agent as a CO shift catalyst.
Further, the Fe-containing compound21.333O32The desulfurizing agent also comprises potassium oxide and anatase type Ti02One or more of copper oxide, lead oxide, zinc oxide and manganese dioxide.
Further, the Fe-containing compound21.333O32The waste desulfurizer is Fe21.333O32The desulfurizer which is the main active component removes the sulfur-containing component in the sulfur-containing gas to generate the waste agent.
Further, the sulfur-containing gas is at least one of tail gas, coke oven gas, pyrolysis coal gas and calcium carbide furnace tail gas generated after oil products are subjected to hydrogenation and quality improvement.
Further, the Fe-containing compound21.333O32The waste desulfurizer is Fe21.333O32The desulfurizer which is a main active component is a waste agent generated after the sulfur-containing component in the sulfur-containing wastewater is removed.
Further, the Fe-containing compound21.333O32The waste desulfurizer is Fe21.333O32The desulfurizer which is the main active component removes the sulfur-containing component in the oil product to produce the waste agent.
Further, the sulfur-containing component includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum byproducts, gasoline, heavy oil and residual oil.
Compared with the prior art, the invention has the following beneficial effects:
(1) the Fe-containing alloy provided by the embodiment of the invention 21.333O32The waste desulfurizer is used as a CO transformation catalyst, and the existing Fe is used21.333O32The waste agent formed after the desulfurization treatment of the desulfurizer can be directly used as a CO conversion catalyst, and the development of Fe21.333O32The application field of the waste desulfurizer reduces Fe21.333O32The cost of the waste desulfurizer regeneration is reduced, and Fe is reduced21.333O32The landfill amount of the waste desulfurizer reduces the harm to the environment, and simultaneously, the waste desulfurizer is Fe21.333O32The waste desulfurizer is used as an idle resource, and the price of the waste desulfurizer is far lower than that of a CO conversion catalyst, so that the production cost of the CO conversion industry is reduced.
(2) The Fe contained in the embodiment of the invention21.333O32The use of the waste desulfurizer as a CO conversion catalyst is detected to be the existing Fe21.333O32The waste desulfurizer is used as a CO shift catalyst, and the effect of the waste desulfurizer is equivalent to that of the conventional CO shift catalyst.
Further, contains Fe21.333O32The waste desulfurizer is regenerated and then used as a CO shift catalyst.
Further, the Fe-containing compound21.333O32The desulfurizing agent also comprises potassium oxide and anatase type Ti02One or more of copper oxide, lead oxide, zinc oxide and manganese dioxide.
Further, the Fe-containing compound21.333O32The waste desulfurizer is regenerated into Fe21.333O32The desulfurizer which is the main active component removes the sulfur-containing component in the sulfur-containing gas to produce waste agent.
Further, the sulfur-containing gas is at least one of tail gas, coke oven gas, coal pyrolysis gas and calcium carbide furnace tail gas which are generated after oil products are hydrogenated and upgraded.
Further, the Fe-containing compound21.333O32The waste desulfurizer is regenerated into Fe21.333O32The desulfurizer which is the main active component removes the sulfur-containing component in the sulfur-containing wastewater to produce the waste agent.
Further, the Fe-containing compound21.333O32The waste desulfurizer is regenerated into Fe21.333O32The desulfurizer which is the main active component removes the sulfur-containing component in the oil product to produce the waste agent.
Further, the sulfur-containing component includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum by-products, gasoline, heavy oil and residual oil.
Further, the Fe-containing compound21.333O32The method for regenerating the waste desulfurizer comprises the following steps:
the said Fe-containing21.333O32The waste desulfurizer is mixed with water or alkali solution to prepare slurry;
adding an oxidant into the slurry to perform an oxidation reaction;
carrying out solid-liquid separation on the slurry after the oxidation reaction, and collecting solids, namely the slurry containing Fe21.333O32The regenerant of the spent desulfurizing agent of (1).
Further, before the solid-liquid separation, adding a vulcanizing agent into the slurry after the oxidation reaction to generate a vulcanization reaction; then adding an oxidant into the mixture to perform oxidation reaction; finally, the sulfurization reaction and the oxidation reaction are carried out in a circulating mode until the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction is 1: 0.5-10;
The vulcanizing agent comprises Na2S、Na2S2O3、(NH4)2S、(NH4)2S2O3Thiol, thiourea, dimethyl sulfide, carbonyl sulfide, H2At least one of S;
the oxidant comprises H2O2、NaClO、O2、O3At leastOne kind of the medicine.
Compared with the prior art, the invention has the following beneficial effects:
(1) the Fe-containing alloy provided by the embodiment of the invention21.333O32The waste desulfurizer is used as a CO transformation catalyst, and the existing Fe is used21.333O32The waste agent formed after the desulfurization treatment of the desulfurizer can be directly used as a CO conversion catalyst, and the development of Fe21.333O32The application field of the waste desulfurizer reduces Fe21.333O32The cost of the waste desulfurizer regeneration is reduced, and Fe is reduced21.333O32The landfill amount of the waste desulfurizer reduces the harm to the environment, and simultaneously, the waste desulfurizer is Fe21.333O32The waste desulfurizer is used as an idle resource, and the price of the waste desulfurizer is far lower than that of a CO conversion catalyst, so that the production cost of the CO conversion industry is reduced.
(2) The Fe-containing alloy provided by the embodiment of the invention21.333O32The waste desulfurizer is used as a CO transformation catalyst, and the detection shows that the existing Fe21.333O32The waste desulfurizer is used as a CO shift catalyst, and the effect of the waste desulfurizer is equivalent to that of the conventional CO shift catalyst.
Further, a catalyst containing Fe21.333O32The use of a spent agent of a desulphurisation agent or a spent agent regenerant in an organic matter conversion process.
Above-mentioned containing Fe21.333O32In the use of the waste agent or the waste agent regenerant of the desulfurizing agent in an organic matter conversion process, the Fe-containing catalyst is used21.333O32The desulfurizer also comprises one or more of potassium oxide, anatase type Ti02, copper oxide, lead oxide, zinc oxide or manganese dioxide.
The above-mentioned Fe-containing21.333O32In the use of the waste agent or the waste agent regenerant of the desulfurizing agent in an organic matter conversion process, the Fe-containing catalyst is used21.333O32The waste desulfurizer contains Fe21.333O32The desulfurizing agent removes H in the gas2Spent chemical produced after S, containing Fe21.333O32Desulfurizing agent removalWaste agent generated after removing sulfur-containing components in coke oven gas and containing Fe21.333O32The desulfurizer generates a waste agent or contains Fe after removing sulfur-containing components in the wastewater21.333O32The desulfurizer removes waste agent generated by sulfur-containing components in coal pyrolysis gas and/or calcium carbide furnace tail gas.
The above-mentioned Fe-containing21.333O32The use of a spent agent or a spent agent regenerant of a desulfurizing agent in an organic matter conversion process, wherein the spent agent or the spent agent regenerant contains Fe21.333O32The method for preparing the waste agent regenerant by regenerating the waste agent of the desulfurizing agent comprises but is not limited to the following methods, and one method for preparing the waste agent regenerant is A121.333O32Grinding the waste agent of the desulfurizer into particles to obtain waste agent powder; a2, preparing the waste agent powder into suspension, introducing oxygen-containing gas for oxidation to convert iron sulfide in the suspension, and forming slurry containing amorphous iron oxyhydroxide and elemental sulfur; a3, filtering the slurry to obtain a solid material, extracting elemental sulfur in the solid material by using a solvent, wherein the solid left after extraction is the Fe-containing solid 21.333O32A regenerant of a spent desulfurizing agent. The other method for preparing the regenerant of the waste agent is B121.333O32Grinding the waste agent of the desulfurizer into particles to obtain waste agent powder; b2, preparing the waste agent powder into a suspension, introducing oxygen-containing gas for oxidation to convert iron sulfide in the suspension, and forming slurry containing amorphous iron oxyhydroxide and elemental sulfur; b3, placing the slurry or the solid material obtained by filtering the slurry into a container, introducing air to enable the elemental sulfur to float upwards, and obtaining the precipitate at the lower part of the container, namely the Fe-containing precipitate21.333O32A regenerant of a waste desulfurizer. The method for preparing the regenerant of the waste agent comprises the following steps of C121.333O32The waste desulfurizer is dispersed by weak acid water to form dispersion liquid; c2, heating the dispersion liquid, adding an oxidant into the heated dispersion liquid for reaction, and rapidly transferring generated sulfur dioxide gas during the reaction; c3, after the reaction is finished, filtering and reactingReacting, washing and drying the obtained precipitate to obtain the Fe-containing solution21.333O32A regenerant of the waste desulfurizer. The method for preparing the waste agent regenerant comprises the following step of 21.333O32The regenerant of the waste desulfurizer is prepared by a slurry method for the regeneration of the waste desulfurizer containing Fe21.333O32The waste desulfurizer is oxidized, vulcanized and oxidized to obtain the regenerant. The provided method for preparing the regenerant of the waste agent comprises the following step of adding Fe21.333O32The waste desulfurizer is mixed with water or alkali solution to prepare slurry; adding an oxidant into the slurry to perform primary oxidation reaction; adding a vulcanizing agent into the slurry after the oxidation reaction to perform a vulcanization reaction; adding an oxidant into the slurry after the vulcanization reaction to perform secondary oxidation reaction; circularly carrying out the sulfuration reaction and the secondary oxidation reaction; carrying out solid-liquid separation on the slurry after the secondary oxidation reaction to obtain the slurry containing Fe21.333O32The regenerant of the spent desulfurizing agent of (1).
The method for preparing the regenerant of the waste agent comprises the following step D121.333O32The waste desulfurizer is dispersed by using weak acid aqueous solution to form dispersion liquid; d2, heating the dispersion liquid, then adding an oxidant into the dispersion liquid for reaction, and rapidly transferring generated sulfur dioxide gas during the reaction; d3, after the reaction is finished, filtering the reaction solution, washing and drying the obtained precipitate to obtain the Fe-containing iron 21.333O32The regenerant of the desulfurization agent waste agent.
The provided method for preparing the regenerant of the waste agent comprises the following step of adding the regenerant containing Fe21.333O32The waste desulfurizer is regenerated in a regeneration atmosphere at the temperature of 800 ℃ and the space velocity of 3000h < -1 >, and the regeneration atmosphere is O2/SO215-28 mol% O with a volume ratio of 1:1002/SO2And 72-85 mol% of N2 to obtain the Fe-containing alloy21.333O32The regenerant of the desulfurization agent waste agent.
It also provides a method for preparing the waste agent regenerantThe method comprises E1, passing superheated steam into the solution containing Fe21.333O32Blowing and heating the waste desulfurizer, and collecting the solid waste; e2, introducing reducing gas to reduce the solid waste agent to obtain the Fe-containing iron21.333O32The regenerant of the waste desulfurizer.
Above-mentioned containing Fe21.333O32In the application of the waste agent of the desulfurizer or the waste agent regenerant in the organic matter conversion process,
will contain Fe21.333O32The waste agent of the desulfurizer and/or the regenerant of the waste agent and organic matters are prepared into slurry, and the slurry is mixed with pure CO or CO-containing gas for conversion reaction. Preferably, the method further comprises adding a sulfur-containing compound to enable the molar ratio of the iron element to the sulfur element in the slurry to be 1 (0.5-5).
The above-mentioned Fe-containing21.333O32In the application of the waste agent or the waste agent regenerant of the desulfurizer in the organic matter conversion process, the reaction pressure of the conversion reaction is 5-22MPa, and the reaction temperature is 200-470 ℃.
The above-mentioned Fe-containing21.333O32The use of a spent agent or a spent agent regenerant of a desulfurizing agent in an organic matter conversion process, said slurry containing Fe21.333O32The content of the waste agent and/or the regenerant of the waste agent of the desulfurizing agent is 0.1-10 wt%, and the average particle size of the waste agent and/or the regenerant is 0.1-5 mm.
The above-mentioned Fe-containing21.333O32In the use of the waste agent or waste agent regenerant of a desulfurizing agent in an organic matter conversion process, the volume content of CO in the CO-containing gas is not less than 15%, preferably not less than 50%, and most preferably not less than 90%.
The technical scheme of the invention has the following advantages:
(1) the Fe contained in the embodiment of the invention21.333O32The waste agent of the desulfurizer or the regenerant of the waste agent is used as a catalyst of an organic matter conversion process, and the Fe-containing catalyst is developed21.333O32The application field of the waste desulfurizer or the regenerant thereof reduces Fe21.333O32The landfill quantity of the waste desulfurizer reduces the harm to the environment, and simultaneously, the waste desulfurizer contains Fe21.333O32The waste desulfurizer is an idle resource and has low price, thereby reducing the cost of the organic matter conversion process.
(2) The Fe-containing alloy provided by the embodiment of the invention21.333O32The waste agent of the desulfurizer or the regenerant of the waste agent can be suitable for liquefying the non-pure hydrogen atmosphere of the biomass, so that the limitation that pure hydrogen must be used for biomass liquefaction and conversion is avoided, the cost is reduced, the process path of biomass conversion is expanded, and the large-scale quantitative production of the biomass conversion process in the industry is realized.
(3) The Fe-containing alloy provided by the embodiment of the invention21.333O32The waste desulfurizer or the regenerant of the waste desulfurizer is used as a catalyst of an organic matter conversion process, the carbonylation can be effectively utilized to block the free radical polycondensation of organic matters in the cracking process in the presence of CO, and the active hydrogen hydrogenation of CO and water is realized.
(4) The Fe-containing alloy provided by the embodiment of the invention21.333O32The waste desulfurizer or the regenerant of the waste desulfurizer is used as a catalyst of an organic matter conversion process, a proper amount of sulfur and organic matters are added to form slurry, the catalysts are firstly combined with CO in a CO atmosphere to form a carbonyl compound, then carbon atoms are grafted on small molecular active sites formed after thermal cracking of the organic matters (such as biomass and the like) through the carbonyl compound, and meanwhile, the effects of CO conversion in-situ hydrogen production and catalytic hydrodeoxygenation are realized under the catalytic action of iron and sulfur elements, the oxygen content of an oil product is reduced, and the liquefaction yield of solid organic matters and the yield of the oil product converted from long molecular chains to small molecules are greatly improved;
Preferably, the waste desulfurizer is alternately subjected to vulcanization and oxygen by a slurry methodRegenerating to obtain a regenerant, further, subjecting the iron oxide compound and the iron sulfur compound to reconstruction and transformation in the process through multiple sulfurization-oxidation reactions, and adding S2-Ionic radius (0.18nm) greater than O2-The ionic radius (0.14nm), so with the conversion between Fe-O bond and Fe-S bond, the unit cell of the ferrite compound also undergoes contraction and expansion, and further causes the crystal particles of the iron oxide compound with stable structure to become loose and crack, and generates a large amount of nano iron compound which has good thiophilic property and is easy to be vulcanized. Meanwhile, the surface of the nano iron compound is covered with a non-polar elemental sulfur layer, the elemental sulfur layer can not only prevent the agglomeration and growth among the nano iron compound particles and greatly improve the dispersibility of the nano iron compound, but also can highly disperse the nano iron compound in a non-polar oil product by utilizing the similar compatibility characteristics existing among substances; moreover, the sulfur-covered nano iron compound can react with the nano iron compound at low temperature to generate pyrrhotite (Fe) with poor heavy oil hydrogenation activity because of the close sulfur-iron connection and the small particle size of the nano iron compound 1-xS), finally, the regenerated substance obtained by the method has small particle size and good lipophilicity, the structure of the regenerated substance is a flaky nano structure, and the adsorbed sulfur blocks the chips, thereby avoiding the agglomeration of the chips, greatly improving the adsorption capacity of CO, and enhancing the carbonylation, hydrogen production conversion and hydrogenation catalytic capacity.
(5) The Fe contained in the embodiment of the invention21.333O32The waste agent of the desulfurizer or the regenerant of the waste agent is used as a catalyst of an organic matter conversion process, the organic matter conversion process comprises the steps of sequentially carrying out primary crushing, compression and secondary crushing on biomass solids, then mixing the biomass solids with the catalyst to obtain a mixture, adding the mixture into a solvent, grinding and pulping to obtain the slurry with the biomass content of 10-60 wt%The density and the specific gravity of the biomass solid are high, so that the biomass solid is favorably dispersed in an oil product, the content of the biomass solid in the oil product can be improved, the concentration of reaction materials is increased, the solid content in the slurry can reach 10-60 wt%, and meanwhile, the conveying capacity of a pump to the biomass solid in unit time is inevitably increased due to the increase of the concentration of the biomass solid in the slurry, so that the efficiency of the whole liquefaction process is improved, and the industrial cost and the energy consumption are reduced; in addition, the increase of the specific gravity of the biomass solid is also beneficial to the suspension and dispersion of the biomass solid in the slurry, so that the viscosity of the slurry can be reduced, the smooth flowing of the slurry in a pipeline is realized, the pipeline is prevented from being blocked, the stable running and conveying of a pump are realized, and meanwhile, high-viscosity waste oil which cannot be used as a liquefied solvent in the prior art, such as waste engine oil, kitchen waste oil, rancid oil and the like, can also be utilized. Further, the bulk density of the biomass after primary crushing and compression is regulated and controlled to be not less than 0.4 g/cm 3Regulating and controlling the average particle size of the biomass subjected to secondary crushing to be less than 5mm, and adding the biomass into a solvent for grinding and pulping conveniently by the regulation and control mode so as to improve the solid content of the biomass in the slurry; the compression temperature is controlled to be 30-60 ℃, and the biomass is compressed at the temperature, so that the rheological property of biomass solid can be obviously enhanced, the viscosity of slurry is reduced, smooth flowing of the slurry in a pipeline is realized, the pipeline is prevented from being blocked, and the stable running and conveying of a pump are realized.
(6) The Fe contained in the embodiment of the invention21.333O32The waste agent of the desulfurizer or the regenerant of the waste agent is used as a catalyst of an organic matter conversion process, and the catalytic reaction raw material and CO-containing gas are subjected to reactions such as cracking, carbonylation, conversion, hydrogenation and the like in a reactor; further, by adopting a slurry bed reactor, firstly, the reaction raw material is fed into the slurry bed reactor from the bottom of the reactor to react, and simultaneously, the gas containing CO is injected into the reactor, so that the difference control of the flow rate of each phase can be realized in the reactor by depending on the different specific gravities of the gas, liquid and solid materials and matching with the change of the specific gravity difference caused by the yield of the light oil product after the reaction, and the cracking and carbonylation of the biomass solid raw material are carried out from bottom to top in the reactor, During the conversion, hydrogenation and reaction, even if the biomass solid and the catalyst solid particles with large specific gravity rise along with the gas and the light oil product, the biomass solid and the catalyst solid particles return to the bottom to participate in the reaction again under the action of the gas containing CO at the upper part, the gas containing CO returns to the bottom to take part in the reaction again, the gas containing CO and the injection amount thereof in the slurry entering the reactor are properly adjusted according to the material density at the upper part, the middle part and the lower part of the reactor, thereby realizing the circulation of unconverted organic matters in the reactor and the balanced discharge of the catalyst, ensuring the full progress of various reactions, and being beneficial to improving the conversion rate of the organic matters and the yield of the bio-oil
(7) The Fe-containing alloy provided by the embodiment of the invention21.333O32The waste agent of the desulfurizer or the regenerant of the waste agent is used as a catalyst of the organic matter conversion process, organic matters do not need to be dehydrated in the organic matter conversion process, and the drying cost is reduced; the gas containing CO is used in the reaction process, the gas containing CO can be pure CO or impure, for example, the gas contains CO, hydrogen sulfide, methane and the like, and can also be synthesis gas generated by gasifying coal, biomass, natural gas and mineral oil, the rest gas except CO in the synthesis gas can be a mixture containing hydrogen, carbon dioxide or methane and ethane, and the gas manufacturing cost is greatly reduced; in the reaction process, the combined processes of cracking reaction, carbonylation reaction, shift reaction, hydrogenation reaction and the like are realized by using CO-containing gas and adopting the action of a cheap iron-based catalyst or a waste agent, sufficient free radicals are easily provided, carbonization and coking of organic matters are avoided, the conversion rate of the organic matters and the liquid yield are high, and the reaction temperature and the pressure are reduced; the oil produced by the liquefaction process can also be used in a preceding process to prepare a slurry.
(8) Containing Fe as mentioned in the present application21.333O32The desulfurizing agent is Fe21.333O32Desulfurizing agents formed directly, or with Fe21.333O32A desulfurizing agent formed as a main active ingredient supported on a carrier, or Fe21.333O32Desulfurizing agent formed by mixing with organic binder or other additives, or Fe21.333O32With organic binders or thereofThe additive is mixed with desulfurizer formed by loading on carrier. In summary, the present application contains Fe21.333O32The desulfurizer is suitable for the prior art containing Fe21.333O32The waste desulfurizer is prepared by the method for preparing all desulfurizers, wherein the waste desulfurizer is prepared by mixing the Fe-containing desulfurizer21.333O32The desulfurizer is applied to waste agents generated by various desulfurization methods in the prior art, and is particularly suitable for Fe generated after desulfurization of methane, liquid, coal gas, flue gas, petroleum and gasoline21.333O32The waste desulfurizer and the waste regenerant obtained by the regeneration method of the waste desulfurizer can adopt all the existing regeneration methods.
Further, the use of the spent agent of the iron oxide desulfurizer as a hydrogenation catalyst.
Further, the application of the catalyst as a biomass hydrogenation catalyst.
Further, the active ingredient in the iron oxide desulfurizer is ferric oxide and/or ferroferric oxide.
Further, the ferric oxide is alpha-Fe 2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, amorphous Fe2O3Amorphous Fe2O3.H2At least one of O;
the ferroferric oxide is cubic system ferroferric oxide.
Further, the waste agent of the iron oxide desulfurizer is a waste agent generated after the sulfur-containing component in the sulfur-containing gas is removed by the iron oxide desulfurizer.
Further, the sulfur-containing gas is at least one of tail gas, coke oven gas, pyrolysis coal gas and calcium carbide furnace tail gas generated after oil products are subjected to hydrogenation and quality improvement.
Further, the waste agent of the iron oxide desulfurizer is a waste agent generated after the sulfur-containing components in the sulfur-containing wastewater are removed by the iron oxide desulfurizer.
Further, the waste agent of the iron oxide desulfurizer is a waste agent generated after the sulfur-containing components in the oil product are removed by the iron oxide desulfurizer.
Further, the sulfur-containing component includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum by-products, gasoline, heavy oil and residual oil.
Compared with the prior art, the invention has the following beneficial effects:
(1) the waste agent of the iron oxide desulfurizer is used as the hydrogenation catalyst, the waste agent formed after the desulfurization treatment of the existing iron oxide desulfurizer is directly used as the hydrogenation catalyst, the application field of the waste agent of the iron oxide desulfurizer is expanded, the regeneration cost of the waste agent of the iron oxide desulfurizer is reduced, the landfill quantity of the waste agent of the iron oxide desulfurizer is reduced, the harm to the environment is reduced, and meanwhile, the price of the waste agent of the iron oxide desulfurizer is far lower than that of the hydrogenation catalyst because the waste agent of the iron oxide desulfurizer is used as an idle resource, so that the production cost of the hydrogenation industry is reduced.
(2) The detection shows that the waste agent of the iron oxide desulfurizer is used as a hydrogenation catalyst, and the effect of the waste agent of the iron oxide desulfurizer is equivalent to that of a conventional hydrogenation catalyst.
Further, the waste desulfurizer containing iron oxide as a main active component is used as a hydrogenation catalyst.
Further, the application of the catalyst is used as a biomass hydrogenation catalyst.
Further, the desulfurizer taking the iron oxide as the main active component also comprises one or more of iron salt chromium mixture, polymeric ferric sulfate, basic copper carbonate, calcium bicarbonate, zinc oxide, calcium sulfate dihydrate, nickel oxide, cobalt oxide, molybdenum oxide, copper oxide and manganese oxide.
Further, the active ingredient in the desulfurizer which takes the ferric oxide as the main active ingredient is ferric oxide and/or ferroferric oxide.
Further, the ferric oxide is alpha-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, amorphous Fe2O3Amorphous Fe2O3.H2At least one of O;
the ferroferric oxide is cubic system ferroferric oxide.
Further, the waste agent of the desulfurizer which takes the iron oxide as the main active component is generated after the sulfur-containing component in the sulfur-containing gas is removed by the desulfurizer which takes the iron oxide as the main active component.
Further, the sulfur-containing gas is at least one of tail gas, coke oven gas, coal pyrolysis gas and calcium carbide furnace tail gas which are generated after oil products are hydrogenated and upgraded.
Further, the waste agent of the desulfurizer using the iron oxide as the main active component is the waste agent generated after the sulfur-containing component in the sulfur-containing wastewater is removed by the desulfurizer using the iron oxide as the main active component.
Further, the waste agent of the desulfurizer using the iron oxide as the main active component is the waste agent generated after the sulfur-containing component in the oil product is removed by the desulfurizer using the iron oxide as the main active component.
Further, the sulfur-containing component includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum byproducts, gasoline, heavy oil and residual oil.
Compared with the prior art, the invention has the following beneficial effects:
(1) the waste agent of the desulfurizer which takes the iron oxide as the main active component is used as the hydrogenation catalyst, the waste agent formed after the desulfurization treatment of the existing iron oxide desulfurizer is directly used as the hydrogenation catalyst, the application field of the waste agent of the iron oxide desulfurizer is expanded, the regeneration cost of the waste agent of the iron oxide desulfurizer is reduced, the landfill quantity of the waste agent of the iron oxide desulfurizer is reduced, and the harm to the environment is reduced.
(2) The detection shows that the waste desulfurizer using the iron oxide as the main active component is used as the hydrogenation catalyst, and the effect of the waste desulfurizer is equivalent to that of the conventional hydrogenation catalyst.
Further, the waste agent of the iron oxide desulfurizer is regenerated and then is used as a hydrogenation catalyst.
Further, the application of the catalyst as a biomass hydrogenation catalyst.
Further, the active ingredient in the iron oxide desulfurizer is ferric oxide and/or ferroferric oxide.
Further, the ferric oxide is alpha-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, amorphous Fe2O3Amorphous Fe2O3.H2At least one of O;
the ferroferric oxide is cubic system ferroferric oxide.
Further, the waste agent of the iron oxide desulfurizer is a waste agent generated after the sulfur-containing components in the sulfur-containing gas are removed by the iron oxide desulfurizer.
Further, the sulfur-containing gas is at least one of tail gas, coke oven gas, pyrolysis coal gas and calcium carbide furnace tail gas generated after oil products are subjected to hydrogenation and quality improvement.
Further, the waste agent of the iron oxide desulfurizer is a waste agent generated after the sulfur-containing components in the sulfur-containing wastewater are removed by the iron oxide desulfurizer.
Further, the waste agent of the iron oxide desulfurizer is a waste agent generated after the iron oxide desulfurizer removes sulfur-containing components in oil products.
Further, the sulfur-containing component includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum by-products, gasoline, heavy oil and residual oil.
Further, the method for regenerating the waste agent of the iron oxide desulfurizer comprises the following steps:
mixing the waste agent of the iron oxide desulfurizer with water or an alkali solution to prepare slurry;
adding an oxidant into the slurry to perform an oxidation reaction;
and carrying out solid-liquid separation on the slurry after the oxidation reaction, and collecting solids, namely the regenerant of the waste agent of the iron oxide desulfurizer.
Further, before the solid-liquid separation, adding a vulcanizing agent into the slurry after the oxidation reaction to generate a vulcanization reaction; then adding an oxidant into the mixture to perform oxidation reaction; finally, the sulfurization reaction and the oxidation reaction are carried out in a circulating mode until the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction is 1: 0.5-10;
the vulcanizing agent comprises Na2S、Na2S2O3、(NH4)2S、(NH4)2S2O3Thiol, thiourea, dimethyl sulfide, carbonyl sulfide, H 2At least one of S;
the oxidizing agent comprises H2O2、NaClO、O2、O3At least one of (1).
Further, the method for regenerating the waste agent of the iron oxide desulfurizer comprises the following steps:
(1) dispersing the waste ferric oxide desulfurizer with weak acid water to form a dispersion liquid;
(2) heating the dispersion liquid, adding an oxidant into the heated dispersion liquid for reaction, and rapidly transferring generated sulfur dioxide gas during the reaction;
(3) and after the reaction is finished, filtering the reaction solution, and washing and drying the obtained precipitate to obtain the regenerated substance.
Further, the method for regenerating the waste agent of the iron oxide desulfurizer comprises the following steps:
1) grinding the waste iron oxide desulfurizer into particles to obtain waste agent powder;
2) preparing the waste agent powder into a suspension, and introducing oxygen-containing gas for oxidation to form slurry;
3) and filtering the slurry to obtain a solid material, extracting elemental sulfur in the solid material by using a solvent, and obtaining the residual solid after extraction as the regenerated substance.
Further, the method for regenerating the waste agent of the iron oxide desulfurizer comprises the following steps:
1) crushing and grinding the waste iron oxide desulfurizer to obtain waste agent particles;
2) Heating the waste agent particles in an inert gas atmosphere to sublimate sulfur;
3) and then introducing air into the waste agent particles, heating to oxidize the waste desulfurizer, and stopping heating until the powder is cooled to obtain the regenerated substance.
Further, the regeneration method of the waste agent of the iron oxide desulfurizer comprises the following steps:
1) introducing superheated steam into the waste iron oxide desulfurizer, blowing and heating the waste iron oxide desulfurizer, and collecting the solid waste;
2) and introducing reducing gas to reduce the solid waste agent to obtain a regenerated substance.
Compared with the prior art, the invention has the following beneficial effects:
(1) the waste agent of the iron oxide desulfurizer is regenerated and then directly used as the hydrogenation catalyst, so that the application field of the waste agent of the iron oxide desulfurizer is expanded, the cost of the regeneration of the waste agent of the iron oxide desulfurizer is reduced, the landfill amount of the waste agent of the iron oxide desulfurizer is reduced, the harm to the environment is reduced, and meanwhile, the price of the waste agent of the iron oxide desulfurizer is far lower than that of the hydrogenation catalyst as the waste agent of the iron oxide desulfurizer is used as an idle resource, so that the production cost of the hydrogenation catalyst industry is reduced.
(2) The waste agent of the iron oxide desulfurizer provided by the invention is regenerated and then used as a hydrogenation catalyst, and the detection shows that the waste agent of the desulfurizer is regenerated and then used as a hydrogenation catalyst, and the effect of the waste agent of the iron oxide desulfurizer is equivalent to or even superior to that of the conventional hydrogenation catalyst.
Further, the waste agent of the desulfurizing agent containing iron oxide is regenerated and then used as a hydrogenation catalyst.
Further, the application of the catalyst is used as a biomass hydrogenation catalyst.
Further, the desulfurizer containing the ferric oxide also comprises one or more of ferric salt chromium mixture, polymeric ferric sulfate, basic copper carbonate, calcium bicarbonate, zinc oxide, calcium sulfate dihydrate, nickel oxide, cobalt oxide, molybdenum oxide, copper oxide and manganese oxide.
Further, the active ingredient in the desulfurizer using iron oxide as the main active ingredient is ferric oxide and/or ferroferric oxide.
Further, the ferric oxide is alpha-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, amorphous Fe2O3Amorphous Fe2O3.H2At least one of O;
the ferroferric oxide is cubic system ferroferric oxide.
Further, the waste agent of the desulfurizer containing the iron oxide is regenerated to be a waste agent generated after the sulfur-containing component in the sulfur-containing gas is removed by the desulfurizer using the iron oxide as a main active component; or
The waste agent of the desulfurizer containing the ferric oxide is regenerated and is generated after the sulfur-containing component in the sulfur-containing wastewater is removed by the desulfurizer which takes the ferric oxide as the main active component; or
The waste agent of the desulfurizer containing the ferric oxide is regenerated and is generated after the sulfur-containing component in the oil product is removed by the desulfurizer using the ferric oxide as the main active component.
Further, the sulfur-containing component includes at least hydrogen sulfide.
Further, the sulfur-containing gas is at least one of tail gas, coke oven gas, pyrolysis coal gas and calcium carbide furnace tail gas generated after oil products are subjected to hydrogenation and quality improvement; or
The oil product is at least one of petroleum, petroleum by-products, gasoline, heavy oil and residual oil.
Further, the method for regenerating the waste agent of the desulfurizer containing the iron oxide comprises the following steps:
mixing the waste agent of the desulfurizer containing the ferric oxide with water or an alkali solution to prepare slurry;
adding an oxidant into the slurry to perform an oxidation reaction;
and carrying out solid-liquid separation on the slurry after the oxidation reaction, and collecting solids, namely the regenerant of the waste agent of the desulfurizer containing the ferric oxide.
Further, before the solid-liquid separation, adding a vulcanizing agent into the slurry after the oxidation reaction to generate a vulcanization reaction; then adding an oxidant into the mixture to perform oxidation reaction; and finally, circularly carrying out the sulfuration reaction and the oxidation reaction until the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction is 1: 0.5-10.
Further, the vulcanizing agent includes Na2S、Na2S2O3、(NH4)2S、(NH4)2S2O3Thiol, thiourea, dimethyl sulfide, carbonyl sulfide, H2At least one of S;
the oxidizing agent comprises H2O2、NaClO、O2、O3At least one of (a).
Further, the method for regenerating the waste agent of the desulfurizing agent containing the iron oxide comprises the following steps:
(1) dispersing the waste desulfurizer containing the ferric oxide by weak acid water to form dispersion liquid;
(2) heating the dispersion liquid, adding an oxidant into the heated dispersion liquid for reaction, and rapidly transferring generated sulfur dioxide gas during the reaction;
(3) and after the reaction is finished, filtering the reaction solution, washing and drying the obtained precipitate to obtain the regenerated substance.
Further, the method for regenerating the waste agent of the desulfurizer containing the iron oxide comprises the following steps:
1) grinding the waste agent of the desulfurizer with the ferric oxide into particles to obtain waste agent powder;
2) preparing the waste agent powder into a suspension, and introducing oxygen-containing gas for oxidation to form slurry;
3) and filtering the slurry to obtain a solid material, extracting elemental sulfur in the solid material by using a solvent, and obtaining the residual solid after extraction as the regenerated substance.
Further, the method for regenerating the waste agent of the desulfurizer containing the iron oxide comprises the following steps:
1) Crushing and grinding the waste agent of the desulfurizer containing the ferric oxide to obtain waste agent particles;
2) heating the waste agent particles in an inert gas atmosphere to sublimate sulfur;
3) and then introducing air into the waste agent particles, heating to oxidize the waste desulfurizer, and stopping heating until the powder is cooled to obtain the regenerated substance.
Further, the method for regenerating the waste agent of the desulfurizer containing the iron oxide comprises the following steps:
1) introducing superheated steam into the waste agent of the desulfurizer containing the ferric oxide, purging and heating the waste agent, and collecting the solid waste agent;
2) and introducing reducing gas to reduce the solid waste agent to obtain a regenerated substance.
Compared with the prior art, the invention has the following beneficial effects:
(1) the waste agent of the desulfurizer containing the iron oxide is regenerated and then used as the hydrogenation catalyst, the waste agent formed after the desulfurization treatment of the existing iron oxide desulfurizer is regenerated and then directly used as the hydrogenation catalyst, the application field of the regenerated substance of the waste agent of the iron oxide desulfurizer is developed, the landfill amount of the waste agent of the iron oxide desulfurizer is reduced, the harm to the environment is reduced, and meanwhile, the price of the waste agent of the iron oxide desulfurizer is far lower than that of the hydrogenation catalyst as the waste agent of the iron oxide desulfurizer is used as an idle resource, so that the production cost of the hydrogenation industry is reduced.
(2) The waste agent of the desulfurizer containing the ferric oxide provided by the invention is regenerated and then used as a hydrogenation catalyst, and the detection shows that the waste agent of the desulfurizer is regenerated and then used as a hydrogenation catalyst, and the effect of the waste agent of the desulfurizer is equivalent to or even superior to that of the conventional hydrogenation catalyst.
(3) The waste agent of the desulfurizer containing the ferric oxide is regenerated and then used as a hydrogenation catalyst, the waste agent of the desulfurizer containing the ferric oxide is firstly oxidized and regenerated, and further undergoes multiple sulfuration-oxidation reactions, iron oxide and iron-sulfur compound crystal phases undergo multiple reconstruction and transformation in the process, and S is added2-The ionic radius (0.18nm) is larger than O2-The ionic radius (0.14nm), so with the conversion between Fe-O bond and Fe-S bond, the unit cell of ferric oxide also undergoes contraction and expansion, and further causes the ferric oxide crystal particles with stable structure to become loose and crack, and generates a large amount of nano ferric oxide which has good thiophilic property and is easy to be vulcanized. Meanwhile, the surface of the nano iron oxide is covered with a non-polar elemental sulfur layer, the elemental sulfur layer can not only prevent the agglomeration and growth among the nano iron oxide particles and greatly improve the dispersibility of the nano iron oxide particles, but also can highly disperse the nano iron oxide in a non-polar oil product by utilizing the similar compatibility characteristics existing among substances. Moreover, the sulfur-covered nano iron oxide has excellent hydrogenation catalytic capability due to the close sulfur-iron connection and the small particle size of the nano iron oxide.
Further, the use of the waste agent of the iron oxide desulfurizing agent as a CO shift catalyst.
Further, the active ingredient in the iron oxide desulfurizer is ferric oxide and/or ferroferric oxide.
Further, the ferric oxide is alpha-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, amorphous Fe2O3Amorphous Fe2O3.H2At least one of O;
the ferroferric oxide is cubic system ferroferric oxide.
Further, the waste agent of the iron oxide desulfurizer is a waste agent generated after the sulfur-containing component in the sulfur-containing gas is removed by the iron oxide desulfurizer.
Further, the sulfur-containing gas is at least one of tail gas, coke oven gas, pyrolysis coal gas and calcium carbide furnace tail gas generated after oil products are subjected to hydrogenation and quality improvement.
Further, the waste agent of the iron oxide desulfurizer is a waste agent generated after the sulfur-containing components in the sulfur-containing wastewater are removed by the iron oxide desulfurizer.
Further, the waste agent of the iron oxide desulfurizer is a waste agent generated after the sulfur-containing components in the oil product are removed by the iron oxide desulfurizer.
Further, the sulfur-containing component includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum by-products, gasoline, heavy oil and residual oil.
Compared with the prior art, the invention has the following beneficial effects:
(1) The waste agent of the iron oxide desulfurizer provided by the invention is used as a CO conversion catalyst, the waste agent formed after the desulfurization treatment of the existing iron oxide desulfurizer is directly used as the CO conversion catalyst, the application field of the waste agent of the iron oxide desulfurizer is developed, the regeneration cost of the waste agent of the iron oxide desulfurizer is reduced, the landfill amount of the waste agent of the iron oxide desulfurizer is reduced, and the harm to the environment is reduced.
(2) The detection shows that the waste agent of the iron oxide desulfurizer is used as the CO shift catalyst, and the effect of the waste agent of the iron oxide desulfurizer is equivalent to that of the conventional CO shift catalyst.
Further, the use of a waste desulfurizer containing iron oxide as a main active component as a CO shift catalyst.
Further, the desulfurizer using iron oxide as a main active component also comprises one or more of iron salt chromium mixture, polymeric ferric sulfate, basic copper carbonate, calcium bicarbonate, zinc oxide, calcium sulfate dihydrate, nickel oxide, cobalt oxide, molybdenum oxide, copper oxide and manganese oxide.
Further, the active ingredient in the desulfurizer which takes the ferric oxide as the main active ingredient is ferric oxide and/or ferroferric oxide.
Further, the ferric oxide is alpha-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, amorphous Fe2O3Amorphous Fe2O3.H2At least one of O;
the ferroferric oxide is cubic system ferroferric oxide.
Further, the waste agent of the desulfurizer which takes the iron oxide as the main active component is generated after the sulfur-containing component in the sulfur-containing gas is removed by the desulfurizer which takes the iron oxide as the main active component.
Further, the sulfur-containing gas is at least one of tail gas, coke oven gas, pyrolysis coal gas and calcium carbide furnace tail gas generated after oil products are subjected to hydrogenation and quality improvement.
Further, the waste agent of the desulfurizer which takes the iron oxide as the main active component is generated after the sulfur-containing component in the sulfur-containing wastewater is removed by the desulfurizer which takes the iron oxide as the main active component.
Further, the waste agent of the desulfurizer which takes the iron oxide as the main active component is the waste agent generated after the sulfur-containing component in the oil product is removed by the desulfurizer which takes the iron oxide as the main active component.
Further, the sulfur-containing component includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum by-products, gasoline, heavy oil and residual oil.
Compared with the prior art, the invention has the following beneficial effects:
(1) the waste agent of the desulfurizer which takes the iron oxide as the main active component is used as the CO conversion catalyst, the waste agent formed after the existing iron oxide desulfurizer is subjected to desulfurization treatment is directly used as the CO conversion catalyst, the application field of the waste agent of the iron oxide desulfurizer is expanded, the regeneration cost of the waste agent of the iron oxide desulfurizer is reduced, the landfill quantity of the waste agent of the iron oxide desulfurizer is reduced, the harm to the environment is reduced, and meanwhile, the price of the waste agent of the iron oxide desulfurizer is far lower than the price of the CO conversion catalyst because the waste agent of the iron oxide desulfurizer is used as an idle resource, so that the production cost of the CO conversion industry is reduced.
(2) The detection shows that the waste desulfurizer using the iron oxide as the main active component is used as the CO shift catalyst, and the effect of the waste desulfurizer is equivalent to that of the conventional CO shift catalyst.
Further, the waste iron oxide desulfurizer is regenerated and then used as a CO shift catalyst.
Further, the active ingredient in the iron oxide desulfurizer is ferric oxide and/or ferroferric oxide.
Further, the ferric oxide is alpha-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, amorphous Fe2O3Amorphous Fe2O3.H2At least one of O;
the ferroferric oxide is cubic system ferroferric oxide.
Further, the waste agent of the iron oxide desulfurizer is a waste agent generated after the sulfur-containing component in the sulfur-containing gas is removed by the iron oxide desulfurizer.
Further, the sulfur-containing gas is at least one of tail gas, coke oven gas, pyrolysis coal gas and calcium carbide furnace tail gas generated after oil products are subjected to hydrogenation and quality improvement.
Further, the waste agent of the iron oxide desulfurizer is a waste agent generated after the sulfur-containing components in the sulfur-containing wastewater are removed by the iron oxide desulfurizer.
Further, the waste agent of the iron oxide desulfurizer is a waste agent generated after the sulfur-containing components in the oil product are removed by the iron oxide desulfurizer.
Further, the sulfur-containing component includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum by-products, gasoline, heavy oil and residual oil.
Further, the regeneration method of the waste agent of the iron oxide desulfurizer comprises the following steps:
mixing the waste agent of the iron oxide desulfurizer with water or an alkali solution to prepare slurry;
adding an oxidant into the slurry to perform an oxidation reaction;
And carrying out solid-liquid separation on the slurry after the oxidation reaction, and collecting solids, namely the regenerant of the waste agent of the iron oxide desulfurizer.
Further, before the solid-liquid separation, adding a vulcanizing agent into the slurry after the oxidation reaction to generate a vulcanization reaction; then adding an oxidant into the mixture to perform oxidation reaction; finally, circularly performing the sulfurization reaction and the oxidation reaction until the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction is 1: 0.5-10;
the vulcanizing agent comprises Na2S、Na2S2O3、(NH4)2S、(NH4)2S2O3Thiol, thiourea, dimethyl sulfide, carbonyl sulfide, H2At least one of S;
the oxidant comprises H2O2、NaClO、O2、O3At least one of (1).
Compared with the prior art, the invention has the following beneficial effects:
(1) the waste agent of the iron oxide desulfurizer provided by the invention is regenerated and then used as a CO conversion catalyst, the waste agent formed after the desulfurization treatment of the existing iron oxide desulfurizer is regenerated and then directly used as the CO conversion catalyst, the application field of the waste agent of the iron oxide desulfurizer is developed, the regeneration cost of the waste agent of the iron oxide desulfurizer is reduced, the landfill amount of the waste agent of the iron oxide desulfurizer is reduced, the harm to the environment is reduced, and meanwhile, the price of the waste agent of the iron oxide desulfurizer is far lower than that of the CO conversion catalyst because the waste agent of the iron oxide desulfurizer is used as an idle resource, so that the production cost of the CO conversion industry is reduced.
(2) The waste agent of the iron oxide desulfurizer provided by the invention is regenerated and then used as a CO shift catalyst, and the detection shows that the waste agent of the desulfurizer is regenerated and then used as the CO shift catalyst, and the effect of the waste agent is equivalent to that of the conventional CO shift catalyst.
Further, the waste agent of the desulfurizing agent containing iron oxide is regenerated and then used as a CO shift catalyst.
Further, the desulfurizer containing the iron oxide also comprises one or more of iron salt chromium mixture, polymeric ferric sulfate, basic copper carbonate, calcium bicarbonate, zinc oxide, calcium sulfate dihydrate, nickel oxide, cobalt oxide, molybdenum oxide, copper oxide and manganese oxide.
Further, the active ingredient in the desulfurizer using iron oxide as the main active ingredient is ferric oxide and/or ferroferric oxide.
Further, the ferric oxide is alpha-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, amorphous Fe2O3Amorphous Fe2O3.H2At least one of O;
the ferroferric oxide is cubic system ferroferric oxide.
Further, the waste agent of the desulfurizer containing the iron oxide is regenerated to be the waste agent generated after the sulfur-containing component in the sulfur-containing gas is removed by the desulfurizer using the iron oxide as the main active component; or
The waste agent of the desulfurizer containing the ferric oxide is regenerated and is generated after the sulfur-containing component in the sulfur-containing wastewater is removed by the desulfurizer which takes the ferric oxide as the main active component; or
The waste agent of the desulfurizer containing the ferric oxide is regenerated and is generated after the sulfur-containing component in the oil product is removed by the desulfurizer using the ferric oxide as the main active component.
Further, the sulfur-containing component includes at least hydrogen sulfide.
Further, the sulfur-containing gas is at least one of tail gas, coke oven gas, pyrolysis coal gas and calcium carbide furnace tail gas generated after oil products are subjected to hydrogenation and quality improvement; or
The oil product is at least one of petroleum, petroleum by-products, gasoline, heavy oil and residual oil.
Further, the method for regenerating the waste agent of the desulfurizer containing the iron oxide comprises the following steps:
mixing the waste desulfurizer containing the ferric oxide with water or an alkali solution to prepare slurry;
adding an oxidant into the slurry to perform an oxidation reaction;
and carrying out solid-liquid separation on the slurry after the oxidation reaction, and collecting solids, namely the regenerant of the waste agent of the desulfurizer containing the ferric oxide.
Further, before the solid-liquid separation, adding a vulcanizing agent into the slurry after the oxidation reaction to generate a vulcanization reaction; then adding an oxidant into the mixture to perform oxidation reaction; and finally, circularly performing the sulfurization reaction and the oxidation reaction until the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction is 1: 0.5-10.
Further, the vulcanizing agent includes Na2S、Na2S2O3、(NH4)2S、(NH4)2S2O3Thiol, thiourea, dimethyl sulfide, carbonyl sulfide, H2At least one of S;
the oxidizing agent comprises H2O2、NaClO、O2、O3At least one of (1).
Compared with the prior art, the invention has the following beneficial effects:
(1) the waste agent of the desulfurizer containing the iron oxide is regenerated and then used as the CO conversion catalyst, the waste agent formed after the desulfurization treatment of the existing iron oxide desulfurizer is regenerated and then directly used as the CO conversion catalyst, the application field of the regenerated substance of the waste agent of the iron oxide desulfurizer is developed, the landfill amount of the waste agent of the iron oxide desulfurizer is reduced, the harm to the environment is reduced, and meanwhile, the price of the waste agent of the iron oxide desulfurizer is far lower than that of the CO conversion catalyst because the waste agent of the iron oxide desulfurizer is used as an idle resource, so that the production cost of the CO conversion industry is reduced.
(2) The waste agent of the desulfurizer containing the iron oxide provided by the invention is regenerated and then used as a CO shift catalyst, and the detection shows that the waste agent of the desulfurizer is regenerated and then used as the CO shift catalyst, and the effect of the waste agent is equivalent to or even superior to that of the conventional CO shift catalyst.
(3) The waste agent of the desulfurizer containing the iron oxide is regenerated and then used as a CO conversion catalyst, the waste agent of the desulfurizer containing the iron oxide is firstly oxidized and regenerated, and further undergoes multiple sulfuration-oxidation reactions, iron oxide and iron-sulfur compound crystal phases undergo multiple reconstruction and transformation in the process, and S is added2-The ionic radius (0.18nm) is larger than O2-The ionic radius (0.14nm), so with the conversion between Fe-O bond and Fe-S bond, the unit cell of ferric oxide also undergoes contraction and expansion, and further causes the ferric oxide crystal particles with stable structure to become loose and crack, and generates a large amount of nano ferric oxide which has good thiophilic property and is easy to be vulcanized. Meanwhile, the surface of the nano iron oxide is covered with a non-polar elemental sulfur layer, the elemental sulfur layer can not only prevent the agglomeration and growth among nano iron oxide particles and greatly improve the dispersibility of the nano iron oxide, but also can utilize the similar compatibility characteristics existing among substances to highly disperse the nano iron oxide in a non-polar oil product. Moreover, the sulfur-covered nano iron oxide has excellent CO conversion catalytic capability due to the close sulfur-iron connection and the small particle size of the nano iron oxide.
Further, use of a spent agent of a ferric oxide containing desulphurisation agent or a spent agent regenerant in an organic matter conversion process.
Further, the active ingredient in the desulfurizer which takes the ferric oxide as the main active ingredient is ferric oxide and/or ferroferric oxide.
Further, the ferric oxide is alpha-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, amorphous Fe2O3Amorphous Fe2O3.H2At least one of O;
the ferroferric oxide is cubic system ferroferric oxide.
Further, the desulfurizer containing the ferric oxide also comprises one or more of ferric salt chromium mixture, polymeric ferric sulfate, basic copper carbonate, calcium bicarbonate, zinc oxide, calcium sulfate dihydrate, nickel oxide, cobalt oxide, molybdenum oxide, copper oxide and manganese oxide.
Further, the waste agent of the desulfurizer containing the iron oxide is generated after the sulfur-containing component in the sulfur-containing gas is removed by the desulfurizer containing the iron oxide; or
The waste agent of the desulfurizer containing the ferric oxide is generated after the desulfurizer containing the ferric oxide removes sulfur-containing components in sulfur-containing wastewater; or
The waste agent of the desulfurizer containing the ferric oxide is generated after the sulfur-containing components in the oil product are removed by the desulfurizer containing the ferric oxide.
Further, the sulfur-containing component includes at least hydrogen sulfide; or the like, or a combination thereof,
the sulfur-containing gas is at least one of tail gas, coke oven gas, coal pyrolysis gas and calcium carbide furnace tail gas generated after oil products are subjected to hydrogenation upgrading; or the like, or a combination thereof,
the oil product is at least one of petroleum, petroleum by-products, gasoline, heavy oil and residual oil.
Further, the step of preparing the waste agent regenerant by regenerating the waste agent of the desulfurizer containing the iron oxide comprises the following steps,
a1, mixing the waste agent of the desulfurizer containing the ferric oxide with water or alkali solution to prepare slurry;
a2, adding an oxidizing agent into the slurry to carry out an oxidation reaction;
a3, carrying out solid-liquid separation on the slurry after the oxidation reaction, and collecting solids, namely the waste agent regenerant;
or the like, or a combination thereof,
the step of preparing the waste agent regenerant by regenerating the waste agent of the desulfurizer containing the ferric oxide comprises the following steps,
b1, dispersing the waste agent of the desulfurizer containing the ferric oxide by weak acid water to form dispersion liquid;
b2, heating the dispersion liquid, adding an oxidant into the heated dispersion liquid for reaction, and rapidly transferring generated sulfur dioxide gas during the reaction;
b3, after the reaction is finished, filtering the reaction solution, washing and drying the obtained precipitate to obtain the waste agent regenerant;
Or the like, or a combination thereof,
the step of preparing the waste agent regenerant by regenerating the waste agent of the desulfurizer containing the ferric oxide comprises the following steps,
c1, grinding the waste agent of the desulfurizer with the ferric oxide into particles to obtain waste agent powder;
c2, preparing the waste agent powder into a suspension, and introducing oxygen-containing gas for oxidation to form slurry;
c3, filtering the slurry to obtain a solid material, extracting elemental sulfur in the solid material by using a solvent, wherein the residual solid after extraction is the waste agent regenerant
Or the like, or a combination thereof,
the step of preparing the waste agent regenerant by regenerating the waste agent of the desulfurizer containing the ferric oxide comprises the following steps,
d1, crushing and grinding the waste agent of the desulfurizer containing the iron oxide to obtain waste agent particles;
d2, heating the waste agent particles in an inert gas atmosphere to sublimate sulfur;
d3, introducing air into the waste agent particles, heating to oxidize the waste desulfurizer, stopping heating until the powder is cooled, and obtaining the waste agent regenerant;
or the like, or a combination thereof,
the step of preparing the waste agent regenerant by regenerating the waste agent of the desulfurizer containing the ferric oxide comprises the following steps,
e1, introducing superheated steam into the waste agent of the desulfurizer containing the ferric oxide, purging and heating the waste agent, and collecting the solid waste agent;
E2, introducing reducing gas to reduce the solid waste agent to obtain the waste agent regenerant.
Further, before the solid-liquid separation, adding a vulcanizing agent into the slurry after the oxidation reaction to carry out a vulcanization reaction; then adding an oxidant into the mixture to perform oxidation reaction; finally, the sulfurization reaction and the oxidation reaction are carried out in a circulating mode until the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction is 1: 0.5-10;
the vulcanizing agent comprises Na2S、Na2S2O3、(NH4)2S、(NH4)2S2O3Thiol, thiourea, dimethyl sulfide, carbonyl sulfide, H2S、CS2At least one of (a);
the oxidizing agent comprises H2O2、NaClO、O2、O3At least one of (1).
Further, waste agents of the desulfurizer containing the iron oxide and/or regenerants of the waste agents and organic matters are prepared to form slurry, the slurry is mixed with pure CO or CO-containing gas for conversion reaction, preferably, a sulfur-containing compound is added to the reaction system, wherein the molar ratio of iron element to sulfur element is 1 (0.5-5).
Further, the reaction pressure of the conversion reaction is 5-22MPa, and the reaction temperature is 200-470 ℃; or,
in the slurry, the content of the waste agent and/or the regenerant of the waste agent of the desulfurizer containing the ferric oxide is 0.1-10 wt%, and the average particle size of the waste agent and/or the regenerant is 0.1-5 mm; or,
The CO-containing gas has a CO content of not less than 15% by volume, preferably not less than 50% by volume, most preferably not less than 90% by volume.
The technical scheme of the invention has the following advantages:
(1) the waste agent of the desulfurizer containing the iron oxide or the regenerant of the waste agent provided by the embodiment of the invention is used as a catalyst of an organic matter conversion process, the application field of the waste agent of the desulfurizer containing the iron oxide or the regenerant thereof is expanded, the landfill amount of the waste agent of the desulfurizer containing the iron oxide is reduced, the harm to the environment is reduced, and meanwhile, the waste agent of the desulfurizer containing the iron oxide is an idle resource and is low in price, so that the cost of the organic matter conversion process is reduced.
(2) The waste agent of the desulfurizer containing the iron oxide or the regenerant of the waste agent provided by the embodiment of the invention can be suitable for liquefying the non-pure hydrogen atmosphere of the biomass, so that the limitation that pure hydrogen must be used for liquefying and converting the biomass is avoided, the cost is reduced, the process path of biomass conversion is expanded, and the large-scale quantitative production of the biomass conversion process in the industry is realized.
(3) The waste agent of the desulfurizer containing the iron oxide or the regenerant of the waste agent provided by the embodiment of the invention is used as a catalyst of an organic matter conversion process, can effectively utilize carbonylation to block free radical polycondensation of organic matters in a cracking process in the presence of CO and realize the conversion active hydrogen hydrogenation of the CO and water, organic matters, particularly biomass solids, can be directly subjected to conversion reaction without dehydration in the conversion reaction, water can be additionally added into biomass liquid or mineral oil, the liquefaction yield is improved, the heat productivity of the prepared oil product can be improved, and a large amount of wastewater cannot be generated after the conversion reaction is finished.
(4) The waste agent of the desulfurizer containing the iron oxide or the regenerant of the waste agent provided by the embodiment of the invention is used as a catalyst of an organic matter conversion process, a proper amount of sulfur and organic matter are added to form slurry, under the atmosphere of CO, the catalysts are firstly combined with CO to form carbonyl compounds, then carbon atoms are grafted on micromolecule active sites formed after the organic matter (such as biomass and the like) is thermally cracked through the carbonyl compounds, and meanwhile, the effects of CO conversion in-situ hydrogen production and catalytic hydrodeoxygenation are realized under the catalytic action of iron and sulfur elements, the oxygen content of oil products is reduced, and the liquefaction yield of solid organic matter and the oil product yield of long molecular chain conversion to micromolecules are greatly improved;
preferably, the regenerant is obtained by alternately carrying out vulcanization and oxidation regeneration on the waste desulfurizer by a slurry method, and further, an iron oxide compound and an iron sulfur compound crystal phase undergo reconstruction and transformation in the process through multiple vulcanization-oxidation reactions, and S is added2-Ionic radius (0.18nm) greater than O2-The ionic radius (0.14nm), so with the transformation between Fe-O bond and Fe-S bond, the unit cell of the ferrite compound also undergoes contraction and expansion, and further the crystal particles of the ferrite compound with stable structure become loose and crack, and a large amount of nano iron compound is generated. Meanwhile, the surface of the nano iron compound is covered with a non-polar elemental sulfur layer, the elemental sulfur layer can not only prevent the agglomeration and growth among the nano iron compound particles and greatly improve the dispersibility of the nano iron compound, but also can highly disperse the nano iron compound in a non-polar oil product by utilizing the similar compatibility characteristics existing among substances; moreover, because of the close sulfur-iron connection and the small particle size of the nano-iron compound, the sulfur and the nano-iron compound can react at low temperature to generate pyrrhotite (Fe) with poor heavy oil hydrogenation activity 1-xS), the regenerated product obtained by the method is small in particle size and good in lipophilicity, the structure of the regenerated product is a flaky nano structure, and the adsorbed sulfur is blocked between sheets, so that the agglomeration of the regenerated product is avoided, the adsorption capacity of CO is greatly improved, and the carbonylation, hydrogen production conversion and hydrogenation catalytic capacities are enhanced.
(5) The waste agent of the desulfurizer containing the iron oxide or the regenerant of the waste agent provided by the embodiment of the invention is used as a catalyst of an organic matter conversion process, the organic matter conversion process comprises the steps of sequentially carrying out primary crushing, compression and secondary crushing on biomass solids, then mixing the biomass solids with the catalyst to obtain a mixture, adding the mixture into a solvent, grinding and pulping to obtain the slurry with the biomass content of 10-60 wt%The process comprises the steps of compressing biomass solids, enabling loose biomass solids to sequentially undergo the stages of collapse, closure and the like, rearrangement and mechanical deformation, and enabling the volume of the biomass solids to be greatly reduced, so that the porosity of the biomass can be reduced, the density and the specific gravity of the biomass can be increased, the biomass solids can be favorably dispersed in oil products, the content of the biomass solids in the oil products can be increased, the concentration of reaction materials is increased, the solid content in slurry can reach 10-60 wt%, and meanwhile, the increase of the concentration of the biomass solids in the slurry can also increase the conveying capacity of a pump to the biomass solids in unit time, so that the efficiency of the whole liquefaction process is improved, and the industrial cost and the energy consumption are reduced; in addition, the increase of the specific gravity of the biomass solid is also beneficial to the suspension and dispersion of the biomass solid in the slurry, so that the viscosity of the slurry can be reduced, the smooth flowing of the slurry in a pipeline is realized, the pipeline is prevented from being blocked, the stable running and conveying of a pump are realized, and meanwhile, high-viscosity waste oil which cannot be used as a liquefied solvent in the prior art, such as waste engine oil, kitchen waste oil, rancid oil and the like, can also be utilized. Further, the bulk density of the biomass after primary crushing and compression is regulated and controlled to be not less than 0.4 g/cm 3Regulating and controlling the average particle size of the biomass subjected to secondary crushing to be less than 5mm, and adding the biomass into a solvent for grinding and pulping conveniently by the regulation and control mode, so that the solid content of the biomass in the slurry is improved; the compression temperature is controlled to be 30-60 ℃, and the biomass is compressed at the temperature, so that the rheological property of biomass solid can be obviously enhanced, the viscosity of slurry is reduced, smooth flowing of the slurry in a pipeline is realized, the pipeline is prevented from being blocked, and the stable running and conveying of a pump are realized.
(6) The waste agent of the desulfurizer containing the ferric oxide or the regenerant of the waste agent provided by the embodiment of the invention is used as a catalyst of an organic matter conversion process, and a catalytic reaction raw material and CO-containing gas are subjected to reactions such as cracking, carbonylation, conversion, hydrogenation and the like in a reactor; further, by adopting a slurry bed reactor, firstly, reaction raw materials are fed into the slurry bed reactor from the bottom of the reactor to react, and simultaneously, gas containing CO is injected into the reactor, so that the difference control of the flow rate of each phase state can be realized in the reactor by depending on the different specific gravities of the gas, liquid and solid materials and matching with the change of the specific gravity difference caused by the yield of the light oil product after the reaction, the cracking, the carbonylation, the transformation, the hydrogenation and the reaction of the biomass solid raw materials are carried out in the reactor from bottom to top, even if the biomass solid with large specific gravity and the catalyst solid particles rise along with the gas and the light oil product in the process, the biomass solid and the catalyst solid particles return to the bottom to participate in the reaction again under the action of the gas containing CO at the upper part, and the injection quantity of the gas containing CO in the slurry entering the reactor are properly adjusted according to the material densities at the upper part, the middle part and the lower part of the reactor, therefore, the circulation of the unconverted organic matters in the reactor and the balanced discharge of the catalyst are realized, and the full progress of various reactions can be ensured, thereby being beneficial to improving the conversion rate of the organic matters and the yield of the bio-oil.
(7) The waste agent of the desulfurizer containing the ferric oxide or the regenerant of the waste agent provided by the embodiment of the invention is used as a catalyst of an organic matter conversion process, organic matters are not required to be dehydrated in the organic matter conversion process, and the drying cost is reduced; the gas containing CO is used in the reaction process, the gas containing CO can be pure CO or impure, for example, the gas contains CO, hydrogen sulfide, methane and the like, and can also be synthesis gas generated by gasifying coal, biomass, natural gas and mineral oil, the rest gas except CO in the synthesis gas can be a mixture containing hydrogen, carbon dioxide or methane and ethane, and the gas manufacturing cost is greatly reduced; in the reaction process, the combined processes of cracking reaction, carbonylation reaction, shift reaction, hydrogenation reaction and the like are realized by using CO-containing gas and adopting the action of a cheap iron-based catalyst or a waste agent, sufficient free radicals are easily provided, carbonization and coking of organic matters are avoided, the conversion rate of the organic matters and the liquid yield are high, and the reaction temperature and the pressure are reduced; the oil produced by the liquefaction process can also be used in a preceding process to prepare a slurry.
(8) The desulfurizer containing the ferric oxide mentioned in the application is a desulfurizer formed by directly forming the ferric oxide, or a desulfurizer formed by loading the ferric oxide as a main active component on a carrier, or a desulfurizer formed by mixing the ferric oxide with an organic binder or other additives, or a desulfurizer formed by mixing the ferric oxide with the organic binder or other additives and loading the mixture on the carrier, and the like. In conclusion, the desulfurizer containing iron oxide is applicable to the desulfurizer prepared by all preparation methods of the desulfurizer containing iron oxide in the prior art, the waste agent is the waste agent generated by applying the desulfurizer containing iron oxide to various desulfurization methods in the prior art, and is particularly applicable to the waste agent of the desulfurizer containing iron oxide generated after desulfurization of methane, liquid, coal gas, flue gas, petroleum and gasoline, and the waste agent regenerant obtained by the regeneration method of the waste agent can adopt all regeneration methods in the prior art.
Further, the waste agent of the hydrogenation catalyst which takes Ni-Mo as the main active component is used as the CO shift catalyst.
Furthermore, the hydrogenation catalyst with Ni-Mo as the main active component also comprises a carrier, a binder and an auxiliary agent.
Further, the carrier is alumina, activated carbon, a molecular sieve, titanium dioxide, a silicon oxide/alumina composite carrier, amorphous silicon-aluminum and zeolite;
the binder is at least one of attapulgite, sesbania powder, nitric acid, citric acid, silica sol, carboxymethyl cellulose, bentonite and diatomite;
the auxiliary agent is at least one of tungsten oxide, cobalt oxide, rare earth elements, chromic oxide, phosphorus pentoxide, VIB group transition metals, VIIB group transition metals, platinum, palladium, phosphorus, silicon, boron, titanium, zinc, fluorine and zirconium; preferably, the group VIB transition metals are chromium, molybdenum, tungsten; the group VIIB transition metal is manganese.
Furthermore, the mass fraction of nickel oxide and molybdenum oxide in the hydrogenation catalyst taking Ni-Mo as the main active component is 10-60%.
Further, the molar ratio of the nickel oxide to the molybdenum oxide is (0.3-0.5): 1.
furthermore, the waste agent of the hydrogenation catalyst with Ni-Mo as the main active component is generated after the hydrogenation of heavy oil by the hydrogenation catalyst with Ni-Mo as the main active component.
Further, the heavy oil comprises one or more of atmospheric residue, vacuum residue, deasphalted oil, oil sand asphalt, heavy crude oil, coal tar and coal liquefaction heavy oil.
Furthermore, the waste agent of the hydrogenation catalyst with Ni-Mo as the main active component is generated after catalytic hydrogenation of cracked diesel oil of the hydrogenation catalyst with Ni-Mo as the main active component.
Furthermore, the waste agent of the hydrogenation catalyst with Ni-Mo as the main active component is the waste agent generated after the hydrogenation of the hydrogenation catalyst with Ni-Mo as the main active component catalyzes and hydrogenates petroleum resin.
Compared with the prior art, the invention has the following beneficial effects:
(1) the waste agent of the hydrogenation catalyst with Ni-Mo as the main active ingredient provided by the invention can be directly used as the CO conversion catalyst, the application field of the waste agent of the hydrogenation catalyst with Ni-Mo as the main active ingredient is developed, the cost of regenerating the waste agent of the hydrogenation catalyst with Ni-Mo as the main active ingredient is reduced, the landfill amount of the waste agent of the hydrogenation catalyst with Ni-Mo as the main active ingredient is reduced, the harm to the environment is reduced, and simultaneously, because the waste agent of the hydrogenation catalyst which takes Ni-Mo as the main active component is taken as idle resource, the price of the catalyst is far lower than that of the CO conversion catalyst, so that the production cost of the CO conversion industry is reduced.
(2) According to the application of the waste agent of the hydrogenation catalyst with Ni-Mo as the main active component as the CO shift catalyst, the detection proves that the waste agent of the existing hydrogenation catalyst with Ni-Mo as the main active component is used as the CO shift catalyst, and the effect is equivalent to that of the conventional CO shift catalyst.
Detailed Description
The FeOOH desulfurizer mentioned in the application can be a desulfurizer directly formed by FeOOH, or can be a desulfurizer formed by loading FeOOH as an active component on a carrier, and the waste agent is a waste agent generated by applying the FeOOH desulfurizer to various desulfurization methods in the prior art, and is particularly suitable for waste agents of the FeOOH desulfurizer generated after desulfurization of biogas, liquid, coal gas, flue gas, petroleum and gasoline.
The desulfurizer mainly taking FeOOH as an active component is a desulfurizer formed by matching FeOOH and other active components in the prior art, and the waste agent is a waste agent generated by applying the desulfurizer to various desulfurization methods in the prior art, and is particularly suitable for the waste agent of the desulfurizer generated after desulfurization of biogas, liquid, coal gas, flue gas, petroleum and gasoline. Wherein, the other active components matched with FeOOH include but are not limited to one or more of iron salt chromium mixture, polymeric ferric sulfate, basic copper carbonate, calcium bicarbonate, zinc oxide, calcium sulfate dihydrate, nickel oxide, cobalt oxide and nickel oxide.
The desulfurizer containing FeOOH mentioned in the application is a desulfurizer formed directly by FeOOH, or a desulfurizer formed by loading FeOOH as a main active component on a carrier, or a desulfurizer formed by mixing FeOOH with an organic binder or other additives and loading on a carrier, and the like. In a word, the FeOOH-containing desulfurizer is applicable to desulfurizer prepared by all preparation methods of FeOOH-containing desulfurizer in the prior art, the waste agent is waste agent generated by applying the FeOOH-containing desulfurizer to various desulfurization methods in the prior art, and is particularly applicable to FeOOH desulfurizer waste agent generated after desulfurization of biogas, liquid, coal gas, flue gas, petroleum and gasoline, and the regeneration method of the waste agent is applicable to all regeneration methods.
Reference is made to Fe21.333O32The desulfurizing agent may be Fe21.333O32The desulfurizing agent directly formed can also be Fe21.333O32A desulfurizing agent comprising the above Fe as an active ingredient supported on a carrier, wherein the above Fe is used as a waste agent21.333O32The desulfurizer is applied to waste agents generated by various desulfurization methods in the prior art, and is particularly suitable for biogas, liquid, coal gas, flue gas, petroleum and steam Fe produced after oil desulfurization21.333O32Waste desulfurizer.
Reference herein to predominantly Fe21.333O32The desulfurizer used as an active component refers to Fe in the prior art21.333O32The waste desulfurizer is produced by applying the desulfurizer to various desulfurization methods in the prior art, and is particularly suitable for the waste desulfurizer produced after desulfurization of methane, liquid, coal gas, flue gas, petroleum and gasoline. Wherein, with Fe21.333O32Other active ingredients that may be incorporated include, but are not limited to, potassium oxide, anatase Ti02One or more of copper oxide, zinc oxide, lead oxide and manganese dioxide.
Reference is made to Fe21.333O32The desulfurizing agent may be Fe21.333O32The desulfurizing agent directly formed can also be Fe21.333O32The desulfurizing agent as active component supported on the carrier may be Fe21.333O32The waste desulfurizer is produced by applying the desulfurizer to various desulfurization methods in the prior art, and is particularly suitable for the waste desulfurizer produced after desulfurization of methane, liquid, coal gas and flue gas. Wherein, with Fe21.333O32Other active ingredients that may be incorporated include, but are not limited to, potassium oxide, anatase Ti02One or more of copper oxide, lead oxide, zinc oxide or manganese dioxide.
The iron oxide desulfurizer mentioned in the application can be a desulfurizer formed by directly forming iron oxide, or can be a desulfurizer formed by loading iron oxide as an active component on a carrier, and the waste agent is a waste agent generated by applying the iron oxide desulfurizer to various desulfurization methods in the prior art, and is particularly suitable for the waste agent of the iron oxide desulfurizer generated after desulfurization of methane, liquid, coal gas, flue gas, petroleum and gasoline.
The desulfurizer mainly taking iron oxide as an active component is the desulfurizer formed by matching iron oxide and other active components in the prior art, and the waste agent is the waste agent generated by applying the desulfurizer to various desulfurization methods in the prior art, and is particularly suitable for the desulfurizer waste agent generated after desulfurization of methane, liquid, coal gas, flue gas, petroleum and gasoline. Wherein, the other active ingredients matched with the iron oxide include but are not limited to one or more of iron salt chromium mixture, polymeric ferric sulfate, basic copper carbonate, calcium bicarbonate, zinc oxide, calcium sulfate dihydrate, nickel oxide, cobalt oxide, molybdenum oxide, copper oxide and manganese oxide.
1. The application of the FeOOH desulfurizer waste agent as a biomass hydrogenation liquefaction catalyst comprises the following steps:
Example 1
The embodiment of the invention provides a waste FeOOH desulfurizer, wherein the content of amorphous FeOOH in the FeOOH desulfurizer is 60%, the content of carrier kieselguhr is 30%, and the content of binder cellulose powder is 10%, based on the total mass of the FeOOH desulfurizer.
The desulfurization process of the catalyst as coal pyrolysis gas is summarized as follows:
(1) and (3) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a coarse desulfurization tower, and adopting a flow of feeding the coal pyrolysis gas from bottom to top to prevent liquid water from entering a desulfurizer bed layer. Only the crude removal of hydrogen sulphide and the removal of part of the R-SH and thiophene takes place here.
(2) And heating the gas after the coarse desulfurization to 110-125 ℃ for hydrolysis, and hydrolyzing most of COS and CS2 into H2S.
(3) And cooling the hydrolyzed gas to 20-25 ℃ again, and removing H2S, wherein in order to ensure the purification effect and the service life, a double-tower series-parallel operation mode is adopted to completely remove H2S generated by hydrolysis, and further remove the rest R-SH and thiophene. The residual sulfide is completely removed in the process, and the final purification requirement that the total sulfur content is less than 0.1ppm is achieved.
The desulfurizer becomes a waste agent after being used for many times and is deleted from a desulfurizer bed layer, namely the FeOOH desulfurizer waste agent in the application.
Example 2
The embodiment of the invention provides a waste FeOOH desulfurizer, wherein the content of amorphous FeOOH in the FeOOH desulfurizer is 80%, the content of carrier aluminum oxide is 15%, and the content of binder sesbania powder is 5%, based on the total mass of the FeOOH desulfurizer. The desulfurization process of the catalyst for gas field water comprises the following operation steps:
the catalyst is loaded in a fixed bed reactor, and gas field water containing H2S is fully contacted and reacted with the catalyst under the following conditions: the temperature is 35 ℃, the pressure is 0.2MPa, the volume space velocity is 10000h < -1 >, and the catalyst waste agent after gas field water desulfurization is the FeOOH desulfurizer waste agent.
Example 3
The embodiment of the invention provides a waste FeOOH desulfurizer, wherein the content of gamma-FeOOH, alpha-FeOOH, a carrier molecular sieve and sesbania powder in the FeOOH desulfurizer is 45%, 35%, 15% and 5%, respectively.
The catalyst removes H in the exhaust gas2S, the matrix process comprises the following steps: h is to be2The S content is 5500mg/cm3In 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section 2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section to be used as a catalyst for the biomass liquefaction reaction.
Example 4
The embodiment of the invention provides a waste FeOOH desulfurizer, wherein based on the total mass of the FeOOH desulfurizer, the content of beta-FeOOH in the FeOOH desulfurizer is 49%, the content of theta-FeOOH is 45%, and the balance is impurities and water.
The desulfurization process of the coke oven gas by the catalyst comprises the following operation steps:
mixing the FeOOH desulfurizer with water to prepare slurry serving as the desulfurizer, wherein the total concentration of iron oxyhydroxide in the slurry is 10 wt%, introducing the deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizer at the top of the desulfurizing tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the FeOOH desulfurizer waste agent.
Example 5
The waste collected in the above examples 1 to 4 was used as a catalyst for biomass liquefaction reaction, and the activity of the catalyst was tested as follows: preparing slurry containing corn straws and a catalyst, conveying the slurry into a slurry bed reactor for biomass liquefaction reaction, and controlling the reaction pressure to be 20MPa and the temperature to be 380 ℃, wherein the addition amount of the catalyst is 2 wt% of the addition amount of the corn straws, and the activity of the catalyst is represented by the distribution of products prepared by the biomass liquefaction reaction, and is shown in the following table 1:
TABLE 1 comparison of product distributions for examples 1-6
As can be seen from table 1, the catalyst of the present invention can effectively promote the biomass liquefaction reaction of biomass.
2. Waste desulfurizer using FeOOH as main active component and used as biomass hydrogenation liquefaction catalyst
Application of the composition in preparing medicine
Example 1
The embodiment of the invention provides a waste desulfurizer agent mainly comprising FeOOH as an active component, wherein in the desulfurizer mainly comprising FeOOH as the active component, 8g of soluble iron salt FeSO4 & 7H2O, 9g of disodium EDTA, 2g of sodium carbonate, 0.2g of polyethylene glycol, 1g of sorbitol, 7g of amorphous iron oxyhydroxide and 7g of gamma-FeOOH.
The desulfurization process of the catalyst as coal pyrolysis gas is summarized as follows:
(1) and (3) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a coarse desulfurization tower, and adopting a flow of feeding liquid water from bottom to top so as to prevent the liquid water from entering a desulfurizer bed layer. Only the crude removal of hydrogen sulphide and the removal of a portion of the R-SH and thiophene is carried out here.
(2) And heating the gas after the coarse desulfurization to 110-125 ℃ for hydrolysis, and hydrolyzing most of COS and CS2 into H2S.
(3) And cooling the hydrolyzed gas to 20-25 ℃ again, and removing H2S, wherein in order to ensure the purification effect and the service life, a double-tower series-parallel operation mode is adopted to completely remove H2S generated by hydrolysis, and further remove the rest R-SH and thiophene. The residual sulfide is completely removed in the process, and the total sulfur content required by final purification is less than 0.1 ppm.
The desulfurizer becomes a waste agent after being used for many times and is deleted from a desulfurizer bed layer, namely the desulfurizer waste agent taking FeOOH as a main active component in the application.
Example 2
The embodiment of the invention provides a waste desulfurizer using FeOOH as an active component, wherein in the desulfurizer using FeOOH as the active component, 30g of alpha-FeOOH, 40g of beta-FeOOH, 30g of basic copper carbonate and 1g of sesbania powder are contained.
The desulfurization process of the catalyst for gas field water comprises the following operation steps:
the catalyst is loaded in a fixed bed reactor, and gas field water containing H2S is fully contacted and reacted with the catalyst under the following conditions: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h < -1 >, and the catalyst waste agent after gas field water desulfurization is the desulfurizer waste agent taking FeOOH as the main active component.
Example 3
The embodiment of the invention provides a waste desulfurizer mainly taking FeOOH as an active ingredient, wherein 70g of amorphous FeOOH, 25g of Co2O3 and 5g of NiO are contained in the desulfurizer mainly taking FeOOH as the active ingredient.
The catalyst removes H in the exhaust gas2The matrix process of S comprises the following steps: h is to be2The S content is 5500mg/cm 3Exhaust gas of 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section to be used as a catalyst for the biomass hydrogenation liquefaction reaction.
Example 4
The embodiment of the invention provides a waste desulfurizer mainly taking FeOOH as an active ingredient, wherein 60g of amorphous iron oxyhydroxide, 25g of polymeric ferric sulfate, 20g of basic copper carbonate, 20g of calcium bicarbonate and 45g of polyvinyl alcohol are contained in the desulfurizer mainly taking FeOOH as the active ingredient.
The desulfurization process of the coke oven gas by the catalyst comprises the following operation steps:
mixing the desulfurizer with water to prepare desulfurizer slurry, wherein the total concentration of iron oxyhydroxide in the slurry is 10 wt%, introducing deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizer at the top of the desulfurizing tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the desulfurizer waste agent which takes FeOOH as a main active component.
Example 5
The waste collected in the above examples 1-4 was used as a catalyst for the biomass hydrogenation liquefaction reaction, and the activity test of the catalyst was performed as follows: preparing slurry containing corn straws and a catalyst, conveying the slurry into a slurry bed reactor to perform biomass hydrogenation liquefaction reaction, and controlling the reaction pressure to be 20MPa and the temperature to be 380 ℃, wherein the addition amount of the catalyst is 2 wt% of the addition amount of the corn straws, and the activity of the catalyst is represented by the distribution of products prepared by the biomass hydrogenation liquefaction reaction, as shown in the following table 1:
TABLE 1 comparison of product distributions for examples 1-6
As can be seen from table 1, the catalyst of the present invention can effectively promote the biomass hydro-liquefaction reaction of biomass.
3. The application of regenerated waste desulfurizer containing FeOOH as a biomass hydrogenation liquefaction catalyst.
Example 1
The embodiment of the invention provides a method for regenerating waste desulfurizer containing FeOOH, wherein based on the total mass of the FeOOH-containing desulfurizer, the content of amorphous iron oxyhydroxide in the FeOOH-containing desulfurizer is 60%, the content of carrier kieselguhr is 30%, and the content of binder cellulose powder is 10%.
The desulfurization process of the catalyst as coal pyrolysis gas is summarized as follows:
(1) and (3) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a coarse desulfurization tower, and adopting a flow of feeding liquid water from bottom to top so as to prevent the liquid water from entering a desulfurizer bed layer. Only the crude removal of hydrogen sulphide and the removal of a portion of the R-SH and thiophene is carried out here.
(2) And heating the gas after the coarse desulfurization to 110-125 ℃ for hydrolysis, and hydrolyzing most of COS and CS2 into H2S.
(3) And cooling the hydrolyzed gas to 20-25 ℃ again, and removing H2S, wherein in order to ensure the purification effect and the service life, a double-tower series-parallel operation mode is adopted to completely remove H2S generated by hydrolysis, and further remove the rest R-SH and thiophene. The residual sulfide is completely removed in the process, and the total sulfur content required by final purification is less than 0.1 ppm.
The desulfurizer becomes a waste agent after being used for many times and is deleted from a desulfurizer bed layer, and the waste agent of the FeOOH desulfurizer is the FeOOH desulfurizer in the application.
The regeneration method of the waste desulfurizer comprises the following steps,
1) introducing water vapor with the pressure of 1.5MPa into a heating furnace, and heating the water vapor to 450 ℃;
2) introducing the heated water vapor into a desulfurization tank containing a waste desulfurizer at the speed of 15m/s, and heating the waste desulfurizer;
3) ensuring that the bed temperature of the waste desulfurizer is heated to 450 ℃ by water vapor and the operation is carried out for 2 hours, wherein the steam consumption is 5.5 t/h;
4) analyzing the pH value of the outlet of the desulfurization tank, and introducing a small amount of coke oven gas into the desulfurization tank for reduction when the pH value is more than or equal to 7.5 for 3 times continuously;
5) introducing into the coke oven gas subjected to primary hydrogenation in the fine desulfurization process at a flow rate of 800m3Reducing the waste desulfurizer;
6) analyzing the import and export H every 30min after the coke oven gas is introduced2Concentration change when discharging H2Concentration stable greater than or equal to inlet H2After the concentration (3 times of analysis), the regeneration of the waste desulfurizer can be obtained.
Example 2
The embodiment of the invention provides a method for regenerating waste desulfurizer containing FeOOH, wherein the content of amorphous iron oxyhydroxide in the FeOOH-containing desulfurizer is 96.5% by total mass of the FeOOH-containing desulfurizer, and the balance is impurities and water. The catalyst removes H in the exhaust gas 2S, the matrix process comprises the following steps: will H2The S content is 5500mg/cm3In 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section, namely the waste desulfurizer.
The waste desulfurizer formed in the process is the waste FeOOH desulfurizer in the application.
The regeneration method of the waste desulfurizer comprises the following steps:
washing the desulfurizer waste agent with water, and grinding the washed desulfurizer waste agent with water in a wet ball mill into particles of 100 meshes to obtain waste agent powder; preparing the waste agent powder into aqueous suspension with the solid mass percentage content of 5%, introducing compressed air, carrying out sampling inspection after reaction for a period of time, when a sample taken out does not react with hydrochloric acid to generate H2S, completely converting iron sulfide in the waste agent into iron oxyhydroxide and elemental sulfur to form slurry containing the iron oxyhydroxide and the elemental sulfur, filtering the slurry to obtain a solid material, placing the solid material in a flotation tank, adding water, introducing air, overflowing the elemental sulfur due to hydrophobicity, and drying precipitates at the lower part of a container to obtain the regenerated substance of the waste desulfurizer.
Example 3
The embodiment of the invention provides a method for regenerating waste desulfurizer containing FeOOH, wherein based on the total mass of the FeOOH-containing desulfurizer, the content of amorphous iron oxyhydroxide in the FeOOH-containing desulfurizer is 80%, the content of carrier aluminum oxide is 15%, and the content of binder sesbania powder is 5%. The desulfurization process of the catalyst for gas field water comprises the following operation steps:
the catalyst is filled in a fixed bed reactor, and gas field water containing H2S is subjected to sufficient contact reaction with the catalyst under the following contact conditions: the temperature is 35 ℃, the pressure is 0.2MPa, the volume space velocity is 10000h < -1 >, and the catalyst waste agent after gas field water desulfurization is the FeOOH desulfurizer waste agent.
The method for regenerating the waste desulfurizer comprises the following steps
Washing the desulfurizer waste agent with water, and grinding the waste agent powder with water in a wet ball mill to obtain waste agent powder particles with 200 meshes; preparing the waste agent powder into aqueous suspension with the solid mass percentage content of 7%, introducing compressed air, carrying out sampling inspection after reaction for a period of time, when a sample taken out does not react with hydrochloric acid to generate H2S, completely converting iron sulfide in the waste agent into iron oxyhydroxide and elemental sulfur to form slurry containing the iron oxyhydroxide and the elemental sulfur, filtering the slurry to obtain a solid material, placing the solid material in a flotation tank, adding water, introducing air, overflowing the elemental sulfur due to hydrophobicity, and drying precipitates at the lower part of a container to obtain the regenerated substance of the waste desulfurizer.
Example 4
The embodiment of the invention provides a method for regenerating waste desulfurizer containing FeOOH, wherein the content of gamma-FeOOH, the content of alpha-FeOOH, the content of carrier molecular sieve and the content of sesbania powder in the FeOOH containing desulfurizer are respectively 45%, 35%, 15% and 5%, respectively.
As described aboveCatalyst for removing H in waste gas2The matrix process of S comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section, namely the waste desulfurizer.
The regeneration method of the waste desulfurizer comprises the following steps
Washing the desulfurizer waste agent with water, and grinding the washed desulfurizer waste agent with water in a wet ball mill into 80-mesh particles to obtain waste agent powder; preparing the waste agent powder into an aqueous suspension with the solid mass percentage content of 8%, introducing compressed air, reacting for a period of time, sampling and inspecting, when a sample taken out does not react with hydrochloric acid to generate H2S, completely converting iron sulfide in the waste agent into iron oxyhydroxide and elemental sulfur to form slurry containing the iron oxyhydroxide and the elemental sulfur, filtering the slurry to obtain a solid material, extracting the filtered solid material by using CC14, co-extracting for three times, combining extraction solutions, recovering a solvent by using a distillation method, simultaneously obtaining crystallized elemental sulfur, mixing the solid remaining after the extraction solutions are separated with adhesive sesbania powder to obtain the regeneration of the desulfurizer waste agent, wherein the amount of the adhesive sesbania powder is 5% of the solid mass.
Example 5
The embodiment of the invention provides a method for regenerating waste desulfurizer containing FeOOH, wherein based on the total mass of the FeOOH-containing desulfurizer, the content of beta-FeOOH in the FeOOH-containing desulfurizer is 49%, the content of theta-FeOOH is 45%, and the balance is impurities and water.
The desulfurization process of coke oven gas by the catalyst comprises the following operation steps:
mixing the FeOOH desulfurizer with water to prepare slurry serving as the desulfurizer, wherein the total concentration of iron oxyhydroxide in the slurry is 10 wt%, introducing the deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizer at the top of the desulfurizing tower through a nozzle to perform leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the FeOOH desulfurizer waste agent.
The method for regenerating the waste desulfurizer comprises the following steps
1) Introducing water vapor with the pressure of 1MPa into a heating furnace, and heating the water vapor to 400 ℃;
2) introducing the heated water vapor into a desulfurization tank containing a waste desulfurizer at the speed of 20m/s, and heating the waste desulfurizer;
3) ensuring that the bed layer temperature of the waste desulfurizer is heated to 450 ℃ by water vapor and the operation lasts for 2 hours, wherein the steam consumption is 8 t/h;
4) Analyzing the pH value of the outlet of the desulfurization tank, and introducing a small amount of coke oven gas into the desulfurization tank for reduction when the pH value is more than or equal to 7.5 continuously for 3 times;
5) the coke oven gas after the first-stage hydrogenation in the fine desulfurization procedure is introduced at the height of 800m3H, reducing the waste desulfurizer;
6) analyzing the inlet and outlet H every 30min after the coke oven gas is introduced2Concentration change when outlet H2Concentration stable greater than or equal to inlet H2After the concentration (3 times of analysis), the regeneration of the waste desulfurizer can be obtained.
Example 6
The embodiment of the invention provides a waste desulfurizer mainly taking FeOOH as an active ingredient, wherein 70g of amorphous FeOOH, 25g of Co2O3 and 5g of NiO are contained in the desulfurizer mainly taking FeOOH as the active ingredient.
The catalyst removes H in the exhaust gas2The matrix process of S comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section, namely the desulfurizer waste agent.
The regeneration method of the waste desulfurizer comprises the following steps,
washing the desulfurizer waste agent with water, and grinding the waste agent powder with water in a wet ball mill to obtain 80-mesh particles; preparing the waste agent powder into aqueous suspension with the solid mass percentage content of 8%, introducing compressed air, carrying out sampling inspection after reacting for a period of time, when a sample taken out does not react with hydrochloric acid to generate H2S, completely converting iron sulfide in the waste agent into iron oxyhydroxide and elemental sulfur to form slurry containing the iron oxyhydroxide and the elemental sulfur, filtering the slurry to obtain a solid material, extracting the filtered solid material by using CC14, carrying out co-extraction for three times, combining extraction liquid, recovering a solvent by using a distillation method, simultaneously obtaining crystallized elemental sulfur, and obtaining the residual solid after separating the extraction liquid, namely the regeneration of the waste desulfurizer.
Example 7
The embodiment of the invention provides a waste desulfurizer using FeOOH as an active component, wherein the waste desulfurizer using FeOOH as an active component comprises 60g of amorphous iron oxyhydroxide, 25g of polyferric sulfate, 20g of basic copper carbonate, 20g of calcium bicarbonate and 45g of polyvinyl alcohol.
The desulfurization process of coke oven gas by the catalyst comprises the following operation steps:
mixing the desulfurizer with water to prepare desulfurizer slurry, wherein the total concentration of iron oxyhydroxide in the slurry is 10 wt%, introducing deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizer at the top of the desulfurizing tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the desulfurizer waste agent which takes FeOOH as a main active component.
The method for regenerating the waste desulfurizer comprises the following steps
Washing the desulfurizer waste agent with water, and grinding the waste agent powder with water in a wet ball mill to obtain 80-mesh particles; preparing the waste agent powder into aqueous suspension with the solid mass percentage content of 8%, introducing compressed air, carrying out sampling inspection after reacting for a period of time, when a sample taken out does not react with hydrochloric acid to generate H2S, completely converting iron sulfide in the waste agent into iron oxyhydroxide and elemental sulfur to form slurry containing the iron oxyhydroxide and the elemental sulfur, filtering the slurry to obtain a solid material, extracting the filtered solid material by using CC14, carrying out co-extraction for three times, combining extraction liquid, recovering a solvent by using a distillation method to obtain crystallized elemental sulfur, mixing the solid remaining after the extraction liquid is separated with adhesive sesbania powder to prepare the regeneration of the desulfurizer waste agent, wherein the amount of the adhesive sesbania powder is 5% of the solid mass.
Example 8
The embodiment of the invention provides a waste desulfurizer agent mainly comprising FeOOH as an active component, wherein in the desulfurizer mainly comprising FeOOH as the active component, 8g of soluble iron salt FeSO4 & 7H2O, 9g of disodium EDTA, 2g of sodium carbonate, 0.2g of polyethylene glycol, 1g of sorbitol, 7g of amorphous iron oxyhydroxide and 7g of gamma-FeOOH.
The desulfurization process of the catalyst as coal pyrolysis gas is summarized as follows:
(1) and (3) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a coarse desulfurization tower, and adopting a flow of feeding liquid water from bottom to top so as to prevent the liquid water from entering a desulfurizer bed layer. Only the crude removal of hydrogen sulphide and the removal of a portion of the R-SH and thiophene is carried out here.
(2) And heating the gas after the coarse desulfurization to 110-125 ℃ for hydrolysis, and hydrolyzing most of COS and CS2 into H2S.
(3) And cooling the hydrolyzed gas to 20-25 ℃ again, and removing H2S, wherein in order to ensure the purification effect and the service life, a double-tower series-parallel operation mode is adopted to completely remove H2S generated by hydrolysis, and further remove the rest R-SH and thiophene. The residual sulfide is completely removed in the process, and the final purification requirement that the total sulfur content is less than 0.1ppm is achieved.
The desulfurizer becomes a waste agent after being used for many times and is deleted from a desulfurizer bed layer, namely the desulfurizer waste agent taking FeOOH as a main active component in the application.
The above-mentioned desulfurizing agent waste
Washing the waste agent with water, and grinding the waste agent into particles of 200 meshes in a wet ball mill with water to obtain waste agent powder; preparing the waste agent powder into aqueous suspension with the solid mass percentage content of 7%, introducing compressed air, carrying out sampling inspection after reaction for a period of time, when a sample taken out does not react with hydrochloric acid to generate H2S, completely converting iron sulfide in the waste agent into iron oxyhydroxide and elemental sulfur to form slurry containing the iron oxyhydroxide and the elemental sulfur, filtering the slurry to obtain a solid material, placing the solid material in a flotation tank, adding water, introducing air, overflowing the elemental sulfur due to hydrophobicity, and drying precipitates at the lower part of a container to obtain the regenerated substance of the waste desulfurizer.
Example 9
The waste collected in the above examples 1 to 8 was used as a catalyst for the biomass liquefaction reaction, and the activity test of the catalyst was performed while applying the desulfurizing agent used in 9 as comparative example 1, respectively, as follows: preparing slurry containing corn straws and a catalyst, conveying the slurry into a slurry bed reactor for biomass liquefaction reaction, and controlling the reaction pressure to be 20MPa and the temperature to be 380 ℃, wherein the addition amount of the catalyst is 2 wt% of the addition amount of the corn straws, and the activity of the catalyst is represented by the distribution of products prepared by the biomass liquefaction reaction, and is shown in the following table 1:
TABLE 1 comparison of product distribution
As can be seen from Table 1, the conversion rate of the biomass obtained by the method of the invention is 95.4-97.8%, and the yield of the oil phase is 43.5-48.3%, which shows that the catalyst of the invention can effectively promote the biomass liquefaction reaction of the biomass.
4. The application of the FeOOH desulfurizer waste agent as a CO conversion catalyst comprises the following steps:
example 1
The embodiment of the invention provides a waste FeOOH desulfurizer, wherein the content of amorphous FeOOH in the FeOOH desulfurizer is 60%, the content of carrier kieselguhr is 30%, and the content of binder cellulose powder is 10%, based on the total mass of the FeOOH desulfurizer.
The desulfurization process of the catalyst as coal pyrolysis gas is summarized as follows:
(1) and (3) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a coarse desulfurization tower, and adopting a flow of feeding liquid water from bottom to top so as to prevent the liquid water from entering a desulfurizer bed layer. Here only a crude removal of hydrogen sulphide is carried out.
(2) And heating the gas after the coarse desulfurization to 110-125 ℃ for hydrolysis, and hydrolyzing most of COS and CS2 into H2S.
(3) And cooling the hydrolyzed gas to 20-25 ℃ again, and removing H2S, wherein in order to ensure the purification effect and the service life, the H2S generated by hydrolysis is completely removed in a double-tower series-parallel operation mode. The residual sulfide is completely removed in the process, and the final purification requirement that the total sulfur content is less than 0.1ppm is achieved.
The desulfurizer becomes a waste agent after being used for many times and is deleted from a desulfurizer bed layer, and the waste agent of the FeOOH desulfurizer is the FeOOH desulfurizer in the application.
Example 2
The embodiment of the invention provides a waste FeOOH desulfurizer, wherein the content of amorphous FeOOH in the FeOOH desulfurizer is 80%, the content of carrier aluminum oxide is 15%, and the content of binder sesbania powder is 5%, based on the total mass of the FeOOH desulfurizer. The desulfurization process of the catalyst for gas field water comprises the following operation steps:
the catalyst is filled in a fixed bed reactor, and gas field water containing H2S is subjected to sufficient contact reaction with the catalyst under the following contact conditions: the temperature is 35 ℃, the pressure is 0.2MPa, the volume space velocity is 10000h < -1 >, and the catalyst waste agent after gas field water desulfurization is the FeOOH desulfurizer waste agent.
Example 3
The embodiment of the invention provides a waste FeOOH desulfurizer, wherein the content of gamma-FeOOH, alpha-FeOOH, a carrier molecular sieve and sesbania powder in the FeOOH desulfurizer is 45%, 35%, 15% and 5%, respectively.
The catalyst removes H in the exhaust gas2The matrix process of S comprises the following steps: will H 2The S content is 5500mg/cm3In 3000h-1Is introduced into the desulfurization zone at a space velocity ofPerforming desulfurization reaction at 30 ℃, wherein H in the outlet gas of the desulfurization section2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section to be used as a catalyst for CO conversion reaction.
Example 4
The embodiment of the invention provides a waste FeOOH desulfurizer, wherein based on the total mass of the FeOOH desulfurizer, the content of beta-FeOOH in the FeOOH desulfurizer is 49%, the content of theta-FeOOH is 45%, and the balance is impurities and water.
The desulfurization process of the coke oven gas by the catalyst comprises the following operation steps:
mixing the FeOOH desulfurizer with water to prepare slurry serving as the desulfurizer, wherein the total concentration of iron oxyhydroxide in the slurry is 10 wt%, introducing the deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizer at the top of the desulfurizing tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the FeOOH desulfurizer waste agent.
Example 5 (use of waste desulfurizing agent)
The collected waste desulfurizer reagents from the above examples 1 to 5 were used as catalysts for CO shift reaction, and the activity tests were performed as follows:
The composition of the raw material gas is 15 vol% CO and 55 vol% H2、6vol％CO2、24vol％N2And the reaction steam-gas ratio is 1: 1, the airspeed is 4000h-1The catalyst activity test temperature zone is 250-450 ℃;
the activity of the catalyst is expressed in terms of CO conversion and is calculated as follows:
CO conversion rate (1-V)CO'/VCO)/(1+VCO)×100％
Wherein, VCO'Is the volume percent of CO in the reactor off-gas, VCOIs the volume percentage of CO in the raw material gas;
the corresponding test results are shown in table 1 below:
TABLE 1 CO conversion at different test temperatures
5. The waste desulfurizer using FeOOH as main active component is used as CO conversion catalyst.
Example 1
The embodiment of the invention provides a waste desulfurizer mainly using FeOOH as an active component, wherein in the desulfurizer mainly using FeOOH as the active component, 8g of soluble iron salt FeSO4 & 7H2O, 9g of disodium EDTA, 2g of sodium carbonate, 0.2g of polyethylene glycol, 1g of sorbitol, 7g of amorphous iron oxyhydroxide and 7g of gamma-FeOOH are contained.
The desulfurization process of the catalyst as coal pyrolysis gas is summarized as follows:
(1) and (3) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a coarse desulfurization tower, and adopting a flow of feeding the coal pyrolysis gas from bottom to top to prevent liquid water from entering a desulfurizer bed layer. Only a crude removal of hydrogen sulphide is carried out here.
(2) And heating the gas after the coarse desulfurization to 110-125 ℃ for hydrolysis, and hydrolyzing most of COS and CS2 into H2S.
(3) And (3) cooling the hydrolyzed gas to 20-25 ℃ again, and removing H2S, wherein in order to ensure the purification effect and the service life, the H2S generated by hydrolysis is completely removed in a double-tower series-parallel operation mode. The residual sulfide is completely removed in the process, and the total sulfur content required by final purification is less than 0.1 ppm.
The desulfurizer becomes a waste agent after being used for many times and is deleted from a desulfurizer bed layer, namely the desulfurizer waste agent taking FeOOH as a main active component in the application.
Example 2
The embodiment of the invention provides a waste desulfurizer using FeOOH as an active component, wherein in the desulfurizer using FeOOH as an active component, 30g of alpha-FeOOH, 40g of beta-FeOOH, 30g of basic copper carbonate and 1g of sesbania powder are contained.
The desulfurization process of the catalyst for gas field water comprises the following operation steps:
the catalyst is filled in a fixed bed reactor, and gas field water containing H2S is subjected to sufficient contact reaction with the catalyst under the following contact conditions: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h < -1 >, and the catalyst waste agent after gas field water desulfurization is the desulfurizer waste agent which takes FeOOH as the main active component.
Example 3
The embodiment of the invention provides a waste desulfurizer mainly taking FeOOH as an active ingredient, wherein 70g of amorphous FeOOH, 25g of Co2O3 and 5g of NiO are contained in the desulfurizer mainly taking FeOOH as the active ingredient.
The catalyst removes H in the exhaust gas2S, the matrix process comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section to be used as a catalyst for CO conversion reaction.
Example 4
The embodiment of the invention provides a waste desulfurizer mainly taking FeOOH as an active ingredient, wherein 60g of amorphous iron oxyhydroxide, 25g of polymeric ferric sulfate, 20g of basic copper carbonate, 20g of calcium bicarbonate and 45g of polyvinyl alcohol are contained in the desulfurizer mainly taking FeOOH as the active ingredient.
The desulfurization process of the coke oven gas by the catalyst comprises the following operation steps:
mixing the desulfurizer with water to prepare desulfurizer slurry, wherein the total concentration of iron oxyhydroxide in the slurry is 10 wt%, introducing deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizer at the top of the desulfurizing tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the desulfurizer waste agent which takes FeOOH as a main active component.
Example 5 (use of waste desulfurizing agent)
The collected waste desulfurizer reagents from the above examples 1-4 were used as catalysts for CO shift reaction, and the activity tests were performed as follows:
the composition of the raw material gas is 15 vol% CO and 55 vol% H2、6vol％CO2、24vol％N2And the reaction steam-gas ratio is 1: 1, the airspeed is 4000h-1The catalyst activity test temperature zone is 250-450 ℃;
the activity of the catalyst is expressed in terms of CO conversion and is calculated as follows:
CO conversion rate (1-V)CO'/VCO)/(1+VCO)×100％
Wherein, VCO'Is the volume percent of CO in the reactor off-gas, VCOIs the volume percentage of CO in the raw material gas;
the corresponding test results are shown in table 1 below:
TABLE 1 CO conversion at different test temperatures
6. The waste desulfurizer containing FeOOH is regenerated and then used as a CO shift catalyst.
Example 1
The embodiment of the invention provides a method for regenerating waste desulfurizer containing FeOOH, wherein the content of amorphous iron oxyhydroxide in the FeOOH desulfurizer is 60%, the content of carrier diatomite is 30%, and the content of binder cellulose powder is 10% by total mass of the FeOOH desulfurizer.
The desulfurization process of the catalyst as coal pyrolysis gas is summarized as follows:
(1) And (3) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a coarse desulfurization tower, and adopting a flow of feeding the coal pyrolysis gas from bottom to top to prevent liquid water from entering a desulfurizer bed layer. Only a crude removal of hydrogen sulphide is carried out here.
(2) And heating the gas after the coarse desulfurization to 110-125 ℃ for hydrolysis, and hydrolyzing most of COS and CS2 into H2S.
(3) And cooling the hydrolyzed gas to 20-25 ℃ again, and removing H2S, wherein in order to ensure the purification effect and the service life, a double-tower series-parallel operation mode is adopted to completely remove H2S generated by hydrolysis, and further remove the rest R-SH and thiophene. The residual sulfide is completely removed in the process, and the final purification requirement that the total sulfur content is less than 0.1ppm is achieved.
The desulfurizer becomes a waste agent after being used for many times and is deleted from a desulfurizer bed layer, namely the FeOOH desulfurizer waste agent in the application.
The regeneration method of the waste desulfurizer comprises the following steps,
1) introducing water vapor with the pressure of 1.5MPa into a heating furnace, and heating the water vapor to 450 ℃;
2) introducing the heated water vapor into a desulfurization tank containing a waste desulfurizer at the speed of 15m/s, and heating the waste desulfurizer;
3) ensuring that the bed temperature of the waste desulfurizer is heated to 450 ℃ by water vapor and the operation is carried out for 2 hours, wherein the steam consumption is 5.5 t/h;
4) Analyzing the pH value of the outlet of the desulfurization tank, and introducing a small amount of coke oven gas into the desulfurization tank for reduction when the pH value is more than or equal to 7.5 continuously for 3 times;
5) the coke oven gas after the first-stage hydrogenation in the fine desulfurization procedure is introduced at the height of 800m3H, reducing the waste desulfurizer;
6) analyzing the inlet and outlet H every 30min after the coke oven gas is introduced2Concentration change when outlet H2Concentration stable greater than or equal to inlet H2After the concentration (3 times of analysis), the regeneration of the waste desulfurizer can be obtained.
Example 2
The embodiment of the invention provides a method for regenerating waste desulfurizer containing FeOOH, wherein the content of amorphous iron oxyhydroxide in the FeOOH-containing desulfurizer is 96.5% by total mass of the FeOOH-containing desulfurizer, and the balance is impurities and water. The catalyst removes H in the exhaust gas2The matrix process of S comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section, namely the waste desulfurizer.
The waste desulfurizer formed in the process is the waste FeOOH desulfurizer in the application.
The regeneration method of the waste desulfurizer comprises the following steps:
washing the desulfurizer waste agent with water, and grinding the washed desulfurizer waste agent with water in a wet ball mill into particles of 100 meshes to obtain waste agent powder; preparing the waste agent powder into aqueous suspension with the solid mass percentage content of 5%, introducing compressed air, carrying out sampling inspection after reaction for a period of time, when a sample taken out does not react with hydrochloric acid to generate H2S, completely converting iron sulfide in the waste agent into iron oxyhydroxide and elemental sulfur to form slurry containing the iron oxyhydroxide and the elemental sulfur, filtering the slurry to obtain a solid material, placing the solid material in a flotation tank, adding water, introducing air, overflowing the elemental sulfur due to hydrophobicity, and drying precipitates at the lower part of a container to obtain the regenerated substance of the waste desulfurizer.
Example 3
The embodiment of the invention provides a method for regenerating waste desulfurizer containing FeOOH, wherein based on the total mass of the FeOOH-containing desulfurizer, the content of amorphous iron oxyhydroxide in the FeOOH-containing desulfurizer is 80%, the content of carrier aluminum oxide is 15%, and the content of binder sesbania powder is 5%. The desulfurization process of the catalyst for gas field water comprises the following operation steps:
The catalyst is loaded in a fixed bed reactor, and gas field water containing H2S is fully contacted and reacted with the catalyst under the following conditions: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h < -1 >, and the catalyst waste agent after gas field water desulfurization is the FeOOH desulfurizer waste agent.
The regeneration method of the waste desulfurizer comprises the following steps
Washing the desulfurizer waste agent with water, and grinding the washed desulfurizer waste agent with water in a wet ball mill into particles of 200 meshes to obtain waste agent powder; preparing the waste agent powder into aqueous suspension with the solid mass percentage content of 7%, introducing compressed air, carrying out sampling inspection after reaction for a period of time, when a sample taken out does not react with hydrochloric acid to generate H2S, completely converting iron sulfide in the waste agent into iron oxyhydroxide and elemental sulfur to form slurry containing the iron oxyhydroxide and the elemental sulfur, filtering the slurry to obtain a solid material, placing the solid material in a flotation tank, adding water, introducing air, overflowing the elemental sulfur due to hydrophobicity, and drying precipitates at the lower part of a container to obtain the regenerated substance of the waste desulfurizer.
Example 4
The embodiment of the invention provides a method for regenerating waste desulfurizer containing FeOOH, wherein the content of gamma-FeOOH, the content of alpha-FeOOH, the content of carrier molecular sieve and the content of sesbania powder in the FeOOH containing desulfurizer are respectively 45%, 35%, 15% and 5%, respectively.
The catalyst removes H in the exhaust gas2S, the matrix process comprises the following steps: will H2The S content is 5500mg/cm3In 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section, namely the waste desulfurizer.
The method for regenerating the waste desulfurizer comprises the following steps
Washing the desulfurizer waste agent with water, and grinding the washed desulfurizer waste agent with water in a wet ball mill into 80-mesh particles to obtain waste agent powder; preparing the waste agent powder into aqueous suspension with the solid mass percentage content of 8%, introducing compressed air, carrying out sampling inspection after reacting for a period of time, when a sample taken out does not react with hydrochloric acid to generate H2S, completely converting iron sulfide in the waste agent into iron oxyhydroxide and elemental sulfur to form slurry containing the iron oxyhydroxide and the elemental sulfur, filtering the slurry to obtain a solid material, extracting the filtered solid material by using CC14, carrying out co-extraction for three times, combining extraction liquid, recovering a solvent by using a distillation method to obtain crystallized elemental sulfur, mixing the solid remaining after the extraction liquid is separated with adhesive sesbania powder to prepare the regeneration of the desulfurizer waste agent, wherein the amount of the adhesive sesbania powder is 5% of the solid mass.
Example 5
The embodiment of the invention provides a method for regenerating waste desulfurizer containing FeOOH, wherein based on the total mass of the FeOOH-containing desulfurizer, the content of beta-FeOOH in the FeOOH-containing desulfurizer is 49%, the content of theta-FeOOH is 45%, and the balance is impurities and water.
The desulfurization process of coke oven gas by the catalyst comprises the following operation steps:
mixing the FeOOH desulfurizer with water to prepare slurry serving as the desulfurizer, wherein the total concentration of iron oxyhydroxide in the slurry is 10 wt%, introducing the deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizer at the top of the desulfurizing tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the FeOOH desulfurizer waste agent.
The method for regenerating the waste desulfurizer comprises the following steps
1) Introducing water vapor with the pressure of 1MPa into a heating furnace, and heating the water vapor to 400 ℃;
2) introducing the heated water vapor into a desulfurization tank containing a waste desulfurizer at the speed of 20m/s, and heating the waste desulfurizer;
3) ensuring that the bed layer temperature of the waste desulfurizer is heated to 450 ℃ by water vapor and the operation lasts for 2 hours, wherein the steam consumption is 8 t/h;
4) Analyzing the pH value of the outlet of the desulfurization tank, and introducing a small amount of coke oven gas into the desulfurization tank for reduction when the pH value is more than or equal to 7.5 continuously for 3 times;
5) the coke oven gas after the first-stage hydrogenation in the fine desulfurization procedure is introduced at the height of 800m3Reducing the waste desulfurizer;
6) analyzing the import and export H every 30min after the coke oven gas is introduced2Concentration change when discharging H2Concentration stable greater than or equal to inlet H2After the concentration (3 times of analysis), the regeneration of the waste desulfurizer can be obtained.
Example 6
The embodiment of the invention provides a waste desulfurizer mainly taking FeOOH as an active ingredient, wherein 70g of amorphous FeOOH, 25g of Co2O3 and 5g of NiO are contained in the desulfurizer mainly taking FeOOH as the active ingredient.
The catalyst removes H in the exhaust gas2The matrix process of S comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section to be used as a catalyst for CO conversion reaction.
The regeneration method of the waste desulfurizer comprises the following steps
Washing the desulfurizer waste agent with water, and grinding the waste agent powder with water in a wet ball mill to obtain 80-mesh particles; preparing the waste agent powder into aqueous suspension with the solid mass percentage content of 8%, introducing compressed air, carrying out sampling inspection after reacting for a period of time, when a sample taken out does not react with hydrochloric acid to generate H2S, completely converting iron sulfide in the waste agent into iron oxyhydroxide and elemental sulfur to form slurry containing the iron oxyhydroxide and the elemental sulfur, filtering the slurry to obtain a solid material, extracting the filtered solid material by using CC14, carrying out co-extraction for three times, combining extraction liquid, recovering a solvent by using a distillation method, simultaneously obtaining crystallized elemental sulfur, and obtaining the residual solid after separating the extraction liquid, namely the regeneration of the waste desulfurizer.
Example 7
The embodiment of the invention provides a waste desulfurizer using FeOOH as an active component, wherein the waste desulfurizer using FeOOH as an active component comprises 60g of amorphous iron oxyhydroxide, 25g of polyferric sulfate, 20g of basic copper carbonate, 20g of calcium bicarbonate and 45g of polyvinyl alcohol.
The desulfurization process of the coke oven gas by the catalyst comprises the following operation steps:
mixing the desulfurizer with water to prepare desulfurizer slurry, wherein the total concentration of iron oxyhydroxide in the slurry is 10 wt%, introducing deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizer at the top of the desulfurizing tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the desulfurizer waste agent which takes FeOOH as a main active component.
The method for regenerating the waste desulfurizer comprises the following steps
Washing the desulfurizer waste agent with water, and grinding the washed desulfurizer waste agent with water in a wet ball mill into 80-mesh particles to obtain waste agent powder; preparing the waste agent powder into aqueous suspension with the solid mass percentage content of 8%, introducing compressed air, carrying out sampling inspection after reacting for a period of time, when a sample taken out does not react with hydrochloric acid to generate H2S, completely converting iron sulfide in the waste agent into iron oxyhydroxide and elemental sulfur to form slurry containing the iron oxyhydroxide and the elemental sulfur, filtering the slurry to obtain a solid material, extracting the filtered solid material by using CC14, carrying out co-extraction for three times, combining extraction liquid, recovering a solvent by using a distillation method to obtain crystallized elemental sulfur, mixing the solid remaining after the extraction liquid is separated with adhesive sesbania powder to prepare the regeneration of the desulfurizer waste agent, wherein the amount of the adhesive sesbania powder is 5% of the solid mass.
Example 8
The embodiment of the invention provides a waste desulfurizer mainly using FeOOH as an active component, wherein in the desulfurizer mainly using FeOOH as the active component, 8g of soluble iron salt FeSO4 & 7H2O, 9g of disodium EDTA, 2g of sodium carbonate, 0.2g of polyethylene glycol, 1g of sorbitol, 7g of amorphous iron oxyhydroxide and 7g of gamma-FeOOH are contained.
The desulfurization process of the catalyst as coal pyrolysis gas is summarized as follows:
(1) and (3) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a coarse desulfurization tower, and adopting a flow of feeding liquid water from bottom to top so as to prevent the liquid water from entering a desulfurizer bed layer. Only the crude removal of hydrogen sulphide and the removal of a portion of the R-SH and thiophene is carried out here.
(2) And heating the gas after the coarse desulfurization to 110-125 ℃ for hydrolysis, and hydrolyzing most of COS and CS2 into H2S.
(3) And (3) cooling the hydrolyzed gas to 20-25 ℃ again, and removing H2S, wherein in order to ensure the purification effect and the service life, a double-tower series-parallel connection operation mode is adopted to completely remove H2S generated by hydrolysis and further remove the rest R-SH and thiophene. The residual sulfide is completely removed in the process, and the total sulfur content required by final purification is less than 0.1 ppm.
The desulfurizer becomes a waste agent after being used for many times and is deleted from a desulfurizer bed layer, namely the desulfurizer waste agent taking FeOOH as a main active component in the application.
The regeneration method of the waste desulfurizer comprises the following steps,
washing the desulfurizer waste agent with water, and grinding the washed desulfurizer waste agent with water in a wet ball mill into particles of 200 meshes to obtain waste agent powder; preparing the waste agent powder into aqueous suspension with the solid mass percentage content of 7%, introducing compressed air, carrying out sampling inspection after reaction for a period of time, when a sample taken out does not react with hydrochloric acid to generate H2S, completely converting iron sulfide in the waste agent into iron oxyhydroxide and elemental sulfur to form slurry containing the iron oxyhydroxide and the elemental sulfur, filtering the slurry to obtain a solid material, placing the solid material in a flotation tank, adding water, introducing air, overflowing the elemental sulfur due to hydrophobicity, and drying precipitates at the lower part of a container to obtain the regenerated substance of the waste desulfurizer.
Example 9 (application after regeneration of waste desulfurizing agent)
The catalysts collected in examples 1 to 8 were regenerated as waste desulfurizing agents to be used as catalysts for CO shift reaction, and the desulfurizing agents used in examples 2 and 8 were also used in the activity tests as comparative examples 1 and 2, respectively, as follows:
The composition of the raw material gas is 15 vol% CO and 55 vol% H2、6vol％CO2、24vol％N2And the reaction steam-gas ratio is 1: 1, the space velocity is 4000h-1The temperature zone for testing the activity of the catalyst is 250-450 ℃;
the activity of the catalyst is expressed in terms of CO conversion and is calculated as follows:
CO conversion ═ 1-VCO'/VCO)/(1+VCO)×100％
Wherein, VCO'Is the volume percent of CO in the reactor off-gas, VCOIs the volume percentage of CO in the raw material gas;
the corresponding test results are shown in table 1 below:
TABLE 1 CO conversion at different test temperatures
7. The waste desulfurizer containing FeOOH or the waste regenerant is used in organic matter conversion process.
Example 1
The embodiment provides a co-conversion process of biomass and hogwash oil, which comprises the following steps:
pretreatment of biomass:
the method comprises the steps of taking rice straws and reed straws as biomass solids, feeding the rice straws and the reed straws with the water content of 4% by the total weight of the biomass into a superfine pulverizer for primary pulverization, compressing the rice straws and the reed straws in a briquetting machine at the temperature of 30 ℃ and under the pressure of 3MPa, and carrying out extrusion molding until the bulk density is 0.8g/cm3Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 3mm for later use;
Catalyst:
the catalyst is a waste desulfurizer using FeOOH as an active component, wherein soluble iron salt Fe (NO) is contained in the desulfurizer using FeOOH as the active component3)3·9H26g of O, 9g of ferric salt complexing agent triethanolamine and 15g of amorphous iron oxyhydroxide;
the desulfurizer which takes FeOOH as the active component is used for removing H in waste gas2The process of S is as follows: will H2Has an S content of5500mg/cm3In 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2When the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section, namely the waste agent of the desulfurizer which takes FeOOH as the active component in the embodiment.
Preparing biomass slurry:
mixing the pretreated biomass with the catalyst to obtain a mixture, adding the mixture into hogwash oil, stirring, grinding and pulping to form slurry, detecting that the total content of rice straws and reed straws in the slurry is 60 wt%, the viscosity of the slurry is 500mPa (50 ℃), the content of the catalyst in the slurry is 5 wt%, and the average particle size of the added catalyst is 5 micrometers;
and (3) conversion reaction:
reacting CO with H2Mixed gas (CO accounts for 60% and H)240 percent) of the slurry is pressurized to 21MPa and heated to 350 ℃, then the slurry is introduced into a pipeline for conveying the slurry, the rest of the slurry is pressurized to 21MPa and heated to 500 ℃, then the slurry is injected into a slurry bed reactor from an inlet of the slurry bed reactor, simultaneously H2S is introduced into the reactor to ensure that the molar ratio of iron element to sulfur element in a reaction system is 1:5, the slurry is subjected to cracking, carbonylation, transformation and hydrogenation reaction, the reaction pressure of the conversion reaction is controlled to be 20MPa, the reaction temperature is 380 ℃, the reaction time is 60min, and CO and H are reacted for 60min 2The volume ratio of the mixed gas to the slurry is 3000: 1, preparing an oil product.
Example 2
The embodiment provides a biomass liquefaction process, which comprises the following steps:
pretreatment of biomass:
wheat straw and flax straw are used as biomass solid, the water content of the biomass is 9% based on the total weight of the biomass, the wheat straw and the flax straw are sent into a superfine pulverizer for primary pulverization, the median particle size after primary pulverization is 300 mu m, and then the wheat straw and the flax straw after primary pulverization are subjected to secondary pulverizationThe hemp straw is sent into a plodder to be compressed at the temperature of 60 ℃ and under the pressure of 3MPa, and the hemp straw is extruded and molded until the bulk density is 1.1g/cm3Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 2mm for later use;
catalyst:
the catalyst is a regeneration of a waste desulfurizer of which the FeOOH is taken as an active component, wherein the total mass of the desulfurizer of which the FeOOH is taken as the active component is 30g, the amorphous FeOOH is 20g, the potassium oxide is 8g, and the adhesive kaolin is 10 g;
the desulfurization process of the tail gas generated after the desulfurization agent with the FeOOH as the active component is used for hydrogenation upgrading of medium and low temperature coal tar in industry is as follows:
1) Collecting tail gas generated after the medium and low temperature coal tar is subjected to fixed bed hydrogenation catalysis;
2) the desulfurizer of the embodiment is prepared into columnar catalyst particles with the diameter of 1mm and the length of 15mm, and the columnar catalyst particles are filled in a desulfurizing tower to form a desulfurization layer;
3) the tail gas is treated for 2000h-1The air speed of the catalyst passes through the desulfurization layer, and the air speed and a desulfurizer in the desulfurization layer are subjected to desulfurization reaction at 50 ℃, so that hydrogen sulfide in tail gas is removed, after the reaction is finished, the waste agent of the reacted desulfurizer is taken out, and the waste agent is cooled to room temperature, so that the waste agent of the desulfurizer with the active component is obtained;
the regeneration method of the waste agent comprises the following steps:
1) stirring the waste agent and an aqueous solution of sodium hydroxide in a slurry tank to prepare slurry, and maintaining the pH value of the slurry to be 8.0, wherein the solid content of the slurry is 4 wt%;
2) introducing air into the slurry, and carrying out oxidation reaction at 90 ℃ and 0.1MPa to carry out oxidation regeneration;
3) then introducing hydrogen sulfide into the oxidized slurry, and carrying out a vulcanization reaction at 10 ℃ and 5 MPa;
4) introducing air into the vulcanized slurry, and carrying out oxidation reaction at 90 ℃ and 0.1MPa to carry out oxidation regeneration;
5) repeating the steps 3) and 4) once to enable the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction to be 1: 2;
6) And carrying out solid-liquid separation on the slurry after the oxidation reaction to obtain the regenerant of the waste agent.
Preparing biomass slurry:
mixing the pretreated biomass, sulfur powder and the catalyst to obtain a mixture, adding the mixture into mixed oil of palm oil and petroleum-based wax oil, and stirring and pulping to form slurry; through detection, the total content of wheat straws and flax straws in the slurry is 45 wt%, the molar ratio of iron element to sulfur element is 1:2.5, the viscosity of the slurry is 530mPa ≤ (50 ℃), the content of the regenerant of the waste agent of the desulfurizing agent with ferric oxyhydroxide as an active component in the slurry is 0.3 wt%, and the average particle size of the added regenerant of the waste agent of the desulfurizing agent with ferric oxyhydroxide as an active component is 20 μm;
and (3) conversion reaction:
reacting CO with H2Mixed gas (CO accounts for 80% and H)220 percent of the total weight of the slurry, pressurizing to 19.5MPa, heating to 300 ℃, introducing the slurry into a pipeline for conveying the slurry, pressurizing the rest to 19.3MPa, heating to 480 ℃, injecting the slurry into the slurry bed reactor from 3 injection ports on the bottom and the side wall of the slurry bed reactor, and carrying out cracking, carbonylation, transformation and hydrogenation reaction with the slurry entering the slurry, controlling the reaction pressure to be 19MPa, the reaction temperature to be 390 ℃, the reaction time to be 100min, and reacting CO and H for 100min 2The volume ratio of the mixed gas to the slurry is 800: 1, preparing an oil product.
Example 3
The embodiment provides a biomass liquefaction process, which comprises the following steps:
pretreatment of biomass:
corn stalks and ramie stalks are taken as biomass solids, the water content of the biomass is 20 percent based on the total weight of the biomass, the corn stalks and the ramie stalks are sent into a superfine pulverizer for primary pulverization,the median particle size after primary crushing is 300 mu m, and then the corn stalks and the ramie stalks after primary crushing are sent into a briquetting machine to be compressed and extruded and formed at the temperature of 50 ℃ and the pressure of 2.5MPa until the bulk density is 0.8g/cm3Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 3mm for later use;
catalyst:
the catalyst is a waste agent of the desulfurizer taking FeOOH as an active component, wherein, in the desulfurizer taking FeOOH as the active component, 70g of amorphous FeOOH and 70g of Co2O325g and NiO is 5 g;
the desulfurizer which takes FeOOH as the active component removes H in the waste gas2The basic process of S comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section 2When the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section, namely the waste agent of the desulfurizer which takes FeOOH as the active component in the embodiment.
Preparing biomass slurry:
mixing the pretreated biomass, sulfur and the catalyst to obtain a mixture, adding the mixture into kitchen waste oil for emulsification pulping to form slurry, detecting that the total content of corn straws and ramie straws in the slurry is 57 wt%, the molar ratio of iron element to sulfur element is 1:3, the viscosity of the slurry is 1130mPa (50 ℃), the content of waste agent of the desulfurizer taking FeOOH as an active component in the slurry is 4 wt%, and the average particle size of the added waste agent of the desulfurizer taking FeOOH as the active component is 120 microns;
and (3) conversion reaction:
pressurizing part of pure CO gas to 18MPa, heating to 250 ℃, introducing the pure CO gas into the slurry, pressurizing the rest part of the pure CO gas to 18MPa, heating to 500 ℃, injecting the pure CO gas into the slurry bed reactor from 4 injection ports on the bottom and the side wall of the slurry bed reactor, simultaneously introducing H2S into the reactor to ensure that the molar ratio of iron element to sulfur element in a reaction system is 1:3, carrying out slurry cracking, carbonylation, transformation and hydrogenation reaction, controlling the reaction pressure to be 17MPa, the reaction temperature to be 400 ℃, and the reaction time to be 40min, wherein the volume ratio of the pure CO gas to the slurry is 950: 1, preparing an oil product.
Example 4
The embodiment provides a biomass liquefaction process, which comprises the following steps:
pretreatment of biomass:
pea straw, sorghum straw and rice straw are used as biomass solid, the water content of the biomass is 15% based on the total weight of the biomass, the pea straw, the sorghum straw and the rice straw are sent into an ultrafine grinder to be primarily ground, the median particle size after primary grinding is 250 mu m, and then the primarily ground pea straw, sorghum straw and rice straw are sent into a plodder to be compressed and extruded and formed at the temperature of 55 ℃ and under the pressure of 1.5MPa until the bulk density is 0.9g/cm3Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 0.9mm for later use;
catalyst:
the catalyst adopts a desulfurizer waste agent taking FeOOH as an active component, wherein the content of amorphous FeOOH in the desulfurizer taking FeOOH as the active component is 60%, the content of carrier kieselguhr is 30%, and the content of binder cellulose powder is 10% by total mass of the desulfurizer taking FeOOH as the active component;
the process of using the desulfurizer with FeOOH as the active component to remove H2S in the waste gas is as follows: introducing the waste gas with the H2S content of 5500mg/cm3 into a desulfurization section at the space velocity of 3000H < -1 >, carrying out desulfurization reaction at the temperature of 30 ℃, and collecting waste in the desulfurization section when the content of H2S in the outlet gas of the desulfurization section is less than or equal to 0.01ppm, namely the waste agent of the desulfurizer taking FeOOH as an active component in the embodiment.
Preparing biomass slurry:
mixing the pretreated biomass, sulfur and the catalyst to obtain a mixture, adding the mixture into mixed oil of kitchen waste oil and rapeseed oil for homogeneous pulping to form slurry, wherein the molar ratio of iron element to sulfur element is 1:4, the kitchen waste oil and the rapeseed oil adopted in the subsequent pulp preparation process can be replaced by oil products prepared by the biomass liquefaction process in the embodiment, through detection, the total content of pea straws, sorghum straws and rice straws in the slurry is 40 wt%, the viscosity of the slurry is 820mPa s (50 ℃), the content of a desulfurizing agent taking FeOOH as an active component in the slurry is 8 wt%, and the average particle size of the added desulfurizing agent taking FeOOH as an active component is 300 μm;
and (3) liquefaction reaction:
reacting CO with H2The mixed gas (wherein the volume ratio of CO in the mixed gas is 50%) is pressurized to 18MPa, heated to 380 ℃, injected into the slurry bed reactor from 5 injection ports on the bottom and the side wall of the slurry bed reactor, and subjected to cracking, carbonylation, transformation and hydrogenation reaction with the slurry entering the slurry bed reactor, the reaction pressure is controlled to be 17MPa, the reaction temperature is controlled to be 420 ℃, the reaction time is 50min, and the CO and the H are reacted for 50min2The volume ratio of the mixed gas to the slurry is 900: 1, preparing an oil product.
Example 5
The embodiment provides a co-conversion process of oil sand oil and hogwash oil, which comprises the following steps:
catalyst:
the catalyst is a waste desulfurizer using FeOOH as an active component, wherein soluble iron salt Fe (NO) is contained in the desulfurizer using FeOOH as the active component3)3·9H26g of O, 9g of ferric salt complexing agent triethanolamine and 15g of amorphous iron oxyhydroxide;
the desulfurizer using FeOOH as the active component is used for removing H in waste gas2The process of S is as follows: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2When the content of S is less than or equal to 0.01ppm, the waste in the desulfurization section is collected, namely the desulfurizer which takes FeOOH as an active component in the embodimentThe waste agent of (4);
preparing slurry:
mixing oil sand oil, hogwash oil, sulfur and the catalyst to obtain a mixture, adding a proper amount of water into the mixture, stirring and pulping to form slurry, wherein the average particle size of the added catalyst is 5 mu m, and the molar ratio of iron element to sulfur element is 1: 2;
and (3) conversion reaction:
reacting CO with H2Mixed gas (CO accounts for 60% and H)240 percent) of the mixture is pressurized to 5.7MPa and heated to 500 ℃, then the mixture is introduced into a pipeline for conveying the slurry, the rest of the mixture is pressurized to 5.2MPa and heated to 500 ℃, then the mixture is injected into a slurry bed reactor from an inlet of the slurry bed reactor and undergoes cracking, carbonylation, transformation and hydrogenation reaction with the slurry entering the slurry, the reaction pressure of the transformation reaction is controlled to be 5MPa, the reaction temperature is 470 ℃, the reaction time is 90min, and CO and H are reacted for 90min 2The volume ratio of the mixed gas to the slurry is 8000: 1, preparing an oil product.
Example 6
The embodiment provides a co-conversion process of oil residue, wheat straw and kitchen waste oil, which comprises the following steps:
pretreatment of oil residue and wheat straw:
oil residues and wheat straws are used as biomass solids, the water content of the biomass is 5 percent based on the total weight of the biomass, the oil residues and the excrement are sent into a superfine pulverizer for primary pulverization, the median particle size after primary pulverization is 200 mu m, then the oil residues and the excrement after primary pulverization are sent into a plodder for compression at the temperature of 55 ℃ and under the pressure of 1.5MPa, and the compression molding is carried out until the bulk density is 0.95g/cm3Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 60 mu m for later use;
catalyst:
the catalyst is a regenerant of a waste desulfurizer containing FeOOH, wherein the content of gamma-FeOOH in the FeOOH-containing desulfurizer is 45%, the content of alpha-FeOOH is 35%, the content of a carrier molecular sieve is 15%, and the content of a binder sesbania powder is 5% by total mass of the FeOOH-containing desulfurizer;
the catalyst removes H in the exhaust gas2The basic process of S comprises the following steps: will H2The S content is 5500mg/cm 3In 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2When the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section, namely the desulfurizer waste agent;
the regeneration method of the waste desulfurizer comprises the following steps: washing the desulfurizer waste agent with water, and grinding the waste agent powder with water in a wet ball mill to obtain 80-mesh particles; preparing the waste agent powder into aqueous suspension with the solid mass percentage content of 8%, introducing compressed air, reacting for a period of time, sampling and inspecting, and when the sample taken out does not react with hydrochloric acid to generate H2S, completely converting iron sulfide in the waste agent into iron oxyhydroxide and elemental sulfur to form slurry containing the iron oxyhydroxide and the elemental sulfur, filtering the slurry to obtain a solid material, and using CC1 to obtain the solid material4And (3) extracting the solid material obtained after the extraction and filtration for three times, combining the extraction liquid, recovering the solvent by using a distillation method, simultaneously obtaining the crystallized elemental sulfur, and mixing the residual solid after the extraction liquid is separated with adhesive sesbania powder to obtain the regenerated product of the desulfurizer waste agent, wherein the using amount of the adhesive sesbania powder is 5% of the mass of the solid.
Preparing slurry:
Mixing the pretreated oil residue, wheat straws, carbon disulfide and the catalyst to obtain a mixture, adding the mixture into kitchen waste oil to be dispersed and pulped to form slurry, detecting that the total content of the oil residue and excrement in the slurry is 55 wt%, the molar ratio of iron element to sulfur element is 1:2, the viscosity of the slurry is 400mPa & (50 ℃), wherein the content of the catalyst in the slurry is 10 wt%, and the average particle size of the added catalyst is 5 mm;
and (3) conversion reaction:
reacting CO with H2Mixed gas (CO 60% and H)240 percent) of the mixture is pressurized to 16.8MPa and heated to 250 ℃, the mixture is introduced into a pipeline for conveying the slurry, the rest of the mixture is pressurized to 16.2MPa and heated to 550 ℃, the mixture is injected into the fluidized bed reactor from the inlet of the fluidized bed reactor and undergoes cracking, carbonylation, transformation and hydrogenation reaction with the slurry entering the fluidized bed reactor, the reaction pressure of the transformation reaction is controlled to be 16MPa, the reaction temperature is controlled to be 420 ℃, the reaction time is 60min, and CO and H are reacted with each other2The volume ratio of the mixed gas to the slurry is 5000: 1, preparing an oil product.
Example 7
This example is the same as example 2, except that the regeneration method of the waste agent is different, and the regeneration method of the waste agent in this example is,
1) Introducing water vapor with the pressure of 1MPa into a heating furnace, and heating the water vapor to 400 ℃;
2) introducing the heated water vapor into a desulfurization tank containing a waste desulfurizer at the speed of 20m/s, and heating the waste desulfurizer;
3) ensuring that the bed temperature of the waste desulfurizer is heated to 450 ℃ by water vapor and the operation is carried out for 2 hours, wherein the steam consumption is 8 t/h;
4) analyzing the pH value of the outlet of the desulfurization tank, and introducing a small amount of coke oven gas into the desulfurization tank for reduction when the pH value is more than or equal to 7.5 for 3 times continuously;
5) introducing coke oven gas subjected to primary hydrogenation in the fine desulfurization process to reduce the waste desulfurizer at the rate of 800m 3/h;
6) analyzing the concentration change of the inlet and outlet H2 every 30min after introducing the coke oven gas, and obtaining the regenerant of the waste desulfurizer after the concentration of the outlet H2 is stably more than or equal to the concentration of the inlet H2 (3 times of analysis).
Test examples
The distributions of the products prepared by the processes of examples 1-7 of the present invention were compared and the products were tested as follows:
the percent solid organic matter conversion is (the total mass of solid organic matter in the raw material-the mass of solid organic matter remaining in the reaction product)/the total mass of solid organic matter in the raw material, and the solid organic matter in the percent solid organic matter conversion refers to anhydrous and ashless groups (the same applies hereinafter);
The yield percent of the solid organic matter converted oil is the mass of the liquid phase oil product at normal temperature and normal pressure in the product converted from the solid organic matter/the total feeding mass of the solid organic matter in the raw material;
the reaction water yield = (mass of water of reaction product-total mass of water initially added in the reaction or carried in by raw material)/total mass of raw material fed. When this value is < 0, it is recorded as "none";
the corresponding test results are shown in tables 1 and 2:
table 1 comparison of conversion effect of solid organic matter
The liquid organic matter conversion rate is (the mass of the material with the boiling point of more than 360 ℃ in the total liquid organic matter feeding material-the total mass of the liquid oil product with the boiling point of more than 360 ℃ in the product)/the mass of the material with the boiling point of more than 360 ℃ in the total liquid organic matter feeding material;
the yield of the liquid organic matter converted oil is equal to the mass of the liquid-phase oil product in the converted product at normal temperature and normal pressure/the total feed mass of the raw material liquid organic matter.
TABLE 2 comparison of product distribution after conversion of liquid organic matter feedstock
As can be seen from tables 1 and 2, the solid organic matter conversion oil yield is greater than 50 wt% and the liquid organic matter conversion oil yield is greater than 91% using the method of the present invention; the calorific value of the organic matter converted oil is more than 0.91 time of the calorific value of standard fuel oil with the same mass, and the oxygen content of the organic matter converted oil phase is less than 4.8 wt%; the generated water of the raw materials after the reaction is less than 1.5 wt%.
21.333 328. An application of FeO desulfurizer waste agent as a biomass hydrogenation liquefaction catalyst.
Example 1
The embodiment of the invention provides Fe21.333O32A desulfurizing agent waste agent, wherein the Fe21.333O32Total mass of desulfurizing agent, Fe21.333O32The content of the magnetic iron oxide red in the desulfurizer is 75 percent, and the content of the binder attapulgite is 25 percent.
The desulfurization process of the catalyst as coal pyrolysis gas is summarized as follows:
(1) and (3) cooling the compressed coal pyrolysis gas to 25-40 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a coarse desulfurization tower, and adopting a flow of feeding the coal pyrolysis gas from bottom to top to prevent liquid water from entering a desulfurizer bed layer. Only the crude removal of hydrogen sulphide and the removal of part of the R-SH and thiophene takes place here.
(2) Heating the gas after the coarse desulfurization to 120-135 ℃ for hydrolysis, and adding most of COS and CS2Hydrolysis to H2S。
(3) The gas after hydrolysis is cooled to 20-25 ℃ again for H2S removal, wherein in order to ensure the purification effect and the service life, the H generated by hydrolysis is removed in a mode of double-tower series-parallel connection operation2S is removed completely, and the rest R-SH and thiophene are further removed. The residual sulfide is completely removed in the process, and the final purification requirement that the total sulfur content is less than 0.1ppm is achieved.
The desulfurizer becomes waste agent after being used for many times and is deleted from a desulfurizer bed layer, namely Fe in the application21.333O32A waste desulfurizer.
Example 2
The embodiment of the invention provides Fe21.333O32A desulfurizing agent waste agent, wherein the Fe21.333O32Total mass of desulfurizing agent, said Fe21.333O32The content of the magnetic iron oxide red in the desulfurizer is 89%, and the content of the binder bentonite is 11%. The desulfurization process and operation of the catalyst on gas field waterThe method comprises the following steps:
the catalyst is filled in a fixed bed reactor to contain H2And (3) carrying out full contact reaction on the gas field water of the S with the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h-1The waste catalyst after gas field water desulfurization is the Fe of the application21.333O32Waste desulfurizer.
Example 3
The embodiment of the invention provides Fe21.333O32A desulfurizing agent waste agent, wherein the Fe21.333O32Total mass of desulfurizing agent, Fe21.333O32Fe in desulfurizer21.333O32Content of (2) is 80%, and carrier gamma-Al2O3The content of (A) is 10%, and the content of the binder bentonite is 10%.
The catalyst removes H in the exhaust gas2The matrix process of S comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section 2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section as a catalyst for hydrogenation reaction.
Example 4
The embodiment of the invention provides Fe21.333O32A desulfurizing agent waste agent, wherein the Fe21.333O32Total mass of desulfurizing agent, Fe21.333O32Fe in desulfurizer21.333O32The content is 94%, and the balance is impurities and water.
The desulfurization process of the coke oven gas by the catalyst comprises the following operation steps:
mixing the above Fe21.333O32Mixing a desulfurizing agent and water to prepare slurry serving as the desulfurizing agent, wherein the total concentration of iron oxyhydroxide in the slurry is 10 wt%, introducing the deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, and spraying the desulfurizing agent from the top of the desulfurizing tower through a nozzle to carry out leaching desulfurization on the coke oven gasCollecting and drying the desulfurized waste liquid to obtain the Fe21.333O32Waste desulfurizer.
Example 5
The waste collected in the above examples was used as a catalyst for biomass liquefaction reaction, and the activity of the catalyst was tested as follows: preparing slurry containing corn straws and a catalyst, conveying the slurry into a slurry bed reactor for hydrogenation liquefaction reaction, and controlling the reaction pressure to be 20MPa and the temperature to be 380 ℃, wherein the addition amount of the catalyst is 2 wt% of the addition amount of the corn straws, and the activity of the catalyst is represented by the distribution of products prepared by biomass liquefaction reaction, and is shown in the following table 1:
Table 1 comparison of product distribution in examples 1-4
As can be seen from table 1, the catalyst of the present invention can effectively promote the hydrogenation liquefaction reaction of biomass.
21.333 329. Waste desulfurizer using FeO as main active component as biomass hydrogenation liquefaction catalyst
The use of (1).
Example 1
The embodiment of the invention provides a method for preparing a high-purity Fe-based catalyst mainly from Fe21.333O32A desulfurizing agent waste agent as an active ingredient, wherein the Fe is mainly used21.333O32Among the desulfurizing agents as active ingredients, magnetic iron oxide red Fe21.333O3255g of copper oxide, 12g of carrier ferric oxide and 21g of carrier ferric oxide;
the desulfurization process of the catalyst as coal pyrolysis gas is summarized as follows:
(1) and (3) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a coarse desulfurization tower, and adopting a flow of feeding the coal pyrolysis gas from bottom to top to prevent liquid water from entering a desulfurizer bed layer. Only the crude removal of hydrogen sulphide and the removal of part of the R-SH and thiophene takes place here.
(2) And heating the gas after the coarse desulfurization to 110-125 ℃ for hydrolysis, and hydrolyzing most of COS and CS2 into H2S.
(3) And cooling the hydrolyzed gas to 20-25 ℃ again, and removing H2S, wherein in order to ensure the purification effect and the service life, a double-tower series-parallel operation mode is adopted to completely remove H2S generated by hydrolysis, and further remove the rest R-SH and thiophene. The residual sulfide is completely removed in the process, and the final purification requirement that the total sulfur content is less than 0.1ppm is achieved.
The desulfurizer becomes waste agent after being used for many times and is deleted from a desulfurizer bed layer, namely Fe is used in the application21.333O32The desulfurizer waste agent is a main active component.
Example 2
The embodiment of the invention provides a method for preparing a high-purity Fe-based catalyst mainly from Fe21.333O32A desulfurizing agent waste agent as an active ingredient, wherein the Fe is mainly used21.333O32Among desulfurizing agents as active ingredients, Fe21.333O32Is 55g of anatase type Ti0222g of bentonite, 15g of bentonite;
the desulfurization process of the catalyst for gas field water comprises the following operation steps:
the catalyst is filled in a fixed bed reactor to contain H2And (3) carrying out full contact reaction on the gas field water of the S with the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h-1The waste catalyst after gas field water desulfurization is Fe21.333O32The desulfurizer waste agent is a main active component.
Example 3
The embodiment of the invention provides a method for preparing a high-purity Fe-based catalyst mainly from Fe21.333O32A desulfurizing agent waste agent as an active ingredient, wherein the Fe is mainly used21.333O32Among desulfurizing agents as active ingredients, Fe21.333O3255g of lead oxide, 16g of manganese dioxide and 15g of bentonite;
the catalyst removes H in the exhaust gas2The matrix process of S comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section 2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section as a catalyst for hydrogenation reaction.
Example 4
The embodiment of the invention provides a method for preparing a high-purity Fe-based catalyst mainly from Fe21.333O32A desulfurizing agent waste agent as an active ingredient, wherein the Fe is mainly used21.333O32Among desulfurizing agents as active ingredients, Fe21.333O3247g of anatase type Ti0222g of bentonite, 15g of bentonite;
the desulfurization process of the coke oven gas by the catalyst comprises the following operation steps:
mixing the desulfurizer with water to prepare slurry serving as the desulfurizer, wherein the total concentration of iron oxyhydroxide in the slurry is 10 wt%, introducing the deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizer on the top of the desulfurizing tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the Fe-containing desulfurizer21.333O32The desulfurizer waste agent is a main active component.
Example 5 (use of waste desulfurizing agent)
The waste collected in the above examples was used as a catalyst for biomass liquefaction reaction, and the activity of the catalyst was tested as follows: preparing slurry containing corn straws and a catalyst, conveying the slurry into a slurry bed reactor for hydrogenation liquefaction reaction, and controlling the reaction pressure to be 20MPa and the temperature to be 380 ℃, wherein the addition amount of the catalyst is 2 wt% of the addition amount of the corn straws, and the activity of the catalyst is represented by the distribution of products prepared by biomass liquefaction reaction, and is shown in the following table 1:
Table 1 comparison of product distribution in examples 1-4
As can be seen from table 1, the catalyst of the present invention can effectively promote the hydrogenation liquefaction reaction of biomass.
21.333 3210. The application of regenerated waste desulfurizer containing FeO as a biomass hydrogenation liquefaction catalyst.
Example 1
The embodiment of the invention provides a Fe-containing alloy21.333O32The method for regenerating a desulfurizing agent waste agent, wherein the Fe-containing catalyst is21.333O32The total mass of the desulfurizing agent of (1), the desulfurizing agent containing Fe21.333O32The magnetic iron oxide red Fe in the desulfurizer21.333O3255g of copper oxide, 12g of carrier ferric oxide and 21g of carrier ferric oxide;
the desulfurization process of the catalyst as coal pyrolysis gas is summarized as follows:
(1) and (3) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a coarse desulfurization tower, and adopting a flow of feeding the coal pyrolysis gas from bottom to top to prevent liquid water from entering a desulfurizer bed layer. Only the crude removal of hydrogen sulphide and the removal of part of the R-SH and thiophene takes place here.
(2) And heating the gas after the coarse desulfurization to 110-125 ℃ for hydrolysis, and hydrolyzing most of COS and CS2 into H2S.
(3) And cooling the hydrolyzed gas to 20-25 ℃ again, and removing H2S, wherein in order to ensure the purification effect and the service life, a double-tower series-parallel operation mode is adopted to completely remove H2S generated by hydrolysis, and further remove the rest R-SH and thiophene. The residual sulfide is completely removed in the process, and the final purification requirement that the total sulfur content is less than 0.1ppm is achieved.
The desulfurizer becomes waste agent after being used for many times and is deleted from a desulfurizer bed layer, namely the desulfurizer containing Fe in the application21.333O32The waste desulfurizer of (1).
Above-mentioned Fe-containing21.333O32The regeneration method of the waste desulfurizer comprises the following steps,
the Fe is added21.333O32OfThe sulfur agent waste agent is introduced into a desulfurization reactor, and then O is added2/SO220 mol% O with a volume ratio of 1:1002/SO2And 80 mol% N2The formed regeneration gas is introduced into the bottom inlet of the desulfurization reactor, the temperature of the desulfurization reactor is controlled to be 800 ℃, and the space velocity is 3000h-1Testing the concentration of sulfur dioxide at the inlet and outlet of the desulfurization reactor, and stopping regeneration when the concentration of sulfur dioxide at the inlet and outlet is close to that of sulfur dioxide at the outlet to obtain the Fe-containing material21.333O32The regenerant of the waste desulfurizer.
Example 2
The embodiment of the invention provides a Fe-containing alloy21.333O32The method for regenerating a desulfurizing agent waste agent, wherein the Fe-containing catalyst is21.333O32The total mass of the desulfurizing agent of (1), the desulfurizing agent containing Fe21.333O32Fe in the desulfurizing agent21.333O32Is 55g of anatase type Ti0222g of bentonite, 15g of bentonite;
the desulfurization process of the catalyst for gas field water comprises the following operation steps:
the catalyst is filled in a fixed bed reactor to contain H2And (3) carrying out full contact reaction on the gas field water of the S with the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h -1The waste catalyst after gas field water desulfurization is the catalyst containing Fe in the application21.333O32The waste desulfurizer of (1).
Above-mentioned Fe21.333O32The regeneration method of the waste desulfurizer comprises the following steps,
said Fe is added21.333O32The waste desulfurizer is introduced into a desulfurization reactor, and then O is added2/SO215 mol% O with a volume ratio of 1:1002/SO2And 85 mol% N2The formed regeneration gas is introduced into the bottom inlet of the desulfurization reactor, the temperature of the desulfurization reactor is controlled to be 800 ℃, and the space velocity is 3000h-1Testing the concentration of sulfur dioxide at the inlet and outlet of the desulfurization reactor, and stopping regeneration when the concentration of sulfur dioxide at the inlet and outlet is close to each other to obtain the product containing Fe21.333O32The regenerant of the waste desulfurizer.
Example 3
The embodiment of the invention provides a Fe-containing alloy21.333O32The method for regenerating a desulfurizing agent waste agent of (1), wherein the Fe is contained21.333O32The total mass of the desulfurizing agent of (1), the desulfurizing agent containing Fe21.333O32Fe in the desulfurizing agent21.333O3255g of lead oxide, 16g of manganese dioxide and 15g of bentonite;
the catalyst removes H in the exhaust gas2S, the matrix process comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2When the content of S is less than or equal to 0.01ppm, the waste collected in the desulfurization section is the Fe-containing waste in the application 21.333O32The waste desulfurizer of (1).
Above-mentioned Fe-containing21.333O32The regeneration method of the waste desulfurizer comprises the following steps,
the Fe is added21.333O32The waste desulfurizer is introduced into a desulfurization reactor, and then O is added2/SO228 mol% O with a volume ratio of 1:1002/SO2And 72 mol% N2The formed regeneration gas is introduced into the bottom inlet of the desulfurization reactor, the temperature of the desulfurization reactor is controlled to be 800 ℃, and the space velocity is 3000h-1Testing the concentration of sulfur dioxide at the inlet and outlet of the desulfurization reactor, and stopping regeneration when the concentration of sulfur dioxide at the inlet and outlet is close to that of sulfur dioxide at the outlet to obtain the Fe-containing material21.333O32The regenerant of the waste desulfurizer.
Example 4
The embodiment of the invention provides a Fe-containing alloy21.333O32The method for regenerating a desulfurizing agent waste agent, wherein the Fe-containing catalyst is21.333O32The total mass of the desulfurizing agent of (1), the desulfurizing agent containing Fe21.333O32The content of the magnetic iron oxide red in the desulfurizer is 96.2 percent, and the balance is impurities and water;
the desulfurization process of the coke oven gas by the catalyst comprises the following operation steps:
mixing the desulfurizer with water to prepare slurry serving as the desulfurizer, wherein the total concentration of iron oxyhydroxide in the slurry is 10 wt%, introducing the deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizer at the top of the desulfurizing tower through a nozzle to elute and desulfurize the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the Fe-containing waste liquid 21.333O32The waste desulfurizer of (1).
Above-mentioned Fe-containing21.333O32The regeneration method of the waste desulfurizer comprises the following steps,
(1) introducing water vapor with the pressure of 1.0MPa into a heating furnace, and heating the water vapor to 420 ℃;
(2) introducing the heated water vapor into the container containing Fe at a speed of 10m/s21.333O32The desulfurizing tank of the desulfurizing agent waste agent of (1) to heat the molten steel containing Fe21.333O32The waste desulfurizer of (1);
(3) ensuring Fe content21.333O32The bed temperature of the waste desulfurizer is heated by water vapor to be above 400 ℃ and the operation is carried out for 3 hours, and the steam consumption is 7 t/h;
(4) analyzing the pH value of the outlet of the desulfurization tank, and introducing coke oven gas into the desulfurization tank for reduction when the pH value is more than or equal to 7.5 for 3 times continuously;
(5) analyzing the import and export H every 30min after the coke oven gas is introduced2Concentration change when discharging H2Concentration stable greater than or equal to inlet H2After concentration (3 times of analysis), the Fe content is obtained21.333O32The regenerant of the desulfurization agent waste agent.
Example 5
The collected regenerants of the waste desulfurizer from the above examples 1-4 are used as catalysts for biomass liquefaction reaction, and the catalyst in example 4 contains Fe21.333O32The desulfurizing agent of (1) was used as a catalyst for the biomass liquefaction reaction in comparative example 1;
the catalysts for biomass liquefaction reaction in examples 1 to 4 above and comparative example 1 were subjected to activity tests as follows: preparing slurry containing corn straws and a catalyst, conveying the slurry into a slurry bed reactor for hydrogenation liquefaction reaction, and controlling the reaction pressure to be 20MPa and the temperature to be 380 ℃, wherein the addition amount of the catalyst is 2 wt% of the addition amount of the corn straws, and the activity of the catalyst is represented by the distribution of products prepared by biomass liquefaction reaction, and is shown in the following table 1:
Table 1 examples 1-4 comparison of product distribution
As can be seen from table 1, the catalyst of the present invention can effectively promote the hydrogenation liquefaction reaction of biomass.
21.333 3211. Use of waste desulfurizer of FeO as CO shift catalyst
Example 1
The embodiment of the invention provides Fe21.333O32The desulfurizing agent of (1), wherein the Fe is used21.333O32Total mass of desulfurizing agent, Fe21.333O32The content of the magnetic iron oxide red in the desulfurizer is 70 percent, and the content of the adhesive kaolin is 30 percent;
the desulfurization process of the tail gas generated after the catalyst is used for hydrogenation upgrading of medium and low temperature coal tar in industry is as follows:
1) collecting tail gas generated after the medium and low temperature coal tar is subjected to hydrogenation catalysis by a fixed bed;
2) the desulfurizer of the embodiment is prepared into columnar catalyst particles with the diameter of 1mm and the length of 15mm, and the columnar catalyst particles are filled in a desulfurizing tower to form a desulfurization layer;
3) the tail gas is treated for 2000h-1The air speed of the catalyst passes through the desulfurization layer, and the air speed and a desulfurizing agent in the desulfurization layer are subjected to desulfurization reaction at 50 ℃, hydrogen sulfide in tail gas is removed, after the reaction is finished, a waste agent of the reacted desulfurizing agent is taken out, and the waste agent is cooled to room temperature, namely the Fe in the application21.333O32The waste desulfurizer of (4).
Example 2
The embodiment of the invention provides Fe 21.333O32The desulfurizing agent of (1), wherein the Fe is used21.333O32Total mass of desulfurizing agent, said Fe21.333O32The content of the magnetic iron oxide red in the desulfurizer is 75 percent, and the content of the binder attapulgite is 25 percent;
the desulfurization process of the coal pyrolysis gas containing hydrogen sulfide by the catalyst is as follows:
(1) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a desulfurizing tower filled with the desulfurizing agent mainly comprising ferric oxide as an active component, and adopting a flow of feeding the coal pyrolysis gas from bottom to top to prevent liquid water from entering a desulfurizing agent bed layer to remove hydrogen sulfide;
(2) the desulfurizer becomes waste agent after being used for many times, and is taken out from a desulfurizer bed layer, namely the Fe in the application21.333O32The waste desulfurizing agent of (2).
Example 3
The embodiment of the invention provides Fe21.333O32The desulfurizing agent of (1), wherein the Fe is used21.333O32Total mass of desulfurizing agent, Fe21.333O32The content of the magnetic iron oxide red in the desulfurizer is 96.2 percent, and the balance is impurities and water;
the catalyst is used for desulfurizing the petroleum containing hydrogen sulfide, and the operation steps are as follows:
(1) the desulfurizer of the embodiment is prepared into catalyst particles with the diameter of 1.5mm, and the catalyst particles are filled in a desulfurization tower to form a desulfurization layer;
(2) Spraying hydrogen sulfide petroleum into a desulfurization layer from the top of a desulfurization tower through a nozzle, leaching and desulfurizing, and collecting desulfurized desulfurizer waste agent, namely Fe in the application21.333O32The waste desulfurizer of (4).
Example 4
The embodiment of the invention provides Fe21.333O32Desulfurization ofA waste agent of agent, wherein, the Fe21.333O32Total mass of desulfurizing agent, Fe21.333O32The content of the magnetic iron oxide red in the desulfurizer is 89%, and the content of the binder bentonite is 11%;
the desulfurization process of the catalyst for gas field water comprises the following operation steps:
loading the catalyst in a fixed bed reactor to obtain H2And (2) carrying out full contact reaction on the gas field water of the S and the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h-1The waste catalyst after gas field water desulfurization is the Fe of the application21.333O32The waste desulfurizer of (4).
Example 5
The embodiment of the invention provides Fe21.333O32The desulfurizing agent of (1), wherein the Fe is used21.333O32Total mass of desulfurizing agent, Fe21.333O32Gamma-Fe in desulfurizer21.333O32Is 55% of beta-Fe21.333O32Content of (2) is 25%, carrier gamma-Al2O3The content of (A) is 10%, and the content of the binder bentonite is 10%;
the catalyst removes H in the exhaust gas2The matrix process of S comprises the following steps: h is to be 2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section to be used as a catalyst for CO conversion reaction.
Example 6
The embodiment of the invention provides Fe21.333O32The desulfurizing agent of (1), wherein the Fe is used21.333O32Total mass of desulfurizing agent, Fe21.333O32alpha-Fe in desulfurizing agent21.333O3249% of gamma-Fe21.333O3245 percent of the content and the balance of impurities and water;
the desulfurization process of the catalyst for the coke oven gas containing the hydrogen sulfide comprises the following operation steps:
mixing the desulfurizer with water to prepare slurry serving as the desulfurizer, wherein the solid content in the slurry is 15 wt%, introducing deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizer on the top of the desulfurizing tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the Fe-containing iron-based desulfurizing agent21.333O32The waste desulfurizer of (1).
Example 7 (use of waste desulfurizing agent)
The collected waste desulfurizing agents of the above examples 1 to 6 were used as catalysts for CO shift reaction, and the activity tests of the catalysts were carried out as follows:
The composition of the raw material gas is 15 vol% CO and 55 vol% H2、6vol％CO2、24vol％N2And the reaction steam-gas ratio is 1: 1, the space velocity is 4000h-1The temperature zone for testing the activity of the catalyst is 250-450 ℃;
the activity of the catalyst is expressed in terms of CO conversion and is calculated as follows:
CO conversion ═ 1-VCO'/VCO)/(1+VCO)×100％
Wherein, VCO'Is the volume percent of CO in the reactor off-gas, VCOIs the volume percentage of CO in the raw material gas;
the corresponding test results are shown in table 1 below:
TABLE 1 CO conversion at different test temperatures
From table 1 it can be seen that: fe as used in the present application21.333O32The waste desulfurizer is used as CO conversion catalystThe catalyst can effectively catalyze the CO to generate a change reaction, and improves the conversion rate of CO.
21.333 3212. Use of a spent desulfurization agent containing FeO as a CO shift catalyst.
Example 1
The embodiment of the invention provides a Fe-containing alloy21.333O32Wherein the desulfurizing agent contains Fe21.333O32In the desulfurizing agent of (1), magnetic iron oxide red Fe21.333O3250g of potassium oxide, 8g of adhesive kaolin, 10g of kaolin;
the desulfurization process of the tail gas generated after the catalyst is used for hydrogenation upgrading of medium and low temperature coal tar in industry is as follows:
1) collecting tail gas generated after the medium and low temperature coal tar is subjected to hydrogenation catalysis by a fixed bed;
2) the desulfurizer of the embodiment is prepared into columnar catalyst particles with the diameter of 1mm and the length of 15mm, and the columnar catalyst particles are filled in a desulfurizing tower to form a desulfurization layer;
3) The tail gas is treated for 2000h-1The air speed of the catalyst passes through the desulfurization layer, and the air speed and a desulfurizing agent in the desulfurization layer are subjected to desulfurization reaction at 50 ℃, hydrogen sulfide in tail gas is removed, after the reaction is finished, a waste agent of the reacted desulfurizing agent is taken out, and the waste agent is cooled to room temperature, namely the catalyst containing Fe in the application21.333O32The waste desulfurizer of (4).
Example 2
The embodiment of the invention provides a Fe-containing alloy21.333O32Wherein the desulfurizing agent contains Fe21.333O32In the desulfurizing agent of (1), magnetic iron oxide red Fe21.333O3255g of copper oxide, 12g of carrier ferric oxide and 21g of carrier ferric oxide;
the desulfurization process of the hydrogen sulfide-containing coal pyrolysis gas by the catalyst is as follows:
(1) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a desulfurizing tower filled with the desulfurizing agent mainly comprising ferric oxide as an active component, and adopting a flow of feeding the coal pyrolysis gas from bottom to top to prevent liquid water from entering a desulfurizing agent bed layer to remove hydrogen sulfide;
(2) the desulfurizer becomes waste agent after being used for many times, and is taken out from a desulfurizer bed layer, namely the desulfurizer containing Fe in the application21.333O32The waste desulfurizer of (4).
Example 3
The embodiment of the invention provides a Fe-containing alloy21.333O32Wherein the desulfurizing agent contains Fe21.333O32In the desulfurizing agent of (1), magnetic iron oxide red Fe 21.333O3260g of zinc oxide, 14g of binder kaolin, and 19g of binder kaolin;
the catalyst is used for desulfurizing petroleum containing hydrogen sulfide, and the operation steps are as follows:
(1) the desulfurizer of the embodiment is prepared into catalyst particles with the diameter of 1.5mm, and the catalyst particles are filled in a desulfurization tower to form a desulfurization layer;
(2) spraying petroleum containing hydrogen sulfide into a desulfurization layer from the top of a desulfurization tower through a nozzle, leaching and desulfurizing, and collecting desulfurized desulfurizer waste agent, namely the desulfurizer waste agent containing Fe in the application21.333O32The waste desulfurizing agent of (2).
Example 4
The embodiment of the invention provides a Fe-containing alloy21.333O32Wherein the desulfurizing agent contains Fe21.333O32In the desulfurizing agent of (1), Fe21.333O32Is 55g of anatase type Ti0222g of bentonite, 15g of bentonite;
the desulfurization process of the catalyst for gas field water comprises the following operation steps:
the catalyst is filled in a fixed bed reactor to contain H2And (3) carrying out full contact reaction on the gas field water of the S with the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h-1The waste catalyst after gas field water desulfurization is the Fe-containing catalyst of the present application21.333O32The waste desulfurizing agent of (2).
Example 5
The embodiment of the invention provides a Fe-containing alloy21.333O32Wherein the desulfurizing agent contains Fe 21.333O32In the desulfurizing agent of (2), Fe21.333O3260g of lead oxide, 16g of manganese dioxide and 15g of bentonite;
the catalyst removes H in the exhaust gas2S, the matrix process comprises the following steps: will H2The S content is 5500mg/cm3In 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section to be used as a catalyst for CO conversion reaction.
Example 6
The embodiment of the invention provides a Fe-containing alloy21.333O32Wherein the desulfurizing agent contains Fe21.333O32In the desulfurizing agent of (1), alpha-Fe21.333O32Is 25g of beta-Fe21.333O32Is 22g of gamma-Fe21.333O32Is 20g of anatase type Ti0222g of bentonite, 15g of bentonite;
the desulfurization process of the catalyst for the coke oven gas containing the hydrogen sulfide comprises the following operation steps:
mixing the desulfurizer with water to prepare slurry serving as the desulfurizer, wherein the solid content in the slurry is 15 wt%, introducing deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizer on the top of the desulfurizing tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the Fe-containing waste liquid 21.333O32The desulfurization agent waste agent.
Example 7 (application of desulfurizing agent waste agent)
The collected waste desulfurizing agents of the above examples 1 to 6 were used as catalysts for CO shift reaction, and the activity tests of the catalysts were carried out as follows:
the composition of the raw material gas is 15 vol% CO and 55 vol% H2、6vol％CO2、24vol％N2And the reaction steam-gas ratio is 1: 1, the airspeed is 4000h-1The catalyst activity test temperature zone is 250-450 ℃;
the activity of the catalyst is expressed in terms of CO conversion and is calculated as follows:
CO conversion rate (1-V)CO'/VCO)/(1+VCO)×100％
Wherein, VCO'Is the volume percent of CO in the reactor off-gas, VCOIs the volume percentage of CO in the raw material gas;
the corresponding test results are shown in table 1 below:
TABLE 1 CO conversion at different test temperatures
From table 1 it can be seen that: containing Fe as used herein21.333O32The waste desulfurizer is used as a CO transformation catalyst, and can effectively catalyze CO to generate a transformation reaction and improve the conversion rate of CO.
21.333 3213. The waste desulfurizer containing FeO is regenerated and used as a CO shift catalyst.
Example 1
The embodiment of the invention provides a Fe-containing alloy21.333O32Wherein the desulfurizing agent contains Fe21.333O32In the desulfurizing agent of (1), magnetic iron oxide red Fe21.333O3250g of potassium oxide, 8g of adhesive kaolin, 10g of kaolin;
the desulfurization process of the tail gas generated after the catalyst is used for hydrogenation upgrading of medium and low temperature coal tar in industry is as follows:
1) Collecting tail gas generated after the medium and low temperature coal tar is subjected to fixed bed hydrogenation catalysis;
2) the desulfurizer of the embodiment is prepared into columnar catalyst particles with the diameter of 1mm and the length of 15mm, and the columnar catalyst particles are filled in a desulfurizing tower to form a desulfurization layer;
3) the tail gas is treated for 2000h-1Passes through the desulfurization layer and is removed from the desulfurization layerThe sulfur agent is subjected to desulfurization reaction at 50 ℃, hydrogen sulfide in tail gas is removed, after the reaction is finished, the waste agent of the reacted desulfurizer is taken out and cooled to room temperature, and the waste agent containing Fe in the application is obtained21.333O32The waste agent of the desulfurizing agent of (1);
above-mentioned Fe-containing21.333O32The method for regenerating the waste desulfurizer comprises the following steps:
1) stirring the waste agent and an aqueous solution of sodium hydroxide in a slurry tank to prepare slurry, and maintaining the pH value of the slurry to be 8.0, wherein the solid content of the slurry is 4 wt%;
2) introducing air into the slurry, and carrying out oxidation reaction at 90 ℃ and 0.1MPa to carry out oxidation regeneration;
3) then introducing hydrogen sulfide into the oxidized slurry, and carrying out a vulcanization reaction at 10 ℃ and 5 MPa;
4) introducing air into the vulcanized slurry, and carrying out oxidation reaction at 90 ℃ and 0.1MPa to carry out oxidation regeneration;
5) repeating the steps 3) and 4) twice to enable the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction to be 1: 4.5;
6) And carrying out solid-liquid separation on the slurry after the oxidation reaction to obtain a regenerated product of the waste agent.
Example 2
The embodiment of the invention provides a Fe-containing alloy21.333O32The desulfurizing agent waste agent of (1), wherein the desulfurizing agent contains Fe21.333O32In the desulfurizing agent of (1), magnetic iron oxide red Fe21.333O3255g of copper oxide, 12g of carrier ferric oxide and 21g of carrier ferric oxide;
the desulfurization process of the hydrogen sulfide-containing coal pyrolysis gas by the catalyst is as follows:
(1) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a desulfurizing tower filled with the desulfurizing agent mainly comprising ferric oxide as an active component, and adopting a flow of feeding the coal pyrolysis gas from bottom to top to prevent liquid water from entering a desulfurizing agent bed layer to remove hydrogen sulfide;
(2) the desulfurizer is formed after repeated useThe waste agent is taken out from the desulfurizer bed layer, namely the waste agent containing Fe in the application21.333O32The waste agent of the desulfurizing agent of (1);
above-mentioned Fe-containing21.333O32The method for regenerating the waste desulfurizer comprises the following steps:
1) dispersing the waste agent in water to form slurry;
2) heating the slurry to 60 ℃ under normal pressure, adding hydrogen peroxide into the slurry by using a peristaltic pump, controlling the flow to be 500mL/min, and magnetically stirring to promote the reaction for 10 min;
3) After the reaction is finished, the reaction solution is filtered, the obtained precipitate is washed for 2 times by water and naturally dried to obtain the regeneration of the waste agent.
Example 3
The embodiment of the invention provides a Fe-containing alloy21.333O32Wherein the desulfurizing agent contains Fe21.333O32In the desulfurizing agent of (1), magnetic iron oxide red Fe21.333O3260g of zinc oxide, 14g of adhesive kaolin, 19g of kaolin;
the catalyst is used for desulfurizing petroleum containing hydrogen sulfide, and the operation steps are as follows:
(1) the desulfurizer of the embodiment is prepared into catalyst particles with the diameter of 1.5mm, and the catalyst particles are filled in a desulfurization tower to form a desulfurization layer;
(2) spraying petroleum containing hydrogen sulfide into a desulfurization layer from the top of a desulfurization tower through a nozzle, leaching and desulfurizing, and collecting desulfurized desulfurizer waste agent, namely the desulfurizer waste agent containing Fe in the application21.333O32The waste agent of the desulfurizing agent of (1);
above-mentioned Fe-containing21.333O32The method for regenerating a spent desulfurizing agent comprises the steps of:
1) stirring the waste agent and water in a slurry tank to prepare slurry, wherein the solid content of the slurry is 12 wt%;
2) introducing sodium hypochlorite into the slurry, and carrying out oxidation reaction at 60 ℃ and 1MPa to carry out oxidation regeneration;
3) adding Na into the oxidized slurry 2S, carrying out a vulcanization reaction at 10 ℃ and 5 MPa;
4) introducing hydrogen peroxide into the vulcanized slurry, and carrying out oxidation reaction at 30 ℃ and 1.1MPa to carry out oxidation regeneration;
5) repeating the steps 3) and 4) for four times to ensure that the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction is 1: 5;
6) and carrying out solid-liquid separation on the slurry after the oxidation reaction to obtain a regenerated product of the waste agent.
Example 4
The embodiment of the invention provides a Fe-containing alloy21.333O32Wherein the desulfurizing agent contains Fe21.333O32In the desulfurizing agent of (1), Fe21.333O32Is 55g of anatase type Ti0222g of bentonite, 15g of bentonite;
the desulfurization process of the catalyst for gas field water comprises the following operation steps:
the catalyst is filled in a fixed bed reactor to contain H2And (2) carrying out full contact reaction on the gas field water of the S and the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h-1The waste catalyst after gas field water desulfurization is the Fe-containing catalyst of the present application21.333O32The waste agent of the desulfurizing agent of (1);
above-mentioned Fe-containing21.333O32The method for regenerating the waste desulfurizer comprises the following steps:
1) washing the waste agent with water, and carrying out water-carrying grinding in a wet ball mill to obtain particles of 200 meshes to obtain waste agent powder;
2) Preparing the waste agent powder into a water suspension with the solid mass percentage of 7%, and introducing compressed air for reaction;
3) filtering the water suspension after reaction, putting the solid material into a flotation tank, adding water, then introducing air, and drying the sediment at the lower part of the container to obtain the regeneration of the waste agent.
Example 5
The embodiment of the invention provides a Fe-containing alloy21.333O32Wherein the desulfurizing agent contains Fe21.333O32In the desulfurizing agent of (1), Fe21.333O3260g of lead oxide, 16g of manganese dioxide and 15g of bentonite;
the catalyst removes H in the exhaust gas2The matrix process of S comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2When the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section as a catalyst for CO conversion reaction;
above-mentioned Fe-containing21.333O32The method for regenerating the waste desulfurizer comprises the following steps:
1) dispersing the waste agent in water to form slurry;
2) heating the slurry to 45 ℃ at normal pressure, adding hydrogen peroxide into the slurry by using a peristaltic pump, introducing air, controlling the flow rate of the hydrogen peroxide to be 500mL/min and the air flow to be 100mL/min, and magnetically stirring to promote the reaction for 5 min;
3) After the reaction is finished, the reaction solution is filtered, the obtained precipitate is washed for 3 times by water and naturally dried to obtain the regeneration of the waste agent.
Example 6
The embodiment of the invention provides a Fe-containing alloy21.333O32Wherein the desulfurizing agent contains Fe21.333O32In the desulfurizing agent of (2), alpha-Fe21.333O32Is 25g of beta-Fe21.333O32Is 22g of gamma-Fe21.333O3220g of anatase type Ti0222g of bentonite, 15g of bentonite;
the desulfurization process of the catalyst for the coke oven gas containing the hydrogen sulfide comprises the following operation steps:
mixing the desulfurizing agent with water to prepare slurry as desulfurizing agent, wherein the solid content in the slurry is 15 wt%, and deaminating the cokeIntroducing the coke oven gas into a desulfurizing tower from the bottom, wherein the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizing agent from a nozzle at the top of the desulfurizing tower to perform leaching desulfurization on the coke oven gas, collecting the desulfurized waste liquid, and drying to obtain the Fe-containing waste liquid21.333O32The desulfurizing agent waste agent of (1);
above-mentioned Fe-containing21.333O32The regeneration method of the desulfurizer waste agent comprises the following steps:
1) stirring the waste agent and the aqueous solution of potassium hydroxide in a slurry tank to prepare slurry, and maintaining the pH value of the slurry to be 8.0, wherein the solid content of the slurry is 4 wt%;
2) introducing O into the slurry 2And O3Carrying out oxidation reaction on the mixed gas at 50 ℃ and 1MPa to carry out oxidation regeneration;
3) then introducing hydrogen sulfide into the oxidized slurry, and carrying out a vulcanization reaction at 10 ℃ and 5 MPa;
4) introducing air into the vulcanized slurry, and carrying out oxidation reaction at 90 ℃ and 0.1MPa to carry out oxidation regeneration;
5) repeating the steps 3) and 4) for three times to ensure that the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction is 1: 4.9;
6) and carrying out solid-liquid separation on the slurry after the oxidation reaction to obtain a regenerated product of the waste agent.
Example 7 (application of desulfurizing agent waste agent)
The regenerants of the desulfurizing agent spent collected in examples 1-6 above and Fe-containing compounds of examples 1 and 221.333O32The desulfurizing agent of (2) is used as a catalyst of CO shift reaction, and the activity test of the catalyst is carried out, wherein the activity test is as follows:
the composition of the raw material gas is 15 vol% CO and 55 vol% H2、6vol％CO2、24vol％N2And the reaction steam-gas ratio is 1: 1, the airspeed is 4000h-1The catalyst activity test temperature zone is 250-450 ℃;
the activity of the catalyst is expressed in terms of CO conversion and is calculated as follows:
CO conversion (1-VCO'/VCO)/(1+VCO)×100％
Wherein, VCO'Is the volume percent of CO in the reactor off-gas, VCOIs the volume percentage of CO in the raw material gas;
The corresponding test results are shown in table 1 below:
TABLE 1 CO conversion at different test temperatures
From table 1 it can be seen that: containing Fe as used herein21.333O32The regeneration of the waste desulfurizer is used as a CO transformation catalyst, which can effectively catalyze the CO to generate a transformation reaction and improve the conversion rate of CO.
21.333 3214. Use of waste agent or waste agent regenerant of FeO-containing desulfurizer in organic matter conversion process
Its application is disclosed.
Example 1
The embodiment provides a biomass liquefaction process, which comprises the following steps:
pretreatment of biomass:
pea straw, sorghum straw and rice straw are used as biomass solid, the water content of the biomass is 15% based on the total weight of the biomass, the pea straw, the sorghum straw and the rice straw are sent into an ultrafine grinder to be primarily ground, the median particle size after primary grinding is 250 mu m, and then the primarily ground pea straw, sorghum straw and rice straw are sent into a plodder to be compressed and extruded and formed at the temperature of 55 ℃ and under the pressure of 1.5MPa until the bulk density is 0.9g/cm3Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 0.9mm for later use;
catalyst:
the catalyst is Fe21.333O32A regenerated product of a spent agent of a desulfurizing agent as an active component, wherein the Fe is used 21.333O32Desulfurizing agent as active component, Fe21.333O32Is 55g of anatase type Ti0222g of bentonite, 15g of bentonite;
above with Fe21.333O32The desulfurization process of the desulfurizer which is an active component comprises the following operation steps:
the catalyst is filled in a fixed bed reactor to contain H2And (3) carrying out full contact reaction on the gas field water of the S with the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h-1The waste catalyst after gas field water desulfurization is Fe21.333O32A waste agent of a desulfurizing agent which is an active component;
the regeneration method of the waste agent comprises the following steps:
1) dispersing the waste agent in water to form slurry;
2) heating the slurry to 45 ℃ at normal pressure, adding hydrogen peroxide into the slurry by using a peristaltic pump, introducing air, controlling the flow rate of the hydrogen peroxide to be 500mL/min and the air flow to be 100mL/min, and magnetically stirring to promote the reaction for 5 min;
3) after the reaction is finished, filtering the reaction solution, washing the obtained precipitate for 3 times by using water, and naturally drying to obtain the regenerant of the waste agent.
Preparing biomass slurry:
mixing the pretreated biomass, sulfur and the catalyst to obtain a mixture, adding the mixture into mixed oil of kitchen waste oil and rapeseed oil for homogenizing and pulping to form slurry, wherein the molar ratio of iron element to sulfur element in the slurry is 1:4, the kitchen waste oil and the rapeseed oil adopted in the subsequent slurry preparation process can be replaced by oil prepared by the biomass liquefaction process in the embodiment, through detection, the total content of pea straw, sorghum straw and rice straw in the slurry is 40 wt%, the viscosity of the slurry is 820mPa s (50 ℃), and Fe is used for preparing the slurry 21.333O32The content of the regenerant of the waste desulfurizer as the active component is 8 wt%, and the added component is Fe21.333O32The average particle diameter of a regenerant of a spent agent of a desulfurizing agent which is an active component is 300 μm;
and (3) liquefaction reaction:
reacting CO with H2The mixed gas (wherein the volume ratio of CO in the mixed gas is 50%) is pressurized to 17.5MPa, heated to 380 ℃, injected into the slurry bed reactor from 5 injection ports on the bottom and the side wall of the slurry bed reactor, and undergoes cracking, carbonylation, transformation and hydrogenation reaction with the slurry entering the slurry bed reactor, the reaction pressure is controlled to be 17MPa, the reaction temperature is controlled to be 420 ℃, the reaction time is 50min, and the CO and the H have the same volume ratio as that of the mixed gas2The volume ratio of the mixed gas to the slurry is 1500: 1, preparing an oil product.
Example 2
The embodiment provides a co-transformation process of oil sand oil and palm oil, which comprises the following steps:
catalyst:
the catalyst contains Fe21.333O32Wherein the regeneration product of the spent agent of the desulfurizing agent of (1), wherein the regenerated product contains Fe21.333O32In the desulfurizing agent of (1), magnetic iron oxide red Fe21.333O3255g of copper oxide, 12g of carrier ferric oxide and 21g of carrier ferric oxide;
the desulfurization process of the hydrogen sulfide-containing coal pyrolysis gas by the catalyst is as follows:
(1) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a desulfurizing tower filled with the desulfurizing agent mainly comprising ferric oxide as an active component, and adopting a flow of feeding the coal pyrolysis gas from bottom to top to prevent liquid water from entering a desulfurizing agent bed layer to remove hydrogen sulfide;
(2) The desulfurizer becomes waste agent after being used for many times, and is taken out from a desulfurizer bed layer, namely the desulfurizer containing Fe in the application21.333O32The waste agent of the desulfurizing agent of (1);
above-mentioned Fe-containing21.333O32The method for regenerating the waste desulfurizer comprises the following steps:
1) dispersing the waste agent in water to form slurry;
2) heating the slurry to 60 ℃ under normal pressure, adding hydrogen peroxide into the slurry by using a peristaltic pump, controlling the flow to be 500mL/min, and magnetically stirring to promote the reaction for 10 min;
3) after the reaction is finished, filtering the reaction solution, washing the obtained precipitate with water for 2 times, and naturally drying to obtain the regenerant of the waste agent.
Preparing slurry:
mixing oil sand oil, palm oil, sulfur and the catalyst to obtain a mixture, adding a proper amount of water into the mixture, stirring and pulping to form slurry, wherein the average particle size of the added catalyst is 300 mu m, and the molar ratio of iron element to sulfur element in the slurry is 1: 3;
and (3) conversion reaction:
pressurizing part of pure CO to 5.7MPa, heating to 500 ℃, introducing the pure CO into a pipeline for conveying the slurry, pressurizing the rest part of the pure CO to 5.2MPa, heating to 500 ℃, injecting the pure CO into the slurry bed reactor from an inlet of the slurry bed reactor, carrying out cracking, carbonylation, transformation and hydrogenation reactions with the slurry entering the slurry bed reactor, and introducing hydrogen sulfide gas into the slurry bed reactor in the conversion process, so as to ensure that the molar ratio of iron element to sulfur element in the reaction system is 1:3, and controlling the reaction pressure of the conversion reaction to be 5MPa, the reaction temperature to be 470 ℃, the reaction time to be 90min, wherein CO and H are mixed with the raw materials 2The volume ratio of the mixed gas to the slurry is 3000: 1, preparing an oil product.
Example 3
The embodiment provides a co-conversion process of biomass and hogwash oil, which comprises the following steps:
pretreatment of biomass:
rice straw and flax straw are used as biomass solid, the water content of the biomass is 6% based on the total weight of the biomass, the rice straw and the reed straw are sent into a superfine pulverizer for primary pulverization, the median particle size after the primary pulverization is 150 mu m, and then the rice straw and the reed straw after the primary pulverization are sent into a briquetting machine to be fed into the briquetting machine at the temperature of 30 ℃ and under the pressure of 3MPaCompressing, extruding and molding until the bulk density is 0.8g/cm3Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 3mm for later use;
catalyst:
the catalyst is Fe21.333O32A waste agent of a desulfurizing agent which is an active component, wherein the Fe21.333O32Total mass of desulfurizing agent, Fe21.333O32The content of the magnetic iron oxide red in the desulfurizer is 75 percent, and the content of the binder attapulgite is 25 percent.
The desulfurization process of the catalyst as coal pyrolysis gas is summarized as follows:
(1) and (3) cooling the compressed coal pyrolysis gas to 25-40 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a coarse desulfurization tower, and adopting a flow of feeding the coal pyrolysis gas from bottom to top to prevent liquid water from entering a desulfurizer bed layer. Only a crude removal of hydrogen sulphide is carried out here.
(2) Heating the gas after the coarse desulfurization to 120-135 ℃ for hydrolysis, and adding most of COS and CS2Hydrolysis to H2S。
(3) The gas after hydrolysis is cooled to 20-25 ℃ again for H2S removal, wherein in order to ensure the purification effect and the service life, the H generated by hydrolysis is removed in a mode of double-tower series-parallel connection operation2S is removed completely, and the rest R-SH and thiophene are further removed. The residual sulfide is completely removed in the process, and the final purification requirement that the total sulfur content is less than 0.1ppm is achieved.
The desulfurizer becomes waste agent after being used for many times and is deleted from a desulfurizer bed layer, namely Fe in the application21.333O32Waste desulfurizer.
Preparing biomass slurry:
pretreatment of the catalyst before reaction: detection of Fe in the present example21.333O32If the molar ratio of the iron element to the sulfur element in the waste desulfurizer is not 1:5, adding solid sulfur powder into the catalyst until the iron element and the sulfur element are contained in the catalystThe molar ratio of the element is 1:5, so that the molar ratio of the iron element to the sulfur element in the reaction system is 1: 5;
if the molar ratio of the iron element to the sulfur element is more than 1:5, redundant sulfur can be removed by solvent extraction or heating sulfur melting and other modes;
Mixing the pretreated biomass with the pretreated catalyst to obtain a mixture, adding the mixture into hogwash oil, stirring, grinding and pulping to form slurry, detecting, wherein the total content of rice straws and reed straws in the slurry is 60 wt%, the viscosity of the slurry is 500mPa ℃, (50 ℃), the content of the catalyst in the slurry is 5 wt%, and the average particle size of the added catalyst is 5 μm;
and (3) conversion reaction:
reacting CO with H2Mixed gas (CO accounts for 60% and H)240 percent) of the mixture is pressurized to 21MPa and heated to 350 ℃, then the mixture is introduced into a pipeline for conveying the slurry, the rest of the mixture is pressurized to 21MPa and heated to 500 ℃, the mixture is injected into a slurry bed reactor from an inlet of the slurry bed reactor and undergoes cracking, carbonylation, transformation and hydrogenation reaction with the slurry entering the slurry, the reaction pressure of the conversion reaction is controlled to be 20MPa, the reaction temperature is 380 ℃, the reaction time is 60min, and CO and H are reacted with each other2The volume ratio of the mixed gas to the slurry is 3000: 1, preparing an oil product.
Example 4
The embodiment provides a biomass liquefaction process, which comprises the following steps:
pretreatment of biomass:
wheat straw and reed straw are used as biomass solid, the water content of the biomass is 8% based on the total weight of the biomass, the wheat straw and the flax straw are sent into an ultrafine grinder to be primarily ground, the median particle size after primary grinding is 100 mu m, then the primarily ground wheat straw and flax straw are sent into a plodder to be compressed at the temperature of 60 ℃ and under the pressure of 3MPa, and the compression molding is carried out until the bulk density is 1.1g/cm 3Then performing secondary grinding, wherein the average particle size after the secondary grinding is2mm, for later use;
catalyst:
the catalyst is a waste agent of a desulfurizer which takes hydroxyl ferric oxide as an active component, wherein the Fe is used21.333O32Total mass of desulfurizing agent, Fe21.333O32The content of the magnetic iron oxide red in the desulfurizer is 89%, and the content of the binder bentonite is 11%. The desulfurization process of the catalyst for gas field water comprises the following operation steps:
the catalyst is loaded in a fixed bed reactor, and gas field water containing H2S is fully contacted and reacted with the catalyst under the following conditions: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h < -1 >, and the catalyst waste agent after gas field water desulfurization is the Fe of the application21.333O32Waste desulfurizer.
Preparing biomass slurry:
mixing the pretreated biomass, sulfur and the catalyst to obtain a mixture, adding the mixture into mixed oil of palm oil and petroleum-based wax oil, and stirring to prepare slurry; according to detection, the total content of wheat straw and flax straw in the slurry is 45 wt%, the molar ratio of iron element to sulfur element is 1:2.5, the viscosity of the slurry is 530mPa ℃. (50 ℃), the content of the catalyst in the slurry is 0.3 wt%, and the average particle size is 20 μm.
And (3) conversion reaction:
reacting CO with H2Mixed gas (CO accounts for 80% and H)220 percent) of the mixture is pressurized to 19.5MPa and heated to 300 ℃, then the mixture is introduced into a pipeline for conveying the slurry, the rest of the mixture is pressurized to 19.3MPa and heated to 480 ℃, then the mixture is injected into the slurry bed reactor from 3 injection ports on the bottom and the side wall of the slurry bed reactor and undergoes cracking, carbonylation, transformation and hydrogenation reaction with the slurry entering the slurry bed reactor, the reaction pressure is controlled to be 19MPa, the reaction temperature is controlled to be 390 ℃, the reaction time is 100min, and the CO and the H undergo cracking, carbonylation, transformation and hydrogenation reaction2The volume ratio of the mixed gas to the slurry is 800: 1, preparing an oil product.
Example 5
The embodiment provides a biomass liquefaction process, which comprises the following steps:
pretreatment of biomass:
sorghum straws and ramie straws are taken as biomass solids, the water content of the biomass is 15 percent based on the total weight of the biomass, the corn straws and the ramie straws are sent into a superfine pulverizer for primary pulverization, the median particle size after primary pulverization is 250 mu m, and then the corn straws and the ramie straws after primary pulverization are sent into a briquetting machine for compression and extrusion molding at the temperature of 50 ℃ and under the pressure of 1.5MPa until the bulk density is 0.8g/cm 3Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 3mm for later use;
catalyst:
the embodiment of the invention provides Fe21.333O32A desulfurizing agent waste agent, wherein the Fe21.333O32Total mass of desulfurizing agent, Fe21.333O32Fe in desulfurizer21.333O32The content is 94%, and the balance is impurities and water.
The desulfurization process of the coke oven gas by the catalyst comprises the following operation steps:
mixing the above Fe21.333O32Mixing a desulfurizing agent and water to prepare slurry serving as the desulfurizing agent, wherein the total concentration of iron oxyhydroxide in the slurry is 10 wt%, introducing the deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizing agent from the top of the desulfurizing tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the Fe-containing iron oxide desulfurizing agent21.333O32Waste desulfurizer.
Preparing biomass slurry:
mixing the pretreated biomass, sulfur and the catalyst to obtain a mixture, adding the mixture into kitchen waste oil for emulsification and pulping to form slurry, and detecting that the total content of corn straws and ramie straws in the slurry is 57 wt%, and the iron element isMolar ratio to elemental sulfur of 1:3, viscosity of 1130mPa (50 ℃) and Fe in the slurry 21.333O32The content of the waste desulfurizer which is an active component is 4 wt%, and the added Fe21.333O32The average particle size of the waste agent of the desulfurizing agent as an active component is 120 μm;
and (3) conversion reaction:
pressurizing part of pure CO gas to 18MPa, heating to 250 ℃, introducing the pure CO gas into the slurry, pressurizing the rest part of the pure CO gas to 18MPa, heating to 500 ℃, injecting the rest part of the pure CO gas into the slurry bed reactor from 4 injection ports on the bottom and the side wall of the slurry bed reactor, and performing cracking, carbonylation, transformation and hydrogenation reaction on the pure CO gas and the slurry entering the slurry bed reactor, controlling the reaction pressure to be 17MPa, the reaction temperature to be 400 ℃, the reaction time to be 40min, wherein the volume ratio of the pure CO gas to the slurry is 950: 1, preparing an oil product.
Example 6
The embodiment provides a biomass liquefaction process, which comprises the following steps:
pretreatment of biomass:
pea straw, corn straw and rice straw are used as biomass solid, the water content of the biomass is 20% based on the total weight of the biomass, the pea straw, sorghum straw and rice straw are sent into an ultrafine grinder for primary grinding, the median particle size after primary grinding is 300 mu m, and then the pea straw, sorghum straw and rice straw after primary grinding are sent into a plodder for compression and extrusion forming at the temperature of 55 ℃ and under the pressure of 2.5MPa until the bulk density is 0.9g/cm 3Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 0.9mm for later use;
catalyst:
the catalyst adopts Fe21.333O32A regenerant of the desulfurizer waste agent which is an active component,
wherein the Fe is contained21.333O32The total mass of the desulfurizing agent of (1), the desulfurizing agent containing Fe21.333O32Desulfurizing agent ofThe content of the medium magnetic iron oxide red is 96.2 percent, and the balance is impurities and water;
the desulfurization process of the coke oven gas by the catalyst comprises the following operation steps:
mixing the desulfurizer with water to prepare slurry serving as the desulfurizer, wherein the total concentration of iron oxyhydroxide in the slurry is 10 wt%, introducing the deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizer on the top of the desulfurizing tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the Fe-containing waste liquid21.333O32The waste desulfurizer of (1).
Above-mentioned Fe-containing21.333O32The regeneration method of the waste desulfurizer comprises the following steps,
(1) introducing water vapor with the pressure of 1.0MPa into a heating furnace, and heating the water vapor to 420 ℃;
(2) introducing the heated water vapor into the container containing Fe at a speed of 10m/s21.333O32The desulfurizing tank for heating the waste desulfurizing agent containing Fe 21.333O32The desulfurizing agent waste agent of (1);
(3) ensure the content of Fe21.333O32The bed layer temperature of the desulfurizer waste agent is heated by water vapor to be more than 400 ℃ and the operation is carried out for 3 hours, and the steam consumption is 7 t/h;
(4) analyzing the pH value of the outlet of the desulfurization tank, and introducing coke oven gas into the desulfurization tank for reduction when the pH value is more than or equal to 7.5 for 3 times continuously;
(5) analyzing the concentration change of the inlet and outlet H2 every 30min after the coke oven gas is introduced, and when the outlet H is2Concentration steadily greater than or equal to inlet H2After concentration (3 times of analysis), the Fe content is obtained21.333O32The regenerant of the waste desulfurizer.
Preparing biomass slurry:
mixing the pretreated biomass, sulfur and the catalyst to obtain a mixture, adding the mixture into mixed oil of kitchen waste oil and rapeseed oil for homogeneous pulping to form a molar ratio of iron element to sulfur elementThe slurry is 1:4, the waste kitchen oil and rapeseed oil used in the subsequent slurry preparation process can be replaced by the oil product prepared by the biomass liquefaction process in the embodiment, the total content of pea straw, sorghum straw and rice straw in the slurry is 40 wt%, the viscosity of the slurry is 820mPa ℃ (50 ℃), and Fe is added into the slurry21.333O32The content of desulfurizer which is an active component is 8 wt%, and the added Fe 21.333O32The average particle size of the desulfurizing agent as an active component was 300 μm;
and (3) liquefaction reaction:
reacting CO with H2The mixed gas (wherein the volume ratio of CO in the mixed gas is 50%) is pressurized to 18MPa, heated to 380 ℃, injected into the slurry bed reactor from 5 injection ports on the bottom and the side wall of the slurry bed reactor, and subjected to cracking, carbonylation, transformation and hydrogenation reaction with the slurry entering the slurry bed reactor, the reaction pressure is controlled to be 17MPa, the reaction temperature is controlled to be 420 ℃, the reaction time is 50min, and the CO and the H are reacted for 50min2The volume ratio of the mixed gas to the slurry is 900: 1, preparing an oil product.
Example 7
The embodiment provides a co-conversion process of oil residue, wheat straw and kitchen waste oil, which comprises the following steps:
pretreatment of oil residue and wheat straw:
oil residue and wheat straw are taken as biomass solid, the water content of the biomass is 7 percent based on the total weight of the biomass, the oil residue and the excrement are sent into an ultrafine grinder for primary grinding, the median particle size after primary grinding is 250 mu m, then the oil residue and the excrement after primary grinding are sent into a plodder for compression at the temperature of 50 ℃ and under the pressure of 1.5MPa, and extrusion forming is carried out until the bulk density is 0.95g/cm3Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 60 mu m for later use;
Catalyst:
the catalyst contains Fe21.333O32The regenerant of the desulfurizing agent waste agent of (1), wherein the regenerant contains Fe21.333O32The total mass of the desulfurizing agent of (1), the desulfurizing agent containing Fe21.333O32Fe in the desulfurizing agent of (2)21.333O32The content of (A) is 80%, the content of the carrier molecular sieve is 15%, and the content of the adhesive sesbania powder is 5%;
the catalyst removes H in the exhaust gas2The basic process of S comprises the following steps: will H2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2When the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section, namely the desulfurizer waste agent;
the regeneration method of the waste desulfurizer comprises the following steps: washing the desulfurizer waste agent with water, and grinding the washed desulfurizer waste agent with water in a wet ball mill into 80-mesh particles to obtain waste agent powder; preparing the waste agent powder into aqueous suspension with the solid mass percentage content of 8%, introducing compressed air, sampling and inspecting after reacting for a period of time, and when the sample taken out is reacted with hydrochloric acid, H is not generated2S, completely converting iron sulfide in the waste agent into iron oxyhydroxide and elemental sulfur to form slurry containing the iron oxyhydroxide and the elemental sulfur, filtering the slurry to obtain a solid material, and using CC1 to obtain the solid material 4And (3) extracting the solid material obtained after the extraction and filtration for three times, combining the extraction liquid, recovering the solvent by using a distillation method, simultaneously obtaining the crystallized elemental sulfur, and mixing the residual solid after the extraction liquid is separated with adhesive sesbania powder to obtain the regenerated product of the desulfurizer waste agent, wherein the using amount of the adhesive sesbania powder is 5% of the mass of the solid.
Preparing slurry:
mixing the pretreated oil residue, wheat straws, carbon disulfide and the catalyst to obtain a mixture, adding the mixture into the kitchen waste oil to be dispersed and pulped to form slurry, detecting that the total content of the oil residue and the excrement in the slurry is 55 wt%, the molar ratio of iron element to sulfur element is 1:2, the viscosity of the slurry is 400mPa & (50 ℃), wherein the content of the catalyst in the slurry is 10 wt%, and the average particle size of the added catalyst is 5 mm;
and (3) conversion reaction:
reacting CO with H2Mixed gas (CO accounts for 60% and H)240 percent) of the mixture is pressurized to 16.8MPa and heated to 250 ℃, the mixture is introduced into a pipeline for conveying the slurry, the rest of the mixture is pressurized to 16.2MPa and heated to 550 ℃, the mixture is injected into the fluidized bed reactor from the inlet of the fluidized bed reactor and undergoes cracking, carbonylation, transformation and hydrogenation reaction with the slurry entering the fluidized bed reactor, the reaction pressure of the transformation reaction is controlled to be 16MPa, the reaction temperature is controlled to be 420 ℃, the reaction time is 60min, and CO and H are reacted with each other 2The volume ratio of the mixed gas to the slurry is 5000: 1, preparing an oil product.
Example 8
This example is the same as example 6, except that the regeneration method of the waste agent is different, and the regeneration method of the waste agent in this example is,
1) introducing water vapor with the pressure of 1MPa into a heating furnace, and heating the water vapor to 400 ℃;
2) introducing the heated water vapor into a desulfurization tank containing a waste desulfurizer at the speed of 20m/s, and heating the waste desulfurizer;
3) ensuring that the bed layer temperature of the waste desulfurizer is heated to 450 ℃ by water vapor and the operation lasts for 2 hours, wherein the steam consumption is 8 t/h;
4) analyzing the pH value of the outlet of the desulfurization tank, and introducing a small amount of coke oven gas into the desulfurization tank for reduction when the pH value is more than or equal to 7.5 for 3 times continuously;
5) introducing coke oven gas subjected to primary hydrogenation in the fine desulfurization process to reduce the waste desulfurizer at the rate of 800m 3/h;
6) analyzing the inlet and outlet H every 30min after the coke oven gas is introduced2Concentration change when outlet H2Concentration stable greater than or equal to inlet H2After the concentration (3 times of analysis), the regenerant of the waste desulfurizer can be obtained.
Test examples
The distributions of the products prepared by the processes of examples 1-8 of the present invention were compared and the products were tested as follows:
The percent solid organic matter conversion is (the total mass of solid organic matter in the raw material-the mass of solid organic matter remaining in the reaction product)/the total mass of solid organic matter in the raw material, and the solid organic matter in the percent solid organic matter conversion refers to anhydrous and ashless groups (the same applies hereinafter);
the yield percent of the solid organic matter converted oil is the mass of the liquid phase oil product at normal temperature and normal pressure in the product converted from the solid organic matter/the total feeding mass of the solid organic matter in the raw material;
the reaction water yield = (mass of water of reaction product-total mass of water initially added in the reaction or carried in by raw material)/total mass of raw material fed. When this value is < 0, it is marked as "none";
the corresponding test results are shown in tables 1 and 2:
table 1 comparison of conversion effect of solid organic matter
The liquid organic matter conversion rate is (the mass of the material with the boiling point of more than 360 ℃ in the total liquid organic matter feeding material-the total mass of the liquid oil product with the boiling point of more than 360 ℃ in the product)/the mass of the material with the boiling point of more than 360 ℃ in the total liquid organic matter feeding material;
the yield of the liquid organic matter converted oil is equal to the mass of the liquid-phase oil product in the converted product at normal temperature and normal pressure/the total feed mass of the raw material liquid organic matter.
TABLE 2 comparison of product distribution after conversion of liquid organic matter feedstock
As can be seen from tables 1 and 2, the solid organic matter conversion oil yield is > 50 wt% and the liquid organic matter conversion oil yield is > 91% using the method of the present invention; the calorific value of the organic matter converted oil is more than 0.91 time of that of standard fuel oil with the same mass, and the oxygen content of the organic matter converted oil is less than 4.8 wt%; the water generated by the raw materials after the reaction is less than 1.5 wt%.
15. Use of spent agent of iron oxide desulfurizer as hydrogenation catalyst:
example 1 (Tail gas)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein amorphous Fe in the iron oxide desulfurizer is calculated by the total mass of the iron oxide desulfurizer2O3The content of (A) is 55%, the content of the carrier is 30% of bentonite, and the content of the binder sesbania powder is 15%.
The desulfurization process of the tail gas generated after the catalyst is used for hydrogenation upgrading of medium and low temperature coal tar in industry is as follows:
1) collecting tail gas generated after the medium and low temperature coal tar is subjected to fixed bed hydrogenation catalysis;
2) the desulfurizer of the embodiment is prepared into columnar catalyst particles with the diameter of 1mm and the length of 15mm, and the columnar catalyst particles are filled in a desulfurizing tower to form a desulfurization layer;
3) the tail gas is treated for 2000h-1The air speed of the desulfurizer passes through the desulfurization layer, and the air speed and the desulfurizer in the desulfurization layer are subjected to desulfurization reaction at 50 ℃, so that hydrogen sulfide in tail gas is removed, after the reaction is finished, the waste agent of the reacted desulfurizer is taken out, and the waste agent is cooled to room temperature, so that the waste agent of the iron oxide desulfurizer is obtained.
Example 2 (pyrolysis of coal gas)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein gamma-Fe in the iron oxide desulfurizer is calculated by the total mass of the iron oxide desulfurizer2O3The content of (b) is 65%, the content of carrier natural zeolite is 30%, and the content of binder cellulose powder is 5%.
The desulfurization process of the hydrogen sulfide-containing coal pyrolysis gas by the catalyst is as follows:
(1) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a desulfurizing tower filled with the desulfurizing agent mainly comprising iron oxide as an active component, and adopting a flow of feeding liquid water from bottom to top to prevent the liquid water from entering a desulfurizing agent bed layer to remove hydrogen sulfide;
(2) the desulfurizer is used for many times to form a waste agent, and the waste agent is taken out from a desulfurizer bed layer to form the waste agent of the iron oxide desulfurizer.
Example 3 (oil)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein the content of cubic system ferroferric oxide in the iron oxide desulfurizer is 97.3 percent, and the balance is impurities and water, based on the total mass of the iron oxide desulfurizer;
the catalyst is used for desulfurizing petroleum containing hydrogen sulfide, and the operation steps are as follows:
(1) The desulfurizer of the embodiment is prepared into catalyst particles with the diameter of 1.5mm, and the catalyst particles are filled in a desulfurizing tower to form a desulfurizing layer;
(2) and spraying petroleum containing hydrogen sulfide into the desulfurization layer from the top of the desulfurization tower through a nozzle, leaching and desulfurizing, and collecting the desulfurized waste desulfurizer, namely the waste desulfurizer of the iron oxide desulfurizer.
Example 4 (gas field water)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein amorphous Fe in the iron oxide desulfurizer is calculated by the total mass of the iron oxide desulfurizer2O3.H2The content of O is 75 percent, the content of carrier aluminum oxide is 10 percent, and the content of adhesive sesbania powder is 15 percent;
the desulfurization process of the catalyst for gas field water comprises the following operation steps:
the catalyst is filled in a fixed bed reactor to contain H2And (2) carrying out full contact reaction on the gas field water of the S and the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h-1The waste catalyst after gas field water desulfurization is the waste iron oxide desulfurizer of the application.
Example 5 (waste gas)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein the iron oxide desulfurizer is calculated by the total mass of the iron oxide desulfurizer The content of cubic ferroferric oxide in the desulfurizer is 5 percent, and the desulfurizer is amorphous Fe2O3Content of (2) is 25%, amorphous Fe2O3.H2The content of O is 60 percent, and the content of the adhesive sesbania powder is 10 percent;
the catalyst removes H in the exhaust gas2The process of S comprises the following steps: will H2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section.
Example 6 (Coke oven gas)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein gamma-Fe in the iron oxide desulfurizer is calculated by the total mass of the iron oxide desulfurizer2O3The content is 23 percent, the content of cubic ferroferric oxide is 50 percent, and the content of sesbania powder serving as a binder is 27 percent;
the desulfurization process of the catalyst for the coke oven gas containing the hydrogen sulfide comprises the following operation steps:
mixing the desulfurizer with water to prepare desulfurizer slurry, wherein the total concentration of iron oxyhydroxide in the desulfurizer slurry is 10 wt%, introducing deaminated coke oven gas into a desulfurization tower from the bottom, the temperature of the tower kettle of the desulfurization tower is 30 ℃, spraying the desulfurizer on the top of the desulfurization tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the waste agent of the iron oxide desulfurizer.
Example 7 (application of spent desulfurizing agent)
The waste agents of the desulfurizing agents collected in the above examples 1 to 6 were used as catalysts for the liquefaction reaction of corn stalks, and the activity tests of the catalysts were performed as follows: preparing slurry containing corn straws and a catalyst, conveying the slurry into a slurry bed reactor, introducing hydrogen into the slurry bed reactor, and performing a hydrogenation liquefaction reaction, wherein the reaction pressure is 20MPa, and the temperature is 380 ℃, the addition amount of the catalyst is 2 wt% of the addition amount of the corn straws, and the activity of the catalyst is represented by the distribution of products prepared by the liquefaction reaction of the corn straws, as shown in the following table 1:
TABLE 1 comparison of product distribution
From table 1 it can be seen that: the waste agent of the iron oxide desulfurizer is used as a hydrogenation catalyst, so that the hydrogenation reaction can be effectively catalyzed, and the biomass conversion rate is improved.
16. The waste desulfurizer using ferric oxide as main active component is used as hydrogenation catalyst.
Example 1 (Tail gas)
The embodiment of the invention provides a waste desulfurizer agent mainly comprising iron oxide as an active ingredient, wherein the waste desulfurizer mainly comprising the iron oxide as the active ingredient comprises 8g of CuO, 9g of ferric salt complexing agent triethanolamine and amorphous Fe 2O3 15g，MnO2Is 8 g;
the desulfurization process of the tail gas generated after the catalyst is used for hydrogenation upgrading of medium and low temperature coal tar in industry is as follows:
1) collecting tail gas generated after the medium and low temperature coal tar is subjected to fixed bed hydrogenation catalysis;
2) the desulfurizer of the embodiment is prepared into columnar catalyst particles with the diameter of 1mm and the length of 15mm, and the columnar catalyst particles are filled in a desulfurizing tower to form a desulfurization layer;
3) the tail gas is treated for 2000h-1The air speed of the desulfurizing agent passes through the desulfurization layer, and the air speed and the desulfurizing agent in the desulfurization layer are subjected to desulfurization reaction at 50 ℃, so that hydrogen sulfide in tail gas is removed, and after the reaction is finished, the waste agent of the reacted desulfurizing agent is taken out and cooled to room temperature, so that the waste agent of the desulfurizing agent mainly taking iron oxide as an active component is obtained.
Example 2 (pyrolysis of coal gas)
The embodiment of the invention provides a waste desulfurizer which mainly takes ferric oxide as an active ingredient, wherein carbon in the desulfurizer which mainly takes ferric oxide as the active ingredient10g of calcium hydrogen carbonate, 12g of basic copper carbonate and gamma-Fe2O3 18g，MnO28g of NiO and 5g of NiO;
the desulfurization process of the hydrogen sulfide-containing coal pyrolysis gas by the catalyst is as follows:
(1) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a desulfurizing tower filled with the desulfurizing agent mainly comprising ferric oxide as an active component, and adopting a flow of feeding the coal pyrolysis gas from bottom to top to prevent liquid water from entering a desulfurizing agent bed layer to remove hydrogen sulfide;
(2) The desulfurizer becomes a waste agent after being used for many times, and is taken out from a desulfurizer bed layer, namely the waste agent of the desulfurizer mainly taking ferric oxide as an active component in the application.
Example 3 (oil)
The embodiment of the invention provides a waste desulfurizer agent mainly comprising iron oxide as an active ingredient, wherein in the desulfurizer mainly comprising the iron oxide as the active ingredient, 50g of cubic ferroferric oxide, 12g of calcium sulfate dihydrate, 20g of basic zinc carbonate and 6g of sodium carboxymethylcellulose are contained;
the catalyst is used for desulfurizing petroleum containing hydrogen sulfide, and the operation steps are as follows:
(1) the desulfurizer of the embodiment is prepared into catalyst particles with the diameter of 1.5mm, and the catalyst particles are filled in a desulfurization tower to form a desulfurization layer;
(2) and spraying petroleum containing hydrogen sulfide into the desulfurization layer from the top of the desulfurization tower through a nozzle, leaching and desulfurizing, and collecting desulfurized waste desulfurizer, namely the waste desulfurizer mainly comprising iron oxide as an active component.
Example 4 (gas field water)
The embodiment of the invention provides a waste desulfurizer using iron oxide as an active ingredient, wherein amorphous Fe is contained in the desulfurizer using the iron oxide as the active ingredient 2O3.H230g of O, 15g of polymeric ferric sulfate, 12g of basic copper carbonate and 6g of sodium carboxymethyl cellulose, and amorphous Fe2O3 8g；
The desulfurization process of the catalyst for gas field water comprises the following operation steps:
the catalyst is filled in a fixed bed reactor to contain H2And (3) carrying out full contact reaction on the gas field water of the S with the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h-1The waste catalyst after gas field water desulfurization is the waste desulfurizer mainly comprising iron oxide as an active component.
Example 5 (exhaust gas)
The embodiment of the invention provides a waste desulfurizer which mainly takes ferric oxide as an active ingredient, wherein in the desulfurizer which mainly takes ferric oxide as an active ingredient, 12g of cubic ferroferric oxide and amorphous Fe2O324g of amorphous Fe2O3.H2O39 g and NiO are 5 g;
the catalyst removes H in the exhaust gas2The process of S comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section as a catalyst for hydrogenation reaction.
Example 6 (Coke oven gas)
The embodiment of the invention provides a waste desulfurizer using ferric oxide as an active ingredient, wherein gamma-Fe is contained in the desulfurizer using ferric oxide as the active ingredient2O323g of amorphous Fe2O324g of amorphous Fe2O3.H242g of O and 8g of MnO;
the desulfurization process of the coke oven gas containing hydrogen sulfide by the catalyst comprises the following operation steps:
mixing the desulfurizer with water to prepare desulfurizer slurry, wherein the total concentration of iron oxyhydroxide in the desulfurizer slurry is 10 wt%, introducing deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizer on the top of the desulfurizing tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the waste desulfurizer mainly comprising iron oxide as an active component.
Example 7 (application of spent desulfurizing agent)
The waste desulfurizer collected in the above examples 1 to 6 was used as a catalyst for liquefaction reaction of corn stalks, and the activity test of the catalyst was performed as follows: preparing slurry containing corn straws and a catalyst, conveying the slurry into a slurry bed reactor, introducing hydrogen into the slurry bed reactor, and performing a hydrogenation liquefaction reaction, wherein the reaction pressure is controlled to be 20MPa, the temperature is 380 ℃, the addition amount of the catalyst is 2 wt% of the addition amount of the corn straws, and the activity of the catalyst is represented by the distribution of products prepared by the liquefaction reaction of the corn straws as shown in the following table 1:
TABLE 1 comparison of product distribution
From table 1 it can be seen that: the waste agent of the iron oxide desulfurizer is used as a hydrogenation catalyst, so that the hydrogenation reaction can be effectively catalyzed, and the biomass conversion rate is improved.
17. The waste agent of the iron oxide desulfurizer is regenerated and then used as a hydrogenation catalyst.
Example 1 (Tail gas)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein amorphous Fe in the iron oxide desulfurizer is calculated by the total mass of the iron oxide desulfurizer2O3The content of (A) is 55%, the content of the carrier is 30% of bentonite, and the content of the binder sesbania powder is 15%.
The desulfurization process of the tail gas generated after the catalyst is used for hydrogenation upgrading of medium and low temperature coal tar in industry is as follows:
1) collecting tail gas generated after the medium and low temperature coal tar is subjected to hydrogenation catalysis by a fixed bed;
2) the desulfurizer of the embodiment is prepared into columnar catalyst particles with the diameter of 1mm and the length of 15mm, and the columnar catalyst particles are filled in a desulfurizing tower to form a desulfurization layer;
3) the tail gas is treated for 2000h-1The air speed of the catalyst passes through the desulfurization layer, and the air speed and a desulfurizer in the desulfurization layer are subjected to desulfurization reaction at 50 ℃, so that hydrogen sulfide in tail gas is removed, after the reaction is finished, a waste agent of the reacted desulfurizer is taken out, and the waste agent is cooled to room temperature, so that the waste agent of the iron oxide desulfurizer is obtained;
The regeneration method of the waste agent of the iron oxide desulfurizer comprises the following steps:
1) dispersing the waste agent of the iron oxide desulfurizer by using weak acid water (containing dilute sulfuric acid) with the pH value of 4.0, wherein the solid-to-liquid ratio of the waste agent of the iron oxide desulfurizer to the weak acid water is 1: 4(g/ml), and the dispersion time is 30min to obtain dispersion liquid;
2) heating the dispersion liquid to 60 ℃ under normal pressure, adding hydrogen peroxide into the dispersion liquid by using a peristaltic pump, controlling the flow to be 500mL/min, controlling the molar ratio of the hydrogen peroxide to sulfur elements in the waste agent of the iron oxide desulfurizer to be 5: 1, carrying out magnetic stirring to promote reaction, and rapidly transferring generated sulfur dioxide gas by vacuumizing during the reaction for 10 min;
3) and after the reaction is finished, filtering the reaction solution, washing the obtained precipitate for 2 times by using water, then drying at 100 ℃ to obtain a regenerant of the iron oxide desulfurizer waste agent, and returning the filtrate obtained by filtering to the dispersion process to be used as weak acid water for recycling.
Example 2 (coal pyrolysis gas)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein gamma-Fe in the iron oxide desulfurizer is calculated by the total mass of the iron oxide desulfurizer2O3The content of (A) is 65%, the content of carrier natural zeolite is 30%, and the content of binder cellulose powder is 5%.
The desulfurization process of the hydrogen sulfide-containing coal pyrolysis gas by the catalyst is as follows:
(1) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a desulfurizing tower filled with the desulfurizing agent mainly comprising ferric oxide as an active component, and adopting a flow of feeding the coal pyrolysis gas from bottom to top to prevent liquid water from entering a desulfurizing agent bed layer to remove hydrogen sulfide;
(2) the desulfurizer is used for many times to form a waste agent, and the waste agent is taken out from a desulfurizer bed layer to form the waste agent of the iron oxide desulfurizer;
the regeneration method of the waste agent of the iron oxide desulfurizer comprises the following steps:
1) dispersing the waste ferric oxide desulfurizer with weak acid water (containing dilute hydrochloric acid) with pH of 5.0, wherein the solid-to-liquid ratio of the waste ferric oxide desulfurizer to the weak acid water is 1: 6(g/ml), and the dispersion time is 30min to obtain a dispersion liquid;
2) heating the dispersion liquid to 60 ℃ under normal pressure, adding hydrogen peroxide into the dispersion liquid by using a peristaltic pump, controlling the flow to be 500mL/min, controlling the molar ratio of the hydrogen peroxide to sulfur elements in the waste agent of the iron oxide desulfurizer to be 6: 1, carrying out magnetic stirring to promote reaction, and rapidly transferring generated sulfur dioxide gas by vacuumizing during the reaction for 10 min;
3) And after the reaction is finished, filtering the reaction solution, washing the obtained precipitate for 2 times by using water, then drying at 100 ℃ to obtain a regenerant of the iron oxide desulfurizer waste agent, and returning the filtrate obtained by filtering to the dispersion process to be used as weak acid water for recycling.
Example 3 (oil)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein the content of cubic system ferroferric oxide in the iron oxide desulfurizer is 97.3 percent, and the balance is impurities and water, based on the total mass of the iron oxide desulfurizer;
the catalyst is used for desulfurizing petroleum containing hydrogen sulfide, and the operation steps are as follows:
(1) the desulfurizer of the embodiment is prepared into catalyst particles with the diameter of 1.5mm, and the catalyst particles are filled in a desulfurization tower to form a desulfurization layer;
(2) spraying petroleum containing hydrogen sulfide into a desulfurization layer from the top of a desulfurization tower through a nozzle, leaching and desulfurizing, and collecting desulfurized waste desulfurizer, namely the waste desulfurizer of the iron oxide desulfurizer;
the regeneration method of the waste agent of the iron oxide desulfurizer comprises the following steps:
1) washing the iron oxide desulfurizer waste agent with water, and carrying out water-carrying grinding in a wet ball mill to obtain 300-mesh particles to obtain waste agent powder;
2) Preparing the waste agent powder into aqueous suspension with the solid mass percentage content of 15%, introducing compressed air, sampling and inspecting after reacting for a period of time, and when the taken sample reacts with hydrochloric acid, generating no H2S, forming slurry containing elemental sulfur, filtering the slurry to obtain solid material, and using CCl4Extracting the solid material obtained after the extraction and filtration for three times, combining the extract liquor, recovering the solvent by a distillation method and simultaneously obtaining the crystallized elemental sulfur, wherein the residual solid after the extract liquor is separated is the regeneration product.
Example 4 (gas field water)
The embodiment of the invention provides a regenerated waste agent of an iron oxide desulfurizer, wherein amorphous Fe in the iron oxide desulfurizer is calculated by the total mass of the iron oxide desulfurizer2O3.H2The content of O is 75 percent, the content of carrier aluminum oxide is 10 percent, and the content of adhesive sesbania powder is 15 percent;
the desulfurization process of the catalyst for gas field water comprises the following operation steps:
the catalyst is filled in a fixed bed reactor to contain H2And (3) carrying out full contact reaction on the gas field water of the S with the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h-1The waste catalyst after gas field water desulfurization is regenerated, namely the waste catalyst of the iron oxide desulfurizer;
The regeneration method of the waste agent of the iron oxide desulfurizer comprises the following steps:
1) washing the waste agent with water, and grinding the waste agent with water in a wet ball mill into particles of 200 meshes to obtain waste agent powder;
2) preparing the waste agent powder into a water suspension with the solid mass percentage of 7%, and introducing compressed air for reaction;
3) filtering the water suspension after reaction, putting the solid material into a flotation tank, adding water, then introducing air, and drying the sediment at the lower part of the container to obtain the regeneration of the waste agent.
Example 5 (exhaust gas)
The embodiment of the invention provides a regenerated waste agent of an iron oxide desulfurizer, wherein the content of cubic system ferroferric oxide in the iron oxide desulfurizer is 5 percent and the waste agent is amorphous Fe based on the total mass of the iron oxide desulfurizer2O3Content of (5%) amorphous Fe2O3.H2The content of O is 60 percent, and the content of the adhesive sesbania powder is 10 percent;
the catalyst removes H in the exhaust gas2The process of S comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2When the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section;
The regeneration method of the waste agent of the iron oxide desulfurizer comprises the following steps:
1) introducing water vapor with the pressure of 1.0MPa into a heating furnace, and heating the water vapor to 420 ℃;
2) introducing the heated water vapor into a desulfurization tank containing the waste iron oxide desulfurizer at the speed of 10m/s, and heating the waste iron oxide desulfurizer;
3) ensuring that the bed temperature of the waste agent of the iron oxide desulfurizer is heated by water vapor to be more than 400 ℃ and the operation is carried out for 3 hours, wherein the steam consumption is 7 t/h;
4) analyzing the pH value of the outlet of the desulfurization tank, and introducing a small amount of coke oven gas into the desulfurization tank for reduction when the pH value is more than or equal to 7.5 for 3 times continuously;
5) the coke oven gas after the first-stage hydrogenation in the fine desulfurization procedure is introduced into the furnace at the position of 900m3Reducing the waste iron oxide desulfurizer;
6) analyzing the import and export H every 30min after the coke oven gas is introduced2Concentration change when discharging H2Concentration stable greater than or equal to inlet H2After concentration (3 analyses) the regenerant was obtained.
Example 6 (Coke oven gas)
The embodiment of the invention provides a regenerated waste agent of an iron oxide desulfurizer, wherein gamma-Fe in the iron oxide desulfurizer is calculated by the total mass of the iron oxide desulfurizer2O3The content is 23 percent, the content of cubic ferroferric oxide is 50 percent, and the content of sesbania powder serving as a binder is 27 percent;
The desulfurization process of the catalyst for the coke oven gas containing the hydrogen sulfide comprises the following operation steps:
mixing the desulfurizer with water to prepare desulfurizer slurry, wherein the total concentration of iron oxyhydroxide in the desulfurizer slurry is 10 wt%, introducing deaminated coke oven gas into a desulfurization tower from the bottom, the temperature of the tower kettle of the desulfurization tower is 30 ℃, spraying the desulfurizer on the top of the desulfurization tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the waste liquid of the iron oxide desulfurizer of the application after regeneration;
the regeneration method of the waste agent of the iron oxide desulfurizer comprises the following steps:
1) introducing water vapor with the pressure of 1.5MPa into a heating furnace, and heating the water vapor to 450 ℃;
2) introducing the heated water vapor into a desulfurization tank containing the waste iron oxide desulfurizer at the speed of 15m/s, and heating the waste iron oxide desulfurizer;
3) ensuring that the bed temperature of the waste agent of the iron oxide desulfurizer is heated by water vapor to be more than 400 ℃ and the operation is carried out for 2 hours, wherein the steam consumption is 6 t/h;
4) analyzing the pH value of the outlet of the desulfurization tank, and introducing a small amount of coke oven gas into the desulfurization tank for reduction when the pH value is more than or equal to 7.5 for 3 times continuously;
5) introducing into the coke oven gas subjected to primary hydrogenation in the fine desulfurization process at a flow rate of 800m 3H, reducing the waste iron oxide desulfurizer;
6) analyzing the inlet and outlet H every 30min after the coke oven gas is introduced2Concentration change when outlet H2Concentration stable greater than or equal to inlet H2After concentration (3 analyses) the regenerant was obtained.
Example 7 (gas field water)
The embodiment of the invention provides a regenerated waste agent of an iron oxide desulfurizer, wherein amorphous Fe in the iron oxide desulfurizer is calculated by the total mass of the iron oxide desulfurizer2O3.H2The content of O is 75 percent, the content of carrier aluminum oxide is 10 percent, and the content of adhesive sesbania powder is 15 percent;
the desulfurization process of the catalyst for gas field water comprises the following operation steps:
the catalyst is filled in a fixed bed reactor to contain H2And (3) carrying out full contact reaction on the gas field water of the S with the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h-1The waste catalyst after gas field water desulfurization is regenerated, namely the waste catalyst of the iron oxide desulfurizer;
the regeneration method of the waste agent of the iron oxide desulfurizer comprises the following steps:
1) stirring the waste agent and an aqueous solution of sodium hydroxide in a slurry tank to prepare slurry, and maintaining the pH value of the slurry to be 8.0, wherein the solid content of the slurry is 4 wt%;
2) Introducing air into the slurry, and carrying out oxidation reaction at 90 ℃ and 0.1MPa to carry out oxidation regeneration;
3) then introducing hydrogen sulfide into the oxidized slurry, and carrying out a vulcanization reaction at 10 ℃ and 5 MPa;
4) introducing air into the vulcanized slurry, and carrying out oxidation reaction at 90 ℃ and 0.1MPa to carry out oxidation regeneration;
5) repeating the steps 3) and 4) twice to enable the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction to be 1: 4.5;
6) and carrying out solid-liquid separation on the slurry after the oxidation reaction to obtain a regenerated product of the waste agent.
Comparative example 1
This comparative example provides an iron oxide desulfurizing agent that is the same desulfurizing agent as the iron oxide desulfurizing agent of example 1, wherein amorphous Fe is present in the iron oxide desulfurizing agent based on the total mass of the iron oxide desulfurizing agent2O3The content of (A) is 55%, the content of the carrier is 30% of bentonite, and the content of the binder sesbania powder is 15%.
Comparative example 2
This comparative example provides an iron oxide desulfurizing agent that is the same as the iron oxide desulfurizing agent of example 5, in which the content of cubic ferrosoferric oxide in the iron oxide desulfurizing agent is 5% and amorphous Fe is present, based on the total mass of the iron oxide desulfurizing agent 2O3Content of (2) is 25%, amorphous Fe2O3.H2The content of O is 60 percent, and the content of the adhesive sesbania powder is 10 percent.
Example 8 (application of a waste desulfurizing agent after regeneration)
The regenerated materials after the waste desulfurizer collected in the above examples 1-7 is regenerated and the iron oxide desulfurizer in the comparative examples 1-2 are respectively used as catalysts for the liquefaction reaction of corn stalks, and the activity tests of the catalysts are as follows: preparing slurry containing corn straws and a catalyst, conveying the slurry into a slurry bed reactor, introducing hydrogen into the slurry bed reactor, and performing a hydrogenation liquefaction reaction, wherein the reaction pressure is controlled to be 20MPa, the temperature is 380 ℃, the addition amount of the catalyst is 2 wt% of the addition amount of the corn straws, and the activity of the catalyst is represented by the distribution of products prepared by the liquefaction reaction of the corn straws as shown in the following table 1:
TABLE 1 comparison of product distribution
From table 1 it can be seen that: the waste agent of the iron oxide desulfurizer adopted by the application is regenerated and then used as a hydrogenation catalyst, so that the hydrogenation reaction can be effectively catalyzed, and the biomass conversion rate is improved.
18. The waste desulfurizer containing ferric oxide is regenerated and used as a hydrogenation catalyst.
Example 1 (Tail gas)
The embodiment of the invention provides a catalyst containing oxygen The waste agent of the desulfurizer for the ferric oxide, wherein the CuO in the desulfurizer containing the ferric oxide is 8g, the ferric salt complexing agent triethanolamine is 9g, and amorphous Fe2O3 15g，MnO2Is 8 g;
the desulfurization process of the tail gas generated after the catalyst is used for hydrogenation upgrading of medium and low temperature coal tar in industry is as follows:
1) collecting tail gas generated after the medium and low temperature coal tar is subjected to hydrogenation catalysis by a fixed bed;
2) the desulfurizer of the embodiment is prepared into columnar catalyst particles with the diameter of 1mm and the length of 15mm, and the columnar catalyst particles are filled in a desulfurizing tower to form a desulfurizing layer;
3) the tail gas is treated for 2000h-1The air speed of the desulfurizer passes through the desulfurization layer, and the air speed and the desulfurizer in the desulfurization layer are subjected to desulfurization reaction at 50 ℃, so that hydrogen sulfide in tail gas is removed, after the reaction is finished, the waste agent of the reacted desulfurizer is taken out, and the waste agent is cooled to room temperature, so that the waste agent of the desulfurizer containing ferric oxide is obtained;
the method for regenerating the waste agent of the desulfurizer containing the ferric oxide comprises the following steps:
1) dispersing the waste agent with weak acid water (containing dilute sulfuric acid) with pH of 4.0, wherein the solid-to-liquid ratio of the waste agent of the iron oxide desulfurizer to the weak acid water is 1: 4(g/ml), and the dispersion time is 30min to obtain a dispersion liquid;
2) heating the dispersion liquid to 60 ℃ under normal pressure, then adding hydrogen peroxide into the dispersion liquid by using a peristaltic pump, controlling the flow to be 500mL/min, controlling the molar ratio of the hydrogen peroxide to sulfur elements in the iron oxide desulfurizer waste agent to be 5: 1, magnetically stirring to promote the reaction, and rapidly transferring generated sulfur dioxide gas by vacuumizing during the reaction for 10 min;
3) After the reaction is finished, filtering the reaction solution, washing the obtained precipitate for 2 times by using water, then drying at 100 ℃ to obtain the regeneration of the waste agent, and returning the filtrate obtained by filtering to the dispersion process to be used as weak acid water for recycling.
Example 2 (pyrolysis of coal gas)
The embodiment of the invention provides a waste agent of a desulfurizer containing ferric oxide, wherein the waste agent is prepared by mixing iron oxide with a carrierIn the desulfurizer containing ferric oxide, 10g of calcium bicarbonate, 12g of basic copper carbonate and gamma-Fe2O3 18g，MnO28g of NiO and 5g of NiO;
the desulfurization process of the hydrogen sulfide-containing coal pyrolysis gas by the catalyst is as follows:
(1) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a desulfurizing tower filled with the desulfurizer containing the ferric oxide, and adopting a flow of feeding the mixture from bottom to top to avoid that liquid water enters a desulfurizer bed layer to remove hydrogen sulfide;
(2) the desulfurizer becomes a waste agent after being used for many times, and is taken out from a desulfurizer bed layer, namely the waste agent of the desulfurizer containing ferric oxide in the application.
The method for regenerating the waste agent of the desulfurizer containing the ferric oxide comprises the following steps:
1) dispersing the waste agent with weak acid water (containing dilute hydrochloric acid) with pH of 5.0, wherein the solid-to-liquid ratio of the waste agent of the iron oxide desulfurizer to the weak acid water is 1: 6(g/ml), and the dispersion time is 30min to obtain a dispersion liquid;
2) Heating the dispersion liquid to 60 ℃ under normal pressure, adding hydrogen peroxide into the dispersion liquid by using a peristaltic pump, controlling the flow to be 500mL/min, controlling the molar ratio of the hydrogen peroxide to sulfur elements in the waste agent of the iron oxide desulfurizer to be 6: 1, carrying out magnetic stirring to promote reaction, and rapidly transferring generated sulfur dioxide gas by vacuumizing during the reaction for 10 min;
3) after the reaction is finished, filtering the reaction solution, washing the obtained precipitate for 2 times by using water, then drying at 100 ℃ to obtain the regeneration of the waste agent, and returning the filtrate obtained by filtering to the dispersion process to be used as weak acid water for recycling.
Example 3 (oil)
The embodiment of the invention provides a waste agent of a desulfurizer containing ferric oxide, wherein in the desulfurizer containing ferric oxide, 50g of cubic system ferroferric oxide, 12g of calcium sulfate dihydrate, 20g of basic zinc carbonate and 6g of sodium carboxymethylcellulose are contained;
the catalyst is used for desulfurizing petroleum containing hydrogen sulfide, and the operation steps are as follows:
(1) the desulfurizer of the embodiment is prepared into catalyst particles with the diameter of 1.5mm, and the catalyst particles are filled in a desulfurization tower to form a desulfurization layer;
(2) spraying petroleum containing hydrogen sulfide into a desulfurization layer from the top of a desulfurization tower through a nozzle, leaching and desulfurizing, and collecting desulfurized waste desulfurizer, namely the waste desulfurizer containing iron oxide in the application;
The method for regenerating the waste agent of the desulfurizer containing the ferric oxide comprises the following steps:
1) washing the waste agent with water, and carrying out water-carrying grinding in a wet ball mill to obtain particles of 300 meshes to obtain waste agent powder;
2) preparing the waste agent powder into aqueous suspension with the solid mass percentage content of 15%, introducing compressed air, sampling and inspecting after reacting for a period of time, and when the sample taken out does not generate H when reacting with hydrochloric acid2S, forming slurry containing elemental sulfur, filtering the slurry to obtain solid material, and using CCl4Extracting the solid material obtained after extraction and filtration for three times, combining the extract liquor, recovering the solvent by a distillation method to obtain crystallized elemental sulfur, and obtaining the residual solid after the extract liquor is separated as the regenerated substance.
Example 4 (gas field water)
The embodiment of the invention provides a waste agent of a desulfurizer containing ferric oxide, wherein amorphous Fe in the desulfurizer containing the ferric oxide2O3.H230g of O, 15g of polymeric ferric sulfate, 12g of basic copper carbonate and 6g of sodium carboxymethyl cellulose, and amorphous Fe2O3 8g；
The desulfurization process of the catalyst for gas field water comprises the following operation steps:
the catalyst is filled in a fixed bed reactor to contain H2And (3) carrying out full contact reaction on the gas field water of the S with the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h -1The waste catalyst after gas field water desulfurization is the waste desulfurizer containing the ferric oxide;
the method for regenerating the waste desulfurizer containing the ferric oxide comprises the following steps:
1) washing the waste agent with water, and grinding the waste agent with water in a wet ball mill into particles of 200 meshes to obtain waste agent powder;
2) preparing the waste agent powder into a water suspension with the solid mass percentage of 7%, and introducing compressed air for reaction;
3) filtering the water suspension after reaction, putting the solid material into a flotation tank, adding water, then introducing air, and drying the sediment at the lower part of the container to obtain the regeneration of the waste agent.
Example 5 (waste gas)
The embodiment of the invention provides a waste agent of a desulfurizer containing ferric oxide, wherein in the desulfurizer containing ferric oxide, 12g of cubic system ferroferric oxide and amorphous Fe2O324g of amorphous Fe2O3.H2O39 g and NiO are 5 g;
the catalyst removes H in the exhaust gas2The process of S comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2When the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section;
The method for regenerating the waste desulfurizer containing the ferric oxide comprises the following steps:
1) dispersing the waste agent in water to form slurry;
2) heating the slurry to 45 ℃ at normal pressure, adding hydrogen peroxide into the slurry by using a peristaltic pump, introducing air, controlling the flow rate of the hydrogen peroxide to be 500mL/min and the air flow to be 100mL/min, and magnetically stirring to promote the reaction for 5 min;
3) after the reaction is finished, filtering the reaction liquid, washing the obtained precipitate for 3 times by using water, and naturally drying to obtain the regenerant of the waste agent.
Example 6 (Coke oven gas)
The embodiment of the invention providesProvides a waste agent of a desulfurizer containing ferric oxide, wherein in the desulfurizer containing ferric oxide, gamma-Fe2O323g of amorphous Fe2O324g of amorphous Fe2O3.H2O is 42g and MnO is 8 g;
the desulfurization process of the catalyst for the coke oven gas containing the hydrogen sulfide comprises the following operation steps:
mixing the desulfurizer with water to prepare desulfurizer slurry, wherein the total concentration of iron oxyhydroxide in the desulfurizer slurry is 10 wt%, introducing deaminated coke oven gas into a desulfurization tower from the bottom, the temperature of the tower kettle of the desulfurization tower is 30 ℃, spraying the desulfurizer on the top of the desulfurization tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the waste agent of the desulfurizer containing iron oxide;
The method for regenerating the waste agent of the desulfurizer containing the ferric oxide comprises the following steps:
1) introducing water vapor with the pressure of 1.5MPa into a heating furnace, and heating the water vapor to 450 ℃;
2) introducing the heated water vapor into a desulfurization tank containing the waste agent at the speed of 15m/s, and heating the waste agent;
3) ensuring that the bed layer temperature of the waste agent is heated to above 400 ℃ by water vapor and runs for 2 hours, wherein the steam consumption is 6 t/h;
4) analyzing the pH value of the outlet of the desulfurization tank, and introducing a small amount of coke oven gas into the desulfurization tank for reduction when the pH value is more than or equal to 7.5 for 3 times continuously;
5) introducing into the coke oven gas subjected to primary hydrogenation in the fine desulfurization process at a flow rate of 800m3Reducing the waste iron oxide desulfurizer;
6) analyzing the import and export H every 30min after the coke oven gas is introduced2Concentration change when discharging H2Concentration stable greater than or equal to inlet H2After concentration (3 analyses) the regenerant was obtained.
Example 7 (gas field water)
The embodiment of the invention provides a waste desulfurizer containing ferric oxide, wherein the waste desulfurizer contains ferric oxideAmorphous Fe in desulfurizing agent with iron oxide2O3.H230g of O, 15g of polymeric ferric sulfate, 12g of basic copper carbonate and 6g of sodium carboxymethyl cellulose, and amorphous Fe2O3 8g；
The desulfurization process of the catalyst for gas field water comprises the following operation steps:
The catalyst is filled in a fixed bed reactor to contain H2And (3) carrying out full contact reaction on the gas field water of the S with the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h-1The waste catalyst after gas field water desulfurization is the waste desulfurizer containing ferric oxide;
the method for regenerating the waste agent of the desulfurizer containing the ferric oxide comprises the following steps:
1) stirring the waste agent and an aqueous solution of sodium hydroxide in a slurry tank to prepare slurry, and maintaining the pH value of the slurry to be 8.0, wherein the solid content of the slurry is 4 wt%;
2) introducing air into the slurry, and carrying out oxidation reaction at 90 ℃ and 0.1MPa to carry out oxidation regeneration;
3) then introducing hydrogen sulfide into the oxidized slurry, and carrying out a vulcanization reaction at 10 ℃ and 5 MPa;
4) introducing air into the vulcanized slurry, and carrying out oxidation reaction at 90 ℃ and 0.1MPa to carry out oxidation regeneration;
5) repeating the steps 3) and 4) twice to enable the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction to be 1: 4.5;
6) and carrying out solid-liquid separation on the slurry after the oxidation reaction to obtain a regenerated product of the waste agent.
Comparative example 1
This comparative example provides an iron oxide-containing desulfurizing agent, which is the same as that of example 1, wherein the iron oxide-containing desulfurizing agent contains 8g of CuO, 9g of triethanolamine, which is an iron salt complexing agent, and amorphous Fe 2O3 15g，MnO2It was 8 g.
Comparative example 2
This comparative example provides a desulfurizing agent containing iron oxide, which is the same as that of example 5, in which 12g of cubic system ferroferric oxide and amorphous Fe were contained in the desulfurizing agent containing iron oxide2O324g of amorphous Fe2O3.H2O39 g and NiO were 5 g.
Example 8 (application after regeneration of waste agent)
The regenerants obtained by regenerating the waste desulfurizer collected in the above examples 1 to 7 and the desulfurizer containing iron oxide in comparative examples 1 and 2 were used as catalysts for liquefaction reaction of corn stover, respectively, and activity tests of the catalysts were performed as follows: preparing slurry containing corn straws and a catalyst, conveying the slurry into a slurry bed reactor, introducing hydrogen into the slurry bed reactor, and performing a hydrogenation liquefaction reaction, wherein the reaction pressure is controlled to be 20MPa, the temperature is 380 ℃, the addition amount of the catalyst is 2 wt% of the addition amount of the corn straws, and the activity of the catalyst is represented by the distribution of products prepared by the liquefaction reaction of the corn straws as shown in the following table 1:
TABLE 1 comparison of product distribution
From table 1 it can be seen that: the waste agent of the iron oxide desulfurizer adopted by the application is regenerated and then used as a hydrogenation catalyst, so that the hydrogenation reaction can be effectively catalyzed, and the biomass conversion rate is improved.
19. The waste iron oxide desulfurizer is used as a CO shift catalyst.
Example 1 (Tail gas)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein amorphous Fe in the iron oxide desulfurizer is calculated by the total mass of the iron oxide desulfurizer2O3The content of (A) is 55%, the content of the carrier is 30% of bentonite, and the content of the binder sesbania powder is 15%.
The catalyst is used for the desulfurization process of tail gas generated after the medium-low temperature coal tar in industry is hydrogenated and upgraded as follows:
1) collecting tail gas generated after the medium and low temperature coal tar is subjected to fixed bed hydrogenation catalysis;
2) the desulfurizer of the embodiment is prepared into columnar catalyst particles with the diameter of 1mm and the length of 15mm, and the columnar catalyst particles are filled in a desulfurizing tower to form a desulfurizing layer;
3) the tail gas is treated for 2000h-1The air speed of the catalyst passes through the desulfurization layer, and the air speed of the catalyst and a desulfurizer in the desulfurization layer are subjected to desulfurization reaction at 50 ℃, hydrogen sulfide in tail gas is removed, after the reaction is finished, a waste agent of the reacted desulfurizer is taken out, and the waste agent is cooled to room temperature, namely the waste agent of the iron oxide desulfurizer in the application.
Example 2 (coal pyrolysis gas)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein based on the total mass of the iron oxide desulfurizer, gamma-Fe in the iron oxide desulfurizer 2O3The content of (b) is 65%, the content of carrier natural zeolite is 30%, and the content of binder cellulose powder is 5%.
The desulfurization process of the coal pyrolysis gas containing hydrogen sulfide by the catalyst is as follows:
(1) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a desulfurizing tower filled with the desulfurizing agent mainly comprising iron oxide as an active component, and adopting a flow of feeding liquid water from bottom to top to prevent the liquid water from entering a desulfurizing agent bed layer to remove hydrogen sulfide;
(2) the desulfurizer is used for many times to form a waste agent, and the waste agent is taken out from a desulfurizer bed layer to form the waste agent of the iron oxide desulfurizer.
Example 3 (oil)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein based on the total mass of the iron oxide desulfurizer, the content of cubic system ferroferric oxide in the iron oxide desulfurizer is 97.3%, and the balance is impurities and water;
the catalyst is used for desulfurizing petroleum containing hydrogen sulfide, and the operation steps are as follows:
(1) the desulfurizer of the embodiment is prepared into catalyst particles with the diameter of 1.5mm, and the catalyst particles are filled in a desulfurizing tower to form a desulfurizing layer;
(2) and spraying petroleum containing hydrogen sulfide into the desulfurization layer from the top of the desulfurization tower through a nozzle, leaching and desulfurizing, and collecting the desulfurized waste desulfurizer, namely the waste desulfurizer of the iron oxide desulfurizer.
Example 4 (gas field water)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein amorphous Fe in the iron oxide desulfurizer is calculated by the total mass of the iron oxide desulfurizer2O3.H2The content of O is 75 percent, the content of carrier aluminum oxide is 10 percent, and the content of adhesive sesbania powder is 15 percent;
the desulfurization process of the catalyst for gas field water comprises the following operation steps:
loading the catalyst into a fixed bed reactor to make it contain H2And (2) carrying out full contact reaction on the gas field water of the S and the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h-1The waste catalyst after gas field water desulfurization is the waste iron oxide desulfurizer of the application.
Example 5 (waste gas)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein the content of cubic system ferroferric oxide in the iron oxide desulfurizer is 5 percent and the content of amorphous Fe is amorphous based on the total mass of the iron oxide desulfurizer2O3Content of (5%) amorphous Fe2O3.H2The content of O is 60 percent, and the content of the adhesive sesbania powder is 10 percent;
the catalyst removes H in the exhaust gas2The process of S comprises the following steps: will H2The S content is 5500mg/cm3Is used for 3000h -1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section as a catalyst for CO shift reaction.
Example 6 (Coke oven gas)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein based on the total mass of the iron oxide desulfurizer, gamma-Fe in the iron oxide desulfurizer2O3The content of the binder is sesbania powder, the content of the cubic ferroferric oxide is 23 percent, the content of the cubic ferroferric oxide is 50 percent, and the content of the binder is 27 percent;
the desulfurization process of the coke oven gas containing hydrogen sulfide by the catalyst comprises the following operation steps:
the desulfurizing agent and water are mixed to prepare desulfurizing agent slurry, the total concentration of iron oxyhydroxide in the desulfurizing agent slurry is 10 wt%, the deaminated coke oven gas is introduced into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, the desulfurizing agent is sprayed from the top of the desulfurizing tower through a nozzle to elute and desulfurize the coke oven gas, and the desulfurized waste liquid is collected and dried to obtain the waste agent of the iron oxide desulfurizing agent.
Example 7 (application of spent desulfurizing agent)
The waste agents of the desulfurizing agents collected in the above examples 1 to 6 were used as catalysts for CO shift reaction, and the activity test of the catalysts was as follows:
The composition of the raw material gas is 15 vol% CO and 55 vol% H2、6vol％CO2、24vol％N2And the reaction steam-gas ratio is 1: 1, the space velocity is 4000h-1The catalyst activity test temperature zone is 250-450 ℃;
the activity of the catalyst is expressed in terms of CO conversion and is calculated as follows:
CO conversion rate (1-V)CO'/VCO)/(1+VCO)×100％
Wherein, VCO'Is the volume percent of CO in the reactor off-gas, VCOIs the volume percentage of CO in the raw material gas;
the corresponding test results are shown in table 1 below:
TABLE 1 CO conversion at different test temperatures
From table 1 it can be seen that: the waste agent of the iron oxide desulfurizer is used as a CO conversion catalyst, and can effectively catalyze the CO to perform a change reaction, so that the conversion rate of CO is improved.
20. The waste desulfurizer using ferric oxide as main active component is used as CO shift catalyst.
Example 1 (Tail gas)
The embodiment of the invention provides a waste desulfurizer using iron oxide as an active ingredient, wherein the waste desulfurizer using iron oxide as an active ingredient contains 8g of CuO, 9g of ferric salt complexing agent triethanolamine and amorphous Fe2O3 15g，MnO2Is 8 g;
the desulfurization process of the tail gas generated after the catalyst is used for hydrogenation upgrading of medium and low temperature coal tar in industry is as follows:
1) collecting tail gas generated after the medium and low temperature coal tar is subjected to hydrogenation catalysis by a fixed bed;
2) The desulfurizer of the embodiment is prepared into columnar catalyst particles with the diameter of 1mm and the length of 15mm, and the columnar catalyst particles are filled in a desulfurizing tower to form a desulfurizing layer;
3) the tail gas is treated for 2000h-1The air speed of the desulfurizing agent passes through the desulfurization layer, and the air speed and the desulfurizing agent in the desulfurization layer are subjected to desulfurization reaction at 50 ℃, so that hydrogen sulfide in tail gas is removed, and after the reaction is finished, the waste agent of the reacted desulfurizing agent is taken out and cooled to room temperature, so that the waste agent of the desulfurizing agent mainly taking iron oxide as an active component is obtained.
Example 2 (coal pyrolysis gas)
The embodiment of the invention provides a waste desulfurizer which mainly takes ferric oxide as an active ingredient, wherein in the desulfurizer which mainly takes ferric oxide as the active ingredient, 10g of calcium bicarbonate, 12g of basic copper carbonate and gamma-Fe are contained2O3 18g，MnO28g and 5g of NiO;
the desulfurization process of the hydrogen sulfide-containing coal pyrolysis gas by the catalyst is as follows:
(1) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a desulfurizing tower filled with the desulfurizing agent mainly comprising ferric oxide as an active component, and adopting a flow of feeding the coal pyrolysis gas from bottom to top to prevent liquid water from entering a desulfurizing agent bed layer to remove hydrogen sulfide;
(2) the desulfurizer becomes a waste agent after being used for many times, and is taken out from a desulfurizer bed layer, namely the waste agent of the desulfurizer mainly taking ferric oxide as an active component in the application.
Example 3 (oil)
The embodiment of the invention provides a waste desulfurizer which mainly takes ferric oxide as an active ingredient, wherein in the desulfurizer which mainly takes ferric oxide as an active ingredient, 50g of cubic ferroferric oxide, 12g of calcium sulfate dihydrate, 20g of basic zinc carbonate and 6g of sodium carboxymethylcellulose are contained;
the catalyst is used for desulfurizing petroleum containing hydrogen sulfide, and the operation steps are as follows:
(1) the desulfurizer of the embodiment is prepared into catalyst particles with the diameter of 1.5mm, and the catalyst particles are filled in a desulfurization tower to form a desulfurization layer;
(2) and spraying petroleum containing hydrogen sulfide into the desulfurization layer from the top of the desulfurization tower through a nozzle, leaching and desulfurizing, and collecting desulfurized waste desulfurizer, namely the waste desulfurizer mainly comprising iron oxide as an active component.
Example 4 (gas field water)
The embodiment of the invention provides a waste desulfurizer which mainly takes ferric oxide as an active ingredient, wherein amorphous Fe in the desulfurizer which mainly takes ferric oxide as the active ingredient2O3.H230g of O, 15g of polymeric ferric sulfate, 12g of basic copper carbonate and 6g of sodium carboxymethyl cellulose, and amorphous Fe2O3 8g；
The desulfurization process of the catalyst for gas field water comprises the following operation steps:
Loading the catalyst into a fixed bed reactor to make it contain H2And (2) carrying out full contact reaction on the gas field water of the S and the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃ and the pressure is 02MPa and a volume space velocity of 10000h-1The waste catalyst after gas field water desulfurization is the waste desulfurizer mainly comprising iron oxide as an active component.
Example 5 (exhaust gas)
The embodiment of the invention provides a waste desulfurizer which mainly takes ferric oxide as an active ingredient, wherein in the desulfurizer which mainly takes ferric oxide as an active ingredient, 12g of cubic ferroferric oxide and amorphous Fe2O324g of amorphous Fe2O3.H2O39 g and NiO are 5 g;
the catalyst removes H in the exhaust gas2The process of S comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2And when the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section to be used as a catalyst for CO conversion reaction.
Example 6 (Coke oven gas)
The embodiment of the invention provides a waste desulfurizer which mainly takes ferric oxide as an active ingredient, wherein gamma-Fe in the desulfurizer which mainly takes ferric oxide as the active ingredient 2O323g of amorphous Fe2O324g of amorphous Fe2O3.H2O is 42g and MnO is 8 g;
the desulfurization process of the coke oven gas containing hydrogen sulfide by the catalyst comprises the following operation steps:
mixing the desulfurizer with water to prepare desulfurizer slurry, wherein the total concentration of iron oxyhydroxide in the desulfurizer slurry is 10 wt%, introducing deaminated coke oven gas into a desulfurizing tower from the bottom, the temperature of the tower kettle of the desulfurizing tower is 30 ℃, spraying the desulfurizer on the top of the desulfurizing tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the waste desulfurizer mainly comprising iron oxide as an active component.
Example 7 (use of waste agent of desulfurizing agent)
The waste agents of the desulfurizing agents collected in the above examples 1 to 6 were used as catalysts for CO shift reaction, and the activity tests of the catalysts were carried out as follows:
the composition of the raw material gas is 15 vol% CO and 55 vol% H2、6vol％CO2、24vol％N2And the reaction steam-gas ratio is 1: 1, the airspeed is 4000h-1The catalyst activity test temperature zone is 250-450 ℃;
the activity of the catalyst is expressed in terms of CO conversion and is calculated as follows:
CO conversion rate (1-V)CO'/VCO)/(1+VCO)×100％
Wherein, VCO'Is the volume percent of CO in the reactor off-gas, V COIs the volume percentage of CO in the raw material gas;
the corresponding test results are shown in table 1 below:
TABLE 1 CO conversion at different test temperatures
From table 1 it can be seen that: the waste desulfurizer mainly containing iron oxide as an active component is used as a CO conversion catalyst, so that the change reaction of CO can be effectively catalyzed, and the conversion rate of CO is improved.
21. The waste agent of the iron oxide desulfurizer is regenerated and then used as a CO shift catalyst.
Example 1 (Tail gas)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein amorphous Fe in the iron oxide desulfurizer is calculated by the total mass of the iron oxide desulfurizer2O3The content of (A) is 55%, the content of the carrier is 30% of bentonite, and the content of the binder sesbania powder is 15%.
The desulfurization process of the tail gas generated after the catalyst is used for hydrogenation upgrading of medium and low temperature coal tar in industry is as follows:
1) collecting tail gas generated after the medium and low temperature coal tar is subjected to fixed bed hydrogenation catalysis;
2) the desulfurizer of the embodiment is prepared into columnar catalyst particles with the diameter of 1mm and the length of 15mm, and the columnar catalyst particles are filled in a desulfurizing tower to form a desulfurization layer;
3) the tail gas is treated for 2000h-1The air speed of the catalyst passes through the desulfurization layer, and the air speed and a desulfurizer in the desulfurization layer are subjected to desulfurization reaction at 50 ℃, so that hydrogen sulfide in tail gas is removed, after the reaction is finished, a waste agent of the reacted desulfurizer is taken out, and the waste agent is cooled to room temperature, so that the waste agent of the iron oxide desulfurizer is obtained;
The regeneration method of the waste agent of the iron oxide desulfurizer comprises the following steps:
1) stirring the waste agent and an aqueous solution of sodium hydroxide in a slurry tank to prepare slurry, and maintaining the pH value of the slurry to be 8.0 and the solid content of the slurry to be 4 wt%;
2) introducing air into the slurry, and performing oxidation reaction at 90 ℃ and 0.1MPa to perform oxidation regeneration;
3) then introducing hydrogen sulfide into the oxidized slurry, and carrying out a vulcanization reaction at 10 ℃ and 5 MPa;
4) introducing air into the vulcanized slurry, and carrying out oxidation reaction at 90 ℃ and 0.1MPa to carry out oxidation regeneration;
5) repeating the steps 3) and 4) twice to enable the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction to be 1: 4.5;
6) and carrying out solid-liquid separation on the slurry after the oxidation reaction to obtain a regenerated product of the waste agent.
Example 2 (coal pyrolysis gas)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein gamma-Fe in the iron oxide desulfurizer is calculated by the total mass of the iron oxide desulfurizer2O3The content of (b) is 65%, the content of carrier natural zeolite is 30%, and the content of binder cellulose powder is 5%.
The desulfurization process of the coal pyrolysis gas containing hydrogen sulfide by the catalyst is as follows:
(1) Cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a desulfurizing tower filled with the desulfurizing agent mainly comprising ferric oxide as an active component, and adopting a flow of feeding the coal pyrolysis gas from bottom to top to prevent liquid water from entering a desulfurizing agent bed layer to remove hydrogen sulfide;
(2) the desulfurizer is used for many times to form a waste agent, and the waste agent is taken out from a desulfurizer bed layer to form the waste agent of the iron oxide desulfurizer in the application;
the regeneration method of the waste agent of the iron oxide desulfurizer comprises the following steps:
1) dispersing the waste agent in water to form slurry;
2) heating the slurry to 60 ℃ under normal pressure, adding hydrogen peroxide into the slurry by using a peristaltic pump, controlling the flow to be 500mL/min, and magnetically stirring to promote the reaction for 10 min;
3) after the reaction is finished, the reaction solution is filtered, the obtained precipitate is washed for 2 times by water and naturally dried to obtain the regeneration of the waste agent.
Example 3 (oil)
The embodiment of the invention provides a waste agent of an iron oxide desulfurizer, wherein based on the total mass of the iron oxide desulfurizer, the content of cubic system ferroferric oxide in the iron oxide desulfurizer is 97.3%, and the balance is impurities and water;
The catalyst is used for desulfurizing petroleum containing hydrogen sulfide, and the operation steps are as follows:
(1) the desulfurizer of the embodiment is prepared into catalyst particles with the diameter of 1.5mm, and the catalyst particles are filled in a desulfurization tower to form a desulfurization layer;
(2) spraying petroleum containing hydrogen sulfide into a desulfurization layer from the top of a desulfurization tower through a nozzle, leaching and desulfurizing, and collecting desulfurized waste desulfurizer, namely the waste desulfurizer of the iron oxide desulfurizer;
the regeneration method of the waste agent of the iron oxide desulfurizer comprises the following steps:
1) stirring the waste agent and water in a slurry tank to prepare slurry, wherein the solid content of the slurry is 12 wt%;
2) introducing sodium hypochlorite into the slurry, and carrying out oxidation reaction at 60 ℃ and 1MPa to carry out oxidation regeneration;
3) adding Na into the oxidized slurry2S, carrying out a vulcanization reaction at 10 ℃ and 5 MPa;
4) introducing hydrogen peroxide into the vulcanized slurry, and carrying out oxidation reaction at 30 ℃ and 1.1MPa to carry out oxidation regeneration;
5) repeating the steps 3) and 4) for four times to ensure that the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction is 1: 5;
6) and carrying out solid-liquid separation on the slurry after the oxidation reaction to obtain a regenerated product of the waste agent.
Example 4 (gas field water)
The embodiment of the invention provides a regenerated waste agent of an iron oxide desulfurizer, wherein amorphous Fe in the iron oxide desulfurizer is calculated by the total mass of the iron oxide desulfurizer2O3.H2The content of O is 75 percent, the content of carrier aluminum oxide is 10 percent, and the content of adhesive sesbania powder is 15 percent;
the desulfurization process of the catalyst for gas field water comprises the following operation steps:
loading the catalyst into a fixed bed reactor to make it contain H2And (3) carrying out full contact reaction on the gas field water of the S with the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h-1The waste catalyst after gas field water desulfurization is regenerated, namely the waste catalyst of the iron oxide desulfurizer;
the regeneration method of the waste agent of the iron oxide desulfurizer comprises the following steps:
1) washing the waste agent with water, and carrying out water-carrying grinding in a wet ball mill to obtain particles of 200 meshes to obtain waste agent powder;
2) preparing the waste agent powder into a water suspension with the solid mass percentage of 7%, and introducing compressed air for reaction;
3) filtering the water suspension after reaction, putting the solid material into a flotation tank, adding water, then introducing air, and drying the sediment at the lower part of the container to obtain the regeneration of the waste agent.
Example 5 (waste gas)
The embodiment of the invention provides a regenerated waste agent of an iron oxide desulfurizer, wherein the content of cubic system ferroferric oxide in the iron oxide desulfurizer is 5 percent and the waste agent is amorphous Fe based on the total mass of the iron oxide desulfurizer2O3Content of (2) is 25%, amorphous Fe2O3.H2The content of O is 60 percent, and the content of the adhesive sesbania powder is 10 percent;
the catalyst removes H in the exhaust gas2The process of S comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2When the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section as a catalyst for CO conversion reaction;
the regeneration method of the waste agent of the iron oxide desulfurizer comprises the following steps:
1) dispersing the waste agent in water to form slurry;
2) heating the slurry to 45 ℃ at normal pressure, adding hydrogen peroxide into the slurry by using a peristaltic pump, introducing air, controlling the flow rate of the hydrogen peroxide to be 500mL/min and the air flow to be 100mL/min, and magnetically stirring to promote the reaction for 5 min;
3) after the reaction is finished, the reaction solution is filtered, the obtained precipitate is washed for 3 times by water and naturally dried to obtain the regeneration of the waste agent.
Example 6 (Coke oven gas)
The embodiment of the invention provides a regenerated waste agent of an iron oxide desulfurizer, wherein gamma-Fe in the iron oxide desulfurizer is calculated by the total mass of the iron oxide desulfurizer2O3The content of the binder is sesbania powder, the content of the cubic ferroferric oxide is 23 percent, the content of the cubic ferroferric oxide is 50 percent, and the content of the binder is 27 percent;
the desulfurization process of the coke oven gas containing hydrogen sulfide by the catalyst comprises the following operation steps:
mixing the desulfurizer with water to prepare desulfurizer slurry, wherein the total concentration of iron oxyhydroxide in the desulfurizer slurry is 10 wt%, introducing deaminated coke oven gas into a desulfurization tower from the bottom, the temperature of the tower kettle of the desulfurization tower is 30 ℃, spraying the desulfurizer on the top of the desulfurization tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the waste liquid of the iron oxide desulfurizer of the application after regeneration;
the regeneration method of the waste agent of the iron oxide desulfurizer comprises the following steps:
1) stirring the waste agent and the aqueous solution of potassium hydroxide in a slurry tank to prepare slurry, and maintaining the pH value of the slurry to be 8.0, wherein the solid content of the slurry is 4 wt%;
2) introducing O into the slurry 2And O3Mixing the gases, and carrying out oxidation reaction at 50 ℃ and 1MPa to carry out oxidation regeneration;
3) then introducing hydrogen sulfide into the oxidized slurry, and carrying out a vulcanization reaction at 10 ℃ and 5 MPa;
4) introducing air into the vulcanized slurry, and carrying out oxidation reaction at 90 ℃ and 0.1MPa to carry out oxidation regeneration;
5) repeating the steps 3) and 4) for three times to ensure that the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction is 1: 4.9;
6) and carrying out solid-liquid separation on the slurry after the oxidation reaction to obtain a regenerated product of the waste agent.
Example 7 (application of waste desulfurizing agent after regeneration)
The regenerated product of the collected waste desulfurizer of examples 1-6 and the iron oxide desulfurizer of examples 1-2 were used as catalysts for CO shift reaction, and activity tests were performed as follows:
the composition of the raw material gas is 15 vol% CO and 55 vol% H2、6vol％CO2、24vol％N2And the reaction steam-gas ratio is 1: 1, the airspeed is 4000h-1The catalyst activity test temperature zone is 250-450 ℃;
the activity of the catalyst is expressed in terms of CO conversion and is calculated as follows:
CO conversion rate (1-V)CO'/VCO)/(1+VCO)×100％
Wherein, VCO'Is the volume percent of CO in the reactor off-gas, VCOIs the volume percentage of CO in the raw material gas;
The corresponding test results are shown in table 1 below:
TABLE 1 CO conversion at different test temperatures
From table 1 it can be seen that: the waste iron oxide desulfurizer adopted by the application can effectively catalyze the CO to generate a change reaction and improve the conversion rate of CO as a CO conversion catalyst after being regenerated.
22. The waste desulfurizer containing ferric oxide is regenerated and used as a CO shift catalyst.
Example 1 (Tail gas)
The embodiment of the invention provides a waste agent of a desulfurizer containing ferric oxide, wherein in the desulfurizer containing ferric oxide, CuO is 8g, ferric salt complexing agent triethanolamine is 9g, and amorphous Fe2O3 15g，MnO2Is 8 g;
the desulfurization process of the tail gas generated after the catalyst is used for hydrogenation upgrading of medium and low temperature coal tar in industry is as follows:
1) collecting tail gas generated after the medium and low temperature coal tar is subjected to hydrogenation catalysis by a fixed bed;
2) the desulfurizer of the embodiment is prepared into columnar catalyst particles with the diameter of 1mm and the length of 15mm, and the columnar catalyst particles are filled in a desulfurizing tower to form a desulfurization layer;
3) the tail gas is treated for 2000h-1The air speed of the desulfurizer passes through the desulfurization layer, and the air speed and the desulfurizer in the desulfurization layer are subjected to desulfurization reaction at 50 ℃, so that hydrogen sulfide in tail gas is removed, after the reaction is finished, the waste agent of the reacted desulfurizer is taken out, and the waste agent is cooled to room temperature, so that the waste agent of the desulfurizer containing ferric oxide is obtained;
The method for regenerating the waste agent of the desulfurizer containing the ferric oxide comprises the following steps:
1) stirring the waste agent and an aqueous solution of sodium hydroxide in a slurry tank to prepare slurry, and maintaining the pH value of the slurry to be 8.0, wherein the solid content of the slurry is 4 wt%;
2) introducing air into the slurry, and carrying out oxidation reaction at 90 ℃ and 0.1MPa to carry out oxidation regeneration;
3) then introducing hydrogen sulfide into the oxidized slurry, and carrying out a vulcanization reaction at 10 ℃ and 5 MPa;
4) introducing air into the vulcanized slurry, and carrying out oxidation reaction at 90 ℃ and 0.1MPa to carry out oxidation regeneration;
5) repeating the steps 3) and 4) twice to enable the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction to be 1: 4.5;
6) and carrying out solid-liquid separation on the slurry after the oxidation reaction to obtain a regenerated product of the waste agent.
Example 2 (pyrolysis of coal gas)
The embodiment of the invention provides a waste agent of a desulfurizer containing iron oxide, wherein in the desulfurizer containing the iron oxide, 10g of calcium bicarbonate, 12g of basic copper carbonate and gamma-Fe are contained2O3 18g，MnO28g of NiO and 5g of NiO;
the desulfurization process of the coal pyrolysis gas containing hydrogen sulfide by the catalyst is as follows:
(1) cooling the compressed coal pyrolysis gas to 30-35 ℃, mixing the coal pyrolysis gas with air from an air pump, feeding the mixture into a desulfurizing tower filled with the desulfurizer containing the ferric oxide, and adopting a flow of feeding the mixture from bottom to top to avoid that liquid water enters a desulfurizer bed layer to remove hydrogen sulfide;
(2) The desulfurizer is used for many times to form a waste agent, and the waste agent is taken out from a desulfurizer bed layer, namely the waste agent of the desulfurizer containing the ferric oxide in the application.
The method for regenerating the waste desulfurizer containing the ferric oxide comprises the following steps:
1) dispersing the waste agent in water to form slurry;
2) heating the slurry to 60 ℃ under normal pressure, adding hydrogen peroxide into the slurry by using a peristaltic pump, controlling the flow to be 500mL/min, and magnetically stirring to promote the reaction for 10 min;
3) after the reaction is finished, filtering the reaction liquid, washing the obtained precipitate for 2 times by using water, and naturally drying to obtain the regenerant of the waste agent.
Example 3 (oil)
The embodiment of the invention provides a waste agent of a desulfurizer containing ferric oxide, wherein in the desulfurizer containing ferric oxide, 50g of cubic system ferroferric oxide, 12g of calcium sulfate dihydrate, 20g of basic zinc carbonate and 6g of sodium carboxymethylcellulose are contained;
the catalyst is used for desulfurizing petroleum containing hydrogen sulfide, and the operation steps are as follows:
(1) the desulfurizer of the embodiment is prepared into catalyst particles with the diameter of 1.5mm, and the catalyst particles are filled in a desulfurizing tower to form a desulfurizing layer;
(2) Spraying petroleum containing hydrogen sulfide into a desulfurization layer from the top of a desulfurization tower through a nozzle, leaching and desulfurizing, and collecting desulfurized waste desulfurizer, namely the waste desulfurizer containing iron oxide in the application;
the method for regenerating the waste agent of the desulfurizer containing the ferric oxide comprises the following steps:
1) stirring the waste agent and water in a slurry tank to prepare slurry, wherein the solid content of the slurry is 12 wt%;
2) introducing sodium hypochlorite into the slurry, and carrying out oxidation reaction at 60 ℃ and 1MPa to carry out oxidation regeneration;
3) adding Na into the oxidized slurry2S, carrying out a vulcanization reaction at 10 ℃ and 5 MPa;
4) introducing hydrogen peroxide into the vulcanized slurry, and carrying out oxidation reaction at 30 ℃ and 1.1MPa to carry out oxidation regeneration;
5) repeating the steps 3) and 4) for four times to ensure that the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction is 1: 5;
6) and carrying out solid-liquid separation on the slurry after the oxidation reaction to obtain a regenerated product of the waste agent.
Example 4 (gas field water)
The embodiment of the invention provides a waste agent of a desulfurizer containing ferric oxide, wherein amorphous Fe in the desulfurizer containing the ferric oxide 2O3.H230g of O, 15g of polymeric ferric sulfate, 12g of basic copper carbonate and 6g of sodium carboxymethyl cellulose, and amorphous Fe2O3 8g；
The desulfurization process of the catalyst for gas field water comprises the following operation steps:
loading the catalyst into a fixed bed reactor to make it contain H2And (2) carrying out full contact reaction on the gas field water of the S and the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h-1The waste catalyst after gas field water desulfurization is the waste desulfurizer containing the ferric oxide;
the method for regenerating the waste desulfurizer containing the ferric oxide comprises the following steps:
1) washing the waste agent with water, and carrying out water-carrying grinding in a wet ball mill to obtain particles of 200 meshes to obtain waste agent powder;
2) preparing the waste agent powder into a water suspension with the solid mass percentage of 7%, and introducing compressed air for reaction;
3) filtering the water suspension after reaction, putting the solid material into a flotation tank, adding water, then introducing air, and drying the sediment at the lower part of the container to obtain the regeneration of the waste agent.
Example 5 (exhaust gas)
The embodiment of the invention provides a waste agent of a desulfurizer containing ferric oxide, wherein in the desulfurizer containing ferric oxide, 12g of cubic system ferroferric oxide and amorphous Fe 2O324g of amorphous Fe2O3.H2O39 g and NiO are 5 g;
the catalyst removes H in the exhaust gas2The process of S comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2When the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section as a catalyst for CO conversion reaction;
the method for regenerating the waste agent of the desulfurizer containing the ferric oxide comprises the following steps:
1) dispersing the waste agent in water to form slurry;
2) heating the slurry to 45 ℃ at normal pressure, adding hydrogen peroxide into the slurry by using a peristaltic pump, introducing air, controlling the flow rate of the hydrogen peroxide to be 500mL/min and the air flow to be 100mL/min, and magnetically stirring to promote the reaction for 5 min;
3) after the reaction is finished, filtering the reaction liquid, washing the obtained precipitate for 3 times by using water, and naturally drying to obtain the regenerant of the waste agent.
Example 6 (Coke oven gas)
The embodiment of the invention provides a waste agent of a desulfurizer containing ferric oxide, wherein gamma-Fe in the desulfurizer containing the ferric oxide2O323g of amorphous Fe2O324g of amorphous Fe 2O3.H2O is 42g and MnO is 8 g;
the desulfurization process of the catalyst for the coke oven gas containing the hydrogen sulfide comprises the following operation steps:
mixing the desulfurizer with water to prepare desulfurizer slurry, wherein the total concentration of iron oxyhydroxide in the desulfurizer slurry is 10 wt%, introducing deaminated coke oven gas into a desulfurization tower from the bottom, the temperature of the tower kettle of the desulfurization tower is 30 ℃, spraying the desulfurizer on the top of the desulfurization tower through a nozzle to carry out leaching desulfurization on the coke oven gas, collecting desulfurized waste liquid, and drying to obtain the waste agent of the desulfurizer containing iron oxide;
the method for regenerating the waste agent of the desulfurizer containing the ferric oxide comprises the following steps:
1) stirring the waste agent and an aqueous solution of potassium hydroxide in a slurry tank to prepare slurry, and maintaining the pH value of the slurry to be 8.0, wherein the solid content of the slurry is 4 wt%;
2) introducing O-containing gas into the slurry2And O3Mixing the gases, and carrying out oxidation reaction at 50 ℃ and 1MPa to carry out oxidation regeneration;
3) then introducing hydrogen sulfide into the oxidized slurry, and carrying out a vulcanization reaction at 10 ℃ and 5 MPa;
4) introducing air into the vulcanized slurry, and carrying out oxidation reaction at 90 ℃ and 0.1MPa to carry out oxidation regeneration;
5) Repeating the steps 3) and 4) for three times to ensure that the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction is 1: 4.9;
6) and carrying out solid-liquid separation on the slurry after the oxidation reaction to obtain a regenerated product of the waste agent.
Comparative example 1
This comparative example provides an iron oxide-containing desulfurizing agent, which is the same as that of example 1, wherein the iron oxide-containing desulfurizing agent contains 8g of CuO, 9g of triethanolamine, which is an iron salt complexing agent, and amorphous Fe2O3 15g，MnO2Was 8 g.
Comparative example 2
This comparative example provides a desulfurizing agent containing iron oxide, which is the same as that of example 5, in which 12g of cubic system ferroferric oxide and amorphous Fe were contained in the desulfurizing agent containing iron oxide2O324g of amorphous Fe2O3.H2O39 g and NiO were 5 g.
Example 7 (use of waste agent of desulfurizing agent)
The regenerated waste agents of the desulfurizing agents collected in the above examples 1 to 6 and the iron oxide-containing desulfurizing agents of comparative examples 1 to 2 were used as catalysts for CO shift reaction, and the activity tests of the catalysts were as follows:
the composition of the raw material gas is 15 vol% CO and 55 vol% H 2、6vol％CO2、24vol％N2And the reaction steam-gas ratio is 1: 1The space velocity is 4000h-1The temperature zone for testing the activity of the catalyst is 250-450 ℃;
the activity of the catalyst is expressed in terms of CO conversion and is calculated as follows:
CO conversion ═ 1-VCO'/VCO)/(1+VCO)×100％
Wherein, VCO'Is the volume percent of CO in the reactor off-gas, VCOIs the volume percentage of CO in the raw material gas;
the corresponding test results are shown in table 1 below:
TABLE 1 CO conversion at different test temperatures
From table 1 it can be seen that: the waste agent of the desulfurizer containing the ferric oxide is regenerated and used as the CO transformation catalyst, so that the CO can be effectively catalyzed to generate a change reaction, and the conversion rate of the CO is improved.
23. Use of a spent agent or spent agent regenerant of a desulfurization agent containing iron oxide in an organic matter conversion process.
Example 1
The embodiment provides a co-conversion process of biomass and hogwash oil, which comprises the following steps:
pretreatment of biomass:
the method comprises the steps of taking rice straws and reed straws as biomass solids, feeding the rice straws and the reed straws with the water content of 4% by the total weight of the biomass into a superfine pulverizer for primary pulverization, compressing the rice straws and the reed straws in a briquetting machine at the temperature of 30 ℃ and under the pressure of 3MPa, and carrying out extrusion molding until the bulk density is 0.8g/cm 3OfThen, performing secondary crushing, wherein the average particle size after the secondary crushing is 3mm for later use;
catalyst:
the catalyst is a regenerant of a waste agent of a desulfurizer containing iron oxide, wherein in the desulfurizer containing the iron oxide, CuO is 8g, ferric salt complexing agent triethanolamine is 9g, and amorphous Fe2O3 15g，MnO2Is 8 g;
the catalyst is used for the desulfurization process of tail gas generated after the medium-low temperature coal tar in industry is hydrogenated and upgraded as follows:
1) collecting tail gas generated after the medium and low temperature coal tar is subjected to fixed bed hydrogenation catalysis;
2) the desulfurizer of the embodiment is prepared into columnar catalyst particles with the diameter of 1mm and the length of 15mm, and the columnar catalyst particles are filled in a desulfurizing tower to form a desulfurization layer;
3) the tail gas is treated for 2000h-1The air speed of the desulfurizer passes through the desulfurization layer, and the air speed and the desulfurizer in the desulfurization layer are subjected to desulfurization reaction at 50 ℃, so that hydrogen sulfide in tail gas is removed, after the reaction is finished, the waste agent of the reacted desulfurizer is taken out, and the waste agent is cooled to room temperature, so that the waste agent of the desulfurizer containing ferric oxide is obtained;
the method for regenerating the waste desulfurizer containing the ferric oxide comprises the following steps:
1) dispersing the waste agent with weak acid water (containing dilute sulfuric acid) with pH of 4.0, wherein the solid-to-liquid ratio of the waste agent of the iron oxide desulfurizer to the weak acid water is 1: 4(g/ml), and the dispersion time is 30min to obtain a dispersion liquid;
2) Heating the dispersion liquid to 60 ℃ under normal pressure, adding hydrogen peroxide into the dispersion liquid by using a peristaltic pump, controlling the flow to be 500mL/min, controlling the molar ratio of the hydrogen peroxide to sulfur elements in the waste agent of the iron oxide desulfurizer to be 5: 1, carrying out magnetic stirring to promote reaction, and rapidly transferring generated sulfur dioxide gas by vacuumizing during the reaction for 10 min;
3) after the reaction is finished, filtering the reaction solution, washing the obtained precipitate with water for 2 times, then drying at 100 ℃ to obtain a regeneration substance of the waste agent, and returning the filtrate obtained by filtering to the dispersion process to be used as weak acid water for recycling;
preparing biomass slurry:
mixing the pretreated biomass, sulfur and the catalyst to obtain a mixture, adding the mixture into hogwash oil, stirring, grinding and pulping to form slurry, detecting, wherein the total content of rice straws and reed straws in the slurry is 60 wt%, the molar ratio of iron element to sulfur element is 1:5, the viscosity of the slurry is 500mPa & (50 ℃), the content of the catalyst in the slurry is 5 wt%, and the average particle size of the added catalyst is 5 micrometers;
and (3) conversion reaction:
reacting CO with H2Mixed gas (CO accounts for 60% and H) 240 percent) of the mixture is pressurized to 21MPa and heated to 350 ℃, then the mixture is introduced into a pipeline for conveying the slurry, the rest of the mixture is pressurized to 21MPa and heated to 500 ℃, the mixture is injected into a slurry bed reactor from an inlet of the slurry bed reactor and undergoes cracking, carbonylation, transformation and hydrogenation reaction with the slurry entering the slurry, the reaction pressure of the conversion reaction is controlled to be 20MPa, the reaction temperature is controlled to be 360 ℃, the reaction time is 65min, and CO and H are reacted with each other2The volume ratio of the mixed gas to the slurry is 3000: 1, preparing an oil product.
Example 2
The embodiment provides a biomass and palm oil co-transformation process, which comprises the following steps:
pretreatment of biomass:
wheat straw and corn straw are used as biomass solid, the water content of the biomass is 10% based on the total weight of the biomass, the wheat straw and the corn straw are sent into a superfine pulverizer for primary pulverization, the median particle size after primary pulverization is 300 mu m, then the wheat straw and the corn straw after primary pulverization are sent into a briquetting machine for compression and extrusion molding at the temperature of 60 ℃ and the pressure of 0.5MPa until the bulk density is 0.9g/cm3Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 5mm for later use;
Catalyst:
the catalyst is a waste agent of a desulfurizer using iron oxide as an active component, wherein in the desulfurizer using the iron oxide as the active component, 10g of calcium bicarbonate, 12g of basic copper carbonate and gamma-Fe are contained2O3 18g，MnO28g and 5g of NiO;
the desulfurization process of the desulfurizing agent using iron oxide as an active component is summarized as follows:
1) collecting tail gas generated after the medium and low temperature coal tar is subjected to fixed bed hydrogenation catalysis;
2) the desulfurizer of the embodiment is prepared into columnar catalyst particles with the diameter of 1mm and the length of 15mm, and the columnar catalyst particles are filled in a desulfurizing tower to form a desulfurization layer;
3) the tail gas is treated for 2000h-1The air speed of the catalyst passes through the desulfurization layer, and the air speed and a desulfurizer in the desulfurization layer are subjected to desulfurization reaction at 50 ℃, so that hydrogen sulfide in tail gas is removed, after the reaction is finished, a waste agent of the reacted desulfurizer is taken out, and the waste agent is cooled to room temperature, so that the waste agent of the desulfurizer which takes iron oxide as an active component is obtained;
preparing biomass slurry:
mixing the pretreated biomass, sulfur and the catalyst to obtain a mixture, adding the mixture into palm oil, stirring and dispersing for pulping to form slurry, detecting that the total content of wheat straws and corn straws in the slurry is 50 wt%, the molar ratio of iron element to sulfur element is 1:1, the viscosity of the slurry is 1400mPa & (50 ℃), wherein the content of the catalyst in the slurry is 1 wt%, and the average particle size of the added catalyst is 10 microns;
And (3) conversion reaction:
reacting CO with H2Mixed gas (CO 60% and H)240 percent) of the slurry is pressurized to 16MPa and heated to 400 ℃, then the slurry is introduced into a pipeline for conveying the slurry, the rest of the slurry is pressurized to 16MPa and heated to 520 ℃, then the slurry is injected into a suspension bed reactor from a reaction inlet of the suspension bed, and the slurry entering the suspension bed reactor undergo cracking, carbonylation, transformation and hydrogenation reactions, and the conversion reaction is controlledThe reaction pressure is 15MPa, the reaction temperature is 420 ℃, the reaction time is 30min, and the CO and the H are reacted2The volume ratio of the mixed gas to the slurry is 2000: 1, preparing an oil product.
Example 3
The embodiment provides a co-transformation process of biomass and rapeseed oil, which comprises the following steps:
pretreatment of biomass:
wood chips and soybean straws are used as biomass solid, the water content of the biomass is 2% based on the total weight of the biomass, the wood chips and the soybean straws are fed into a superfine pulverizer to be primarily pulverized, the median particle size after primary pulverization is 150 mu m, and then the wood chips and the soybean straws after primary pulverization are fed into a briquetting machine to be compressed and extruded and molded at the temperature of 50 ℃ and under the pressure of 1MPa until the bulk density is 1g/cm3Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 4mm for later use;
Catalyst:
the catalyst is a regeneration product of a waste agent of a desulfurizer taking ferric oxide as an active component, wherein in the desulfurizer taking ferric oxide as the active component, 50g of cubic system ferroferric oxide, 12g of calcium sulfate dihydrate, 20g of basic zinc carbonate and 6g of sodium carboxymethylcellulose are contained;
the catalyst is used for desulfurizing petroleum containing hydrogen sulfide, and the operation steps are as follows:
(1) the desulfurizer of the embodiment is prepared into catalyst particles with the diameter of 1.5mm, and the catalyst particles are filled in a desulfurization tower to form a desulfurization layer;
(2) spraying petroleum containing hydrogen sulfide into a desulfurization layer from the top of a desulfurization tower through a nozzle, leaching and desulfurizing, and collecting desulfurized waste desulfurizer, namely the waste desulfurizer containing iron oxide in the application;
the method for regenerating the waste agent of the desulfurizer containing the ferric oxide comprises the following steps:
1) stirring the waste agent and water in a slurry tank to prepare slurry, wherein the solid content of the slurry is 12 wt%;
2) introducing sodium hypochlorite into the slurry, and carrying out oxidation reaction at 60 ℃ and 1MPa to carry out oxidation regeneration;
3) adding Na into the oxidized slurry2S, carrying out a vulcanization reaction at 10 ℃ and 5 MPa;
4) Introducing hydrogen peroxide into the vulcanized slurry, and carrying out oxidation reaction at 30 ℃ and 1.1MPa to carry out oxidation regeneration;
5) repeating the steps 3) and 4) once to enable the molar ratio of the iron element to the sulfur element in the slurry after the oxidation reaction to be 1: 1.8;
6) carrying out solid-liquid separation on the slurry after the oxidation reaction to obtain a regenerated product of the waste agent;
preparing biomass slurry:
mixing the pretreated biomass, sulfur and the catalyst to obtain a mixture, adding the mixture into rapeseed oil, shearing and pulping to form slurry, detecting that the total content of wood chips and soybean straws in the slurry is 40 wt%, the molar ratio of iron element to sulfur element is 1:2, the viscosity of the slurry is 1000mPa ≤ (50 ℃), the content of regenerants of waste agents of the desulfurizing agent with iron oxide as an active component in the slurry is 2 wt%, and the average particle size of the regenerants of the waste agents of the added desulfurizing agent with iron oxide as an active component is 400 μm;
and (3) conversion reaction:
pressurizing synthesis gas (wherein the volume ratio of CO is 20%) to 18.2MPa, heating to 450 ℃, injecting the synthesis gas into the bubbling bed reactor through 4 injection ports on the side wall and the bottom of the bubbling bed reactor, and carrying out cracking, carbonylation, transformation and hydrogenation reactions with the slurry entering the bubbling bed reactor, wherein the reaction pressure of the conversion reaction is controlled to be 18MPa, the reaction temperature is 380 ℃, the reaction time is 100min, and the volume ratio of the synthesis gas to the slurry is 950: 1, preparing an oil product.
Example 4
The embodiment provides a biomass liquefaction process, which comprises the following steps:
pretreatment of biomass:
taking rice straws and broad bean straws as biomass solids, taking the total weight of the biomass as the water content of the biomass, feeding the rice straws and the broad bean straws into a superfine pulverizer for primary pulverization, wherein the median particle size after the primary pulverization is 100 mu m, then feeding the rice straws and the broad bean straws after the primary pulverization into a briquetting machine for compression at the temperature of 30 ℃ and under the pressure of 0.5MPa, and carrying out extrusion molding until the bulk density is 1.0g/cm3Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 1mm for later use;
catalyst:
the catalyst is a regeneration product of a waste agent of a desulfurizer taking ferric oxide as an active component, wherein in the desulfurizer taking ferric oxide as the active component, 12g of cubic system ferroferric oxide and amorphous Fe2O324g of amorphous Fe2O3.H25g of O39 g and NiO;
the desulfurizer removes H in the waste gas2The matrix process of S comprises the following steps: h is to be2The S content is 5500mg/cm3Is used for 3000h-1Is introduced into a desulfurization section to carry out desulfurization reaction at the temperature of 30 ℃, and H in the outlet gas of the desulfurization section2When the content of S is less than or equal to 0.01ppm, collecting the waste in the desulfurization section;
The method for regenerating the waste agent of the desulfurizer by using the ferric oxide as the active component comprises the following steps:
the regeneration method of the waste agent comprises the following steps:
1) washing the waste agent with water, and carrying out water-carrying grinding in a wet ball mill to obtain particles of 200 meshes to obtain waste agent powder;
2) preparing the waste agent powder into a water suspension with the solid mass percentage of 7%, and introducing compressed air for reaction;
3) filtering the water suspension after reaction, putting the solid material into a flotation tank, adding water, introducing air, and drying precipitates at the lower part of a container to obtain the regenerated substance of the waste agent;
preparing biomass slurry:
mixing the pretreated biomass, carbon disulfide and the catalyst to obtain a mixture, adding the mixture into coal tar to disperse and pulp, forming slurry, detecting that the total content of rice straws and broad bean straws in the slurry is 55 wt%, the molar ratio of iron element to sulfur element is 1:0.9, the viscosity of the slurry is 510mPa ≤ (50 ℃), the content of the catalyst in the slurry is 0.2 wt%, and the average particle size of the added catalyst is 2 μm;
and (3) conversion reaction:
reacting CO with H2Mixed gas (CO accounts for 60% and H) 240 percent) of the total amount of the components, pressurizing to 20.4MPa, heating to 500 ℃, injecting the mixture into the slurry bed reactor through 3 injection ports on the side wall of the slurry bed reactor, carrying out cracking, carbonylation, transformation and hydrogenation reactions with the slurry entering the slurry bed reactor, controlling the reaction pressure to be 20MPa, the reaction temperature to be 410 ℃, and the reaction time to be 110min, wherein the CO and the H are mixed2The volume ratio of the mixed gas to the slurry is 650: 1, preparing an oil product.
Example 5
The embodiment provides a co-conversion process of biomass and petroleum-based wax oil, which comprises the following steps:
pretreatment of biomass:
the method comprises the steps of taking cotton straws as biomass solid, enabling the water content of the biomass to be 1% based on the total weight of the biomass, sending the cotton straws into a superfine pulverizer to be primarily pulverized, enabling the median particle size after primary pulverization to be 200 mu m, then sending the primarily pulverized cotton straws into a plodder to be compressed and extruded and molded at the temperature of 40 ℃ and under the pressure of 2MPa until the bulk density of the cotton straws is 0.9g/cm3Then, performing secondary crushing, wherein the average particle size after the secondary crushing is 1mm for later use;
catalyst:
the catalyst is a waste agent of a desulfurizer containing ferric oxide, and amorphous Fe in the desulfurizer containing ferric oxide 2O3.H2O30 g, poly15g of iron sulfate, 12g of basic copper carbonate and 6g of sodium carboxymethyl cellulose, and amorphous Fe2O3 8g；
The desulfurization process of the catalyst for gas field water comprises the following operation steps:
loading the catalyst into a fixed bed reactor to make it contain H2And (3) carrying out full contact reaction on the gas field water of the S with the gas field water, wherein the contact conditions are as follows: the temperature is 35 ℃, the pressure is 0.2MPa and the volume space velocity is 10000h-1The waste catalyst after gas field water desulfurization is the waste desulfurizer containing iron oxide.
Preparing biomass slurry:
mixing the pretreated biomass with the catalyst to obtain a mixture, adding the mixture into petroleum-based wax oil to disperse and pulp to form slurry, detecting that the total content of cotton straws in the slurry is 50 wt%, the viscosity of the slurry is 400mPa ℃, (50 ℃), wherein the content of the catalyst in the slurry is 1 wt%, and the average particle size of the added catalyst is 10 μm;
and (3) conversion reaction:
reacting CO with H2Mixed gas (CO accounts for 60% and H)240 percent) of the mixture is pressurized to 17MPa and heated to 250 ℃, then the mixture is introduced into a pipeline for conveying the slurry, the rest of the mixture is pressurized to 17MPa and heated to 550 ℃, then the mixture is injected into the fluidized bed reactor from the inlet of the fluidized bed reactor, and hydrogen sulfide is introduced into the fluidized bed reactor until the molar ratio of iron element to sulfur element in the reaction system is 1: 2, carrying out cracking, carbonylation, transformation and hydrogenation reactions with the slurry entering the reactor, controlling the reaction pressure of the conversion reaction to be 16MPa, the reaction temperature to be 420 ℃, the reaction time to be 40min, and reacting the CO and the H for 40min 2The volume ratio of the mixed gas to the slurry is 1000: 1, preparing an oil product.
Example 6
The embodiment provides a co-conversion process of biomass and rapeseed oil, which is the same as the embodiment 3, and the only difference is that the regeneration method of the waste agent of the desulfurizer containing iron oxide in the embodiment comprises the following steps: 1) introducing water vapor with the pressure of 1.5MPa into a heating furnace, and heating the water vapor to 450 ℃;
2) introducing the heated water vapor into a desulfurization tank containing the waste agent at the speed of 15m/s, and heating the waste agent;
3) ensuring that the bed layer temperature of the waste agent is heated to above 400 ℃ by water vapor and runs for 2 hours, wherein the steam consumption is 6 t/h;
4) analyzing the pH value of the outlet of the desulfurization tank, and introducing a small amount of coke oven gas into the desulfurization tank for reduction when the pH value is more than or equal to 7.5 for 3 times continuously;
5) introducing coke oven gas subjected to primary hydrogenation in the fine desulfurization process to reduce the iron oxide desulfurizer waste agent at 800m 3/h;
6) analyzing the concentration change of the inlet and outlet H2 every 30min after introducing the coke oven gas, and obtaining the regenerant after the concentration of the outlet H2 is stably more than or equal to the concentration of the inlet H2 (3 times of analysis).
Comparative example 1
This comparative example provides a biomass and rapeseed oil co-conversion process, which is the same as example 3, except that: in the comparative example, the wood chips and the soybean straws are taken as biomass solids, and the water content of the biomass is 80ppm based on the total weight of the biomass; the molar ratio of the iron element to the sulfur element in the reaction system is 1: 0.1.
Test example 1
The distribution of the products prepared using the processes of examples 1-6 of the present invention was compared to comparative example 1 and the products were tested as follows:
the percent solid organic matter conversion is (the total mass of solid organic matter in the raw material-the mass of solid organic matter remaining in the reaction product)/the total mass of solid organic matter in the raw material, and the solid organic matter in the percent solid organic matter conversion refers to anhydrous and ashless groups (the same applies hereinafter);
the yield percent of the solid organic matter converted oil is the mass of the liquid phase oil product at normal temperature and normal pressure in the product converted from the solid organic matter/the total feeding mass of the solid organic matter in the raw material;
the reaction water yield = (mass of water of reaction product-total mass of water initially added in the reaction or carried in by raw material)/total mass of raw material fed. When this value is < 0, it is marked as "none";
the corresponding test results are shown in table 1:
table 1 comparison of conversion effect of solid organic matter
From table 1 it can be seen that: the reaction water generation rate of the conversion process is not more than 1.6 wt%; in the conventional hydrogenation process under pure hydrogen in the prior art, the water yield generated by the reaction is more than 25 wt%.
24. The waste agent of hydrogenation catalyst using Ni-Mo as main active component is used as CO conversion catalyst.
Example 1
The embodiment provides a waste agent of a hydrogenation catalyst with Ni-Mo as a main active ingredient, wherein in the hydrogenation catalyst with Ni-Mo as the main active ingredient, MoO is calculated by the total weight of the hydrogenation catalyst3 30％，NiO 7％，TiO23％，P2O52.5 percent, and the balance being gamma-Al2O3；
The above hydrogenation catalyst is used for hydrogenation of cracked diesel oil, wherein the density (d) of the cracked diesel oil4 20) Is 0.893g/cm3The sulfur content is: 6154 μ g/g, nitrogen content: 1035 mu g/g, 49.0 ℃ of aniline point, 35.8 of cetane number and 171-362 ℃ of distillation range;
the corresponding hydrogenation process is as follows: 100g of catalyst is loaded into a fixed bed, hydrogen is introduced, the system pressure is adjusted to be 6.0MPa, the hydrogen amount is 800ml/min, the reactor is heated to 120 ℃ at the heating rate of 35 ℃/h, and the temperature is kept constant for 2 hours to dehydrate the catalyst. And (3) pumping pre-vulcanized oil after dehydration is finished: the pre-vulcanized oil is aviation kerosene added with 3 percent of carbon disulfide, and the feeding speed is 100 ml/h. Then raising the temperature of the reactor to 200 ℃, 240 ℃, 280 ℃ and 320 ℃ at the heating rate of 40 ℃/h, and keeping the temperature at each temperature point for 1 hour; finally, the temperature is increased to 340 ℃ and kept for 12 hours,after the pre-vulcanization is finished, the raw oil of the cracked diesel oil is pumped in, and the temperature is 350 ℃, the pressure is 6.0MPa and the liquid airspeed is 1.0h -1The hydrogenation is carried out at a hydrogen-oil volume ratio of 480V/V, and after the hydrogenation is finished, a waste agent, namely the waste agent of the hydrogenation catalyst taking Ni-Mo as a main active component in the embodiment, is collected.
Example 2
The embodiment provides a waste agent of a hydrogenation catalyst with Ni-Mo as a main active ingredient, wherein in the hydrogenation catalyst with Ni-Mo as the main active ingredient, MoO is calculated by the total weight of the hydrogenation catalyst330 percent of NiO, 10 percent of carboxymethyl cellulose, 1.5 percent of chromium, 5 percent of tungsten oxide and the balance of silicon oxide/aluminum oxide composite carrier;
the hydrogenation catalyst is used for hydrogenation of petroleum resin, and the corresponding hydrogenation process is as follows: a fixed bed reactor with the catalyst loading of 50-100ml is adopted, firstly, a hydrogenation catalyst with Ni-Mo as a main active component is crushed, 50ml of the catalyst with the granularity of about 1mm is taken to be loaded into the reactor, petroleum resin solution (the petroleum resin content is 40%) dissolved by a solvent and hydrogen (the hydrogen purity is more than 90%) are conveyed to the reactor from the top together through a pump, and hydrogenation reaction is carried out through a catalyst bed layer. The hydrogen pressure of the catalytic reaction is 10.0Mpa, the reaction temperature is 260 ℃, and the mass space velocity of the petroleum resin is 0.3g/h -1The volume ratio (hydrogen-oil ratio) of hydrogen to resin is 1000, and after the hydrogenation is finished, the waste agent, that is, the waste agent of the hydrogenation catalyst in this embodiment, which uses Ni — Mo as the main active component, is collected.
Example 3
The embodiment provides a waste agent of a hydrogenation catalyst with Ni-Mo as a main active component, wherein in the hydrogenation catalyst with Ni-Mo as a main active component, MoO is calculated by the total weight of the hydrogenation catalyst310 percent of NiO, 40 percent of chromium, 1.5 percent of chromium, 6 percent of amorphous silicon-aluminum, 2 percent of zeolite, 5 percent of dichromium trioxide, 1.3 percent of zirconium and the balance of titanium dioxide;
the hydrogenation catalyst is used for hydrogenation of inferior oil-residual oil, and the corresponding hydrogenation process is as follows:
1) firstly, carrying out fluidized treatment on a hydrogenation catalyst taking Ni-Mo as a main active component at 250 ℃ for 30min to obtain a fluidized hydrogenation catalyst;
2) then 60g of inferior oil-residual oil (used as raw oil), 1.85g of the fluidized hydrogenation catalyst and 0.586g of sublimed sulfur are uniformly stirred in a high-speed homogenizer to obtain a mixture;
3) then, 44g of the mixture is added into a high-pressure reaction kettle, hydrogen is firstly introduced into the high-pressure reaction kettle, the pressure in the kettle reaches 24MPa, leakage detection is carried out, and air in the kettle is discharged; then filling hydrogen to make the interior of the reactor reach initial hydrogen pressure of 12.5MPa, raising temperature to 450 deg.C, stirring at stirring speed of 500r/min for 90min, stopping heating and stirring, quickly cooling the interior of the reactor to room temperature by adopting water-cooling mode to terminate reaction, after the hydrogenation is completed, collecting waste agent, namely waste agent of hydrogenation catalyst using Ni-Mo as main active component in said embodiment.
Example 4
The embodiment provides a waste agent of a hydrogenation catalyst with Ni-Mo as a main active ingredient, wherein in the hydrogenation catalyst with Ni-Mo as the main active ingredient, MoO is calculated by the total weight of the hydrogenation catalyst350 percent of NiO, 10 percent of tungsten, 3 percent of molecular sieve, 2 percent of boron, 2 percent of tungsten oxide, 5 percent of chromic oxide, 1.3 percent of zirconium and the balance of activated carbon;
the hydrogenation catalyst is used for hydrogenation of low-temperature coal tar, and the corresponding hydrogenation process is as follows:
(1) fractionating and cutting 1kg of coal tar by adopting a real boiling point distiller to obtain a first component and a heavy component, wherein the cutting temperature of the fractionation and cutting is 300 ℃; the content of heavy components was 60% by weight based on the total amount of coal tar as a raw material;
(2) mixing the recombinant obtained in the step (1) with n-pentane according to the ratio of 1: 6, and extracting and separating to obtain an extract phase and a raffinate phase. Wherein, the extraction conditions comprise: the temperature was 50 ℃ and the pressure was atmospheric pressure. Carrying out normal pressure fractionation on the obtained extract phase, and separating out n-pentane to obtain deasphalted oil;
(3) the deasphalted oil obtained in the step (2) and the second deasphalted oil obtained in the step (1) are used as hydrogenation raw materialsOne component is fed into a 200mL fixed bed reactor (the fixed bed reactor is filled with a hydrogenation catalyst taking Ni-Mo as a main active component) to carry out a hydrogenation process; wherein the loading of the hydrocracking catalyst is 100 mL. The hydrogen partial pressure in the fixed bed reactor was 14.7MPa (in absolute pressure) and the hydrogen-oil volume ratio was 1500; the average temperature in the hydrofinishing catalyst bed was 390 ℃, and the average temperature in the hydrocracking catalyst bed was 400 ℃; the weight hourly space velocity of the hydrogenation raw materials in the fixed bed reactor is 0.15h -1. After the hydrogenation is finished, collecting the waste agent, namely the waste agent of the hydrogenation catalyst taking Ni-Mo as the main active component in the embodiment.
Example 5
The embodiment provides a waste agent of a hydrogenation catalyst with Ni-Mo as a main active ingredient, wherein in the hydrogenation catalyst with Ni-Mo as the main active ingredient, MoO is calculated by the total weight of the hydrogenation catalyst310 percent of NiO, 35 percent of palladium, 3 percent of tungsten, 5 percent of manganese, 2 percent of cobalt oxide, 2 percent of tungsten oxide, 5 percent of chromium oxide, 1.3 percent of zirconium and the balance of activated carbon;
the hydrogenation catalyst is used for hydrogenation of atmospheric residue, and the corresponding hydrogenation process is as follows: the upper part of the reactor is filled with a single-tube fixed bed upflow residual oil hydrogenation reactor
300ml of spherical hydrogenation catalyst taking Ni-Mo as a main active component; bottom loading
50ml of ceramic ring filler; a residual oil feeding distribution area is arranged between the catalyst bed layer and the packing layer, 150 ℃ raw material residual oil and hydrogen enter a reactor at the position, and the raw material is selected from the atmospheric residual oil of Saudi Arabia medium crude oil; a residue settling area is arranged below the packing layer, and the reactor adopts a two-section type electric heating constant-temperature salt bath to provide reaction temperature. In the continuous operation, the operating conditions were: in the hydrogenation zone, the average temperature is 388 ℃, the pressure is 14.4Mpa, the volume ratio of hydrogen to the raw material is 800: 1, and the space velocity of the raw material residual oil is 0.55h -1(ii) a In the solvent extraction zone, the solvent is extracted,the total pressure is 14.4Mpa, the average temperature is 365 ℃, and the mass ratio of the agent to the oil is 7: 100. Injecting 7.0 m% (relative to the flow of the residual oil of the raw material) of mixed oil of gasoline and aviation kerosene (the mass ratio of gasoline to diesel oil is 4: 1) along with the raw material, quantitatively discharging 10 m% of residual oil at the bottom of the reactor, and collecting a waste agent after the hydrogenation is finished, wherein the waste agent is the waste agent of the hydrogenation catalyst taking Ni-Mo as the main active component in the embodiment.
Example 6
The embodiment provides a waste agent of a hydrogenation catalyst with Ni-Mo as a main active ingredient, wherein in the hydrogenation catalyst with Ni-Mo as the main active ingredient, MoO is calculated by the total weight of the hydrogenation catalyst323 percent of NiO, 35 percent of zinc, 1.9 percent of zinc, 5.8 percent of phosphorus pentoxide, 11 percent of silicon, 2 percent of cobalt oxide, 2 percent of tungsten oxide, 5 percent of chromium oxide and the balance of a silicon oxide/aluminum oxide composite carrier;
the hydrogenation catalyst is used for residual oil hydrogenation, and the corresponding hydrogenation process is as follows: the residual oil raw material in a raw material tank is pressurized by a pump and then mixed with high-pressure hydrogen to be fed into a fluidized bed reactor filled with a hydrogenation catalyst taking Ni-Mo as a main active ingredient from the bottom of the reactor to keep the catalyst in a boiling state, partial raw materials from the raw material tank and a raw material pump are fully and uniformly mixed with a catalyst aqueous solution in a multistage shearing tank, the mixture enters a liquid phase region without the catalyst of the fluidized bed reactor through a dispersive catalyst delivery pump, and the heavy residual oil raw material entering from the bottom of the reactor is sequentially contacted with the hydrogenation catalyst taking Ni-Mo as the main active ingredient under the specified reaction condition to carry out catalytic hydrogenation reaction, wherein the hydrogenation temperature is 425 ℃, the reaction pressure is 15Mpa, and the liquid hourly volume space velocity is 0.5h -1The volume ratio of hydrogen to oil is 600:1, and after the hydrogenation is finished, collecting the waste agent, namely the waste agent of the hydrogenation catalyst taking Ni-Mo as the main active component in the embodiment.
Example 7 (use of spent hydrogenation catalyst)
The spent hydrogenation catalysts collected in the above examples 1 to 6 and containing Ni-Mo as the main active component were used as catalysts for CO shift reaction, and the activity tests were carried out as follows:
the composition of raw material gas is15vol％CO、55vol％H2、6vol％CO2、24vol％N2And the reaction steam-gas ratio is 1: 1, the airspeed is 4000h-1The catalyst activity test temperature zone is 250-450 ℃;
the activity of the catalyst is expressed in terms of CO conversion and is calculated as follows:
CO conversion rate (1-V)CO'/VCO)/(1+VCO)×100％
Wherein, VCO'Is the volume percent of CO in the reactor off-gas, VCOIs the volume percentage of CO in the raw material gas;
the corresponding test results are shown in table 1 below:
TABLE 1 CO conversion at different test temperatures
From table 1 it can be seen that: the waste agent of the hydrogenation catalyst taking Ni-Mo as the main active component has excellent CO conversion catalytic effect and can effectively improve the CO conversion rate.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (13)
1. FeOOH waste agent and Fe21.333O32The waste agent and the waste iron oxide agent are used as a biomass hydrogenation liquefaction catalyst, a CO transformation catalyst and an organic matter transformation process;
the FeOOH waste agent is a regenerated substance generated after the FeOOH-containing desulfurizer waste agent is regenerated;
said Fe21.333O32The waste agent is Fe21.333O32The waste desulfurizer of,
With Fe21.333O32A waste agent of desulfurizing agent as a main active ingredient or
Containing Fe21.333O32The regenerated regeneration of the waste desulfurizer;
the waste ferric oxide agent is a regenerated substance obtained by regenerating the waste ferric oxide-containing desulfurizer;
wherein in the organic matter conversion process, FeOOH waste agent and Fe21.333O32Waste agents or ferric oxide waste agents and organic matters are prepared into slurry, and the slurry is mixed with pure CO or CO-containing gas for conversion reaction.
2. The use according to claim 1, wherein the FeOOH is one or more of α -FeOOH, β -FeOOH, γ -FeOOH, δ -FeOOH, θ -FeOOH and amorphous FeOOH.
3. Use according to claim 1 or 2,
the waste desulfurizer containing FeOOH is used for removing H in gas by using the desulfurizer containing FeOOH2The waste agent generated after S, or,
the waste desulfurizer containing FeOOH is generated after sulfur-containing components in the coke oven gas are removed by the FeOOH-containing desulfurizer; or the like, or a combination thereof,
The waste desulfurizer containing FeOOH is generated after the FeOOH-containing desulfurizer removes sulfur-containing components in the wastewater; or the like, or a combination thereof,
the waste desulfurizer containing FeOOH is generated by removing sulfur-containing components in coal pyrolysis gas and/or calcium carbide furnace tail gas by the FeOOH-containing desulfurizer.
4. The use of the catalyst according to claim 1 or 2, wherein the waste desulfurizer containing FeOOH is regenerated and then used as a biomass hydrogenation liquefaction catalyst, and the regeneration method of the waste desulfurizer containing FeOOH is,
(1) grinding the waste desulfurizer containing FeOOH into particles to obtain waste agent powder;
(2) preparing the waste agent powder into suspension, introducing oxygen-containing gas for oxidation to convert iron sulfide in the suspension to form slurry containing amorphous iron oxyhydroxide and elemental sulfur;
(3) filtering the slurry to obtain a solid material, extracting elemental sulfur in the solid material by using a solvent, wherein the residual solid after extraction is the regenerated product of the FeOOH desulfurizer waste agent;
or the waste desulfurizer containing FeOOH is regenerated and then used as a biomass hydrogenation liquefaction catalyst, and the regeneration method of the waste desulfurizer containing FeOOH comprises the following steps,
(1) Grinding the desulfurizer waste agent containing FeOOH into particles to obtain waste agent powder;
(2) preparing the waste agent powder into suspension, introducing oxygen-containing gas for oxidation to convert iron sulfide in the suspension to form slurry containing amorphous FeOOH and elemental sulfur;
(3) placing the slurry or a solid material obtained after filtering the slurry into a container, introducing air to enable the elemental sulfur to float upwards, wherein a precipitate at the lower part of the container is the regenerated substance containing the waste FeOOH desulfurizer;
the regeneration method of the waste desulfurizer containing FeOOH used as the biomass hydrogenation liquefaction catalyst after regeneration also comprises the step of mixing the regenerated product containing the waste desulfurizer containing FeOOH with an organic binder;
or the waste desulfurizer containing FeOOH is regenerated and then used as a biomass hydrogenation liquefaction catalyst, and the regeneration method of the waste desulfurizer containing FeOOH comprises the following steps,
(1) dispersing the waste desulfurizer containing FeOOH with weak acid water to form dispersion liquid;
(2) heating the dispersion liquid, adding an oxidant into the heated dispersion liquid for reaction, and rapidly transferring generated sulfur dioxide gas during the reaction;
(3) And after the reaction is finished, filtering the reaction solution, washing and drying the obtained precipitate to obtain the regenerated product containing the FeOOH desulfurizer waste agent.
5. Use according to claim 1 or 2, wherein, in the use of the waste agent regenerant of the desulfurizer containing FeOOH in the organic matter conversion process, the method for preparing the waste agent regenerant by regenerating the waste agent of the desulfurizer containing FeOOH comprises the following steps:
a method for preparing the waste agent regenerant comprises the steps of A1, grinding the waste agent of the desulfurizer containing FeOOH into particles to obtain waste agent powder; a2, preparing the waste agent powder into suspension, introducing oxygen-containing gas for oxidation to convert iron sulfide in the suspension, and forming slurry containing amorphous iron oxyhydroxide and elemental sulfur; a3, filtering the slurry to obtain a solid material, extracting elemental sulfur in the solid material by using a solvent, wherein the residual solid after extraction is the regenerant of the waste agent containing the FeOOH desulfurizer;
or the method for preparing the waste agent regenerant comprises the following steps of B1, grinding the waste agent of the desulfurizer containing FeOOH into particles to obtain waste agent powder; b2, preparing the waste agent powder into a suspension, introducing oxygen-containing gas for oxidation to convert iron sulfide in the suspension to form slurry containing amorphous iron oxyhydroxide and elemental sulfur; b3, placing the slurry or the solid material obtained by filtering the slurry into a container, introducing air to enable the elemental sulfur to float upwards, wherein the precipitate at the lower part of the container is the regenerant containing the waste FeOOH desulfurizer;
Or the method for preparing the waste agent regenerant comprises the following steps of C1, dispersing the FeOOH-containing desulfurizer waste agent by weak acid water to form a dispersion liquid; c2, heating the dispersion liquid, adding an oxidant into the heated dispersion liquid for reaction, and rapidly transferring the generated sulfur dioxide gas during the reaction; c3, after the reaction is finished, filtering the reaction solution, washing and drying the obtained precipitate to obtain the regenerant containing the FeOOH desulfurizer waste agent;
or the method for preparing the regenerant of the waste agent of the desulfurizer containing FeOOH is the regenerant obtained by oxidizing, vulcanizing and oxidizing the waste agent of the desulfurizer containing FeOOH by a slurry method;
or the method for preparing the waste agent regenerant comprises the steps of mixing the waste agent of the desulfurizer containing FeOOH with water or alkali solution to prepare slurry; adding an oxidant into the slurry to perform primary oxidation reaction; adding a vulcanizing agent into the slurry after the oxidation reaction to carry out a vulcanization reaction; adding an oxidant into the slurry after the vulcanization reaction to perform a secondary oxidation reaction; circularly carrying out the sulfuration reaction and the secondary oxidation reaction; and carrying out solid-liquid separation on the slurry after the secondary oxidation reaction to obtain the regenerant of the waste desulfurizer containing FeOOH.
6. The use according to claim 1 or 2, wherein in the use of the waste agent regenerant of the FeOOH containing desulfurization agent in an organic matter conversion process, the waste agent regenerant of the FeOOH containing desulfurization agent and organic matter are formulated to form a slurry, and the slurry is mixed with pure CO or a CO-containing gas for a conversion reaction; the method also comprises a step of adding a sulfur-containing compound, wherein the molar ratio of the iron element to the sulfur element in the slurry is 1 (0.5-5).
7. The use according to claim 6, wherein, in the use of the waste regenerant of the desulfurizer containing FeOOH in the organic matter conversion process, the reaction pressure of the conversion reaction is 5-22MPa, and the reaction temperature is 200-470 ℃;
in the slurry, the content of the regenerant of the waste desulfurizer containing FeOOH is 0.1-10 wt%, and the average particle size of the regenerant is 0.1-5 mm;
the CO content of the CO-containing gas is not less than 15% by volume.
8. Use according to claim 7, wherein the CO-containing gas has a CO content of not less than 50% by volume.
9. Use according to claim 7 or 8, wherein the CO-containing gas has a CO content of not less than 90% by volume.
10. Use according to claim 1Characterized by being Fe 21.333O32The waste desulfurizer is Fe21.333O32Desulfurizing agent for removing H from gas2Waste agent generated after S; or,
Fe21.333O32use of a waste desulfurizer as a catalyst for biomass hydrogenation liquefaction, and Fe21.333O32The waste desulfurizer is Fe21.333O32The desulfurizer generates waste agent after removing sulfur-containing components in the coke oven gas; or,
Fe21.333O32use of a waste desulfurizer as a catalyst for biomass hydrogenation liquefaction, and Fe21.333O32The waste desulfurizer is Fe21.333O32The desulfurizer generates a waste agent after removing sulfur-containing components in the wastewater; or,
Fe21.333O32use of a waste desulfurizer as a catalyst for biomass hydrogenation liquefaction, and Fe21.333O32The waste desulfurizer is Fe21.333O32The desulfurizer removes waste agent generated by sulfur-containing components in coal pyrolysis gas and/or calcium carbide furnace tail gas.
11. Use according to claim 1 or 10, characterized in that Fe21.333O32Use of a spent agent of a desulfurizing agent as a main active ingredient as a biomass hydro-liquefaction catalyst, the spent agent being made of Fe21.333O32The desulfurizer used as the main active component also comprises potassium oxide and anatase type Ti02One or more of copper oxide, lead oxide, zinc oxide and manganese dioxide; or,
with Fe21.333O32Use of a spent agent of a desulfurizing agent as a main active ingredient as a biomass hydro-liquefaction catalyst, the spent agent being made of Fe21.333O32The waste agent of the desulfurizer as the main active component is used for removing H in gas by the desulfurizer 2(iv) a waste agent produced after S; or,
with Fe21.333O32Use of a spent agent of a desulfurizing agent as a main active ingredient as a biomass hydro-liquefaction catalyst, the spent agent being made of Fe21.333O32The waste agent of the desulfurizer which is the main active component is the waste agent generated after the desulfurizer removes sulfur-containing components in the coke oven gas; or,
with Fe21.333O32Use of a spent agent of a desulfurizing agent as a main active ingredient as a biomass hydro-liquefaction catalyst, the spent agent being made of Fe21.333O32The waste agent of the desulfurizer which is the main active component is the waste agent generated after the sulfur-containing component in the wastewater is removed by the desulfurizer; or,
with Fe21.333O32Use of a spent agent of a desulphurizing agent as a main active ingredient, said spent agent being Fe, as a catalyst for the hydroliquefaction of biomass21.333O32The waste agent of the desulfurizer which is the main active component is the waste agent generated by removing sulfur-containing components in coal pyrolysis gas and/or calcium carbide furnace tail gas by the desulfurizer.
12. The use according to claim 1, characterized in that the active ingredient in the desulfurizing agent for iron oxide is iron sesquioxide and/or ferroferric oxide.
13. Use according to claim 12, wherein the iron sesquioxide is a-Fe2O3、α-Fe2O3．H2O、γ-Fe2O3、γ-Fe2O3．H2O, amorphous Fe2O3Amorphous Fe2O3．H2At least one of O;
The ferroferric oxide is cubic system ferroferric oxide.
Applications Claiming Priority (48)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810403885 | 2018-04-28 | ||
| CN201810403699 | 2018-04-28 | ||
| CN2018104023104 | 2018-04-28 | ||
| CN201810402333 | 2018-04-28 | ||
| CN2018104038858 | 2018-04-28 | ||
| CN2018104023335 | 2018-04-28 | ||
| CN201810403689 | 2018-04-28 | ||
| CN2018104022879 | 2018-04-28 | ||
| CN201810402056 | 2018-04-28 | ||
| CN201810403908 | 2018-04-28 | ||
| CN201810403893 | 2018-04-28 | ||
| CN2018104023227 | 2018-04-28 | ||
| CN2018104036890 | 2018-04-28 | ||
| CN201810404880 | 2018-04-28 | ||
| CN201810403897 | 2018-04-28 | ||
| CN201810404903 | 2018-04-28 | ||
| CN2018104038970 | 2018-04-28 | ||
| CN201810403878 | 2018-04-28 | ||
| CN201810403882 | 2018-04-28 | ||
| CN2018104048807 | 2018-04-28 | ||
| CN201810402322 | 2018-04-28 | ||
| CN2018104020572 | 2018-04-28 | ||
| CN2018104038824 | 2018-04-28 | ||
| CN201810402040 | 2018-04-28 | ||
| CN201810402310 | 2018-04-28 | ||
| CN201810402287 | 2018-04-28 | ||
| CN2018104038788 | 2018-04-28 | ||
| CN201810402300 | 2018-04-28 | ||
| CN201810402284 | 2018-04-28 | ||
| CN2018104022845 | 2018-04-28 | ||
| CN201810402057 | 2018-04-28 | ||
| CN2018104020407 | 2018-04-28 | ||
| CN2018104038932 | 2018-04-28 | ||
| CN2018104039085 | 2018-04-28 | ||
| CN2018104047467 | 2018-04-28 | ||
| CN201810403884 | 2018-04-28 | ||
| CN2018104038947 | 2018-04-28 | ||
| CN2018104049034 | 2018-04-28 | ||
| CN2018104036994 | 2018-04-28 | ||
| CN201810403894 | 2018-04-28 | ||
| CN201810403920 | 2018-04-28 | ||
| CN201810403895 | 2018-04-28 | ||
| CN201810404746 | 2018-04-28 | ||
| CN2018104020568 | 2018-04-28 | ||
| CN2018104038843 | 2018-04-28 | ||
| CN2018104023000 | 2018-04-28 | ||
| CN2018104039206 | 2018-04-28 | ||
| CN2018104038951 | 2018-04-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110404538A CN110404538A (en) | 2019-11-05 |
| CN110404538B true CN110404538B (en) | 2022-07-19 |
Family
ID=68357646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910332501.2A Active CN110404538B (en) | 2018-04-28 | 2019-04-23 | Use of waste agents |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110404538B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111111771A (en) * | 2019-12-25 | 2020-05-08 | 陕西延长石油（集团）有限责任公司 | Recycling method and application of catalytic cracking waste catalyst |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3228482C2 (en) * | 1982-07-30 | 1986-09-11 | VEG-Gasinstituut N.V., Apeldoorn | Process for the reaction of carbon monoxide with water vapor to form carbon dioxide and hydrogen and the use of a catalyst therefor |
| CN101767777A (en) * | 2008-12-30 | 2010-07-07 | 北京三聚环保新材料股份有限公司 | Amorphous FeOOH and method for regenerating desulfurizing agent taking amorphous FeOOH as active ingredient |
| CN103212293B (en) * | 2012-01-19 | 2015-10-14 | 北京三聚环保新材料股份有限公司 | A kind of take FeOOH as the renovation process of the desulfurizing agent of active component |
| CN103055834B (en) * | 2013-01-28 | 2014-10-29 | 长沙理工大学 | Regeneration method for spent ferric oxide desulfurizer |
| CN103990458B (en) * | 2013-02-19 | 2016-08-03 | 北京宝塔三聚能源科技有限公司 | A kind of heat from hydrogenation decomposition catalyst and use the heat from hydrogenation decomposition method of this catalyst |
| CN105126933B (en) * | 2015-09-07 | 2017-09-05 | 北京宝聚能源科技有限公司 | The preparation method of hydrogenation catalyst and the slurry bed system hydrogenation technique using the catalyst |
| CN105597516B (en) * | 2016-02-29 | 2020-01-10 | 北京三聚环保新材料股份有限公司 | Magnetic iron oxide desulfurizer and preparation method thereof |
| CN106582243B (en) * | 2016-12-30 | 2019-12-17 | 北京三聚环保新材料股份有限公司 | Wet desulphurization process using magnetic iron oxide red as desulfurizer |
-
2019
- 2019-04-23 CN CN201910332501.2A patent/CN110404538B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110404538A (en) | 2019-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109536195B (en) | Biomass and coal conversion process | |
| US20120036764A1 (en) | Carbon material conversion process comprising two liquefaction stages in a boiling bed in the presence of hydrogen generated by non-fossil sources | |
| CN108291152B (en) | Conversion of biomass to liquid hydrocarbon material | |
| CN101987962A (en) | Method for liquefying high-oxygen content coal by adopting direct hydrogenation | |
| CN109880654A (en) | A method of utilizing volatile matter Fischer Tropsch waxes in low-order coal | |
| CN110804468B (en) | Dry desulfurization process for synthesis gas | |
| CN110408420B (en) | Organic matter conversion process | |
| CN110819390A (en) | Method and system for low-rank coal fractional conversion | |
| CN108350365B (en) | Conversion of biomass to liquid hydrocarbon materials | |
| CN110404538B (en) | Use of waste agents | |
| CN106635152B (en) | A kind of processing method of full fraction of coal tar oil | |
| US11198820B2 (en) | Conversion process for an organic material | |
| CN109355098B (en) | Multistage conversion process for inferior oil products | |
| US11492563B2 (en) | Conversion process for an inferior oil | |
| CN109536197B (en) | Biomass liquefaction process | |
| CN109536193B (en) | Biomass two-stage conversion refining process | |
| CN108865253A (en) | The method of coal Direct Hydrogenation liquefaction richness production aromatic hydrocarbons | |
| CN110055106A (en) | A kind of method that low-order coal sub-prime prepares methanol and oil using Poly-generation | |
| US20150051427A1 (en) | Integrated process for the production of renewable drop-in fuels | |
| CN110760329B (en) | Process for producing light oil by secondary conversion of biomass | |
| CN101210196B (en) | Conversion method for hydrocarbon oil | |
| EP3608388B1 (en) | Substandard oil product conversion process | |
| CN110747001B (en) | Secondary biomass conversion process | |
| CN109536196B (en) | Biomass two-stage conversion process | |
| CN109355085B (en) | Solid biomass conversion process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 100080 9th floor, Dahang Jiye building, No.1 building, 33 Renmin North Road, Haidian District, Beijing Patentee after: Beijing Haixin Energy Technology Co.,Ltd. Address before: 100044 Beijing Haidian District Xizhimen North Street a 43 Jinyun building A block 9. Patentee before: BEIJING SANJU ENVIRONMENTAL PROTECTION & NEW MATERIALS Co.,Ltd. |