CN110404538A - The new application of useless agent - Google Patents
The new application of useless agent Download PDFInfo
- Publication number
- CN110404538A CN110404538A CN201910332501.2A CN201910332501A CN110404538A CN 110404538 A CN110404538 A CN 110404538A CN 201910332501 A CN201910332501 A CN 201910332501A CN 110404538 A CN110404538 A CN 110404538A
- Authority
- CN
- China
- Prior art keywords
- agent
- useless
- feooh
- desulfurizing agent
- desulfurizing
- 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.)
- Granted
Links
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 1786
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 388
- 229910002588 FeOOH Inorganic materials 0.000 claims abstract description 376
- 239000003054 catalyst Substances 0.000 claims abstract description 322
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 272
- 238000000034 method Methods 0.000 claims abstract description 176
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 173
- 230000009466 transformation Effects 0.000 claims abstract description 172
- 239000005416 organic matter Substances 0.000 claims abstract description 84
- 230000000694 effects Effects 0.000 claims abstract description 67
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910003296 Ni-Mo Inorganic materials 0.000 claims abstract description 24
- 230000003009 desulfurizing effect Effects 0.000 claims description 598
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 215
- 239000002028 Biomass Substances 0.000 claims description 192
- 239000002002 slurry Substances 0.000 claims description 153
- 238000011069 regeneration method Methods 0.000 claims description 149
- 238000006243 chemical reaction Methods 0.000 claims description 132
- 229910052717 sulfur Inorganic materials 0.000 claims description 124
- 239000011593 sulfur Substances 0.000 claims description 124
- 230000001172 regenerating effect Effects 0.000 claims description 104
- 230000008929 regeneration Effects 0.000 claims description 103
- 239000004615 ingredient Substances 0.000 claims description 102
- 239000007787 solid Substances 0.000 claims description 94
- 239000007788 liquid Substances 0.000 claims description 93
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 92
- 238000006477 desulfuration reaction Methods 0.000 claims description 85
- 230000023556 desulfurization Effects 0.000 claims description 83
- 229910001868 water Inorganic materials 0.000 claims description 83
- 238000007254 oxidation reaction Methods 0.000 claims description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 60
- 239000005864 Sulphur Substances 0.000 claims description 54
- 239000000843 powder Substances 0.000 claims description 50
- 239000006185 dispersion Substances 0.000 claims description 45
- 239000003245 coal Substances 0.000 claims description 44
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 238000000197 pyrolysis Methods 0.000 claims description 34
- 239000007800 oxidant agent Substances 0.000 claims description 33
- 230000001590 oxidative effect Effects 0.000 claims description 33
- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 30
- 239000000725 suspension Substances 0.000 claims description 30
- 239000002351 wastewater Substances 0.000 claims description 30
- 239000011343 solid material Substances 0.000 claims description 29
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 25
- 229910052742 iron Inorganic materials 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 22
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 22
- 239000011787 zinc oxide Substances 0.000 claims description 21
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 20
- 238000004073 vulcanization Methods 0.000 claims description 20
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims description 20
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 239000005997 Calcium carbide Substances 0.000 claims description 16
- 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 16
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 14
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 14
- 239000002738 chelating agent Substances 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 12
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 12
- 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 claims description 12
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 12
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 11
- 229940116318 copper carbonate Drugs 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 11
- 230000001376 precipitating effect Effects 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000005751 Copper oxide Substances 0.000 claims description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000000638 solvent extraction Methods 0.000 claims description 9
- 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
- 239000013049 sediment Substances 0.000 claims description 8
- 238000012546 transfer Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000007613 slurry method Methods 0.000 claims description 6
- 229910000464 lead oxide Inorganic materials 0.000 claims description 5
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 25
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000007789 gas Substances 0.000 description 230
- 239000003921 oil Substances 0.000 description 88
- 235000019198 oils Nutrition 0.000 description 88
- 230000008569 process Effects 0.000 description 77
- 239000000047 product Substances 0.000 description 54
- 239000001257 hydrogen Substances 0.000 description 48
- 229910052739 hydrogen Inorganic materials 0.000 description 48
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 46
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 46
- 239000000470 constituent Substances 0.000 description 37
- 239000003208 petroleum Substances 0.000 description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 35
- 150000002506 iron compounds Chemical class 0.000 description 24
- 230000006378 damage Effects 0.000 description 23
- 230000009286 beneficial effect Effects 0.000 description 22
- 239000003502 gasoline Substances 0.000 description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- 239000002699 waste material Substances 0.000 description 19
- 239000000295 fuel oil Substances 0.000 description 18
- 230000008859 change Effects 0.000 description 17
- 238000005336 cracking Methods 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 150000002431 hydrogen Chemical class 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000006227 byproduct Substances 0.000 description 13
- 230000006315 carbonylation Effects 0.000 description 13
- 238000005810 carbonylation reaction Methods 0.000 description 13
- 238000012545 processing Methods 0.000 description 13
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 239000000654 additive Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000003034 coal gas Substances 0.000 description 11
- 230000005611 electricity Effects 0.000 description 11
- 239000003546 flue gas Substances 0.000 description 11
- 229910052750 molybdenum Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000004575 stone Substances 0.000 description 11
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 10
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 10
- 239000011733 molybdenum Substances 0.000 description 10
- 229910003153 β-FeOOH Inorganic materials 0.000 description 10
- 229910006299 γ-FeOOH Inorganic materials 0.000 description 10
- 230000006835 compression Effects 0.000 description 9
- 238000007906 compression Methods 0.000 description 9
- 230000005484 gravity Effects 0.000 description 9
- 241000219782 Sesbania Species 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- -1 alkali metal formate Chemical class 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 230000000903 blocking effect Effects 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon disulfide Substances S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000033228 biological regulation Effects 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 238000011017 operating method Methods 0.000 description 6
- 150000003384 small molecules Chemical class 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
- 239000000243 solution Substances 0.000 description 6
- 229930192474 thiophene Natural products 0.000 description 6
- 229910017135 Fe—O Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000000306 component Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 240000008042 Zea mays Species 0.000 description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 235000005822 corn Nutrition 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 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
- 239000010907 stover Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 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
- 230000008602 contraction Effects 0.000 description 3
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- 238000001035 drying Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
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- 238000011065 in-situ storage Methods 0.000 description 3
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- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000010913 used oil Substances 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 206010054949 Metaplasia Diseases 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000009933 burial Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 230000015689 metaplastic ossification Effects 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 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
- 241000209094 Oryza Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-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
- 230000009471 action Effects 0.000 description 1
- 208000012826 adjustment disease Diseases 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000012752 auxiliary agent 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
- 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
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000000658 coextraction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 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
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical group [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- QXYJCZRRLLQGCR-UHFFFAOYSA-N molybdenum(IV) oxide Inorganic materials O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 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
- 239000004058 oil shale Substances 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000013139 quantization Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 238000004227 thermal cracking Methods 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
- 230000007704 transition Effects 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
- 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
-
- B01J35/33—
-
- 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
Abstract
The invention discloses a kind of new applications of useless agent.New application is related to a kind of FeOOH useless agent, Fe21.333O32Useless agent, iron oxide give up agent, Ni-Mo give up agent as hydrogenation liquefaction catalyst, as CO transformation catalyst, the purposes in organic matter transformation technique.The useless agent is used as slack resources, and price is far below the price of fresh catalyst, to reduce production cost, but it is suitable with conventional catalyst effect as the catalytic effect of hydrogenation liquefaction catalyst or CO transformation catalyst.
Description
Technical field
The invention belongs to catalyst application fields, and in particular to the new application of useless agent, in particular to useless agent is as hydrogenation liquid
Change catalyst, as CO transformation catalyst, the purposes in organic matter transformation technique.
Background technique
CO transformation is common production technology in industry, is reacted using CO and vapor to prepare CO2And hydrogen.
Currently, the technique has been widely used in the processing of hydrogen manufacturing, synthesis ammonia, synthesizing methanol, methanation and synthetic oil etc., it can
To convert the hydrogen-carbon ratio in adjustment reaction system by CO, to meet requirement of the target product to raw material.
In CO conversion reaction, catalyst is essential element in reaction system.Common CO transformation catalyst packet
High temperature catalyst, high temperature catalyst and low temperature catalyst are included, specific as follows:
(1) in high temperature catalyst, mostly with Fe2O3And/or Cr2O3For main active component, using MgO as structural promoter；
(2) in high temperature catalyst, mostly with CoO and/or MoO2For main active component, with MgO, Al2O3It is helped as structure
Agent；
(3) in low temperature catalyst, mostly using copper and zinc as main active component, copper and zinc are dissolved by nitric acid, after dissolution
Solution mixing after be added soda ash solution co-precipitation, later again thereto be added Al (OH)3Or amorphous Al2O3, form support type
Catalyst.
In the industrial production, desulfurization is also common treatment process, and the useless agent of many desulfurization can be generated after desulfurization process, and
Desulfurization agent of giving up needs to carry out subsequent processing, is generally adopted by soil-burial, and landfill disposal not only land occupation, simultaneously
It is very harmful for the residual of soil, influence will also result in for environment.If further considering the recycling of the useless agent of desulfurization, generally
All it is that regeneration treatment is carried out to desulfurization agent of giving up using specific regeneration technology, makes the work of its activity recovery substance to a certain extent
Property, to realize recycling.However, the catalyst after regeneration gives up, its activity of agent decreases, and cannot reach former desulfurizing agent
Desulfurization effect, to limit its a wide range of reuse.For example, using iron oxide as the desulfurizing agent of main active, after regeneration
Sulfur capacity decline at least 3 percentage points so that repeatedly regeneration after desulfurizing agent be unable to satisfy requirement, still need to carry out
Landfill disposal.
Meanwhile hydrogenation liquefaction is partly or entirely to be converted biomass, coal etc. to by heat chemistry or biochemical method
The technology of liquid fuel.The usual technology is divided into the indirect liquefactions such as the direct liquefactions such as biomass, coal and biomass, coal.Hydrogenation liquid
Change Direct liquefaction technology be passed through in equipped with biomass, coal etc., catalyst, the reactor using water or organic matter as solvent H2,
CO or inert gas are thermally decomposed biomass, coal etc. under temperature and pressure appropriate, and then obtain the skill of fluid oil
Art, i.e., a kind of thermochemical reaction process that solid-state biomass is converted into liquefied mixture.Indirect liquefaction be biomass,
After coal etc. first gasifies, further synthetic fluid product, or take Hydrolyze method in biomass cellulose and hemicellulose turn
Polysaccharide is turned to, then generates ethyl alcohol using biomass ferment technology.
In hydrogenate liquefaction process, catalyst is essential element in reaction system, helps to inhibit polycondensation, meet again
Equal side reactions, reduce the production quantity of macromolecular solid residue.Common hydrogenation liquefaction catalyst can be divided into homogeneous catalyst
And heterogeneous catalyst, it is specific as follows:
(1) homogeneous catalyst: acid, alkali, alkali metal carbonic acid (hydrogen) salt, alkali metal formate；
(2) heterogeneous catalyst: metallic catalyst, supported catalyst such as Co-Mo, Ni-Mo series hydrogenation catalyst.
In the industrial production, desulfurization is also common treatment process, and the useless agent of many desulfurization can be generated after desulfurization process, and
Desulfurization agent of giving up needs to carry out subsequent processing, is generally adopted by soil-burial, and landfill disposal not only land occupation, simultaneously
It is very harmful for the residual of soil, influence will also result in for environment.If further considering the recycling of the useless agent of desulfurization, generally
All it is that regeneration treatment is carried out to desulfurization agent of giving up using specific regeneration technology, makes the work of its activity recovery substance to a certain extent
Property, to realize recycling, however, the catalyst after regeneration gives up, its activity of agent decreases, and cannot reach former desulfurizing agent
Desulfurization effect, to limit its a wide range of reuse.For example, the useless agent of ferric oxide desulfurizer, under the Sulfur capacity meeting after regeneration
Drop still needs to carry out landfill disposal so that repeatedly the desulfurizing agent after regeneration is unable to satisfy requirement.
Meanwhile with the rapid development of social economy, the fossils such as coal, crude oil, natural gas, oil shale class non-renewable energy
Increasingly exhausted, at the same time, generated CO after such fossil class non-renewable energy burning2、SO2、NOxCaused by equal pollutants
Environmental pollution also get worse, this force the mankind have to thinking obtain the energy new way and improve environment method.
Currently, biomass liquefying technology becomes a kind of new means for obtaining the energy, which is biomass resource utilization
In important component, liquefaction mechanism is as follows: biomass is cracked into oligomer first, then again through dehydration, dehydroxylation, de-
Hydrogen, deoxidation and decarboxylation and form small molecule compound, small molecule compound then pass through condensation, cyclisation, polymerization etc. react
Generate new compound.The technology is broadly divided into indirect liquefaction and direct liquefaction two major classes at present, wherein biomass direct liquefaction
Technology refers under the action of solvent or catalyst, using hydrolysis, supercritical liquefaction or hydrogen, inert gas is passed through, appropriate
Temperature, biomass is directly liquefied as liquid from solid under pressure.In whole process, pyrolysis liquefaction, catalytic liquid are related generally to
Change and pressurization hydrogenation liquefaction etc..
It in above-mentioned biomass liquefying process, before being liquefied, is required to be carried out dehydrating biomass material, increase
Drying cost is added.Furthermore liquefaction and the expensive precious metal catalyst applied to the technique must be carried out using pure hydrogen atmosphere
Agent, so that the economy of liquefaction process is poor.Furthermore entire technique can also generate the waste water of a large amount of pollution environment, but also liquefaction
The environmental benefit of technique is bad.Therefore, biomass liquefying process economic benefit and the double low reality of environmental benefit become limit at present
The major obstacle of biomass liquefying process promotion and application processed.In theory, either change liquefaction atmosphere, reduce raw material
Processing cost is also or therefore the further development that is conducive to biomass liquefying process of the cheap catalyst of selection has at present
Scholar attempts to carry out biomass liquefying conversion using non-hydrogen environment, but its catalyst low efficiency for using, cannot achieve work
Promotion and application in industry.
Therefore, the agent that how will largely give up carries out reuse, is endangered caused by environment with reducing as carrying out landfill disposal,
Have great importance.
Summary of the invention
For this purpose, problem to be solved by this invention is that existing useless agent is lacked because carrying out landfill disposal to what environment caused damages
It falls into and double low defects of biomass liquefying process economic benefit and environmental benefit in the prior art, to provide a kind of FeOOH
Useless agent, Fe21.333O32Useless agent, iron oxide give up agent, Ni-Mo give up agent as hydrogenation liquefaction catalyst, as CO transformation catalyst, In
Purposes in organic matter transformation technique.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
It gives up agent, Fe the present invention provides FeOOH21.333O32Useless agent, iron oxide agent, Ni-Mo agent of giving up of giving up are urged as hydrogenation liquefaction
Agent, as CO transformation catalyst, the purposes in organic matter transformation technique；
The FeOOH give up agent be FeOOH desulfurizing agent give up agent, using FeOOH as the useless agent of the desulfurizing agent of main active, contain
Regrowth after having the useless agent regeneration of the desulfurizing agent of FeOOH；
The Fe21.333O32Useless agent is Fe21.333O32Desulfurizing agent useless agent, with Fe21.333O32For main active
The useless agent of desulfurizing agent contains Fe21.333O32Desulfurizing agent give up agent regeneration after regrowth；
The useless agent of the iron oxide is the useless agent of ferric oxide desulfurizer, using iron oxide as the useless of the desulfurizing agent of main active
Regrowth after agent, the useless agent of desulfurizing agent containing iron oxide regeneration；
The Ni-Mo gives up agent as using Ni-Mo as the useless agent of the hydrogenation catalyst of main active.
Further, useless purposes of the agent as biomass hydrogenation liquefaction catalyst of a kind of FeOOH desulfurizing agent.
Above-mentioned FeOOH desulfurizing agent gives up purposes of the agent as biomass hydrogenation liquefaction catalyst, the FeOOH be alpha-feooh,
One or more of β-FeOOH, γ-FeOOH, δ-FeOOH, θ-FeOOH and amorphous FeOOH.
Above-mentioned FeOOH desulfurizing agent gives up purposes of the agent as biomass hydrogenation liquefaction catalyst, and the FeOOH desulfurizing agent gives up agent
The useless agent generated after H2S in gas is removed for FeOOH desulfurizing agent.
Above-mentioned FeOOH desulfurizing agent gives up purposes of the agent as biomass hydrogenation liquefaction catalyst, and the FeOOH desulfurizing agent gives up agent
The useless agent generated after sulfur-bearing ingredient in coke-stove gas is removed for the desulfurizing agent of FeOOH.
Above-mentioned FeOOH desulfurizing agent gives up purposes of the agent as biomass hydrogenation liquefaction catalyst, and the FeOOH desulfurizing agent gives up agent
The useless agent generated after sulfur-bearing ingredient in waste water is removed for the desulfurizing agent of FeOOH.
Above-mentioned FeOOH desulfurizing agent gives up purposes of the agent as biomass hydrogenation liquefaction catalyst, and the FeOOH desulfurizing agent gives up agent
The exhaust gas of the sulfur-bearing ingredient generation in coal pyrolysis gas and/or calcium carbide stove exhaust is removed for the desulfurizing agent of FeOOH.
Compared with prior art, the invention has the following beneficial effects:
(1) useless purposes of the agent as biomass hydrogenation liquefaction catalyst of FeOOH desulfurizing agent provided by the embodiment of the present invention,
The useless agent that existing FeOOH desulfurizing agent is formed after carrying out desulfurization process can be directly as biomass hydrogenation liquefaction catalyst
It uses, has opened up the application field of the useless agent of FeOOH desulfurizing agent, reduce the useless regenerated cost of agent of FeOOH desulfurizing agent, reduce
The amount of landfill of the useless agent of FeOOH desulfurizing agent reduces the harm caused by environment, simultaneously as FeOOH desulfurizing agent gives up, agent is as not busy
Resource is set, price is far below the price of biomass hydrogenation liquefaction catalyst, to reduce the production of biomass liquefying industry
Cost.
(2) useless purposes of the agent as biomass hydrogenation liquefaction catalyst of FeOOH desulfurizing agent provided by the embodiment of the present invention,
Through detecting, the useless agent of existing FeOOH desulfurizing agent is used as biomass hydrogenation liquefaction catalyst, effect and conventional biomass
Hydrogenation liquefaction catalyst effect is suitable.
Further, a kind of to be urged by the useless agent of the desulfurizing agent of main active of FeOOH as biomass hydrogenation liquefaction
The purposes of agent.
Above-mentioned by the desulfurizing agent of main active of FeOOH further includes molysite chelating agent, bodied ferric sulfate, basic carbonate
One or more of copper, calcium bicarbonate, zinc oxide, calcium sulphate dihydrate, the oxide of nickel, the oxide of cobalt, oxide of nickel.
Above-mentioned FeOOH is in alpha-feooh, β-FeOOH, γ-FeOOH, δ-FeOOH, θ-FeOOH and amorphous FeOOH
It is one or more of.
Above-mentioned using FeOOH as the useless agent of the desulfurizing agent of main active is that the desulfurizing agent is removed in gas and produced after H2S
Raw useless agent.
Above-mentioned using FeOOH as the useless agent of the desulfurizing agent of main active is that the desulfurizing agent removes sulfur-bearing in coke-stove gas
The useless agent generated after ingredient.
Above-mentioned using FeOOH as the useless agent of the desulfurizing agent of main active is that the desulfurizing agent removes sulfur-bearing ingredient in gasoline
The useless agent generated afterwards.
Above-mentioned using FeOOH as the useless agent of the desulfurizing agent of main active is that the desulfurizing agent removes petroleum or petroleum by-product
The useless agent generated after sulfur-bearing ingredient in product.
Above-mentioned using FeOOH as the useless agent of the desulfurizing agent of main active is that the desulfurizing agent removes sulfur-bearing ingredient in waste water
The useless agent generated afterwards.
It is above-mentioned using FeOOH as the useless agent of the desulfurizing agent of main active be the desulfurizing agent remove coal pyrolysis gas and/or
The exhaust gas that sulfur-bearing ingredient in calcium carbide stove exhaust generates.
Compared with prior art, the invention has the following beneficial effects:
(1) agent is given up as biomass as the desulfurizing agent of main active using FeOOH provided by the embodiment of the present invention to add
The purposes of liquefaction of hydrogen catalyst, the useless agent that existing FeOOH desulfurizing agent is formed after carrying out desulfurization process can be directly as life
Substance hydrogenation liquefaction catalyst uses, and has opened up the application field of the useless agent of FeOOH desulfurizing agent, reduces the useless agent of FeOOH desulfurizing agent
Regenerated cost, the amount of landfill for reducing the useless agent of FeOOH desulfurizing agent reduce the harm caused by environment, simultaneously as
FeOOH desulfurizing agent gives up agent as slack resources, and price is far below the price of biomass hydrogenation liquefaction catalyst, to reduce
The production cost of biomass hydrogenation liquefaction industry.
(2) agent is given up as biomass as the desulfurizing agent of main active using FeOOH provided by the embodiment of the present invention to add
The purposes of liquefaction of hydrogen catalyst, through detecting, the useless agent of existing FeOOH desulfurizing agent is used as biomass hydrogenation liquefaction catalyst,
Its effect is suitable with conventional biomass hydrogenation liquefaction catalyst effect.
Further, the use after a kind of useless agent regeneration of desulfurizing agent containing FeOOH as biomass hydrogenation liquefaction catalyst
On the way.
Purposes after the useless agent regeneration of the above-mentioned desulfurizing agent containing FeOOH as biomass hydrogenation liquefaction catalyst, it is described
FeOOH is one or more of alpha-feooh, β-FeOOH, γ-FeOOH, δ-FeOOH, θ-FeOOH and amorphous FeOOH.
Purposes after the useless agent regeneration of the above-mentioned desulfurizing agent containing FeOOH as biomass hydrogenation liquefaction catalyst, it is described to contain
The desulfurizing agent for having FeOOH further includes molysite chelating agent, bodied ferric sulfate, basic copper carbonate, calcium bicarbonate, zinc oxide, two water sulphur
One or more of sour calcium, the oxide of nickel, the oxide of cobalt, oxide of molybdenum.
Purposes after the useless agent regeneration of the above-mentioned desulfurizing agent containing FeOOH as biomass hydrogenation liquefaction catalyst, it is described to contain
There is the desulfurizing agent of FeOOH to give up agent for the useless agent generated after H2S in the desulfurizing agent removing gas containing FeOOH；Or,
After the desulfurizing agent containing FeOOH gives up agent as sulfur-bearing ingredient in the desulfurizing agent removing coke-stove gas containing FeOOH
The useless agent generated；Or,
The desulfurizing agent containing FeOOH gives up agent to generate after sulfur-bearing ingredient in the desulfurizing agent removing waste water containing FeOOH
Useless agent；Or,
The desulfurizing agent containing FeOOH gives up agent as desulfurizing agent removing coal pyrolysis gas and/or furnace of calcium carbide tail containing FeOOH
The exhaust gas that sulfur-bearing ingredient in gas generates.
Purposes after the useless agent regeneration of the above-mentioned desulfurizing agent containing FeOOH as biomass hydrogenation liquefaction catalyst, it is described
Desulfurizing agent containing FeOOH give up agent regeneration method be,
(1) the useless agent of the desulfurizing agent containing FeOOH is ground into particle, obtains useless agent powder；
(2) the useless agent powder is made into suspension, is passed through oxygenous gas and carries out aoxidizing the iron made in the suspension
Sulfide conversion, forms the slurries containing amorphous FeOOH and elemental sulfur；
(3) slurries are filtered and obtains solid material, the elemental sulfur in the solid material described in solvent extraction remains after extraction
Remaining solid is the regrowth containing the useless agent of FeOOH desulfurizing agent.
Purposes after the useless agent regeneration of the above-mentioned desulfurizing agent containing FeOOH as biomass hydrogenation liquefaction catalyst, it is described
Desulfurizing agent containing FeOOH give up agent regeneration method be,
(1) the useless agent of the desulfurizing agent containing FeOOH is ground into particle, obtains useless agent powder；
(2) the useless agent powder is made into suspension, is passed through oxygenous gas and carries out aoxidizing the iron made in the suspension
Sulfide conversion, forms the slurries containing amorphous FeOOH and elemental sulfur；
(3) it is placed in container by the slurries or by the solid material obtained after slurries filtering, being passed through air makes institute
Elemental sulfur floating is stated, the sediment of lower vessel portion is the regrowth containing the useless agent of FeOOH desulfurizing agent.
Purposes after the useless agent regeneration of the above-mentioned desulfurizing agent containing FeOOH as biomass hydrogenation liquefaction catalyst, regeneration
Further include the steps that mixing the regrowth containing the useless agent of FeOOH desulfurizing agent with organic binder in method.
Purposes after the useless agent regeneration of the above-mentioned desulfurizing agent containing FeOOH as biomass hydrogenation liquefaction catalyst, it is described
Desulfurizing agent containing FeOOH give up agent regeneration method be,
(1) by the useless agent weak acid water dispersion of the desulfurizing agent containing FeOOH, dispersion liquid is formed；
(2) dispersion liquid is heated, then oxidant is added into the dispersion liquid after heating and is reacted, reaction is fast simultaneously
The sulfur dioxide gas that speed transfer generates；
(3) after the reaction was completed, obtained precipitating is washed, is dried by filtering reacting liquid, obtains described containing FeOOH
The regrowth of the useless agent of desulfurizing agent.
Compared with prior art, the invention has the following beneficial effects:
(1) desulfurizing agent containing FeOOH provided by the embodiment of the present invention gives up after agent regenerates and is used as biomass hydrogenation liquefaction
The purposes of catalyst, the useless agent that the existing desulfurizing agent containing FeOOH is formed after carrying out desulfurization process can be directly as life
Substance hydrogenation liquefaction catalyst use, opened up the desulfurizing agent containing FeOOH give up agent regeneration after application field, reduce containing
The amount of landfill of the useless agent of FeOOH desulfurizing agent reduces the harm caused by environment, simultaneously as making containing the useless agent of FeOOH desulfurizing agent
For slack resources, price is far below the price of biomass hydrogenation liquefaction catalyst, to reduce the production of CO transformation industry
Cost.
(2) giving up after agent regenerates provided by the embodiment of the present invention containing FeOOH desulfurizing agent is used as biomass hydrogenation liquefaction to urge
The purposes of agent, through detecting, the existing desulfurizing agent containing FeOOH gives up after agent regenerates to be made as biomass hydrogenation liquefaction catalyst
With effect is suitable with conventional biomass hydrogenation liquefaction catalyst effect.
Further, useless purposes of the agent as CO transformation catalyst of a kind of FeOOH desulfurizing agent.
Preferably, useless purposes of the agent as CO transformation catalyst of above-mentioned FeOOH desulfurizing agent, the FeOOH are α-
One or more of FeOOH, β-FeOOH, γ-FeOOH, δ-FeOOH, θ-FeOOH and amorphous FeOOH.
Preferably, useless purposes of the agent as CO transformation catalyst of above-mentioned FeOOH desulfurizing agent, the FeOOH desulfurizing agent are useless
Agent is that FeOOH desulfurizing agent removes the useless agent generated after H2S in gas.
Preferably, useless purposes of the agent as CO transformation catalyst of above-mentioned FeOOH desulfurizing agent, the FeOOH desulfurizing agent are useless
Agent is that the desulfurizing agent of FeOOH removes the useless agent generated after sulfur-bearing ingredient in coke-stove gas.
Preferably, useless purposes of the agent as CO transformation catalyst of above-mentioned FeOOH desulfurizing agent, the FeOOH desulfurizing agent are useless
The desulfurizing agent that agent is FeOOH removes the exhaust gas that the sulfur-bearing ingredient in coal pyrolysis gas and/or calcium carbide stove exhaust generates.
Compared with prior art, the invention has the following beneficial effects:
(1) useless purposes of the agent as CO transformation catalyst of FeOOH desulfurizing agent provided by the embodiment of the present invention, will be existing
The useless agent that FeOOH desulfurizing agent is formed after carrying out desulfurization process can be used directly as CO transformation catalyst, open up FeOOH
The application field of the useless agent of desulfurizing agent reduces the useless regenerated cost of agent of FeOOH desulfurizing agent, reduces the useless agent of FeOOH desulfurizing agent
Amount of landfill reduces the harm caused by environment, simultaneously as FeOOH desulfurizing agent gives up, as slack resources, price is far low for agent
In the price of CO transformation catalyst, to reduce the production cost of CO transformation industry.
(2) useless purposes of the agent as CO transformation catalyst of FeOOH desulfurizing agent provided by the embodiment of the present invention, through detecting,
The useless agent of existing FeOOH desulfurizing agent is used as CO transformation catalyst, effect and conventional CO transformation catalyst effect phase
When.
Further, it is a kind of using FeOOH be the useless agent of the desulfurizing agent of main active as the use of CO transformation catalyst
On the way.
Preferably, it is described using FeOOH be the useless agent of the desulfurizing agent of main active as the purposes of CO transformation catalyst,
Described by the desulfurizing agent of main active of FeOOH further includes molysite chelating agent, bodied ferric sulfate, basic copper carbonate, carbonic acid
One or more of hydrogen calcium, zinc oxide, calcium sulphate dihydrate, the oxide of nickel, the oxide of cobalt, oxide of nickel.
Preferably, it is described using FeOOH be the useless agent of the desulfurizing agent of main active as the purposes of CO transformation catalyst,
The FeOOH is one of alpha-feooh, β-FeOOH, γ-FeOOH, δ-FeOOH, θ-FeOOH and amorphous FeOOH or several
Kind.
Preferably, it is described using FeOOH be the useless agent of the desulfurizing agent of main active as the purposes of CO transformation catalyst,
It is described using FeOOH as the useless agent of the desulfurizing agent of main active be the desulfurizing agent remove generated after H2S in gas it is useless
Agent.
Preferably, it is described using FeOOH be the useless agent of the desulfurizing agent of main active as the purposes of CO transformation catalyst,
Described using FeOOH as the useless agent of the desulfurizing agent of main active is that the desulfurizing agent removes in coke-stove gas after sulfur-bearing ingredient
The useless agent generated.
Preferably, it is described using FeOOH be the useless agent of the desulfurizing agent of main active as the purposes of CO transformation catalyst,
Described using FeOOH as the useless agent of the desulfurizing agent of main active is that the desulfurizing agent is removed in waste water and generated after sulfur-bearing ingredient
Useless agent.
Preferably, it is described using FeOOH be the useless agent of the desulfurizing agent of main active as the purposes of CO transformation catalyst,
Described using FeOOH as the useless agent of the desulfurizing agent of main active is that the desulfurizing agent removes coal pyrolysis gas and/or furnace of calcium carbide tail
The exhaust gas that sulfur-bearing ingredient in gas generates.
Compared with prior art, the invention has the following beneficial effects:
(1) agent is given up as CO transformation as the desulfurizing agent of main active using FeOOH provided by the embodiment of the present invention to urge
The purposes of agent, the useless agent that existing FeOOH desulfurizing agent is formed after carrying out desulfurization process can be converted directly as CO and be catalyzed
Agent uses, and has opened up the application field of the useless agent of FeOOH desulfurizing agent, reduces the useless regenerated cost of agent of FeOOH desulfurizing agent, reduces
The give up amount of landfill of agent of FeOOH desulfurizing agent reduces the harm caused by environment, the agent conduct simultaneously as FeOOH desulfurizing agent gives up
Slack resources, price are far below the price of CO transformation catalyst, to reduce the production cost of CO transformation industry.
(2) agent is given up as CO transformation as the desulfurizing agent of main active using FeOOH provided by the embodiment of the present invention to urge
The purposes of agent, through detecting, the useless agent of existing FeOOH desulfurizing agent is used as CO transformation catalyst, effect and conventional CO
Transformation catalyst effect is suitable.
Further, the purposes after a kind of useless agent regeneration of desulfurizing agent containing FeOOH as CO transformation catalyst.
Preferably, the purposes after the useless agent regeneration of the above-mentioned desulfurizing agent containing FeOOH as CO transformation catalyst, it is described
FeOOH is one or more of alpha-feooh, β-FeOOH, γ-FeOOH, δ-FeOOH, θ-FeOOH and amorphous FeOOH.
Preferably, the purposes after the useless agent regeneration of the above-mentioned desulfurizing agent containing FeOOH as CO transformation catalyst, it is described to contain
The desulfurizing agent for having FeOOH further includes molysite chelating agent, bodied ferric sulfate, basic copper carbonate, calcium bicarbonate, zinc oxide, two water sulphur
One or more of sour calcium, the oxide of nickel, the oxide of cobalt, oxide of molybdenum.
Preferably, the purposes after the useless agent regeneration of the above-mentioned desulfurizing agent containing FeOOH as CO transformation catalyst, it is described to contain
There is the desulfurizing agent of FeOOH to give up agent for the useless agent generated after H2S in the desulfurizing agent removing gas containing FeOOH；Or,
After the desulfurizing agent containing FeOOH gives up agent as sulfur-bearing ingredient in the desulfurizing agent removing coke-stove gas containing FeOOH
The useless agent generated；Or,
The desulfurizing agent containing FeOOH gives up agent to generate after sulfur-bearing ingredient in the desulfurizing agent removing waste water containing FeOOH
Useless agent；Or,
The desulfurizing agent containing FeOOH gives up agent as desulfurizing agent removing coal pyrolysis gas and/or furnace of calcium carbide tail containing FeOOH
The exhaust gas that sulfur-bearing ingredient in gas generates.
Preferably, the purposes after the useless agent regeneration of the above-mentioned desulfurizing agent containing FeOOH as CO transformation catalyst, it is described
Desulfurizing agent containing FeOOH give up agent regeneration method be,
(1) the useless agent of the desulfurizing agent containing FeOOH is ground into particle, obtains useless agent powder；
(2) the useless agent powder is made into suspension, is passed through oxygenous gas and carries out aoxidizing the iron made in the suspension
Sulfide conversion, forms the slurries containing amorphous FeOOH and elemental sulfur；
(3) slurries are filtered and obtains solid material, the elemental sulfur in the solid material described in solvent extraction remains after extraction
Remaining solid is the regrowth containing the useless agent of FeOOH desulfurizing agent.
Preferably, the purposes after the useless agent regeneration of the above-mentioned desulfurizing agent containing FeOOH as CO transformation catalyst, it is described
Desulfurizing agent containing FeOOH give up agent regeneration method be,
(1) the useless agent of the desulfurizing agent containing FeOOH is ground into particle, obtains useless agent powder；
(2) the useless agent powder is made into suspension, is passed through oxygenous gas and carries out aoxidizing the iron made in the suspension
Sulfide conversion, forms the slurries containing amorphous FeOOH and elemental sulfur；
(3) it is placed in container by the slurries or by the solid material obtained after slurries filtering, being passed through air makes institute
Elemental sulfur floating is stated, the sediment of lower vessel portion is the regrowth containing the useless agent of FeOOH desulfurizing agent.
Preferably, the above-mentioned desulfurizing agent containing FeOOH gives up purposes as CO transformation catalyst after agent regeneration, further includes
The step of regrowth containing the useless agent of FeOOH desulfurizing agent is mixed with organic binder.
Preferably, the purposes after the useless agent regeneration of the above-mentioned desulfurizing agent containing FeOOH as CO transformation catalyst, it is described
Desulfurizing agent containing FeOOH give up agent regeneration method be,
(1) by the useless agent weak acid water dispersion of the desulfurizing agent containing FeOOH, dispersion liquid is formed；
(2) dispersion liquid is heated, then oxidant is added into the dispersion liquid after heating and is reacted, reaction is fast simultaneously
The sulfur dioxide gas that speed transfer generates；
(3) after the reaction was completed, obtained precipitating is washed, is dried by filtering reacting liquid, obtains described containing FeOOH
The regrowth of the useless agent of desulfurizing agent.
Compared with prior art, the invention has the following beneficial effects:
(1) as CO transformation catalyst after the useless agent regeneration of the desulfurizing agent containing FeOOH provided by the embodiment of the present invention
Purposes, the useless agent that the existing desulfurizing agent containing FeOOH is formed after carrying out desulfurization process can be converted directly as CO and be catalyzed
Agent uses, and the application field after having opened up the useless agent regeneration of the desulfurizing agent containing FeOOH reduces containing the useless agent of FeOOH desulfurizing agent
Amount of landfill reduce the harm caused by environment, simultaneously as contain FeOOH desulfurizing agent give up agent as slack resources, valence
Lattice are far below the price of CO transformation catalyst, to reduce the production cost of CO transformation industry.
(2) contain the use after the useless agent regeneration of FeOOH desulfurizing agent as CO transformation catalyst provided by the embodiment of the present invention
On the way, through detecting, the existing desulfurizing agent containing FeOOH gives up after agent regenerates and uses as CO transformation catalyst, effect and routine
CO transformation catalyst effect it is suitable.
Further, a kind of useless agent of desulfurizing agent containing FeOOH or useless agent regenerative agent are in organic matter transformation technique
Purposes.
The use of the useless agent of the above-mentioned desulfurizing agent containing FeOOH or useless agent regenerative agent in organic matter transformation technique on the way,
The FeOOH is one of alpha-feooh, β-FeOOH, γ-FeOOH, δ-FeOOH, θ-FeOOH and amorphous FeOOH or several
Kind.
The use of the useless agent of the above-mentioned desulfurizing agent containing FeOOH or useless agent regenerative agent in organic matter transformation technique on the way,
The desulfurizing agent containing FeOOH further include molysite chelating agent, bodied ferric sulfate, basic copper carbonate, calcium bicarbonate, zinc oxide,
One or more of calcium sulphate dihydrate, the oxide of nickel, the oxide of cobalt, oxide of molybdenum.
The use of the useless agent of the above-mentioned desulfurizing agent containing FeOOH or useless agent regenerative agent in organic matter transformation technique on the way,
The useless agent of the desulfurizing agent containing FeOOH is that the desulfurizing agent containing FeOOH removes the useless agent generated after H2S in gas, contains
Contain in the useless agent generated after sulfur-bearing ingredient in the desulfurizing agent removing coke-stove gas of FeOOH, the desulfurizing agent removing waste water containing FeOOH
Sulfur-bearing ingredient in the useless agent generated after sulphur ingredient or the desulfurizing agent removing coal pyrolysis gas containing FeOOH and/or calcium carbide stove exhaust
The useless agent generated.
The use of the useless agent of the above-mentioned desulfurizing agent containing FeOOH or useless agent regenerative agent in organic matter transformation technique on the way,
The method that the useless agent regeneration of the desulfurizing agent containing FeOOH prepares useless agent regenerative agent is including but not limited to following several,
A kind of method for preparing useless agent regenerative agent provided is that the useless agent of the desulfurizing agent containing FeOOH A1, is ground into particle,
Obtain useless agent powder；A2, the useless agent powder is made into suspension, being passed through oxygenous gas and aoxidize makes in the suspension
Iron sulfide conversion, forms the slurries containing amorphous FeOOH and elemental sulfur；A3, the filtering slurries obtain solids
Expect, the elemental sulfur in the solid material described in solvent extraction, remaining solid is as described after extraction contains FeOOH desulfurizing agent
The regenerative agent of useless agent.Its another method for preparing useless agent regenerative agent provided is, B1, by the desulfurizing agent containing FeOOH
Useless agent be ground into particle, obtain useless agent powder；B2, the useless agent powder is made into suspension, is passed through oxygenous gas and carries out oxygen
Change converts the iron sulfide in the suspension, forms the slurries containing amorphous FeOOH and elemental sulfur；B3, will be described
The solid material obtained after slurries filtering is placed in container by slurries, and being passed through air makes the elemental sulfur float, container
The sediment of lower part is the regenerative agent containing the useless agent of FeOOH desulfurizing agent.Its useless agent regenerative agent of another preparation provided
Method be, C1, by the desulfurizing agent containing FeOOH give up agent weak acid water dispersion, formed dispersion liquid；C2, to the dispersion
Liquid heating, then oxidant is added into the dispersion liquid after heating and is reacted, the reaction sulfur dioxide that transfer generates rapidly simultaneously
Gas；C3, after the reaction was completed, obtained precipitating is washed, is dried by filtering reacting liquid, obtains described containing FeOOH desulfurization
The regenerative agent of the useless agent of agent.Its another method for preparing useless agent regenerative agent provided is that the desulfurizing agent containing FeOOH gives up
The regenerative agent of agent is obtained again after the useless agent of the desulfurizing agent containing FeOOH is aoxidized, vulcanized and aoxidized by slurry method
Raw agent.Its also a kind of method for preparing useless agent regenerative agent provided is, by the useless agent of the desulfurizing agent containing FeOOH and water or alkali soluble
Liquid mixing, is configured to slurries；Oxidant is added into the slurries, and once oxidation reaction occurs；To after the oxidation reaction
Vulcanizing agent is added in slurries, and vulcanization reaction occurs；Oxidant is added into the slurries after the vulcanization reaction, and secondary oxidation occurs
Reaction；Circulation carries out the vulcanization reaction and secondary oxidation reaction；Slurries after secondary oxidation reaction are consolidated
Liquid separation, obtains the regenerative agent of the useless agent of the desulfurizing agent containing FeOOH.
The use of the useless agent of the above-mentioned desulfurizing agent containing FeOOH or useless agent regenerative agent in organic matter transformation technique on the way,
The regenerative agent and organic matter of useless agent and/or the useless agent of desulfurizing agent containing FeOOH are prepared to form slurries, by the slurries with it is pure
CO or gas mixing containing CO carry out conversion reaction.Preferably, further include the steps that sulfur-containing compound is added, make iron member in slurries
The molar ratio of element and element sulphur is 1:(0.5~5).
The use of the useless agent of the above-mentioned desulfurizing agent containing FeOOH or useless agent regenerative agent in organic matter transformation technique on the way,
The reaction pressure of the conversion reaction is 5-22MPa, and reaction temperature is 200-470 DEG C.
The use of the useless agent of the above-mentioned desulfurizing agent containing FeOOH or useless agent regenerative agent in organic matter transformation technique on the way,
In the slurries, the regeneration agent content of useless agent and/or the useless agent of the desulfurizing agent containing FeOOH is 0.1~10wt%, and be averaged grain
Diameter is 0.1 μm of -5mm.
The use of the useless agent of the above-mentioned desulfurizing agent containing FeOOH or useless agent regenerative agent in organic matter transformation technique on the way,
The volume content of CO is not less than 15%, preferably not less than 50% in the gas containing CO, is most preferably not less than 90%.
Compared with prior art, the invention has the following beneficial effects:
(1) contain the regenerative agent conduct of useless agent or the useless agent of the desulfurizing agent of FeOOH provided by the embodiment of the present invention
The catalyst of organic matter transformation technique has opened up the useless agent or the application field of its regenerative agent of the desulfurizing agent containing FeOOH, reduces
The give up amount of landfill of agent of FeOOH desulfurizing agent reduces the harm caused by environment, simultaneously as desulfurizing agent containing FeOOH
Useless agent is a kind of slack resources, cheap, to reduce the cost of organic matter transformation technique.
(2) regenerative agent of useless agent or the useless agent of the desulfurizing agent containing FeOOH provided by the embodiment of the present invention can fit
The liquefaction of non-pure hydrogen atmosphere for biomass, the limitation of pure hydrogen must be used by avoiding biomass liquefying conversion, not only be reduced
Cost, and the processing route of biomass conversion has been expanded, realize the large scale quantities of biomass conversion processes in the industry
Metaplasia produces.
(3) contain the regenerative agent conduct of useless agent or the useless agent of the desulfurizing agent of FeOOH provided by the embodiment of the present invention
The catalyst of organic matter transformation technique can effectively utilize in the presence of CO and oneself for blocking organic matter in cracking process is carbonylated
By base polycondensation, and realize that the shift activity hydrogen of CO and water adds hydrogen, in the conversion reaction, organic matter especially biomass solid
Without dehydration, conversion reaction can be directly carried out, water can additionally be added in bio liquid or mineral oil, is improving liquefaction yield
Simultaneously, moreover it is possible to which the calorific value for improving obtained oil product after conversion reaction, will not generate a large amount of waste water.
(4) contain the regenerative agent conduct of useless agent or the useless agent of the desulfurizing agent of FeOOH provided by the embodiment of the present invention
The catalyst of organic matter transformation technique, is incorporated appropriate sulphur and organic matter forms slurries, and under CO atmosphere, these catalyst are first
In conjunction with CO, carbonyls is formed, then carbon atom is grafted on by organic matter (such as biomass) heat by the carbonyls
Be formed by after cracking on small molecule active position, meanwhile, iron, element sulphur catalytic action under also realize that CO transformation is in situ and produce hydrogen
And the effect of catalytic hydrodeoxygenation, the oxygen content of oil product is reduced, the liquefaction yield and length of SOLID ORGANIC matter are substantially increased
The oil product yield that strand is converted to small molecule；
Preferably, by slurry method by desulfurizing agent give up agent alternately vulcanize and oxidation regeneration after obtain regenerative agent, into one
Step ground, is reacted by multiple vulcanization-oxidization, and iron oxide and iron sulphur compound crystal phase experience reconstruct and turns in this process
Change, in addition S2-Ionic radius (0.18nm) is greater than O2-Ionic radius (0.14nm), so that between Fe-O key and Fe-S key
Conversion, the structure cell of iron oxide also undergo contraction and expansion, in turn result in the iron oxide crystallization of script stable structure
Grain becomes loose and bursts apart, and generates a large amount of nanometer iron compounds, this nanometer of iron compound thiophilicity is good, easily cures.Meanwhile
The Nanoscale Iron compound surface covers one layer of nonpolar elemental sulfur layer, which can not only hinder a nanometer iron compound
The reunion of intergranular is grown up, and is substantially increased its dispersibility, and can use existing similar compatibility characteristic between substance, is made nanometer
Iron compound is highly dispersed in nonpolar oil product；Furthermore sulphur covering nanometer iron compound because sulphur-iron it is closely coupled and
The nanometer lesser partial size of iron compound itself, to make sulphur that can react generation at low temperature with nanometer iron compound with bad
Magnetic iron ore (the Fe of reduced fuel oil hydrogenation activity1-xS), the regrowth partial size for finally obtaining such method is small, lipophilic good,
Structure slabbing nanostructure, the sulphur barrier being adsorbed between piece and piece, avoids its reunion, substantially increases the absorption of CO
Ability enhances carbonylation, transformation produces hydrogen and hydrogenation catalyst ability.
(5) contain the regenerative agent conduct of useless agent or the useless agent of the desulfurizing agent of FeOOH provided by the embodiment of the present invention
The catalyst of organic matter transformation technique, biomass solid by successively being carried out just crushing, compression and two by organic matter transformation technique
Secondary crushing, is then mixed to get mixture with catalyst, feeds the mixture into and grinds slurrying into solvent, obtains biomass content
For the slurries of 10~60wt%, the present invention is initiatively to biomass solid using the processing work of separating twice after first compressing
Skill makes loose biomass solid that collapsing, closure etc. successively be undergone to arrange again by the way that biomass solid is carried out compression processing
Position, mechanically deform stage thus can reduce the porosity of biomass so that the volume of biomass solid is greatly lowered, increase
Its big density and specific gravity, are allowed to be conducive to be dispersed in oil product, and its content in oil product can be improved, increase reaction mass
Concentration, the solid content in slurries may be up to 10~60wt%, simultaneously because the increase of biomass solid concentration also must in slurries
Pump can so be improved within the unit time to the conveying capacity of biomass solid, to improve the efficiency of entire liquefaction process, reduce
Industrial cost and energy consumption；In addition, the increase of biomass solid specific gravity also helps suspension of the biomass solid in slurries and divides
It dissipates, thus can reduce the viscosity of slurries, realize the smooth flow of slurries in the duct, avoid blocking pipeline, realize the flat of pump
Steady operating and conveying, while but also cannot function as the high viscosity waste oil of liquefaction solvent, such as used oil, kitchen in the prior art
Waste oil, rancid oil etc., can also be utilized.Further, by will just crush the heap density tune with compressed biomass
Control is to not less than 0.4 g/cm3, by the regulation of the average particle size of the biomass after separating twice to less than 5mm, pass through above-mentioned regulation
Mode grinds slurrying convenient for being added into solvent, improves its solid content in slurries；By the way that compression temperature control is existed
30-60 DEG C, the rheological characteristic that can significantly increase biomass solid is compressed to biomass at this temperature, reduces the viscous of slurries
Degree, is achieved in the smooth flow of slurries in the duct, avoids the blocking of pipeline, realizes the steady operating and conveying of pump.
(6) contain the regenerative agent conduct of useless agent or the useless agent of the desulfurizing agent of FeOOH provided by the embodiment of the present invention
Cracking, carbonylation, change occur in reactor for the catalyst of organic matter transformation technique, catalysis reaction raw materials and the gas containing CO
It changes plus the reaction such as hydrogen；It is further advanced by using paste state bed reactor, it is anti-that reaction raw materials are first sent into state bed by reactor bottom
It answers to react in device, while injecting the gas containing CO into reactor again, gas, liquid can be relied on so in reactor
Difference in specific gravity variation caused by the yield of light-end products, realizes each phase after the different specific weight and complex reaction of each material of body, solid
The otherness of state flow velocity controls so that biomass solid raw material occur from the bottom to top in reactor cracking, carbonylation, transformation,
Add hydrogen, reaction, even if heavy biomass solid and catalyst solid particle are with gas and light-end products in the process
Rise, but it is again return under gas effect of the top containing CO participate in reacting again to bottom, according to reactor upper, middle and lower portion
Material density appropriate adjustment enter the gas and its injection rate containing CO in the slurries of reactor, to realize unconverted have
Thus machine matter can ensure that the abundant progress of various reactions in the circulation of inside reactor and the balance discharge of catalyst, thus
Be conducive to improve the conversion ratio and biology oil yield of organic matter
(7) contain the regenerative agent conduct of useless agent or the useless agent of the desulfurizing agent of FeOOH provided by the embodiment of the present invention
The catalyst of organic matter transformation technique, in organic matter transformation technique, organic matter does not need to be dehydrated, and reduces dry cost；In
In reaction process is the gas containing CO, this contains the gas of CO either pure CO, can also be impure, such as in addition to containing
CO can also can also be the synthesis that coal, biomass, natural gas, mineral oil gasification produce containing hydrogen, hydrogen sulfide, methane etc.
Gas, in synthesis gas other than CO, remainder gas can be hydrogeneous, carbon dioxide or the mixture of methane, ethane, gas system
It causes originally to substantially reduce；During being reacted, with the gas containing CO, and using cheap ferrum-based catalyst or useless
Under agent effect, realize cracking reaction, carbonylation, conversion reaction, the process integrations such as hydrogenation reaction, be easy to provide it is sufficient from
By group, the carbonization coking of organic matter is avoided, organic matter conversion ratio and liquid yield are high, and reaction temperature and pressure are reduced；
The oil product that the liquefaction process generates can be used for front and continued technique to prepare slurries.
(8) desulfurizing agent containing FeOOH that the application mentions is the desulfurizing agent directly formed with FeOOH, or is made with FeOOH
It is carried on the desulfurizing agent formed on carrier or FeOOH for main active and mixes shape with organic binder or other additives
At desulfurizing agent or FeOOH and organic binder or other additive mixed loads in the desulfurizing agent etc. formed on carrier.In a word
The desulfurizing agent containing FeOOH of the application is suitable for the preparation method system of all desulfurizing agents in the prior art containing FeOOH
Standby obtained desulfurizing agent, useless agent are that the above-mentioned desulfurizing agent containing FeOOH is applied to various sulfur methods in the prior art
The useless agent generated, is particularly suitable for the FeOOH desulfurizing agent by generating after biogas, liquid, coal gas, flue gas, petroleum and gasoline desulfurization
Existing all regeneration methods can be used in useless agent, the useless agent regenerative agent that the regeneration method of above-mentioned useless agent obtains.
Further, a kind of Fe21.333O32Desulfurizing agent gives up purposes of the agent as biomass hydrogenation liquefaction catalyst.
Above-mentioned Fe21.333O32Desulfurizing agent gives up purposes of the agent as biomass hydrogenation liquefaction catalyst, the Fe21.333O32
Desulfurizing agent gives up agent as Fe21.333O32Desulfurizing agent removes H in gas2The useless agent generated after S.
Above-mentioned Fe21.333O32Desulfurizing agent gives up purposes of the agent as biomass hydrogenation liquefaction catalyst, the Fe21.333O32
Desulfurizing agent gives up agent as Fe21.333O32Desulfurizing agent removing coke-stove gas in the useless agent that generates after sulfur-bearing ingredient.
Above-mentioned Fe21.333O32Desulfurizing agent gives up purposes of the agent as biomass hydrogenation liquefaction catalyst, the Fe21.333O32
Desulfurizing agent gives up agent as Fe21.333O32Desulfurizing agent removing waste water in the useless agent that generates after sulfur-bearing ingredient.
Above-mentioned Fe21.333O32Desulfurizing agent gives up purposes of the agent as biomass hydrogenation liquefaction catalyst, the Fe21.333O32
Desulfurizing agent gives up agent as Fe21.333O32Desulfurizing agent removing coal pyrolysis gas and/or calcium carbide stove exhaust in sulfur-bearing ingredient generate it is useless
Gas.
Compared with prior art, the invention has the following beneficial effects:
(1) Fe provided by the embodiment of the present invention21.333O32Desulfurizing agent gives up use of the agent as biomass hydrogenation liquefaction catalyst
On the way, by existing Fe21.333O32The useless agent that desulfurizing agent is formed after carrying out desulfurization process can be urged directly as biomass hydrogenation liquefaction
Agent uses, and has opened up Fe21.333O32The application field of the useless agent of desulfurizing agent, reduces Fe21.333O32The useless agent of desulfurizing agent is regenerated
Cost reduces Fe21.333O32The amount of landfill of the useless agent of desulfurizing agent reduces the harm caused by environment, simultaneously as magnetic oxygenated
Iron oxide red Fe21.333O32Desulfurizing agent gives up agent as slack resources, and price is far below the price of biomass hydrogenation liquefaction catalyst, from
And reduce the production ingredient for adding hydrogen industry.
(2) Fe provided by the embodiment of the present invention21.333O32Desulfurizing agent gives up use of the agent as biomass hydrogenation liquefaction catalyst
On the way, through detecting, existing magnetic iron oxide red Fe21.333O32The useless agent of desulfurizing agent is used as biomass hydrogenation liquefaction catalyst,
Effect is suitable with conventional biomass hydrogenation liquefaction catalyst effect.
Further, one kind is with Fe21.333O32For main active desulfurizing agent useless agent as biomass hydrogenation liquefaction
The purposes of catalyst.
It is above-mentioned with Fe21.333O32For main active desulfurizing agent useless agent as biomass hydrogenation liquefaction catalyst
Purposes, it is described with Fe21.333O32Desulfurizing agent for main active further includes potassium oxide, Detitanium-ore-type Ti02, copper oxide, oxygen
Change one or more of lead, zinc oxide, manganese dioxide.
It is above-mentioned with Fe21.333O32For main active desulfurizing agent useless agent as biomass hydrogenation liquefaction catalyst
Purposes, it is described with Fe21.333O32Useless agent for the desulfurizing agent of main active is H in the desulfurizing agent removing gas2It is produced after S
Raw useless agent.
It is above-mentioned with Fe21.333O32For main active desulfurizing agent useless agent as biomass hydrogenation liquefaction catalyst
Purposes, it is described with Fe21.333O32Useless agent for the desulfurizing agent of main active is to contain in the desulfurizing agent removing coke-stove gas
The useless agent generated after sulphur ingredient.
It is above-mentioned with Fe21.333O32For main active desulfurizing agent useless agent as biomass hydrogenation liquefaction catalyst
Purposes, it is described with Fe21.333O32Useless agent for the desulfurizing agent of main active be in the desulfurizing agent removing waste water sulfur-bearing at
The useless agent generated after point.
It is above-mentioned with Fe21.333O32For main active desulfurizing agent useless agent as biomass hydrogenation liquefaction catalyst
Purposes, it is described with Fe21.333O32Useless agent for the desulfurizing agent of main active be desulfurizing agent removing coal pyrolysis gas and/or
The exhaust gas that sulfur-bearing ingredient in calcium carbide stove exhaust generates.
Compared with prior art, the invention has the following beneficial effects:
(1) with Fe provided by the embodiment of the present invention21.333O32Agent is given up as biomass for the desulfurizing agent of main active
The purposes of hydrogenation liquefaction catalyst, by existing Fe21.333O32The useless agent that desulfurizing agent is formed after carrying out desulfurization process can directly be made
For the use of biomass hydrogenation liquefaction catalyst, Fe has been opened up21.333O32The application field of the useless agent of desulfurizing agent, reduces Fe21.333O32
Desulfurizing agent gives up the regenerated cost of agent, reduces Fe21.333O32The amount of landfill of the useless agent of desulfurizing agent reduces the harm caused by environment,
Simultaneously as Fe21.333O32Desulfurizing agent gives up agent as slack resources, and price is far below the valence of biomass hydrogenation liquefaction catalyst
Lattice, to reduce the production cost for adding hydrogen industry.
(2) with Fe provided by the embodiment of the present invention21.333O32Agent is given up as biomass for the desulfurizing agent of main active
The purposes of hydrogenation liquefaction catalyst, through detecting, existing Fe21.333O32Desulfurizing agent gives up agent as biomass hydrogenation liquefaction catalyst
It uses, effect is suitable with conventional biomass hydrogenation liquefaction catalyst effect.
Further, one kind containing Fe21.333O32Desulfurizing agent give up agent regeneration after as biomass hydrogenation liquefaction catalyst
Purposes.
It is above-mentioned to contain Fe21.333O32Desulfurizing agent give up purposes as biomass hydrogenation liquefaction catalyst after agent regeneration, it is described
Contain Fe21.333O32Desulfurizing agent further include potassium oxide, Detitanium-ore-type Ti02, copper oxide, lead oxide, zinc oxide or manganese dioxide
One or more of.
It is above-mentioned to contain Fe21.333O32Desulfurizing agent give up purposes as biomass hydrogenation liquefaction catalyst after agent regeneration, it is described
Contain Fe21.333O32Desulfurizing agent give up agent be contain Fe21.333O32Desulfurizing agent removes H in gas2The useless agent generated after S；Or
It is described to contain Fe21.333O32Desulfurizing agent give up agent be contain Fe21.333O32Desulfurizing agent removing coke-stove gas in sulfur-bearing
The useless agent generated after ingredient；Or
It is described to contain Fe21.333O32Desulfurizing agent give up agent be contain Fe21.333O32Desulfurizing agent removing waste water in sulfur-bearing ingredient
The useless agent generated afterwards；Or
It is described to contain Fe21.333O32Desulfurizing agent give up agent be contain Fe21.333O32Desulfurizing agent removing coal pyrolysis gas and/or
The exhaust gas that sulfur-bearing ingredient in calcium carbide stove exhaust generates.
It is above-mentioned to contain Fe21.333O32Desulfurizing agent give up purposes as biomass hydrogenation liquefaction catalyst after agent regeneration, it is described
Contain Fe21.333O32Desulfurizing agent give up agent regeneration method be,
(1) contain Fe for described21.333O32Desulfurizing agent give up agent weak acid aqueous dispersion, formed dispersion liquid；
(2) dispersion liquid is heated, oxidant is then added into the dispersion liquid and is reacted, reaction while is rapid
Shift the sulfur dioxide gas generated；
(3) after the reaction was completed, obtained precipitating is washed, dries and contain to get described in by filtering reacting liquid
Fe21.333O32Desulfurizing agent give up agent regenerative agent.
It is above-mentioned to contain Fe21.333O32Desulfurizing agent give up purposes as biomass hydrogenation liquefaction catalyst after agent regeneration, it is described
Contain Fe21.333O32Desulfurizing agent give up agent regeneration method be,
Contain Fe for described21.333O32Desulfurizing agent give up agent temperature be 800 DEG C, air speed 3000h-1, regeneration atmosphere in
It is regenerated, the regeneration atmosphere is by O2/SO2Volume ratio is 15~28mol%O of 1:1002/SO2With 72~85mol%N2 group
At to get containing Fe described in21.333O32Desulfurizing agent give up agent regenerative agent.
It is above-mentioned to contain Fe21.333O32Desulfurizing agent give up purposes as biomass hydrogenation liquefaction catalyst after agent regeneration, it is described
Contain Fe21.333O32Desulfurizing agent give up agent regeneration method be,
(1) superheated steam is passed through and described contains Fe21.333O32Desulfurizing agent give up agent in, it is purged and is heated, receive
Collect the useless agent of solid；
(2) reducing gas is passed through to restore the useless agent of the solid to get Fe is contained described in21.333O32Desulfurizing agent
The regenerative agent of useless agent.
Compared with prior art, the invention has the following beneficial effects:
(1) contain Fe provided by the embodiment of the present invention21.333O32Desulfurizing agent give up agent as biomass hydrogenation liquefaction catalysis
The purposes of agent, by existing Fe21.333O32The useless agent that desulfurizing agent is formed after carrying out desulfurization process can add hydrogen directly as biomass
Deliquescence accelerant uses, and has opened up Fe21.333O32The application field of the useless agent of desulfurizing agent, reduces Fe21.333O32Desulfurizing agent gives up agent again
Raw cost, reduces Fe21.333O32The amount of landfill of the useless agent of desulfurizing agent reduces the harm caused by environment, simultaneously as
Fe21.333O32Desulfurizing agent gives up agent as slack resources, and price is far below the price of biomass hydrogenation liquefaction catalyst, to drop
Low plus hydrogen industry production cost.
(2) contain Fe provided by the embodiment of the present invention21.333O32Desulfurizing agent give up agent as biomass hydrogenation liquefaction catalysis
The purposes of agent, through detecting, existing Fe21.333O32Desulfurizing agent give up agent used as biomass hydrogenation liquefaction catalyst, effect and
Conventional biomass hydrogenation liquefaction catalyst effect is suitable.
Further, the present invention provides Fe21.333O32Desulfurizing agent purposes of the useless agent as CO transformation catalyst.
Further, the Fe21.333O32Desulfurizing agent useless agent be Fe21.333O32Contain in desulfurizing agent removing sulfurous gas
The useless agent generated after sulphur ingredient.
Further, the sulfurous gas is the tail gas, coke-stove gas, coal pyrolysis gas, the electricity that generate after oil hydrogenation upgrading
At least one of stone furnace exhaust gas.
Further, the Fe21.333O32Desulfurizing agent useless agent be Fe21.333O32Desulfurizing agent removes in sulfur-containing waste water
The useless agent generated after sulfur-bearing ingredient.
Further, the Fe21.333O32Desulfurizing agent useless agent be Fe21.333O32Desulfurizing agent remove oil product in sulfur-bearing at
The useless agent generated after point.
Further, the sulfur-bearing ingredient includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum by-product, gasoline, heavy oil, residual oil.
Compared with prior art, the invention has the following beneficial effects:
(1) Fe provided by the embodiment of the present invention21.333O32Desulfurizing agent give up purposes of the agent as CO transformation catalyst, general
Existing Fe21.333O32The useless agent that desulfurizing agent is formed after carrying out desulfurization process can be used directly as CO transformation catalyst, be opened
Fe is opened up21.333O32The application field of the useless agent of desulfurizing agent, reduces Fe21.333O32Desulfurizing agent gives up the regenerated cost of agent, reduces
Fe21.333O32The amount of landfill of the useless agent of desulfurizing agent reduces the harm caused by environment, simultaneously as Fe21.333O32Desulfurizing agent gives up agent
As slack resources, price is far below the price of CO transformation catalyst, to reduce the production cost of CO transformation industry.
(2) Fe provided by the embodiment of the present invention21.333O32Desulfurizing agent give up purposes of the agent as CO transformation catalyst, pass through
Detection, existing Fe21.333O32The useless agent of desulfurizing agent is used as CO transformation catalyst, effect and conventional CO transformation catalyst
Effect is suitable.
Further, containing Fe21.333O32Desulfurizing agent purposes of the useless agent as CO transformation catalyst.
Further, described to contain Fe21.333O32Desulfurizing agent further include potassium oxide, Detitanium-ore-type Ti02, copper oxide, oxygen
Change one or more of lead, zinc oxide, manganese dioxide.
Further, described to contain Fe21.333O32Desulfurizing agent useless agent be with Fe21.333O32For main active
The useless agent generated after sulfur-bearing ingredient in desulfurizing agent removing sulfurous gas.
Further, the sulfurous gas is the tail gas, coke-stove gas, coal pyrolysis gas, the electricity that generate after oil hydrogenation upgrading
At least one of stone furnace exhaust gas.
Further, described to contain Fe21.333O32Desulfurizing agent useless agent be with Fe21.333O32For main active
The useless agent generated after sulfur-bearing ingredient in desulfurizing agent removing sulfur-containing waste water.
Further, described to contain Fe21.333O32Desulfurizing agent useless agent be with Fe21.333O32For main active
The useless agent generated after sulfur-bearing ingredient in desulfurizing agent removing oil product.
Further, the sulfur-bearing ingredient includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum by-product, gasoline, heavy oil, residual oil.
Compared with prior art, the invention has the following beneficial effects:
(1) contain Fe provided by the embodiment of the present invention21.333O32Desulfurizing agent give up use of the agent as CO transformation catalyst
On the way, by existing Fe21.333O32The useless agent that desulfurizing agent is formed after carrying out desulfurization process can make directly as CO transformation catalyst
With having opened up Fe21.333O32The application field of the useless agent of desulfurizing agent, reduces Fe21.333O32Desulfurizing agent gives up the regenerated cost of agent, subtracts
Fe is lacked21.333O32The amount of landfill of the useless agent of desulfurizing agent reduces the harm caused by environment, simultaneously as Fe21.333O32Desulfurizing agent
Useless agent is far below the price of CO transformation catalyst as slack resources, price, to reduce being produced into for CO transformation industry
This.
(2) contain Fe provided by the embodiment of the present invention21.333O32Desulfurizing agent give up use of the agent as CO transformation catalyst
On the way, through detecting, existing Fe21.333O32The useless agent of desulfurizing agent is used as CO transformation catalyst, and effect and conventional CO transformation are urged
Agent effect is suitable.
Further, containing Fe21.333O32Desulfurizing agent useless agent regeneration after purposes as CO transformation catalyst.
Further, described to contain Fe21.333O32Desulfurizing agent further include potassium oxide, Detitanium-ore-type Ti02, copper oxide, oxygen
Change one or more of lead, zinc oxide, manganese dioxide.
Further, described to contain Fe21.333O32Desulfurizing agent useless agent regeneration after for Fe21.333O32For chief active
The useless agent generated after sulfur-bearing ingredient in the desulfurizing agent removing sulfurous gas of ingredient.
Further, the sulfurous gas is the tail gas, coke-stove gas, coal pyrolysis gas, the electricity that generate after oil hydrogenation upgrading
At least one of stone furnace exhaust gas.
Further, described to contain Fe21.333O32Desulfurizing agent useless agent regeneration after for Fe21.333O32For chief active
The useless agent generated after sulfur-bearing ingredient in the desulfurizing agent removing sulfur-containing waste water of ingredient.
Further, described to contain Fe21.333O32Desulfurizing agent useless agent regeneration after for Fe21.333O32For chief active
The useless agent generated after sulfur-bearing ingredient in the desulfurizing agent removing oil product of ingredient.
Further, the sulfur-bearing ingredient includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum by-product, gasoline, heavy oil, residual oil.
Further, described to contain Fe21.333O32Desulfurizing agent useless agent regeneration method, include the following steps:
Described is contained into Fe21.333O32The useless agent of desulfurizing agent mixed with water or aqueous slkali, be configured to slurries；
Oxidant is added into the slurries, carries out oxidation reaction；
Slurries after the oxidation reaction are separated by solid-liquid separation, solid is collected, as described contains Fe21.333O32's
The regrowth of the useless agent of desulfurizing agent.
It further, further include adding sulphur in the slurries after the oxidation reaction before carrying out the separation of solid and liquid
Vulcanization reaction occurs for agent；It adds oxidant thereto again, oxidation reaction occurs；Finally circulation carry out the vulcanization reaction and
The molar ratio of ferro element and element sulphur is 1:0.5~10 in slurries after the oxidation reaction to the oxidation reaction；
The vulcanizing agent includes Na2S、Na2S2O3、(NH4)2S、(NH4)2S2O3, mercaptan, thiocarbamide, dimethylsulphide, carbonyl
Base sulphur, H2At least one of S；
The oxidant includes H2O2、NaClO、O2、O3At least one of.
Compared with prior art, the invention has the following beneficial effects:
(1) contain Fe provided by the embodiment of the present invention21.333O32Desulfurizing agent give up use of the agent as CO transformation catalyst
On the way, by existing Fe21.333O32The useless agent that desulfurizing agent is formed after carrying out desulfurization process can make directly as CO transformation catalyst
With having opened up Fe21.333O32The application field of the useless agent of desulfurizing agent, reduces Fe21.333O32Desulfurizing agent gives up the regenerated cost of agent, subtracts
Fe is lacked21.333O32The amount of landfill of the useless agent of desulfurizing agent reduces the harm caused by environment, simultaneously as Fe21.333O32Desulfurizing agent
Useless agent is far below the price of CO transformation catalyst as slack resources, price, to reduce being produced into for CO transformation industry
This.
(2) contain Fe provided by the embodiment of the present invention21.333O32Desulfurizing agent give up use of the agent as CO transformation catalyst
On the way, through detecting, existing Fe21.333O32The useless agent of desulfurizing agent is used as CO transformation catalyst, and effect and conventional CO transformation are urged
Agent effect is suitable.
Further, one kind containing Fe21.333O32Desulfurizing agent useless agent or useless agent regenerative agent in organic matter transformation technique
Purposes.
Above-mentioned contains Fe21.333O32Desulfurizing agent purposes in organic matter transformation technique of useless agent or useless agent regenerative agent
In, it is described to contain Fe21.333O32Desulfurizing agent further include potassium oxide, Detitanium-ore-type Ti02, copper oxide, lead oxide, zinc oxide or
One or more of manganese dioxide.
Above-mentioned contains Fe21.333O32Desulfurizing agent purposes in organic matter transformation technique of useless agent or useless agent regenerative agent
In, it is described to contain Fe21.333O32Desulfurizing agent useless agent be contain Fe21.333O32Desulfurizing agent removing gas in H2It is generated after S
Useless agent contains Fe21.333O32Desulfurizing agent removing coke-stove gas in generate after sulfur-bearing ingredient useless agent, contain Fe21.333O32It is de-
Sulphur agent removes the useless agent generated after sulfur-bearing ingredient in waste water or contains Fe21.333O32Desulfurizing agent removing coal pyrolysis gas and/or calcium carbide
The useless agent that sulfur-bearing ingredient in furnace exhaust gas generates.
Above-mentioned contains Fe21.333O32Desulfurizing agent purposes in organic matter transformation technique of useless agent or useless agent regenerative agent
In, described contains Fe21.333O32The useless agent regeneration method for preparing useless agent regenerative agent of desulfurizing agent include but is not limited to following
Several, a kind of method for preparing useless agent regenerative agent provided is A1, to contain Fe for described21.333O32The useless agent of desulfurizing agent grind
Particle is worn into, useless agent powder is obtained；A2, the useless agent powder is made into suspension, be passed through oxygenous gas carry out oxidation make it is described
Iron sulfide conversion in suspension, forms the slurries containing amorphous FeOOH and elemental sulfur；A3, the filtering slurries obtain
To solid material, elemental sulfur in the solid material described in solvent extraction, remaining solid is described contains after extraction
Fe21.333O32The regenerative agent of the useless agent of desulfurizing agent.Its another method for preparing useless agent regenerative agent provided is B1, to contain by described in
There is Fe21.333O32The useless agent of desulfurizing agent be ground into particle, obtain useless agent powder；B2, the useless agent powder is made into suspension, be passed through
Oxygenous gas, which carries out oxidation, converts the iron sulfide in the suspension, is formed and contains amorphous FeOOH and simple substance
The slurries of sulphur；B3, it is placed in container by the slurries or by the solid material obtained after slurries filtering, being passed through air makes institute
Elemental sulfur floating is stated, the sediment of lower vessel portion is as described to contain Fe21.333O32The regenerative agent of the useless agent of desulfurizing agent.What it was provided
Another method for preparing useless agent regenerative agent is C1, to contain Fe for described21.333O32Desulfurizing agent give up agent weak acid water dispersion, shape
At dispersion liquid；C2, the dispersion liquid is heated, then oxidant is added into the dispersion liquid after heating and is reacted, reaction is simultaneously
The sulfur dioxide gas that transfer generates rapidly；C3, after the reaction was completed, obtained precipitating is washed, is dried by filtering reacting liquid
It is dry, it obtains described containing Fe21.333O32The regenerative agent of the useless agent of desulfurizing agent.Its another method for preparing useless agent regenerative agent provided
It is described to contain Fe21.333O32The regenerative agent of useless agent of desulfurizing agent be by slurry method to containing Fe21.333O32Desulfurizing agent
Useless agent aoxidized, vulcanized and aoxidized after obtained regenerative agent.Its provide also a kind of method for preparing useless agent regenerative agent be,
Fe will be contained21.333O32The useless agent of desulfurizing agent mixed with water or aqueous slkali, be configured to slurries；Oxidation is added into the slurries
Once oxidation reaction occurs for agent；Vulcanizing agent is added into the slurries after the oxidation reaction, and vulcanization reaction occurs；To the sulphur
Oxidant is added in slurries after changing reaction, and secondary oxidation reaction occurs；Circulation carries out the vulcanization reaction and the secondary oxygen
Change reaction；Slurries after secondary oxidation reaction are separated by solid-liquid separation, are obtained containing Fe21.333O32Desulfurizing agent useless agent
Regenerative agent.
Its also a kind of method for preparing useless agent regenerative agent provided is D1, to contain Fe for described21.333O32Desulfurizing agent it is useless
The aqueous dispersion of agent weak acid forms dispersion liquid；D2, the heating dispersion liquid, are then added oxidation into the dispersion liquid
Agent is reacted, and reaction while shifts rapidly the sulfur dioxide gas of generation；D3, after the reaction was completed, filtering reacting liquid, will
To precipitating washed, dried to get containing Fe described in21.333O32Desulfurizing agent give up agent regenerative agent.
Its also a kind of method for preparing useless agent regenerative agent provided is to contain Fe for described21.333O32Desulfurizing agent give up agent exist
Temperature is 800 DEG C, is regenerated in air speed 3000h-1, regeneration atmosphere that the regeneration atmosphere is by O2/SO2Volume ratio is 1:100
15~28mol%O2/SO2It is formed with 72~85mol%N2 to get Fe is contained described in21.333O32Desulfurizing agent give up agent again
Raw agent.
Its also a kind of method for preparing useless agent regenerative agent provided is that superheated steam E1, is passed through described contain
Fe21.333O32Desulfurizing agent give up agent in, it is purged and is heated, collect solid give up agent；E2, reducing gas is passed through to described
The useless agent of solid is restored to get Fe is contained described in21.333O32Desulfurizing agent give up agent regenerative agent.
Above-mentioned contains Fe21.333O32Desulfurizing agent purposes in organic matter transformation technique of useless agent or useless agent regenerative agent
In,
Fe will be contained21.333O32The regenerative agent and organic matter of useless agent and/or useless agent of desulfurizing agent prepare to form slurries, will
Gas mixing of the slurries with pure CO or containing CO carries out conversion reaction.Preferably, further include that sulfur-containing compound is added, make to starch
The molar ratio of ferro element and element sulphur is 1:(0.5~5 in liquid).
Above-mentioned contains Fe21.333O32Desulfurizing agent purposes in organic matter transformation technique of useless agent or useless agent regenerative agent
In, the reaction pressure of the conversion reaction is 5-22MPa, and reaction temperature is 200-470 DEG C.
Above-mentioned contains Fe21.333O32Desulfurizing agent purposes in organic matter transformation technique of useless agent or useless agent regenerative agent
In, in the slurries, contain Fe21.333O32Desulfurizing agent useless agent and/or useless agent regeneration agent content be 0.1~10wt%,
Average grain diameter is 0.1 μm of -5mm.
Above-mentioned contains Fe21.333O32Desulfurizing agent purposes in organic matter transformation technique of useless agent or useless agent regenerative agent
In, the volume content of CO is not less than 15%, preferably not less than 50% in the gas containing CO, is most preferably not less than
90%.
Technical solution of the present invention has the advantages that
(1) contain Fe provided by the embodiment of the present invention21.333O32Desulfurizing agent useless agent or the useless agent regenerative agent make
For the catalyst of organic matter transformation technique, opens up and contained Fe21.333O32Desulfurizing agent useless agent or its regenerative agent application neck
Domain reduces Fe21.333O32The amount of landfill of the useless agent of desulfurizing agent reduces the harm caused by environment, simultaneously as containing
Fe21.333O32The useless agent of desulfurizing agent be a kind of slack resources, it is cheap, thus reduce organic matter transformation technique at
This.
(2) contain Fe provided by the embodiment of the present invention21.333O32The regenerative agent of useless agent or the useless agent of desulfurizing agent can
The liquefaction of non-pure hydrogen atmosphere suitable for biomass, the limitation of pure hydrogen must be used by avoiding biomass liquefying conversion, not only be dropped
Low cost, and expanded the processing route of biomass conversion realizes biomass conversion processes in the industry extensive
Quantization production.
(3) contain Fe provided by the embodiment of the present invention21.333O32Desulfurizing agent useless agent or the useless agent regenerative agent make
For the catalyst of organic matter transformation technique, carbonylation can be effectively utilized in the presence of CO and blocks organic matter in cracking process
Free radical polycondensation, and realize that the shift activity hydrogen of CO and water adds hydrogen, in the conversion reaction, organic matter especially biomass solid
Without dehydration, conversion reaction can be directly carried out, water can additionally be added in bio liquid or mineral oil, is improving liquefaction yield
Simultaneously, moreover it is possible to which the calorific value for improving obtained oil product after conversion reaction, will not generate a large amount of waste water.
(4) contain Fe provided by the embodiment of the present invention21.333O32Desulfurizing agent useless agent or the useless agent regenerative agent make
For the catalyst of organic matter transformation technique, it is incorporated appropriate sulphur and organic matter forms slurries, under CO atmosphere, these catalyst are first
First in conjunction with CO, carbonyls is formed, then carbon atom is grafted on by organic matter (such as biomass) by the carbonyls
Be formed by after thermal cracking on small molecule active position, meanwhile, iron, element sulphur catalytic action under also realize that CO transformation is in situ and produce
The effect of hydrogen and catalytic hydrodeoxygenation reduces the oxygen content of oil product, substantially increase SOLID ORGANIC matter liquefaction yield and
The oil product yield that long chain is converted to small molecule；
Preferably, by slurry method by desulfurizing agent give up agent alternately vulcanize and oxidation regeneration after obtain regenerative agent, into one
Step ground, is reacted by multiple vulcanization-oxidization, and iron oxide and iron sulphur compound crystal phase experience reconstruct and turns in this process
Change, in addition S2-Ionic radius (0.18nm) is greater than O2-Ionic radius (0.14nm), so that between Fe-O key and Fe-S key
Conversion, the structure cell of iron oxide also undergo contraction and expansion, in turn result in the iron oxide crystallization of script stable structure
Grain becomes loose and bursts apart, and generates a large amount of nanometer iron compounds, this nanometer of iron compound thiophilicity is good, easily cures.Meanwhile
The Nanoscale Iron compound surface covers one layer of nonpolar elemental sulfur layer, which can not only hinder a nanometer iron compound
The reunion of intergranular is grown up, and is substantially increased its dispersibility, and can use existing similar compatibility characteristic between substance, is made nanometer
Iron compound is highly dispersed in nonpolar oil product；Furthermore sulphur covering nanometer iron compound because sulphur-iron it is closely coupled and
The nanometer lesser partial size of iron compound itself, to make sulphur that can react generation at low temperature with nanometer iron compound with bad
Magnetic iron ore (the Fe of reduced fuel oil hydrogenation activity1-xS), the regrowth partial size for finally obtaining such method is small, lipophilic good,
Structure slabbing nanostructure, the sulphur barrier being adsorbed between piece and piece, avoids its reunion, substantially increases the absorption of CO
Ability enhances carbonylation, transformation produces hydrogen and hydrogenation catalyst ability.
(5) contain Fe provided by the embodiment of the present invention21.333O32Desulfurizing agent useless agent or the useless agent regenerative agent make
For the catalyst of organic matter transformation technique, organic matter transformation technique by biomass solid successively being carried out just crush, compression and
Separating twice is then mixed to get mixture with catalyst, feeds the mixture into and grinds slurrying into solvent, obtains biomass and contains
Amount is the slurries of 10~60wt%, and the present invention is initiatively to biomass solid using the processing of separating twice after first compressing
Technique makes loose biomass solid that collapsing, closure etc. successively be undergone to arrange again by the way that biomass solid is carried out compression processing
Position, mechanically deform stage thus can reduce the porosity of biomass so that the volume of biomass solid is greatly lowered, increase
Its big density and specific gravity, are allowed to be conducive to be dispersed in oil product, and its content in oil product can be improved, increase reaction mass
Concentration, the solid content in slurries may be up to 10~60wt%, simultaneously because the increase of biomass solid concentration also must in slurries
Pump can so be improved within the unit time to the conveying capacity of biomass solid, to improve the efficiency of entire liquefaction process, reduce
Industrial cost and energy consumption；In addition, the increase of biomass solid specific gravity also helps suspension of the biomass solid in slurries and divides
It dissipates, thus can reduce the viscosity of slurries, realize the smooth flow of slurries in the duct, avoid blocking pipeline, realize the flat of pump
Steady operating and conveying, while but also cannot function as the high viscosity waste oil of liquefaction solvent, such as used oil, kitchen in the prior art
Waste oil, rancid oil etc., can also be utilized.Further, by will just crush the heap density tune with compressed biomass
Control is to not less than 0.4 g/cm3, by the regulation of the average particle size of the biomass after separating twice to less than 5mm, pass through above-mentioned regulation
Mode grinds slurrying convenient for being added into solvent, improves its solid content in slurries；By the way that compression temperature control is existed
30-60 DEG C, the rheological characteristic that can significantly increase biomass solid is compressed to biomass at this temperature, reduces the viscous of slurries
Degree, is achieved in the smooth flow of slurries in the duct, avoids the blocking of pipeline, realizes the steady operating and conveying of pump.
(6) contain Fe provided by the embodiment of the present invention21.333O32Desulfurizing agent useless agent or the useless agent regenerative agent make
For the catalyst of organic matter transformation technique, it is catalyzed reaction raw materials and cracking, carbonylation, change occurs in reactor for the gas containing CO
It changes plus the reaction such as hydrogen；It is further advanced by using paste state bed reactor, it is anti-that reaction raw materials are first sent into state bed by reactor bottom
It answers to react in device, while injecting the gas containing CO into reactor again, gas, liquid can be relied on so in reactor
Difference in specific gravity variation caused by the yield of light-end products, realizes each phase after the different specific weight and complex reaction of each material of body, solid
The otherness of state flow velocity controls so that biomass solid raw material occur from the bottom to top in reactor cracking, carbonylation, transformation,
Add hydrogen, reaction, even if heavy biomass solid and catalyst solid particle are with gas and light-end products in the process
Rise, but it is again return under gas effect of the top containing CO participate in reacting again to bottom, according to reactor upper, middle and lower portion
Material density appropriate adjustment enter the gas and its injection rate containing CO in the slurries of reactor, to realize unconverted have
Thus machine matter can ensure that the abundant progress of various reactions in the circulation of inside reactor and the balance discharge of catalyst, thus
Be conducive to improve the conversion ratio and biology oil yield of organic matter
(7) contain Fe provided by the embodiment of the present invention21.333O32Desulfurizing agent useless agent or the useless agent regenerative agent make
For the catalyst of organic matter transformation technique, in organic matter transformation technique, organic matter does not need to be dehydrated, and reduces dry cost；
During the reaction be the gas containing CO, this contains the gas of CO either pure CO, can also be impure, such as in addition to containing
There is CO, can also can also be the conjunction that coal, biomass, natural gas, mineral oil gasification produce containing hydrogen, hydrogen sulfide, methane etc.
At gas, in synthesis gas other than CO, remainder gas can be hydrogeneous, carbon dioxide or the mixture of methane, ethane, gas
Manufacturing cost substantially reduces；During being reacted, with the gas containing CO, and using cheap ferrum-based catalyst or
It gives up under agent effect, realizes the process integrations such as cracking reaction, carbonylation, conversion reaction, hydrogenation reaction, be easy to provide abundance
Free group avoids the carbonization coking of organic matter, and organic matter conversion ratio and liquid yield are high, and reaction temperature and pressure are dropped
It is low；The oil product that the liquefaction process generates can be used for front and continued technique to prepare slurries.
(8) what the application mentioned contains Fe21.333O32Desulfurizing agent be with Fe21.333O32The desulfurizing agent directly formed, or with
Fe21.333O32The desulfurizing agent or Fe formed on carrier is carried on as main active21.333O32With organic binder or its
The desulfurizing agent or Fe that its additive is mixed to form21.333O32With organic binder or other additive mixed loads in shape on carrier
At desulfurizing agent etc..The application contains Fe in a word21.333O32Desulfurizing agent be suitable in the prior art containing Fe21.333O32
All desulfurizing agents the desulfurizing agent that is prepared of preparation method, agent of giving up is by above-mentioned containing Fe21.333O32Desulfurizing agent application
In the useless agent that various sulfur methods in the prior art generate, it is particularly suitable for by biogas, liquid, coal gas, flue gas, petroleum and vapour
The Fe generated after oily desulfurization21.333O32Desulfurizing agent gives up agent, and the useless agent regenerative agent that the regeneration method of above-mentioned useless agent obtains can be used existing
All regeneration methods.
Further, purposes of the useless agent of ferric oxide desulfurizer as hydrogenation catalyst.
Further, the purposes as biomass hydrogenation catalyst.
Further, the active constituent in the ferric oxide desulfurizer is di-iron trioxide and/or ferroso-ferric oxide.
Further, the di-iron trioxide is α-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, without fixed
Shape Fe2O3, amorphous Fe2O3.H2At least one of O；
The ferroso-ferric oxide is the ferroso-ferric oxide of cubic system.
Further, the useless agent of the ferric oxide desulfurizer is that ferric oxide desulfurizer removes in sulfurous gas after sulfur-bearing ingredient
The useless agent generated.
Further, the sulfurous gas is the tail gas, coke-stove gas, coal pyrolysis gas, the electricity that generate after oil hydrogenation upgrading
At least one of stone furnace exhaust gas.
Further, the useless agent of the ferric oxide desulfurizer is the sulfur-bearing ingredient in ferric oxide desulfurizer removing sulfur-containing waste water
The useless agent generated afterwards.
Further, the useless agent of the ferric oxide desulfurizer is to generate after sulfur-bearing ingredient in ferric oxide desulfurizer removing oil product
Useless agent.
Further, the sulfur-bearing ingredient includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum by-product, gasoline, heavy oil, residual oil.
Compared with prior art, the invention has the following beneficial effects:
(1) purposes of the useless agent of ferric oxide desulfurizer provided by the present invention as hydrogenation catalyst, by existing oxidation
The useless agent that iron desulfurizing agent is formed after carrying out desulfurization process is used directly as hydrogenation catalyst, and it is useless to have opened up ferric oxide desulfurizer
The application field of agent reduces the useless regenerated cost of agent of ferric oxide desulfurizer, reduces the amount of landfill of the useless agent of ferric oxide desulfurizer
The harm caused by environment is reduced, agent is as slack resources simultaneously as ferric oxide desulfurizer gives up, and price is far below plus hydrogen
The price of catalyst, to reduce the production cost for adding hydrogen industry.
(2) purposes of the useless agent of ferric oxide desulfurizer provided by the present invention as hydrogenation catalyst, through detecting, the present invention
The useless agent of middle desulfurizing agent is used as hydrogenation catalyst, and effect is suitable with conventional hydrogenation catalyst effect.
It further, is the useless agent of the desulfurizing agent of main active as the purposes of hydrogenation catalyst using iron oxide.
Further, the purposes as biomass hydrogenation catalyst.
Further, described by the desulfurizing agent of main active of iron oxide further includes molysite chelating agent, polyaluminum sulfate
Iron, basic copper carbonate, calcium bicarbonate, zinc oxide, calcium sulphate dihydrate, the oxide of nickel, the oxide of cobalt, the oxide of molybdenum, copper
Oxide, one or more of the oxide of manganese.
Further, described by the active constituent in the desulfurizing agent of main active of iron oxide is di-iron trioxide
And/or ferroso-ferric oxide.
Further, the di-iron trioxide is α-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, without fixed
Shape Fe2O3, amorphous Fe2O3.H2At least one of O；
The ferroso-ferric oxide is the ferroso-ferric oxide of cubic system.
Further, it is described using iron oxide be the useless agent of the desulfurizing agent of main active be using iron oxide as chief active
The useless agent generated after sulfur-bearing ingredient in the desulfurizing agent removing sulfurous gas of ingredient.
Further, the sulfurous gas is the tail gas, coke-stove gas, coal pyrolysis gas, the electricity that generate after oil hydrogenation upgrading
At least one of stone furnace exhaust gas.
Further, it is described using iron oxide be the useless agent of the desulfurizing agent of main active be using iron oxide as chief active
The useless agent generated after sulfur-bearing ingredient in the desulfurizing agent removing sulfur-containing waste water of ingredient.
Further, it is described using iron oxide be the useless agent of the desulfurizing agent of main active be using iron oxide as chief active
The useless agent generated after sulfur-bearing ingredient in the desulfurizing agent removing oil product of ingredient.
Further, the sulfur-bearing ingredient includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum by-product, gasoline, heavy oil, residual oil.
Compared with prior art, the invention has the following beneficial effects:
(1) it is provided by the present invention using iron oxide be the useless agent of the desulfurizing agent of main active as hydrogenation catalyst
Purposes, the useless agent that existing ferric oxide desulfurizer is formed after carrying out desulfurization process are used directly as hydrogenation catalyst, are opened
The application field for having opened up the useless agent of ferric oxide desulfurizer reduces the useless regenerated cost of agent of ferric oxide desulfurizer, reduces iron oxide
The amount of landfill of the useless agent of desulfurizing agent reduces the harm caused by environment, simultaneously as ferric oxide desulfurizer gives up, agent is as idle money
Source, price are far below the price of hydrogenation catalyst, to reduce the production cost for adding hydrogen industry.
(2) it is provided by the present invention using iron oxide be the useless agent of the desulfurizing agent of main active as hydrogenation catalyst
Purposes, through detecting, the useless agent of desulfurizing agent is used as hydrogenation catalyst in the present invention, and effect and conventional hydrogenation catalyst are imitated
Fruit is suitable.
Further, the purposes after the useless agent regeneration of ferric oxide desulfurizer as hydrogenation catalyst.
Further, the purposes as biomass hydrogenation catalyst.
Further, the active constituent in the ferric oxide desulfurizer is di-iron trioxide and/or ferroso-ferric oxide.
Further, the di-iron trioxide is α-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, without fixed
Shape Fe2O3, amorphous Fe2O3.H2At least one of O；
The ferroso-ferric oxide is the ferroso-ferric oxide of cubic system.
Further, the useless agent of the ferric oxide desulfurizer is that ferric oxide desulfurizer removes in sulfurous gas after sulfur-bearing ingredient
The useless agent generated.
Further, the sulfurous gas is the tail gas, coke-stove gas, coal pyrolysis gas, the electricity that generate after oil hydrogenation upgrading
At least one of stone furnace exhaust gas.
Further, the useless agent of the ferric oxide desulfurizer is the sulfur-bearing ingredient in ferric oxide desulfurizer removing sulfur-containing waste water
The useless agent generated afterwards.
Further, the useless agent of the ferric oxide desulfurizer is to generate after sulfur-bearing ingredient in ferric oxide desulfurizer removing oil product
Useless agent.
Further, the sulfur-bearing ingredient includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum by-product, gasoline, heavy oil, residual oil.
Further, the regeneration method of the useless agent of the ferric oxide desulfurizer, includes the following steps:
The useless agent of the ferric oxide desulfurizer is mixed with water or aqueous slkali, is configured to slurries；
Oxidant is added into the slurries, carries out oxidation reaction；
Slurries after the oxidation reaction are separated by solid-liquid separation, solid is collected, the as described ferric oxide desulfurizer gives up
The regrowth of agent.
It further, further include adding sulphur in the slurries after the oxidation reaction before carrying out the separation of solid and liquid
Vulcanization reaction occurs for agent；It is middle thereto again to add oxidant, oxidation reaction occurs；Finally circulation carries out the vulcanization reaction
It is 1:0.5~10 with the molar ratio of ferro element and element sulphur in the slurries after the oxidation reaction to the oxidation reaction；
The vulcanizing agent includes Na2S、Na2S2O3、(NH4)2S、(NH4)2S2O3, mercaptan, thiocarbamide, dimethylsulphide, carbonyl
Base sulphur, H2At least one of S；
The oxidant includes H2O2、NaClO、O2、O3At least one of.
Further, the regeneration method of the useless agent of the ferric oxide desulfurizer, includes the following steps:
(1) by the useless agent weak acid water dispersion of the ferric oxide desulfurizer, dispersion liquid is formed；
(2) dispersion liquid is heated, then oxidant is added into the dispersion liquid after heating and is reacted, reaction is fast simultaneously
The sulfur dioxide gas that speed transfer generates；
(3) after the reaction was completed, obtained precipitating is washed, is dried, obtains regrowth by filtering reacting liquid.
Further, the regeneration method of the useless agent of the ferric oxide desulfurizer, includes the following steps:
1) the useless agent of the ferric oxide desulfurizer is ground into particle, obtains useless agent powder；
2) the useless agent powder is made into suspension, is passed through oxygenous gas and is aoxidized, form slurries；
3) slurries are filtered and obtains solid material, the elemental sulfur in the solid material described in solvent extraction remains after extraction
The namely regenerated object of remaining solid.
Further, the regeneration method of the useless agent of the ferric oxide desulfurizer, includes the following steps:
1) the useless agent of the ferric oxide desulfurizer is smashed and ground, obtains useless agent particle；
2) useless agent particle is heated under inert gas atmosphere, sulphur is made to distil；
3) it is then passed through air into the useless agent particle and heating aoxidizes waste desulfurizing agent, it is cold that stopping is heated to powder
But, regrowth is obtained.
Further, the regeneration method of the useless agent of the ferric oxide desulfurizer, includes the following steps:
1) superheated steam is passed through in the useless agent of the ferric oxide desulfurizer, it is purged and is heated, it is useless to collect solid
Agent；
2) it is passed through also Primordial Qi to restore the useless agent of the solid, obtains regrowth.
Compared with prior art, the invention has the following beneficial effects:
(1) purposes after the useless agent regeneration of ferric oxide desulfurizer provided by the present invention as hydrogenation catalyst, will be existing
Ferric oxide desulfurizer formed after carrying out desulfurization process useless agent regeneration after directly as hydrogenation catalyst use, opened up oxygen
The application field for changing the useless agent of iron desulfurizing agent, reduces the regenerated cost of useless agent of ferric oxide desulfurizer, and it is de- to reduce iron oxide
The amount of landfill of the useless agent of sulphur agent reduces the harm caused by environment, simultaneously as the useless agent of ferric oxide desulfurizer is as idle
Resource, price is far below the price of hydrogenation catalyst, to reduce the production cost of hydrogenation catalyst industry.
(2) purposes after the useless agent regeneration of ferric oxide desulfurizer provided by the present invention as hydrogenation catalyst, through detecting,
It is used after the useless agent regeneration of desulfurizing agent as hydrogenation catalyst in the present invention, effect and conventional hydrogenation catalyst effect phase
When even better than conventional hydrogenation catalyst.
Further, the purposes after the useless agent regeneration of the desulfurizing agent containing iron oxide as hydrogenation catalyst.
Further, the purposes as biomass hydrogenation catalyst.
Further, the desulfurizing agent containing iron oxide further includes molysite chelating agent, bodied ferric sulfate, basic carbonate
Copper, calcium bicarbonate, zinc oxide, calcium sulphate dihydrate, the oxide of nickel, the oxide of cobalt, the oxide of molybdenum, the oxide of copper, manganese
One or more of oxide.
Further, described by the active constituent in the desulfurizing agent of main active of iron oxide is di-iron trioxide
And/or ferroso-ferric oxide.
Further, the di-iron trioxide is α-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, without fixed
Shape Fe2O3, amorphous Fe2O3.H2At least one of O；
The ferroso-ferric oxide is the ferroso-ferric oxide of cubic system.
Further, for using iron oxide as main active after the useless agent regeneration of the desulfurizing agent containing iron oxide
The useless agent generated after sulfur-bearing ingredient in desulfurizing agent removing sulfurous gas；Or
It is de- by the desulfurizing agent of main active of iron oxide after the useless agent regeneration of the desulfurizing agent containing iron oxide
Except the useless agent generated after the sulfur-bearing ingredient in sulfur-containing waste water；Or
It is de- by the desulfurizing agent of main active of iron oxide after the useless agent regeneration of the desulfurizing agent containing iron oxide
Except the useless agent generated after sulfur-bearing ingredient in oil product.
Further, the sulfur-bearing ingredient includes at least hydrogen sulfide.
Further, the sulfurous gas is the tail gas, coke-stove gas, coal pyrolysis gas, the electricity that generate after oil hydrogenation upgrading
At least one of stone furnace exhaust gas；Or
The oil product is at least one of petroleum, petroleum by-product, gasoline, heavy oil, residual oil.
Further, the regeneration method of the useless agent of the desulfurizing agent containing iron oxide, includes the following steps:
The useless agent of the desulfurizing agent containing iron oxide is mixed with water or aqueous slkali, is configured to slurries；
Oxidant is added into the slurries, carries out oxidation reaction；
Slurries after the oxidation reaction are separated by solid-liquid separation, solid is collected, as described is de- containing iron oxide
The regrowth of the useless agent of sulphur agent.
It further, further include adding sulphur in the slurries after the oxidation reaction before carrying out the separation of solid and liquid
Vulcanization reaction occurs for agent；It is middle thereto again to add oxidant, oxidation reaction occurs；Finally circulation carries out the vulcanization reaction
It is 1:0.5~10 with the molar ratio of ferro element and element sulphur in the slurries after the oxidation reaction to the oxidation reaction.
Further, the vulcanizing agent includes Na2S、Na2S2O3、(NH4)2S、(NH4)2S2O3, mercaptan, thiocarbamide, dimethyl
Sulfide, carbonyl sulfur, H2At least one of S；
The oxidant includes H2O2、NaClO、O2、O3At least one of.
Further, the regeneration method of the useless agent of the desulfurizing agent containing iron oxide, includes the following steps:
(1) by the useless agent weak acid water dispersion of the desulfurizing agent containing iron oxide, dispersion liquid is formed；
(2) dispersion liquid is heated, then oxidant is added into the dispersion liquid after heating and is reacted, reaction is fast simultaneously
The sulfur dioxide gas that speed transfer generates；
(3) after the reaction was completed, obtained precipitating is washed, is dried, obtains regrowth by filtering reacting liquid.
Further, the regeneration method of the useless agent of the desulfurizing agent containing iron oxide, includes the following steps:
1) the useless agent of the desulfurizing agent for having iron oxide is ground into particle, obtains useless agent powder；
2) the useless agent powder is made into suspension, is passed through oxygenous gas and is aoxidized, form slurries；
3) slurries are filtered and obtains solid material, the elemental sulfur in the solid material described in solvent extraction remains after extraction
The namely regenerated object of remaining solid.
Further, the regeneration method of the useless agent of the desulfurizing agent containing iron oxide, includes the following steps:
1) the useless agent of the desulfurizing agent containing iron oxide is smashed and ground, obtains useless agent particle；
2) useless agent particle is heated under inert gas atmosphere, sulphur is made to distil；
3) it is then passed through air into the useless agent particle and heating aoxidizes waste desulfurizing agent, it is cold that stopping is heated to powder
But, regrowth is obtained.
Further, the regeneration method of the useless agent of the desulfurizing agent containing iron oxide, includes the following steps:
1) superheated steam is passed through in the useless agent of the desulfurizing agent containing iron oxide, it is purged and is heated, is received
Collect the useless agent of solid；
2) it is passed through also Primordial Qi to restore the useless agent of the solid, obtains regrowth.
Compared with prior art, the invention has the following beneficial effects:
(1) purposes after the useless agent regeneration of the desulfurizing agent provided by the present invention containing iron oxide as hydrogenation catalyst,
Existing ferric oxide desulfurizer is used after the useless agent regeneration formed after carrying out desulfurization process directly as hydrogenation catalyst, is opened
Opened up ferric oxide desulfurizer give up agent regrowth application field, reducing the give up amount of landfill of agent of ferric oxide desulfurizer reduces pair
It is endangered caused by environment, simultaneously as ferric oxide desulfurizer gives up, agent is as slack resources, and price is far below hydrogenation catalyst
Price, to reduce the production cost for adding hydrogen industry.
(2) purposes after the useless agent regeneration of the desulfurizing agent provided by the present invention containing iron oxide as hydrogenation catalyst,
Through detecting, used after the useless agent regeneration of desulfurizing agent as hydrogenation catalyst in the present invention, effect and conventional hydrogenation catalyst
Effect is suitable, even better than conventional hydrogenation catalyst.
(3) purposes after the useless agent regeneration of the desulfurizing agent provided by the present invention containing iron oxide as hydrogenation catalyst,
The useless agent of desulfurizing agent containing iron oxide first passes around oxidation reaction, carries out oxidation regeneration, further, by repeatedly vulcanize-
Oxidation reaction, iron oxide and iron sulphur compound crystal phase experience are repeatedly reconstructed and are converted in this process, in addition S2-Ionic radius
(0.18nm) is greater than O2-Ionic radius (0.14nm), so that with the conversion between Fe-O key and Fe-S key, the structure cell of iron oxide
Experience is shunk and expansion, the iron oxide crystalline particle in turn resulting in script stable structure become loose and burst apart, and generation is largely received
Rice iron oxide, the nano iron oxide thiophilicity is good, easily cures.Meanwhile the nano oxidized iron surface covers one layer of nonpolarity
Elemental sulfur layer, the elemental sulfur layer can not only hinder nano iron oxide it is intergranular reunion grow up, substantially increase its dispersibility,
And can use existing similar compatibility characteristic between substance, it is highly dispersed at nano iron oxide in nonpolar oil product.Again
Person, the nano iron oxide of sulphur covering is because sulphur-iron is closely coupled and the lesser partial size of nano iron oxide itself, to make regrowth
With excellent hydrogenation catalyst ability.
Further, purposes of the useless agent of ferric oxide desulfurizer as CO transformation catalyst.
Further, the active constituent in the ferric oxide desulfurizer is di-iron trioxide and/or ferroso-ferric oxide.
Further, the di-iron trioxide is α-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, without fixed
Shape Fe2O3, amorphous Fe2O3.H2At least one of O；
The ferroso-ferric oxide is the ferroso-ferric oxide of cubic system.
Further, the useless agent of the ferric oxide desulfurizer is that ferric oxide desulfurizer removes in sulfurous gas after sulfur-bearing ingredient
The useless agent generated.
Further, the sulfurous gas is the tail gas, coke-stove gas, coal pyrolysis gas, the electricity that generate after oil hydrogenation upgrading
At least one of stone furnace exhaust gas.
Further, the useless agent of the ferric oxide desulfurizer is the sulfur-bearing ingredient in ferric oxide desulfurizer removing sulfur-containing waste water
The useless agent generated afterwards.
Further, the useless agent of the ferric oxide desulfurizer is to generate after sulfur-bearing ingredient in ferric oxide desulfurizer removing oil product
Useless agent.
Further, the sulfur-bearing ingredient includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum by-product, gasoline, heavy oil, residual oil.
Compared with prior art, the invention has the following beneficial effects:
(1) purposes of the useless agent of ferric oxide desulfurizer provided by the present invention as CO transformation catalyst, by existing oxygen
Change the useless agent that iron desulfurizing agent is formed after carrying out desulfurization process to use directly as CO transformation catalyst, opens up iron oxide desulfurization
The application field of the useless agent of agent reduces the useless regenerated cost of agent of ferric oxide desulfurizer, reduces filling out for the useless agent of ferric oxide desulfurizer
The amount of burying reduces the harm caused by environment, simultaneously as ferric oxide desulfurizer gives up, as slack resources, price is far below for agent
The price of CO transformation catalyst, to reduce the production cost of CO transformation industry.
(2) purposes of the useless agent of ferric oxide desulfurizer provided by the present invention as CO transformation catalyst, through detecting, this hair
The useless agent of bright middle desulfurizing agent is used as CO transformation catalyst, and effect is suitable with conventional CO transformation catalyst effect.
It further, is the useless agent of the desulfurizing agent of main active as the purposes of CO transformation catalyst using iron oxide.
Further, described by the desulfurizing agent of main active of iron oxide further includes molysite chelating agent, polyaluminum sulfate
Iron, basic copper carbonate, calcium bicarbonate, zinc oxide, calcium sulphate dihydrate, the oxide of nickel, the oxide of cobalt, the oxide of molybdenum, copper
Oxide, one or more of the oxide of manganese.
Further, described by the active constituent in the desulfurizing agent of main active of iron oxide is di-iron trioxide
And/or ferroso-ferric oxide.
Further, the di-iron trioxide is α-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, without fixed
Shape Fe2O3, amorphous Fe2O3.H2At least one of O；
The ferroso-ferric oxide is the ferroso-ferric oxide of cubic system.
Further, it is described using iron oxide be the useless agent of the desulfurizing agent of main active be using iron oxide as chief active
The useless agent generated after sulfur-bearing ingredient in the desulfurizing agent removing sulfurous gas of ingredient.
Further, the sulfurous gas is the tail gas, coke-stove gas, coal pyrolysis gas, the electricity that generate after oil hydrogenation upgrading
At least one of stone furnace exhaust gas.
Further, it is described using iron oxide be the useless agent of the desulfurizing agent of main active be using iron oxide as chief active
The useless agent generated after sulfur-bearing ingredient in the desulfurizing agent removing sulfur-containing waste water of ingredient.
Further, it is described using iron oxide be the useless agent of the desulfurizing agent of main active be using iron oxide as chief active
The useless agent generated after sulfur-bearing ingredient in the desulfurizing agent removing oil product of ingredient.
Further, the sulfur-bearing ingredient includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum by-product, gasoline, heavy oil, residual oil.
Compared with prior art, the invention has the following beneficial effects:
(1) it is provided by the present invention using iron oxide be the useless agent of the desulfurizing agent of main active as CO transformation catalyst
Purposes, the useless agent that existing ferric oxide desulfurizer is formed after carrying out desulfurization process is made directly as CO transformation catalyst
With, opened up ferric oxide desulfurizer give up agent application field, reduce ferric oxide desulfurizer give up the regenerated cost of agent, reduce oxygen
The amount of landfill for changing the useless agent of iron desulfurizing agent reduces the harm caused by environment, simultaneously as ferric oxide desulfurizer gives up, agent is as not busy
Resource is set, price is far below the price of CO transformation catalyst, to reduce the production cost of CO transformation industry.
(2) it is provided by the present invention using iron oxide be the useless agent of the desulfurizing agent of main active as CO transformation catalyst
Purposes, through detecting, the useless agent of desulfurizing agent is used as CO transformation catalyst in the present invention, and the CO of effect and routine, which is converted, to be urged
Agent effect is suitable.
Further, the purposes after the useless agent regeneration of ferric oxide desulfurizer as CO transformation catalyst.
Further, the active constituent in the ferric oxide desulfurizer is di-iron trioxide and/or ferroso-ferric oxide.
Further, the di-iron trioxide is α-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, without fixed
Shape Fe2O3, amorphous Fe2O3.H2At least one of O；
The ferroso-ferric oxide is the ferroso-ferric oxide of cubic system.
Further, the useless agent of the ferric oxide desulfurizer is that ferric oxide desulfurizer removes in sulfurous gas after sulfur-bearing ingredient
The useless agent generated.
Further, the sulfurous gas is the tail gas, coke-stove gas, coal pyrolysis gas, the electricity that generate after oil hydrogenation upgrading
At least one of stone furnace exhaust gas.
Further, the useless agent of the ferric oxide desulfurizer is the sulfur-bearing ingredient in ferric oxide desulfurizer removing sulfur-containing waste water
The useless agent generated afterwards.
Further, the useless agent of the ferric oxide desulfurizer is to generate after sulfur-bearing ingredient in ferric oxide desulfurizer removing oil product
Useless agent.
Further, the sulfur-bearing ingredient includes at least hydrogen sulfide.
Further, the oil product is at least one of petroleum, petroleum by-product, gasoline, heavy oil, residual oil.
Further, the regeneration method of the useless agent of the ferric oxide desulfurizer, includes the following steps:
The useless agent of the ferric oxide desulfurizer is mixed with water or aqueous slkali, is configured to slurries；
Oxidant is added into the slurries, carries out oxidation reaction；
Slurries after the oxidation reaction are separated by solid-liquid separation, solid is collected, the as described ferric oxide desulfurizer gives up
The regrowth of agent.
It further, further include adding sulphur in the slurries after the oxidation reaction before carrying out the separation of solid and liquid
Vulcanization reaction occurs for agent；It is middle thereto again to add oxidant, oxidation reaction occurs；Finally circulation carries out the vulcanization reaction
It is 1:0.5~10 with the molar ratio of ferro element and element sulphur in the slurries after the oxidation reaction to the oxidation reaction；
The vulcanizing agent includes Na2S、Na2S2O3、(NH4)2S、(NH4)2S2O3, mercaptan, thiocarbamide, dimethylsulphide, carbonyl
Base sulphur, H2At least one of S；
The oxidant includes H2O2、NaClO、O2、O3At least one of.
Compared with prior art, the invention has the following beneficial effects:
(1) purposes after the useless agent regeneration of ferric oxide desulfurizer provided by the present invention as CO transformation catalyst, will show
Some ferric oxide desulfurizers use after the useless agent regeneration formed after carrying out desulfurization process directly as CO transformation catalyst, developing
Ferric oxide desulfurizer gives up the application field of agent, reduces ferric oxide desulfurizer and gives up agent regenerated cost, it is de- to reduce iron oxide
The give up amount of landfill of agent of sulphur agent reduces the harm caused by environment, simultaneously as ferric oxide desulfurizer gives up, agent is as slack resources,
Its price is far below the price of CO transformation catalyst, to reduce the production cost of CO transformation industry.
(2) purposes after the useless agent regeneration of ferric oxide desulfurizer provided by the present invention as CO transformation catalyst, through examining
It surveys, is used after the useless agent regeneration of desulfurizing agent as CO transformation catalyst in the present invention, effect and conventional CO transformation catalyst
Effect is suitable.
Further, the purposes after the useless agent regeneration of the desulfurizing agent containing iron oxide as CO transformation catalyst.
Further, the desulfurizing agent containing iron oxide further includes molysite chelating agent, bodied ferric sulfate, basic carbonate
Copper, calcium bicarbonate, zinc oxide, calcium sulphate dihydrate, the oxide of nickel, the oxide of cobalt, the oxide of molybdenum, the oxide of copper, manganese
One or more of oxide.
Further, described by the active constituent in the desulfurizing agent of main active of iron oxide is di-iron trioxide
And/or ferroso-ferric oxide.
Further, the di-iron trioxide is α-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, without fixed
Shape Fe2O3, amorphous Fe2O3.H2At least one of O；
The ferroso-ferric oxide is the ferroso-ferric oxide of cubic system.
Further, for using iron oxide as main active after the useless agent regeneration of the desulfurizing agent containing iron oxide
The useless agent generated after sulfur-bearing ingredient in desulfurizing agent removing sulfurous gas；Or
It is de- by the desulfurizing agent of main active of iron oxide after the useless agent regeneration of the desulfurizing agent containing iron oxide
Except the useless agent generated after the sulfur-bearing ingredient in sulfur-containing waste water；Or
It is de- by the desulfurizing agent of main active of iron oxide after the useless agent regeneration of the desulfurizing agent containing iron oxide
Except the useless agent generated after sulfur-bearing ingredient in oil product.
Further, the sulfur-bearing ingredient includes at least hydrogen sulfide.
Further, the sulfurous gas is the tail gas, coke-stove gas, coal pyrolysis gas, the electricity that generate after oil hydrogenation upgrading
At least one of stone furnace exhaust gas；Or
The oil product is at least one of petroleum, petroleum by-product, gasoline, heavy oil, residual oil.
Further, the regeneration method of the useless agent of the desulfurizing agent containing iron oxide, includes the following steps:
The useless agent of the desulfurizing agent containing iron oxide is mixed with water or aqueous slkali, is configured to slurries；
Oxidant is added into the slurries, carries out oxidation reaction；
Slurries after the oxidation reaction are separated by solid-liquid separation, solid is collected, as described is de- containing iron oxide
The regrowth of the useless agent of sulphur agent.
It further, further include adding sulphur in the slurries after the oxidation reaction before carrying out the separation of solid and liquid
Vulcanization reaction occurs for agent；It is middle thereto again to add oxidant, oxidation reaction occurs；Finally circulation carries out the vulcanization reaction
It is 1:0.5~10 with the molar ratio of ferro element and element sulphur in the slurries after the oxidation reaction to the oxidation reaction.
Further, the vulcanizing agent includes Na2S、Na2S2O3、(NH4)2S、(NH4)2S2O3, mercaptan, thiocarbamide, dimethyl
Sulfide, carbonyl sulfur, H2At least one of S；
The oxidant includes H2O2、NaClO、O2、O3At least one of.
Compared with prior art, the invention has the following beneficial effects:
(1) use after the useless agent regeneration of the desulfurizing agent provided by the present invention containing iron oxide as CO transformation catalyst
On the way, existing ferric oxide desulfurizer is made after the useless agent regeneration formed after carrying out desulfurization process directly as CO transformation catalyst
With, opened up ferric oxide desulfurizer give up agent regrowth application field, reduce ferric oxide desulfurizer give up agent amount of landfill drop
Low to endanger caused by environment, simultaneously as ferric oxide desulfurizer gives up, agent is used as slack resources, and price is far below CO transformation
The price of catalyst, to reduce the production cost of CO transformation industry.
(2) use after the useless agent regeneration of the desulfurizing agent provided by the present invention containing iron oxide as CO transformation catalyst
On the way, it through detecting, is used after the useless agent regeneration of desulfurizing agent as CO transformation catalyst in the present invention, effect and conventional CO are converted
Catalyst effect is suitable, even better than conventional CO transformation catalyst.
(3) use after the useless agent regeneration of the desulfurizing agent provided by the present invention containing iron oxide as CO transformation catalyst
On the way, the useless agent containing the desulfurizing agent for having iron oxide first passes around oxidation reaction, oxidation regeneration is carried out, further, by multiple
Vulcanization-oxidization reaction, iron oxide and iron sulphur compound crystal phase undergo repeatedly reconstruct and conversion in this process, in addition S2-Ion half
Diameter (0.18nm) is greater than O2-Ionic radius (0.14nm), so that with the conversion between Fe-O key and Fe-S key, the structure cell of iron oxide
Also experience is shunk and expansion, the iron oxide crystalline particle in turn resulting in script stable structure become loose and burst apart, and is generated a large amount of
Nano iron oxide, the nano iron oxide thiophilicity is good, easily cures.Meanwhile the nano oxidized iron surface covers one layer of non-pole
Property elemental sulfur layer, the elemental sulfur layer can not only hinder nano iron oxide it is intergranular reunion grow up, substantially increase its dispersion
Property, and can use existing similar compatibility characteristic between substance, it is highly dispersed at nano iron oxide in nonpolar oil product.
Furthermore the nano iron oxide of sulphur covering is because sulphur-iron is closely coupled and the lesser partial size of nano iron oxide itself, to make to regenerate
There is object excellent CO to convert catalytic capability.
Further, the use of the useless agent of the desulfurizing agent containing iron oxide or useless agent regenerative agent in organic matter transformation technique
On the way.
Further, described by the active constituent in the desulfurizing agent of main active of iron oxide is di-iron trioxide
And/or ferroso-ferric oxide.
Further, the di-iron trioxide is α-Fe2O3、α-Fe2O3.H2O、γ-Fe2O3、γ-Fe2O3.H2O, without fixed
Shape Fe2O3, amorphous Fe2O3.H2At least one of O；
The ferroso-ferric oxide is the ferroso-ferric oxide of cubic system.
Further, the desulfurizing agent containing iron oxide further includes molysite chelating agent, bodied ferric sulfate, basic carbonate
Copper, calcium bicarbonate, zinc oxide, calcium sulphate dihydrate, the oxide of nickel, the oxide of cobalt, the oxide of molybdenum, the oxide of copper, manganese
One or more of oxide.
Further, the useless agent of the desulfurizing agent containing iron oxide is that the desulfurizing agent containing iron oxide removes sulfurous gas
The useless agent generated after middle sulfur-bearing ingredient；Or
The useless agent of the desulfurizing agent containing iron oxide is the sulfur-bearing in the desulfurizing agent removing sulfur-containing waste water containing iron oxide
The useless agent generated after ingredient；Or
The useless agent of the desulfurizing agent containing iron oxide is that the desulfurizing agent containing iron oxide removes in oil product after sulfur-bearing ingredient
The useless agent generated.
Further, the sulfur-bearing ingredient includes at least hydrogen sulfide；Or,
The sulfurous gas be the tail gas generated after oil hydrogenation upgrading, coke-stove gas, coal pyrolysis gas, in calcium carbide stove exhaust
At least one；Or,
The oil product is at least one of petroleum, petroleum by-product, gasoline, heavy oil, residual oil.
Further, the step of useless agent regeneration of the desulfurizing agent containing iron oxide prepares useless agent regenerative agent be,
A1, the useless agent of the desulfurizing agent containing iron oxide is mixed with water or aqueous slkali, is configured to slurries；
Oxidant is added in A2, Xiang Suoshu slurries, carries out oxidation reaction；
A3, the slurries after the oxidation reaction are separated by solid-liquid separation, collect solid, the as described useless agent regenerative agent；
Or,
The useless agent regeneration of the desulfurizing agent containing iron oxide prepares the step of giving up agent regenerative agent and is,
B1, the useless agent weak acid water dispersion by the desulfurizing agent containing iron oxide form dispersion liquid；
B2, the dispersion liquid is heated, then oxidant is added into the dispersion liquid after heating and is reacted, reaction is fast simultaneously
The sulfur dioxide gas that speed transfer generates；
B3, after the reaction was completed, obtained precipitating is washed, is dried by filtering reacting liquid, obtains the useless agent regeneration
Agent；
Or,
The useless agent regeneration of the desulfurizing agent containing iron oxide prepares the step of giving up agent regenerative agent and is,
C1, the useless agent of the desulfurizing agent for having iron oxide is ground into particle, obtains useless agent powder；
C2, the useless agent powder is made into suspension, is passed through oxygenous gas and is aoxidized, form slurries；
C3, the filtering slurries obtain solid material, and the elemental sulfur in the solid material described in solvent extraction remains after extraction
Remaining solid is the useless agent regenerative agent
Or,
The useless agent regeneration of the desulfurizing agent containing iron oxide prepares the step of giving up agent regenerative agent and is,
D1, the useless agent of the desulfurizing agent containing iron oxide is smashed and ground, obtains useless agent particle；
D2, useless agent particle is heated under inert gas atmosphere, sulphur is made to distil；
D3, air is then passed through into the useless agent particle and heating aoxidizes waste desulfurizing agent, to be heated to powder cold for stopping
But, the useless agent regenerative agent is obtained；
Or,
The useless agent regeneration of the desulfurizing agent containing iron oxide prepares the step of giving up agent regenerative agent and is,
E1, superheated steam is passed through in the useless agent of the desulfurizing agent containing iron oxide, it is purged and is heated, is received
Collect the useless agent of solid；
E2, it is passed through and Primordial Qi restores the useless agent of the solid, obtains the useless agent regenerative agent.
It further, further include adding sulphur in the slurries after the oxidation reaction before carrying out the separation of solid and liquid
Vulcanization reaction occurs for agent；It is middle thereto again to add oxidant, oxidation reaction occurs；Finally circulation carries out the vulcanization reaction
It is 1:0.5~10 with the molar ratio of ferro element and element sulphur in the slurries after the oxidation reaction to the oxidation reaction；
The vulcanizing agent includes Na2S、Na2S2O3、(NH4)2S、(NH4)2S2O3, mercaptan, thiocarbamide, dimethylsulphide, carbonyl
Base sulphur, H2S、CS2At least one of；
The oxidant includes H2O2、NaClO、O2、O3At least one of.
Further, the regenerative agent and organic matter of the useless agent of the desulfurizing agent containing iron oxide and/or useless agent are prepared to be formed
The slurries and pure CO or the gas mixing containing CO are carried out conversion reaction, wherein preferably, it is preferable that further include adding by slurries
Entering sulfur-containing compound molar ratio of ferro element and element sulphur into reaction system is 1:(0.5~5).
Further, the reaction pressure of the conversion reaction is 5-22MPa, and reaction temperature is 200-470 DEG C；Or,
In the slurries, the regeneration agent content of useless agent and/or the useless agent of the desulfurizing agent containing iron oxide is 0.1~
10wt%, average grain diameter are 0.1 μm of -5mm；Or,
The volume content of CO is not most preferably small not less than 15%, preferably not less than 50% in the gas containing CO
In 90%.
Technical solution of the present invention has the advantages that
(1) contain the regenerative agent conduct of useless agent or the useless agent of the desulfurizing agent of iron oxide provided by the embodiment of the present invention
The catalyst of organic matter transformation technique has been opened up the useless agent or the application field of its regenerative agent of the desulfurizing agent containing iron oxide, has been subtracted
The amount of landfill for having lacked the useless agent of ferric oxide desulfurizer reduces the harm caused by environment, simultaneously as the desulfurization containing iron oxide
The useless agent of agent is a kind of slack resources, cheap, to reduce the cost of organic matter transformation technique.
(2) regenerative agent of useless agent or the useless agent of the desulfurizing agent containing iron oxide provided by the embodiment of the present invention can fit
The liquefaction of non-pure hydrogen atmosphere for biomass, the limitation of pure hydrogen must be used by avoiding biomass liquefying conversion, not only be reduced
Cost, and the processing route of biomass conversion has been expanded, realize the large scale quantities of biomass conversion processes in the industry
Metaplasia produces.
(3) contain the regenerative agent conduct of useless agent or the useless agent of the desulfurizing agent of iron oxide provided by the embodiment of the present invention
The catalyst of organic matter transformation technique can effectively utilize in the presence of CO and oneself for blocking organic matter in cracking process is carbonylated
By base polycondensation, and realize that the shift activity hydrogen of CO and water adds hydrogen, in the conversion reaction, organic matter especially biomass solid
Without dehydration, conversion reaction can be directly carried out, water can additionally be added in bio liquid or mineral oil, is improving liquefaction yield
Simultaneously, moreover it is possible to which the calorific value for improving obtained oil product after conversion reaction, will not generate a large amount of waste water.
(4) contain the regenerative agent conduct of useless agent or the useless agent of the desulfurizing agent of iron oxide provided by the embodiment of the present invention
The catalyst of organic matter transformation technique, is incorporated appropriate sulphur and organic matter forms slurries, and under CO atmosphere, these catalyst are first
In conjunction with CO, carbonyls is formed, then carbon atom is grafted on by organic matter (such as biomass) heat by the carbonyls
Be formed by after cracking on small molecule active position, meanwhile, iron, element sulphur catalytic action under also realize that CO transformation is in situ and produce hydrogen
And the effect of catalytic hydrodeoxygenation, the oxygen content of oil product is reduced, the liquefaction yield and length of SOLID ORGANIC matter are substantially increased
The oil product yield that strand is converted to small molecule；
Preferably, by slurry method by desulfurizing agent give up agent alternately vulcanize and oxidation regeneration after obtain regenerative agent, into one
Step ground, is reacted by multiple vulcanization-oxidization, and iron oxide and iron sulphur compound crystal phase experience reconstruct and turns in this process
Change, in addition S2-Ionic radius (0.18nm) is greater than O2-Ionic radius (0.14nm), so that between Fe-O key and Fe-S key
Conversion, the structure cell of iron oxide also undergo contraction and expansion, in turn result in the iron oxide crystallization of script stable structure
Grain becomes loose and bursts apart, and generates a large amount of nanometer iron compounds, this nanometer of iron compound thiophilicity is good, easily cures.Meanwhile
The Nanoscale Iron compound surface covers one layer of nonpolar elemental sulfur layer, which can not only hinder a nanometer iron compound
The reunion of intergranular is grown up, and is substantially increased its dispersibility, and can use existing similar compatibility characteristic between substance, is made nanometer
Iron compound is highly dispersed in nonpolar oil product；Furthermore sulphur covering nanometer iron compound because sulphur-iron it is closely coupled and
The nanometer lesser partial size of iron compound itself, to make sulphur that can react generation at low temperature with nanometer iron compound with bad
Magnetic iron ore (the Fe of reduced fuel oil hydrogenation activity1-xS), the regrowth partial size for finally obtaining such method is small, lipophilic good,
Structure slabbing nanostructure, the sulphur barrier being adsorbed between piece and piece, avoids its reunion, substantially increases the absorption of CO
Ability enhances carbonylation, transformation produces hydrogen and hydrogenation catalyst ability.
(5) contain the regenerative agent conduct of useless agent or the useless agent of the desulfurizing agent of iron oxide provided by the embodiment of the present invention
The catalyst of organic matter transformation technique, biomass solid by successively being carried out just crushing, compression and two by organic matter transformation technique
Secondary crushing, is then mixed to get mixture with catalyst, feeds the mixture into and grinds slurrying into solvent, obtains biomass content
For the slurries of 10~60wt%, the present invention is initiatively to biomass solid using the processing work of separating twice after first compressing
Skill makes loose biomass solid that collapsing, closure etc. successively be undergone to arrange again by the way that biomass solid is carried out compression processing
Position, mechanically deform stage thus can reduce the porosity of biomass so that the volume of biomass solid is greatly lowered, increase
Its big density and specific gravity, are allowed to be conducive to be dispersed in oil product, and its content in oil product can be improved, increase reaction mass
Concentration, the solid content in slurries may be up to 10~60wt%, simultaneously because the increase of biomass solid concentration also must in slurries
Pump can so be improved within the unit time to the conveying capacity of biomass solid, to improve the efficiency of entire liquefaction process, reduce
Industrial cost and energy consumption；In addition, the increase of biomass solid specific gravity also helps suspension of the biomass solid in slurries and divides
It dissipates, thus can reduce the viscosity of slurries, realize the smooth flow of slurries in the duct, avoid blocking pipeline, realize the flat of pump
Steady operating and conveying, while but also cannot function as the high viscosity waste oil of liquefaction solvent, such as used oil, kitchen in the prior art
Waste oil, rancid oil etc., can also be utilized.Further, by will just crush the heap density tune with compressed biomass
Control is to not less than 0.4 g/cm3, by the regulation of the average particle size of the biomass after separating twice to less than 5mm, pass through above-mentioned regulation
Mode grinds slurrying convenient for being added into solvent, improves its solid content in slurries；By the way that compression temperature control is existed
30-60 DEG C, the rheological characteristic that can significantly increase biomass solid is compressed to biomass at this temperature, reduces the viscous of slurries
Degree, is achieved in the smooth flow of slurries in the duct, avoids the blocking of pipeline, realizes the steady operating and conveying of pump.
(6) contain the regenerative agent conduct of useless agent or the useless agent of the desulfurizing agent of iron oxide provided by the embodiment of the present invention
Cracking, carbonylation, change occur in reactor for the catalyst of organic matter transformation technique, catalysis reaction raw materials and the gas containing CO
It changes plus the reaction such as hydrogen；It is further advanced by using paste state bed reactor, it is anti-that reaction raw materials are first sent into state bed by reactor bottom
It answers to react in device, while injecting the gas containing CO into reactor again, gas, liquid can be relied on so in reactor
Difference in specific gravity variation caused by the yield of light-end products, realizes each phase after the different specific weight and complex reaction of each material of body, solid
The otherness of state flow velocity controls so that biomass solid raw material occur from the bottom to top in reactor cracking, carbonylation, transformation,
Add hydrogen, reaction, even if heavy biomass solid and catalyst solid particle are with gas and light-end products in the process
Rise, but it is again return under gas effect of the top containing CO participate in reacting again to bottom, according to reactor upper, middle and lower portion
Material density appropriate adjustment enter the gas and its injection rate containing CO in the slurries of reactor, to realize unconverted have
Thus machine matter can ensure that the abundant progress of various reactions in the circulation of inside reactor and the balance discharge of catalyst, thus
Be conducive to improve the conversion ratio and biology oil yield of organic matter.
(7) contain the regenerative agent conduct of useless agent or the useless agent of the desulfurizing agent of iron oxide provided by the embodiment of the present invention
The catalyst of organic matter transformation technique, in organic matter transformation technique, organic matter does not need to be dehydrated, and reduces dry cost；In
In reaction process is the gas containing CO, this contains the gas of CO either pure CO, can also be impure, such as in addition to containing
There is CO, can also can also be the conjunction that coal, biomass, natural gas, mineral oil gasification produce containing hydrogen, hydrogen sulfide, methane etc.
At gas, in synthesis gas other than CO, remainder gas can be hydrogeneous, carbon dioxide or the mixture of methane, ethane, gas system
It causes originally to substantially reduce；During being reacted, with the gas containing CO, and using cheap ferrum-based catalyst or useless
Under agent effect, realize cracking reaction, carbonylation, conversion reaction, the process integrations such as hydrogenation reaction, be easy to provide it is sufficient from
By group, the carbonization coking of organic matter is avoided, organic matter conversion ratio and liquid yield are high, and reaction temperature and pressure are reduced；
The oil product that the liquefaction process generates can be used for front and continued technique to prepare slurries.
(8) desulfurizing agent containing iron oxide that the application mentions is the desulfurizing agent directly formed with iron oxide, or with oxidation
Iron is carried on the desulfurizing agent formed on carrier or iron oxide and organic binder as main active or other additives are mixed
The desulfurizing agent formed or iron oxide and organic binder or other additive mixed loads are closed in the desulfurizing agent formed on carrier
Deng.The desulfurizing agent containing iron oxide of the application is suitable for the system of all desulfurizing agents in the prior art containing iron oxide in a word
The desulfurizing agent that Preparation Method is prepared, useless agent are by the above-mentioned desulfurizing agent containing iron oxide applied in the prior art various
The useless agent that sulfur method generates, is particularly suitable for the oxidation by generating after biogas, liquid, coal gas, flue gas, petroleum and gasoline desulfurization
Iron desulfurizing agent gives up agent, and existing all regeneration methods can be used in the useless agent regenerative agent that the regeneration method of above-mentioned useless agent obtains.
It further, is the useless agent of the hydrogenation catalyst of main active as the use of CO transformation catalyst using Ni-Mo
On the way.
Further, described to further include carrier, binder as the hydrogenation catalyst of main active using Ni-Mo and help
Agent.
Further, the carrier is aluminium oxide, active carbon, molecular sieve, titanium dioxide, the compound load of silica/alumina
Body, amorphous silicon aluminium, zeolite；
The binder is attapulgite, sesbania powder, nitric acid, citric acid, silica solution, carboxymethyl cellulose, bentonite, silicon
At least one of diatomaceous earth；
The auxiliary agent be tungsten oxide, cobalt oxide, rare earth element, chrome green, phosphorus pentoxide, group vib transition metal,
At least one of VIIB group 4 transition metal, platinum, palladium, phosphorus, silicon, boron, titanium, zinc, fluorine, zirconium；Preferably, the group vib transition gold
Belong to is chromium, molybdenum, tungsten；The VIIB group 4 transition metal is manganese.
Further, described using Ni-Mo as the quality of nickel oxide and molybdenum oxide in the hydrogenation catalyst of main active
Score is 10-60%.
Further, the molar ratio of the nickel oxide and the molybdenum oxide is (0.3-0.5): 1.
Further, described by the useless agent of the hydrogenation catalyst of main active of Ni-Mo is described based on Ni-Mo
Want the useless agent to generating after heavy oil catalytic hydrogenation of the hydrogenation catalyst of active constituent.
Further, the heavy oil includes reduced crude, decompression residuum, deasphalted oil, oil sands bitumen, consistency crude oil, coal tar
One or more of oil and coal liquefaction heavy oil.
Further, described by the useless agent of the hydrogenation catalyst of main active of Ni-Mo is described based on Ni-Mo
That wants the hydrogenation catalyst of active constituent adds the useless agent generated after hydrogen to cracking diesel catalytic.
Further, described by the useless agent of the hydrogenation catalyst of main active of Ni-Mo is described based on Ni-Mo
Want the useless agent to generating after Petropols catalytic hydrogenation of the hydrogenation catalyst of active constituent.
Compared with prior art, the invention has the following beneficial effects:
(1) provided by the present invention to be urged using Ni-Mo as the useless agent of the hydrogenation catalyst of main active as CO transformation
The purposes of agent is given up existing using Ni-Mo as what the hydrogenation catalyst of main active was formed after carrying out catalytic hydrogenation
Agent can be used directly as CO transformation catalyst, opened up using Ni-Mo as the useless agent of the hydrogenation catalyst of main active
Application field reduces the regenerated cost of useless agent using Ni-Mo as the hydrogenation catalyst of main active, reduces with Ni-
Mo is the amount of landfill of the useless agent of the hydrogenation catalyst of main active, reduces the harm caused by environment, simultaneously as with
Ni-Mo is the useless agent of the hydrogenation catalyst of main active as slack resources, and price is far below CO transformation catalyst
Price, to reduce the production cost of CO transformation industry.
(2) provided by the present invention to be urged using Ni-Mo as the useless agent of the hydrogenation catalyst of main active as CO transformation
The purposes of agent, through detecting, existing converted using Ni-Mo as the useless agent of the hydrogenation catalyst of main active as CO is catalyzed
Agent uses, and effect is suitable with conventional CO transformation catalyst effect.
Specific embodiment
The FeOOH desulfurizing agent that the application mentions can be the desulfurizing agent directly formed with FeOOH, be also possible to FeOOH
The desulfurizing agent formed on carrier is carried on as active constituent, useless agent is that above-mentioned FeOOH desulfurizing agent is applied to the prior art
In various sulfur methods generate useless agent, be particularly suitable for by being produced after biogas, liquid, coal gas, flue gas, petroleum and gasoline desulfurization
The useless agent of raw FeOOH desulfurizing agent.
What the application mentioned main refers in the prior art by the desulfurizing agent of active constituent of FeOOH with FeOOH and other
The desulfurizing agent that active constituent cooperatively forms, useless agent are that above-mentioned desulfurizing agent is applied to various sulfur methods in the prior art to produce
Raw useless agent is particularly suitable for agent of being given up by the desulfurizing agent generated after biogas, liquid, coal gas, flue gas, petroleum and gasoline desulfurization.Its
In, the other active constituents matched with FeOOH include but is not limited to molysite chelating agent, bodied ferric sulfate, basic copper carbonate, carbon
One or more of sour hydrogen calcium, zinc oxide, calcium sulphate dihydrate, the oxide of nickel, the oxide of cobalt, oxide of nickel.
The desulfurizing agent containing FeOOH that the application mentions is the desulfurizing agent directly formed with FeOOH, or using FeOOH as
Main active is carried on the desulfurizing agent formed on carrier or FeOOH and is mixed to form with organic binder or other additives
Desulfurizing agent or FeOOH and organic binder or other additive mixed loads in the desulfurizing agent etc. formed on carrier.In a word
The desulfurizing agent containing FeOOH of the application is suitable for the preparation method system of all desulfurizing agents in the prior art containing FeOOH
Standby obtained desulfurizing agent, useless agent are that the above-mentioned desulfurizing agent containing FeOOH is applied to various sulfur methods in the prior art
The useless agent generated, is particularly suitable for the FeOOH desulfurizing agent by generating after biogas, liquid, coal gas, flue gas, petroleum and gasoline desulfurization
The regeneration method of useless agent, above-mentioned useless agent is suitable for all regeneration methods.
The Fe that the application mentions21.333O32Desulfurizing agent can be with Fe21.333O32The desulfurizing agent directly formed, is also possible to
With Fe21.333O32The desulfurizing agent formed on carrier is carried on as active constituent, agent of giving up is by above-mentioned Fe21.333O32Desulfurizing agent
Applied to the useless agent that various sulfur methods in the prior art generate, it is particularly suitable for by biogas, liquid, coal gas, flue gas, petroleum
With the Fe generated after gasoline desulfurization21.333O32Desulfurizing agent gives up agent.
The application mentions main with Fe21.333O32Refer in the prior art for the desulfurizing agent of active constituent with Fe21.333O32
The desulfurizing agent cooperatively formed with other active constituents, useless agent are that above-mentioned desulfurizing agent is applied to various desulfurization in the prior art
The useless agent that method generates, is particularly suitable for being given up by the desulfurizing agent generated after biogas, liquid, coal gas, flue gas, petroleum and gasoline desulfurization
Agent.Wherein, with Fe21.333O32The other active constituents matched include but is not limited to potassium oxide, Detitanium-ore-type Ti02, copper oxide,
One or more of zinc oxide, lead oxide, manganese dioxide.
The Fe that the application mentions21.333O32Desulfurizing agent can be with Fe21.333O32The desulfurizing agent directly formed, is also possible to
With Fe21.333O32It is carried on the desulfurizing agent formed on carrier as active constituent, can also be with Fe21.333O32With other activity
The desulfurizing agent that components matching is formed, useless agent are that above-mentioned desulfurizing agent is applied to various sulfur methods in the prior art to generate
Useless agent is particularly suitable for agent of being given up by the desulfurizing agent generated after biogas, liquid, coal gas, flue gas desulfurization.Wherein, with Fe21.333O32Phase
Other active constituents of cooperation include but is not limited to potassium oxide, Detitanium-ore-type Ti02, copper oxide, lead oxide, zinc oxide or dioxy
Change one or more of manganese.
The ferric oxide desulfurizer that the application mentions can be the desulfurizing agent directly formed with iron oxide, be also possible to aoxidize
Iron is carried on the desulfurizing agent formed on carrier as active constituent, and useless agent is that above-mentioned ferric oxide desulfurizer is applied to existing skill
The useless agent that various sulfur methods in art generate, is particularly suitable for by after biogas, liquid, coal gas, flue gas, petroleum and gasoline desulfurization
The useless agent of the ferric oxide desulfurizer of generation.
What the application mentioned main refers in the prior art by the desulfurizing agent of active constituent of iron oxide with iron oxide and other
The desulfurizing agent that active constituent cooperatively forms, useless agent are that above-mentioned desulfurizing agent is applied to various sulfur methods in the prior art to produce
Raw useless agent is particularly suitable for agent of being given up by the desulfurizing agent generated after biogas, liquid, coal gas, flue gas, petroleum and gasoline desulfurization.Its
In, the other active constituents matched with iron oxide include but is not limited to molysite chelating agent, bodied ferric sulfate, basic copper carbonate,
Calcium bicarbonate, zinc oxide, calcium sulphate dihydrate, the oxide of nickel, the oxide of cobalt, the oxide of molybdenum, the oxide of copper, manganese oxygen
One or more of compound.
1, useless purposes of the agent as biomass hydrogenation liquefaction catalyst of kind FeOOH desulfurizing agent:
Embodiment 1
The embodiment of the invention provides a kind of useless agent of FeOOH desulfurizing agent, wherein with the gross mass of the FeOOH desulfurizing agent
It counts, the content of amorphous FeOOH is 60% in the FeOOH desulfurizing agent, and the content of carrier diatomaceous earth is 30%, bonding
The content of agent cellulose powder is 10%.
Sweetening process of the above-mentioned catalyst as coal pyrolysis gas, is summarized as follows:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and the air come with air pump is mixed into thick desulfurizing tower,
Using the process of bottom in and top out, to avoid there is liquid water to enter desulfurizing agent bed.It is herein to carry out thick removing hydrogen sulfide and take off
Except part R-SH and thiophene.
(2) gas heating after thick desulfurization is hydrolyzed to 110~125 DEG C, and most of COS and CS2 are hydrolyzed to H2S.
(3) gas after hydrolyzing is cooled to 20-~25 DEG C again, carries out H2S removing, herein to guarantee clean-up effect and make
The H2S that hydrolysis generates is totally removed using the form of double tower series-parallel operation with the service life, and is further removed remaining
R-SH and thiophene.It is totally removed by the remaining sulfide of this technical process, reaches final purification requirement total sulfur content and be less than
0.1ppm。
Desulfurizing agent becomes useless agent after being used for multiple times and deletes from desulfurizing agent bed, the FeOOH desulfurizing agent as in the application
Useless agent.
Embodiment 2
The embodiment of the invention provides a kind of useless agent of FeOOH desulfurizing agent, wherein with the gross mass of the FeOOH desulfurizing agent
It counts, the content of amorphous FeOOH is 80% in the FeOOH desulfurizing agent, and the content of carrier alundum is 15%,
The content of binder sesbania powder is 5%.For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, the gas water containing H2S is made come into full contact with instead with it
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, the catalyst after gas water desulfurization are useless
Agent is the useless agent of FeOOH desulfurizing agent of the application.
Embodiment 3
The embodiment of the invention provides a kind of useless agent of FeOOH desulfurizing agent, wherein with the gross mass of the FeOOH desulfurizing agent
It counts, the content of γ-FeOOH is 45% in the FeOOH desulfurizing agent, and the content of alpha-feooh is 35%, and carrier molecule sieve contains
Amount is 15%, and the content of binder sesbania powder is 5%.
H in above-mentioned catalyst removal exhaust gas2The matrix process of S, includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, the waste in the desulfurization section is collected, the catalyst as biomass liquefaction reaction.
Embodiment 4
The embodiment of the invention provides a kind of useless agent of FeOOH desulfurizing agent, wherein with the gross mass of the FeOOH desulfurizing agent
It counts, it is 45% that β-FeOOH content, which is 49%, θ-FeOOH content, in the FeOOH desulfurizing agent, and surplus is impurity and water.
For above-mentioned catalyst to the sweetening process of coke-stove gas, operating procedure is as follows:
Above-mentioned FeOOH desulfurizing agent and water are hybridly prepared into as desulfurizer slurry, FeOOH in the slurries
Total concentration is 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30
DEG C, the top of the desulfurizing tower carries out elution desulfurization to the coke-stove gas by the agent of nozzle injection desulfurization, after collecting desulfurization
The useless agent of FeOOH desulfurizing agent of the dry as the application of waste liquid.
Embodiment 5
Using waste collected by above-described embodiment 1-4 as the catalyst of biomass liquefaction reaction, catalyst is carried out
Active testing, active testing are as follows: preparing the slurries containing corn stover and catalyst, it is anti-that above-mentioned slurries are delivered to slurry bed system
It answers and carries out biomass liquefaction reaction in device, control reaction pressure is 20MPa, and temperature is 380 DEG C, wherein catalyst loading is
The distribution of the 2wt% of corn stover additive amount, the product that the activity of catalyst is prepared with biomass liquefaction reaction indicate, such as following table
Shown in 1:
1 embodiment 1-6 product profiles versus of table
As it can be seen from table 1 the biomass liquefaction reaction of biomass can be effectively facilitated using catalyst of the invention.
2, it is a kind of using FeOOH be the useless agent of the desulfurizing agent of main active as the use of biomass hydrogenation liquefaction catalyst
On the way
Embodiment 1
The embodiment of the invention provides a kind of mainly using FeOOH as the useless agent of the desulfurizing agent of active constituent, wherein described main
Using FeOOH as in the desulfurizing agent of active constituent, soluble ferric iron salt FeSO47H2O is 8g, EDETATE SODIUM 9g, sodium carbonate 2g, is gathered
Ethylene glycol 0.2g, D-sorbite 1g, amorphous FeOOH 7g and γ-FeOOH are 7g.
Sweetening process of the above-mentioned catalyst as coal pyrolysis gas, is summarized as follows:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and the air come with air pump is mixed into thick desulfurizing tower,
Using the process of bottom in and top out, to avoid there is liquid water to enter desulfurizing agent bed.It is herein to carry out thick removing hydrogen sulfide and take off
Except part R-SH and thiophene.
(2) gas heating after thick desulfurization is hydrolyzed to 110~125 DEG C, and most of COS and CS2 are hydrolyzed to H2S.
(3) gas after hydrolyzing is cooled to 20-~25 DEG C again, carries out H2S removing, herein to guarantee clean-up effect and make
The H2S that hydrolysis generates is totally removed using the form of double tower series-parallel operation with the service life, and is further removed remaining
R-SH and thiophene.It is totally removed by the remaining sulfide of this technical process, reaches final purification requirement total sulfur content and be less than
0.1ppm。
Desulfurizing agent becomes useless agent after being used for multiple times and deletes from desulfurizing agent bed, as in the application based on FeOOH
Want the useless agent of the desulfurizing agent of active constituent.
Embodiment 2
The embodiment of the invention provides a kind of mainly using FeOOH as the useless agent of the desulfurizing agent of active constituent, wherein described main
Using FeOOH as in the desulfurizing agent of active constituent, alpha-feooh 30g, β-FeOOH is 40g, basic copper carbonate 30g and sesbania powder
1g。
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, the gas water containing H2S is made come into full contact with instead with it
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, the catalyst after gas water desulfurization are useless
Agent is the application using FeOOH as the useless agent of the desulfurizing agent of main active.
Embodiment 3
The embodiment of the invention provides a kind of mainly using FeOOH as the useless agent of the desulfurizing agent of active constituent, wherein described main
Using FeOOH as in the desulfurizing agent of active constituent, amorphous FeOOH 70g, Co2O3 are 25g and NiO is 5g.
H in above-mentioned catalyst removal exhaust gas2The matrix process of S, includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, the waste in the desulfurization section is collected, the catalyst as the reaction of biomass hydrogenation liquefaction.
Embodiment 4
The embodiment of the invention provides a kind of mainly using FeOOH as the useless agent of the desulfurizing agent of active constituent, wherein described main
Using FeOOH as in the desulfurizing agent of active constituent, amorphous FeOOH 60g, bodied ferric sulfate 25g, basic copper carbonate 20g,
Calcium bicarbonate 20g and polyvinyl alcohol 45g.
For above-mentioned catalyst to the sweetening process of coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into as desulfurizer slurry, the total concentration of FeOOH in the slurries
For 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, described
The top of desulfurizing tower carries out elution desulfurization to the coke-stove gas by the agent of nozzle injection desulfurization, and the waste liquid after collecting desulfurization is dry
As the application using FeOOH as the desulfurizing agent of main active give up agent.
Embodiment 5
The catalyst reacted using waste collected by above-described embodiment 1-4 as biomass hydrogenation liquefaction, is catalyzed
The active testing of agent, active testing are as follows: preparing the slurries containing corn stover and catalyst, above-mentioned slurries are delivered to slurry
The reaction of biomass hydrogenation liquefaction is carried out in bed reactor, control reaction pressure is 20MPa, and temperature is 380 DEG C, wherein catalyst
Additive amount be corn stover additive amount 2wt%, the activity of catalyst biomass hydrogenation liquefaction reacts the product of preparation
Distribution indicates, as shown in table 1 below:
1 embodiment 1-6 product profiles versus of table
As it can be seen from table 1 being reacted using the biomass hydrogenation liquefaction that catalyst of the invention can effectively facilitate biomass.
3, the purposes after a kind of useless agent regeneration of desulfurizing agent containing FeOOH as biomass hydrogenation liquefaction catalyst.
Embodiment 1
The embodiment of the invention provides a kind of regeneration methods of the useless agent of desulfurizing agent containing FeOOH, wherein is contained with described
The gross mass meter of the desulfurizing agent of FeOOH, the content of amorphous FeOOH is 60% in the desulfurizing agent containing FeOOH,
The content of carrier diatomaceous earth is 30%, and the content of binder fiber element powder is 10%.
Sweetening process of the above-mentioned catalyst as coal pyrolysis gas, is summarized as follows:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and the air come with air pump is mixed into thick desulfurizing tower,
Using the process of bottom in and top out, to avoid there is liquid water to enter desulfurizing agent bed.It is herein to carry out thick removing hydrogen sulfide and take off
Except part R-SH and thiophene.
(2) gas heating after thick desulfurization is hydrolyzed to 110~125 DEG C, and most of COS and CS2 are hydrolyzed to H2S.
(3) gas after hydrolyzing is cooled to 20-~25 DEG C again, carries out H2S removing, herein to guarantee clean-up effect and make
The H2S that hydrolysis generates is totally removed using the form of double tower series-parallel operation with the service life, and is further removed remaining
R-SH and thiophene.It is totally removed by the remaining sulfide of this technical process, reaches final purification requirement total sulfur content and be less than
0.1ppm。
Desulfurizing agent becomes useless agent after being used for multiple times and deletes from desulfurizing agent bed, the FeOOH desulfurizing agent as in the application
Useless agent.
Above-mentioned desulfurizing agent give up agent regeneration method be,
1) water vapour that pressure is 1.5MPa is passed through heating furnace, by steam heating to 450 DEG C；
2) water vapour after heating is passed into the desulfurizer for containing the useless agent of desulfurizing agent with the speed of 15m/s, heats desulfurization
Agent is given up agent；
3) guarantee desulfurizing agent give up agent bed temperature by steam heating to running 2h, steam consumption under conditions of 450 DEG C
For 5.5t/h；
4) analysis desulfurizer export pH, continuous 3 times be more than or equal to 7.5 when, a small amount of oven gas can be passed through into desulfurizer
It is restored；
5) being passed through level-one in fine de-sulfur process adds the oven gas after hydrogen with 800m3/ h restores desulfurizing agent agent of giving up；
6) H is once imported and exported in every 30min analysis after being passed through oven gas2Concentration variation, as outlet H2Concentration stabilization is greater than or waits
In entrance H2The regrowth of the useless agent of desulfurizing agent can be obtained in (3 analyses) after concentration.
Embodiment 2
The embodiment of the invention provides a kind of regeneration methods of the useless agent of desulfurizing agent containing FeOOH, wherein is contained with described
The gross mass meter of the desulfurizing agent of FeOOH, the content of amorphous FeOOH is in the desulfurizing agent containing FeOOH
96.5%, surplus is impurity and water.H in above-mentioned catalyst removal exhaust gas2The matrix process of S, includes the following steps: H2S content
For 5500mg/cm3Exhaust gas with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, in the desulfurization section
Work off one's feeling vent one's spleen middle H2When content≤0.01ppm of S, collecting the waste in the desulfurization section is the useless agent of desulfurizing agent.
The useless agent of desulfurizing agent through being formed in the above process is the useless agent of FeOOH desulfurizing agent in the application.
The regeneration method of the useless agent of above-mentioned desulfurizing agent are as follows:
After the useless agent of the desulfurizing agent is washed with water, the particle for being ground into 100 mesh with water in wet ball mill is given up
Agent powder；The useless agent powder is made into the water slurry that solid masses percentage composition is 5%, compressed air is passed through, when reacting one section
Between after inspection by sampling, when the sample of taking-up is reacted with hydrochloric acid does not generate H2S, then the iron sulfide in useless agent is fully converted to hydroxyl
Base iron oxide and elemental sulfur form the slurries containing the FeOOH and elemental sulfur, filter the slurries and obtain solid material,
The solid material is placed in flotation cell, water is added, then passes to air, elemental sulfur overflow due to it is with hydrophobicity
It out, then is the regrowth of the useless agent of above-mentioned desulfurizing agent after the sediment drying of lower vessel portion.
Embodiment 3
The embodiment of the invention provides a kind of regeneration methods of the useless agent of desulfurizing agent containing FeOOH, wherein is contained with described
The gross mass meter of the desulfurizing agent of FeOOH, the content of amorphous FeOOH is 80% in the desulfurizing agent containing FeOOH,
The content of carrier alundum is 15%, and the content of binder sesbania powder is 5%.Desulfurization of the above-mentioned catalyst to gas water
Journey, operating procedure are as follows:
By above-mentioned Catalyst packing in fixed bed reactors, the gas water containing H2S is made come into full contact with instead with it
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, the catalyst after gas water desulfurization are useless
Agent is the useless agent of FeOOH desulfurizing agent of the application.
Above-mentioned desulfurizing agent give up agent regeneration method be
After the useless agent of the desulfurizing agent is washed with water, the particle for being ground into 200 mesh with water in wet ball mill is given up
Agent powder；The useless agent powder is made into the water slurry that solid masses percentage composition is 7%, compressed air is passed through, when reacting one section
Between after inspection by sampling, when the sample of taking-up is reacted with hydrochloric acid does not generate H2S, then the iron sulfide in useless agent is fully converted to hydroxyl
Base iron oxide and elemental sulfur form the slurries containing the FeOOH and elemental sulfur, filter the slurries and obtain solid material,
The solid material is placed in flotation cell, water is added, then passes to air, elemental sulfur overflow due to it is with hydrophobicity
It out, then is the regrowth of the useless agent of above-mentioned desulfurizing agent after the sediment drying of lower vessel portion.
Embodiment 4
The embodiment of the invention provides a kind of regeneration methods of the useless agent of desulfurizing agent containing FeOOH, wherein is contained with described
The gross mass meter of the desulfurizing agent of FeOOH, the content of γ-FeOOH is 45% in the desulfurizing agent containing FeOOH, alpha-feooh
Content is 35%, and the content of carrier molecule sieve is 15%, and the content of binder sesbania powder is 5%.
H in above-mentioned catalyst removal exhaust gas2The matrix process of S, includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, collecting the waste in the desulfurization section is the useless agent of desulfurizing agent.
Above-mentioned desulfurizing agent give up agent regeneration method be
After the useless agent of the desulfurizing agent is washed with water, the particle for being ground into 80 mesh with water in wet ball mill obtains useless agent
Powder；The useless agent powder is made into the water slurry that solid masses percentage composition is 8%, is passed through compressed air, reaction a period of time
Inspection by sampling afterwards, when the sample of taking-up is reacted with hydrochloric acid does not generate H2S, then the iron sulfide in agent of giving up is fully converted to hydroxyl
Iron oxide and elemental sulfur form the slurries containing the FeOOH and elemental sulfur, filter the slurries and obtain solid material, use
Obtained solid material after CC14 extraction filtering, coextraction combining extraction liquid three times, simultaneously must with the method recycling design of distillation
To the elemental sulfur of crystallization, and extract liquor separates rear remaining solid and mixes with binder sesbania powder, and the useless agent of above-mentioned desulfurizing agent is made
Regrowth, wherein the dosage of binder sesbania powder be the solid masses 5%.
Embodiment 5
The embodiment of the invention provides a kind of regeneration methods of the useless agent of desulfurizing agent containing FeOOH, wherein is contained with described
The gross mass meter of the desulfurizing agent of FeOOH, β-FeOOH content is 49%, θ-FeOOH content in the desulfurizing agent containing FeOOH
It is 45%, surplus is impurity and water.
For above-mentioned catalyst to the sweetening process of coke-stove gas, operating procedure is as follows:
Above-mentioned FeOOH desulfurizing agent and water are hybridly prepared into as desulfurizer slurry, FeOOH in the slurries
Total concentration is 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30
DEG C, the top of the desulfurizing tower carries out elution desulfurization to the coke-stove gas by the agent of nozzle injection desulfurization, after collecting desulfurization
The useless agent of FeOOH desulfurizing agent of the dry as the application of waste liquid.
Above-mentioned desulfurizing agent give up agent regeneration method be
1) water vapour that pressure is 1MPa is passed through heating furnace, by steam heating to 400 DEG C；
2) water vapour after heating is passed into the desulfurizer for containing the useless agent of desulfurizing agent with the speed of 20m/s, heats desulfurization
Agent is given up agent；
3) guarantee desulfurizing agent give up agent bed temperature by steam heating to running 2h, steam consumption under conditions of 450 DEG C
For 8t/h；
4) analysis desulfurizer export pH, continuous 3 times be more than or equal to 7.5 when, a small amount of oven gas can be passed through into desulfurizer
It is restored；
5) being passed through level-one in fine de-sulfur process adds the oven gas after hydrogen with 800m3/ h restores desulfurizing agent agent of giving up；
6) H is once imported and exported in every 30min analysis after being passed through oven gas2Concentration variation, as outlet H2Concentration stabilization is greater than or waits
In entrance H2The regrowth of the useless agent of desulfurizing agent can be obtained in (3 analyses) after concentration.
Embodiment 6
The embodiment of the invention provides a kind of mainly using FeOOH as the useless agent of the desulfurizing agent of active constituent, wherein described main
Using FeOOH as in the desulfurizing agent of active constituent, amorphous FeOOH 70g, Co2O3 are 25g and NiO is 5g.
H in above-mentioned catalyst removal exhaust gas2The matrix process of S, includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, the waste in the desulfurization section, the as useless agent of desulfurizing agent are collected.
Above-mentioned desulfurizing agent give up agent regeneration method be,
After the useless agent of the desulfurizing agent is washed with water, the particle for being ground into 80 mesh with water in wet ball mill obtains useless agent
Powder；The useless agent powder is made into the water slurry that solid masses percentage composition is 8%, is passed through compressed air, reaction a period of time
Inspection by sampling afterwards, when the sample of taking-up is reacted with hydrochloric acid does not generate H2S, then the iron sulfide in agent of giving up is fully converted to hydroxyl
Iron oxide and elemental sulfur form the slurries containing the FeOOH and elemental sulfur, filter the slurries and obtain solid material, use
Obtained solid material after CC14 extraction filtering, coextraction combining extraction liquid three times, simultaneously must with the method recycling design of distillation
To the elemental sulfur of crystallization, and extract liquor separates the regrowth that rear remaining solid is the useless agent of desulfurizing agent.
Embodiment 7
The embodiment of the invention provides a kind of mainly using FeOOH as the useless agent of the desulfurizing agent of active constituent, wherein described main
Using FeOOH as in the desulfurizing agent of active constituent, amorphous FeOOH 60g, bodied ferric sulfate 25g, basic copper carbonate 20g,
Calcium bicarbonate 20g and polyvinyl alcohol 45g.
For above-mentioned catalyst to the sweetening process of coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into as desulfurizer slurry, the total concentration of FeOOH in the slurries
For 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, described
The top of desulfurizing tower carries out elution desulfurization to the coke-stove gas by the agent of nozzle injection desulfurization, and the waste liquid after collecting desulfurization is dry
As the application using FeOOH as the desulfurizing agent of main active give up agent.
Above-mentioned desulfurizing agent give up agent regeneration method be
After the useless agent of the desulfurizing agent is washed with water, the particle for being ground into 80 mesh with water in wet ball mill obtains useless agent
Powder；The useless agent powder is made into the water slurry that solid masses percentage composition is 8%, is passed through compressed air, reaction a period of time
Inspection by sampling afterwards, when the sample of taking-up is reacted with hydrochloric acid does not generate H2S, then the iron sulfide in agent of giving up is fully converted to hydroxyl
Iron oxide and elemental sulfur form the slurries containing the FeOOH and elemental sulfur, filter the slurries and obtain solid material, use
Obtained solid material after CC14 extraction filtering, coextraction combining extraction liquid three times, simultaneously must with the method recycling design of distillation
To the elemental sulfur of crystallization, and extract liquor separates rear remaining solid and mixes with binder sesbania powder, and the useless agent of above-mentioned desulfurizing agent is made
Regrowth, wherein the dosage of binder sesbania powder be the solid masses 5%.
Embodiment 8
The embodiment of the invention provides a kind of mainly using FeOOH as the useless agent of the desulfurizing agent of active constituent, wherein described main
Using FeOOH as in the desulfurizing agent of active constituent, soluble ferric iron salt FeSO47H2O is 8g, EDETATE SODIUM 9g, sodium carbonate 2g, is gathered
Ethylene glycol 0.2g, D-sorbite 1g, amorphous FeOOH 7g and γ-FeOOH are 7g.
Sweetening process of the above-mentioned catalyst as coal pyrolysis gas, is summarized as follows:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and the air come with air pump is mixed into thick desulfurizing tower,
Using the process of bottom in and top out, to avoid there is liquid water to enter desulfurizing agent bed.It is herein to carry out thick removing hydrogen sulfide and take off
Except part R-SH and thiophene.
(2) gas heating after thick desulfurization is hydrolyzed to 110~125 DEG C, and most of COS and CS2 are hydrolyzed to H2S.
(3) gas after hydrolyzing is cooled to 20-~25 DEG C again, carries out H2S removing, herein to guarantee clean-up effect and make
The H2S that hydrolysis generates is totally removed using the form of double tower series-parallel operation with the service life, and is further removed remaining
R-SH and thiophene.It is totally removed by the remaining sulfide of this technical process, reaches final purification requirement total sulfur content and be less than
0.1ppm。
Desulfurizing agent becomes useless agent after being used for multiple times and deletes from desulfurizing agent bed, as in the application based on FeOOH
Want the useless agent of the desulfurizing agent of active constituent.
Above-mentioned desulfurizing agent is useless
After agent is washed with water, the particle for being ground into 200 mesh with water in wet ball mill obtains useless agent powder；By the useless agent
Powder is made into the water slurry that solid masses percentage composition is 7%, is passed through compressed air, reacts inspection by sampling after a period of time, when
The sample of taking-up is reacted with hydrochloric acid when not generating H2S, then the iron sulfide in agent of giving up is fully converted to FeOOH and simple substance
Sulphur forms the slurries containing the FeOOH and elemental sulfur, filters the slurries and obtain solid material, by the solid material
It is placed in flotation cell, water is added, then passes to air, the elemental sulfur is overflowed because it is with hydrophobicity, then under container
It is the regrowth of the useless agent of above-mentioned desulfurizing agent after the sediment drying in portion.
Embodiment 9
Using waste collected by above-described embodiment 1-8 as the catalyst of biomass liquefaction reaction, catalyst is carried out
Active testing, while it being also applied to active testing using the desulfurizing agent used in 9 as comparative example 1, active testing is as follows: matching
The slurries containing corn stover and catalyst are made, it is anti-that above-mentioned slurries are delivered to progress biomass liquefying in paste state bed reactor
It answers, control reaction pressure is 20MPa, and temperature is 380 DEG C, wherein catalyst loading is the 2wt% of corn stover additive amount,
The distribution for the product that the activity of catalyst is prepared with biomass liquefaction reaction indicates, as shown in table 1 below:
1 product profiles versus of table
As it can be seen from table 1 adopting the biomass conversion ratio being obtained by the present invention is 95.4-97.8%, oil is mutually received
Rate is 43.5-48.3%, illustrates the biomass liquefaction reaction that biomass can be effectively facilitated using catalyst of the invention.
4, useless purposes of the agent as CO transformation catalyst of a kind of FeOOH desulfurizing agent:
Embodiment 1
The embodiment of the invention provides a kind of useless agent of FeOOH desulfurizing agent, wherein with the gross mass of the FeOOH desulfurizing agent
It counts, the content of amorphous FeOOH is 60% in the FeOOH desulfurizing agent, and the content of carrier diatomaceous earth is 30%, bonding
The content of agent cellulose powder is 10%.
Sweetening process of the above-mentioned catalyst as coal pyrolysis gas, is summarized as follows:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and the air come with air pump is mixed into thick desulfurizing tower,
Using the process of bottom in and top out, to avoid there is liquid water to enter desulfurizing agent bed.Thick removing hydrogen sulfide is only carried out herein.
(2) gas heating after thick desulfurization is hydrolyzed to 110~125 DEG C, and most of COS and CS2 are hydrolyzed to H2S.
(3) gas after hydrolyzing is cooled to 20-~25 DEG C again, carries out H2S removing, herein to guarantee clean-up effect and make
The H2S that hydrolysis generates is totally removed using the form of double tower series-parallel operation with the service life.It is remaining by this technical process
Sulfide is totally removed, and reaches final purification requirement total sulfur content less than 0.1ppm.
Desulfurizing agent becomes useless agent after being used for multiple times and deletes from desulfurizing agent bed, the FeOOH desulfurizing agent as in the application
Useless agent.
Embodiment 2
The embodiment of the invention provides a kind of useless agent of FeOOH desulfurizing agent, wherein with the gross mass of the FeOOH desulfurizing agent
It counts, the content of amorphous FeOOH is 80% in the FeOOH desulfurizing agent, and the content of carrier alundum is 15%,
The content of binder sesbania powder is 5%.For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, the gas water containing H2S is made come into full contact with instead with it
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, the catalyst after gas water desulfurization are useless
Agent is the useless agent of FeOOH desulfurizing agent of the application.
Embodiment 3
The embodiment of the invention provides a kind of useless agent of FeOOH desulfurizing agent, wherein with the gross mass of the FeOOH desulfurizing agent
It counts, the content of γ-FeOOH is 45% in the FeOOH desulfurizing agent, and the content of alpha-feooh is 35%, and carrier molecule sieve contains
Amount is 15%, and the content of binder sesbania powder is 5%.
H in above-mentioned catalyst removal exhaust gas2The matrix process of S, includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, the waste in the desulfurization section is collected, the catalyst as CO conversion reaction.
Embodiment 4
The embodiment of the invention provides a kind of useless agent of FeOOH desulfurizing agent, wherein with the gross mass of the FeOOH desulfurizing agent
It counts, it is 45% that β-FeOOH content, which is 49%, θ-FeOOH content, in the FeOOH desulfurizing agent, and surplus is impurity and water.
For above-mentioned catalyst to the sweetening process of coke-stove gas, operating procedure is as follows:
Above-mentioned FeOOH desulfurizing agent and water are hybridly prepared into as desulfurizer slurry, FeOOH in the slurries
Total concentration is 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30
DEG C, the top of the desulfurizing tower carries out elution desulfurization to the coke-stove gas by the agent of nozzle injection desulfurization, after collecting desulfurization
The useless agent of FeOOH desulfurizing agent of the dry as the application of waste liquid.
Embodiment 5 (application of the useless agent of desulfurizing agent)
Agent is given up as the catalyst of CO conversion reaction using desulfurizing agent collected by above-described embodiment 1-5, carries out catalyst
Active testing, active testing are as follows:
Unstripped gas group becomes 15vol%CO, 55vol%H2, 6vol%CO2, 24vol%N2, reaction steam-to-gas ratio be 1:1, it is empty
Speed is 4000h-1, it is 250~450 DEG C that catalyst activity, which tests warm area,；
The activity of catalyst indicates that calculation method is as follows with CO conversion ratio:
CO conversion ratio=(1-VCO'/VCO)/(1+VCO) × 100%
Wherein, VCO'For the percentage by volume of CO in reactor outlet gas, VCOFor the percentage by volume of CO in unstripped gas；
It is corresponding that test result is as follows shown in table 1:
CO conversion ratio under table 1, different test temperatures
5, it is a kind of using FeOOH be the useless agent of the desulfurizing agent of main active as the purposes of CO transformation catalyst.
Embodiment 1
The embodiment of the invention provides a kind of mainly using FeOOH as the useless agent of the desulfurizing agent of active constituent, wherein described main
Using FeOOH as in the desulfurizing agent of active constituent, soluble ferric iron salt FeSO47H2O is 8g, EDETATE SODIUM 9g, sodium carbonate 2g, is gathered
Ethylene glycol 0.2g, D-sorbite 1g, amorphous FeOOH 7g and γ-FeOOH are 7g.
Sweetening process of the above-mentioned catalyst as coal pyrolysis gas, is summarized as follows:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and the air come with air pump is mixed into thick desulfurizing tower,
Using the process of bottom in and top out, to avoid there is liquid water to enter desulfurizing agent bed.Thick removing hydrogen sulfide is only carried out herein.
(2) gas heating after thick desulfurization is hydrolyzed to 110~125 DEG C, and most of COS and CS2 are hydrolyzed to H2S.
(3) gas after hydrolyzing is cooled to 20-~25 DEG C again, carries out H2S removing, herein to guarantee clean-up effect and make
The H2S that hydrolysis generates is totally removed using the form of double tower series-parallel operation with the service life.It is remaining by this technical process
Sulfide is totally removed, and reaches final purification requirement total sulfur content less than 0.1ppm.
Desulfurizing agent becomes useless agent after being used for multiple times and deletes from desulfurizing agent bed, as in the application based on FeOOH
Want the useless agent of the desulfurizing agent of active constituent.
Embodiment 2
The embodiment of the invention provides a kind of mainly using FeOOH as the useless agent of the desulfurizing agent of active constituent, wherein described main
Using FeOOH as in the desulfurizing agent of active constituent, alpha-feooh 30g, β-FeOOH is 40g, basic copper carbonate 30g and sesbania powder
1g。
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, the gas water containing H2S is made come into full contact with instead with it
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, the catalyst after gas water desulfurization are useless
Agent is the application using FeOOH as the useless agent of the desulfurizing agent of main active.
Embodiment 3
The embodiment of the invention provides a kind of mainly using FeOOH as the useless agent of the desulfurizing agent of active constituent, wherein described main
Using FeOOH as in the desulfurizing agent of active constituent, amorphous FeOOH 70g, Co2O3 are 25g and NiO is 5g.
H in above-mentioned catalyst removal exhaust gas2The matrix process of S, includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, the waste in the desulfurization section is collected, the catalyst as CO conversion reaction.
Embodiment 4
The embodiment of the invention provides a kind of mainly using FeOOH as the useless agent of the desulfurizing agent of active constituent, wherein described main
Using FeOOH as in the desulfurizing agent of active constituent, amorphous FeOOH 60g, bodied ferric sulfate 25g, basic copper carbonate 20g,
Calcium bicarbonate 20g and polyvinyl alcohol 45g.
For above-mentioned catalyst to the sweetening process of coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into as desulfurizer slurry, the total concentration of FeOOH in the slurries
For 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, described
The top of desulfurizing tower carries out elution desulfurization to the coke-stove gas by the agent of nozzle injection desulfurization, and the waste liquid after collecting desulfurization is dry
As the application using FeOOH as the desulfurizing agent of main active give up agent.
Embodiment 5 (application of the useless agent of desulfurizing agent)
Agent is given up as the catalyst of CO conversion reaction using desulfurizing agent collected by above-described embodiment 1-4, carries out catalyst
Active testing, active testing are as follows:
Unstripped gas group becomes 15vol%CO, 55vol%H2, 6vol%CO2, 24vol%N2, reaction steam-to-gas ratio be 1:1, it is empty
Speed is 4000h-1, it is 250~450 DEG C that catalyst activity, which tests warm area,；
The activity of catalyst indicates that calculation method is as follows with CO conversion ratio:
CO conversion ratio=(1-VCO'/VCO)/(1+VCO) × 100%
Wherein, VCO'For the percentage by volume of CO in reactor outlet gas, VCOFor the percentage by volume of CO in unstripped gas；
It is corresponding that test result is as follows shown in table 1:
CO conversion ratio under table 1, different test temperatures
6, the purposes after a kind of useless agent regeneration of desulfurizing agent containing FeOOH as CO transformation catalyst.
Embodiment 1
The embodiment of the invention provides a kind of regeneration methods of the useless agent of desulfurizing agent containing FeOOH, wherein is contained with described
The gross mass meter of the desulfurizing agent of FeOOH, the content of amorphous FeOOH is 60% in the desulfurizing agent containing FeOOH,
The content of carrier diatomaceous earth is 30%, and the content of binder fiber element powder is 10%.
Sweetening process of the above-mentioned catalyst as coal pyrolysis gas, is summarized as follows:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and the air come with air pump is mixed into thick desulfurizing tower,
Using the process of bottom in and top out, to avoid there is liquid water to enter desulfurizing agent bed.Thick removing hydrogen sulfide is only carried out herein.
(2) gas heating after thick desulfurization is hydrolyzed to 110~125 DEG C, and most of COS and CS2 are hydrolyzed to H2S.
(3) gas after hydrolyzing is cooled to 20-~25 DEG C again, carries out H2S removing, herein to guarantee clean-up effect and make
The H2S that hydrolysis generates is totally removed using the form of double tower series-parallel operation with the service life, and is further removed remaining
R-SH and thiophene.It is totally removed by the remaining sulfide of this technical process, reaches final purification requirement total sulfur content and be less than
0.1ppm。
Desulfurizing agent becomes useless agent after being used for multiple times and deletes from desulfurizing agent bed, the FeOOH desulfurizing agent as in the application
Useless agent.
Above-mentioned desulfurizing agent give up agent regeneration method be,
1) water vapour that pressure is 1.5MPa is passed through heating furnace, by steam heating to 450 DEG C；
2) water vapour after heating is passed into the desulfurizer for containing the useless agent of desulfurizing agent with the speed of 15m/s, heats desulfurization
Agent is given up agent；
3) guarantee desulfurizing agent give up agent bed temperature by steam heating to running 2h, steam consumption under conditions of 450 DEG C
For 5.5t/h；
4) analysis desulfurizer export pH, continuous 3 times be more than or equal to 7.5 when, a small amount of oven gas can be passed through into desulfurizer
It is restored；
5) being passed through level-one in fine de-sulfur process adds the oven gas after hydrogen with 800m3/ h restores desulfurizing agent agent of giving up；
6) H is once imported and exported in every 30min analysis after being passed through oven gas2Concentration variation, as outlet H2Concentration stabilization is greater than or waits
In entrance H2The regrowth of the useless agent of desulfurizing agent can be obtained in (3 analyses) after concentration.
Embodiment 2
The embodiment of the invention provides a kind of regeneration methods of the useless agent of desulfurizing agent containing FeOOH, wherein is contained with described
The gross mass meter of the desulfurizing agent of FeOOH, the content of amorphous FeOOH is in the desulfurizing agent containing FeOOH
96.5%, surplus is impurity and water.H in above-mentioned catalyst removal exhaust gas2The matrix process of S, includes the following steps: H2S content
For 5500mg/cm3Exhaust gas with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, in the desulfurization section
Work off one's feeling vent one's spleen middle H2When content≤0.01ppm of S, collecting the waste in the desulfurization section is the useless agent of desulfurizing agent.
The useless agent of desulfurizing agent through being formed in the above process is the useless agent of FeOOH desulfurizing agent in the application.
The regeneration method of the useless agent of above-mentioned desulfurizing agent are as follows:
After the useless agent of the desulfurizing agent is washed with water, the particle for being ground into 100 mesh with water in wet ball mill is given up
Agent powder；The useless agent powder is made into the water slurry that solid masses percentage composition is 5%, compressed air is passed through, when reacting one section
Between after inspection by sampling, when the sample of taking-up is reacted with hydrochloric acid does not generate H2S, then the iron sulfide in useless agent is fully converted to hydroxyl
Base iron oxide and elemental sulfur form the slurries containing the FeOOH and elemental sulfur, filter the slurries and obtain solid material,
The solid material is placed in flotation cell, water is added, then passes to air, elemental sulfur overflow due to it is with hydrophobicity
It out, then is the regrowth of the useless agent of above-mentioned desulfurizing agent after the sediment drying of lower vessel portion.
Embodiment 3
The embodiment of the invention provides a kind of regeneration methods of the useless agent of desulfurizing agent containing FeOOH, wherein is contained with described
The gross mass meter of the desulfurizing agent of FeOOH, the content of amorphous FeOOH is 80% in the desulfurizing agent containing FeOOH,
The content of carrier alundum is 15%, and the content of binder sesbania powder is 5%.Desulfurization of the above-mentioned catalyst to gas water
Journey, operating procedure are as follows:
By above-mentioned Catalyst packing in fixed bed reactors, the gas water containing H2S is made come into full contact with instead with it
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, the catalyst after gas water desulfurization are useless
Agent is the useless agent of FeOOH desulfurizing agent of the application.
Above-mentioned desulfurizing agent give up agent regeneration method be
After the useless agent of the desulfurizing agent is washed with water, the particle for being ground into 200 mesh with water in wet ball mill is given up
Agent powder；The useless agent powder is made into the water slurry that solid masses percentage composition is 7%, compressed air is passed through, when reacting one section
Between after inspection by sampling, when the sample of taking-up is reacted with hydrochloric acid does not generate H2S, then the iron sulfide in useless agent is fully converted to hydroxyl
Base iron oxide and elemental sulfur form the slurries containing the FeOOH and elemental sulfur, filter the slurries and obtain solid material,
The solid material is placed in flotation cell, water is added, then passes to air, elemental sulfur overflow due to it is with hydrophobicity
It out, then is the regrowth of the useless agent of above-mentioned desulfurizing agent after the sediment drying of lower vessel portion.
Embodiment 4
The embodiment of the invention provides a kind of regeneration methods of the useless agent of desulfurizing agent containing FeOOH, wherein is contained with described
The gross mass meter of the desulfurizing agent of FeOOH, the content of γ-FeOOH is 45% in the desulfurizing agent containing FeOOH, alpha-feooh
Content is 35%, and the content of carrier molecule sieve is 15%, and the content of binder sesbania powder is 5%.
H in above-mentioned catalyst removal exhaust gas2The matrix process of S, includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, collecting the waste in the desulfurization section is the useless agent of desulfurizing agent.
Above-mentioned desulfurizing agent give up agent regeneration method be
After the useless agent of the desulfurizing agent is washed with water, the particle for being ground into 80 mesh with water in wet ball mill obtains useless agent
Powder；The useless agent powder is made into the water slurry that solid masses percentage composition is 8%, is passed through compressed air, reaction a period of time
Inspection by sampling afterwards, when the sample of taking-up is reacted with hydrochloric acid does not generate H2S, then the iron sulfide in agent of giving up is fully converted to hydroxyl
Iron oxide and elemental sulfur form the slurries containing the FeOOH and elemental sulfur, filter the slurries and obtain solid material, use
Obtained solid material after CC14 extraction filtering, coextraction combining extraction liquid three times, simultaneously must with the method recycling design of distillation
To the elemental sulfur of crystallization, and extract liquor separates rear remaining solid and mixes with binder sesbania powder, and the useless agent of above-mentioned desulfurizing agent is made
Regrowth, wherein the dosage of binder sesbania powder be the solid masses 5%.
Embodiment 5
The embodiment of the invention provides a kind of regeneration methods of the useless agent of desulfurizing agent containing FeOOH, wherein is contained with described
The gross mass meter of the desulfurizing agent of FeOOH, β-FeOOH content is 49%, θ-FeOOH content in the desulfurizing agent containing FeOOH
It is 45%, surplus is impurity and water.
For above-mentioned catalyst to the sweetening process of coke-stove gas, operating procedure is as follows:
Above-mentioned FeOOH desulfurizing agent and water are hybridly prepared into as desulfurizer slurry, FeOOH in the slurries
Total concentration is 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30
DEG C, the top of the desulfurizing tower carries out elution desulfurization to the coke-stove gas by the agent of nozzle injection desulfurization, after collecting desulfurization
The useless agent of FeOOH desulfurizing agent of the dry as the application of waste liquid.
Above-mentioned desulfurizing agent give up agent regeneration method be
1) water vapour that pressure is 1MPa is passed through heating furnace, by steam heating to 400 DEG C；
2) water vapour after heating is passed into the desulfurizer for containing the useless agent of desulfurizing agent with the speed of 20m/s, heats desulfurization
Agent is given up agent；
3) guarantee desulfurizing agent give up agent bed temperature by steam heating to running 2h, steam consumption under conditions of 450 DEG C
For 8t/h；
4) analysis desulfurizer export pH, continuous 3 times be more than or equal to 7.5 when, a small amount of oven gas can be passed through into desulfurizer
It is restored；
5) being passed through level-one in fine de-sulfur process adds the oven gas after hydrogen with 800m3/ h restores desulfurizing agent agent of giving up；
6) H is once imported and exported in every 30min analysis after being passed through oven gas2Concentration variation, as outlet H2Concentration stabilization is greater than or waits
In entrance H2The regrowth of the useless agent of desulfurizing agent can be obtained in (3 analyses) after concentration.
Embodiment 6
The embodiment of the invention provides a kind of mainly using FeOOH as the useless agent of the desulfurizing agent of active constituent, wherein described main
Using FeOOH as in the desulfurizing agent of active constituent, amorphous FeOOH 70g, Co2O3 are 25g and NiO is 5g.
H in above-mentioned catalyst removal exhaust gas2The matrix process of S, includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, the waste in the desulfurization section is collected, the catalyst as CO conversion reaction.
Above-mentioned desulfurizing agent give up agent regeneration method be
After the useless agent of the desulfurizing agent is washed with water, the particle for being ground into 80 mesh with water in wet ball mill obtains useless agent
Powder；The useless agent powder is made into the water slurry that solid masses percentage composition is 8%, is passed through compressed air, reaction a period of time
Inspection by sampling afterwards, when the sample of taking-up is reacted with hydrochloric acid does not generate H2S, then the iron sulfide in agent of giving up is fully converted to hydroxyl
Iron oxide and elemental sulfur form the slurries containing the FeOOH and elemental sulfur, filter the slurries and obtain solid material, use
Obtained solid material after CC14 extraction filtering, coextraction combining extraction liquid three times, simultaneously must with the method recycling design of distillation
To the elemental sulfur of crystallization, and extract liquor separates the regrowth that rear remaining solid is the useless agent of desulfurizing agent.
Embodiment 7
The embodiment of the invention provides a kind of mainly using FeOOH as the useless agent of the desulfurizing agent of active constituent, wherein described main
Using FeOOH as in the desulfurizing agent of active constituent, amorphous FeOOH 60g, bodied ferric sulfate 25g, basic copper carbonate 20g,
Calcium bicarbonate 20g and polyvinyl alcohol 45g.
For above-mentioned catalyst to the sweetening process of coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into as desulfurizer slurry, the total concentration of FeOOH in the slurries
For 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, described
The top of desulfurizing tower carries out elution desulfurization to the coke-stove gas by the agent of nozzle injection desulfurization, and the waste liquid after collecting desulfurization is dry
As the application using FeOOH as the desulfurizing agent of main active give up agent.
Above-mentioned desulfurizing agent give up agent regeneration method be
After the useless agent of the desulfurizing agent is washed with water, the particle for being ground into 80 mesh with water in wet ball mill obtains useless agent
Powder；The useless agent powder is made into the water slurry that solid masses percentage composition is 8%, is passed through compressed air, reaction a period of time
Inspection by sampling afterwards, when the sample of taking-up is reacted with hydrochloric acid does not generate H2S, then the iron sulfide in agent of giving up is fully converted to hydroxyl
Iron oxide and elemental sulfur form the slurries containing the FeOOH and elemental sulfur, filter the slurries and obtain solid material, use
Obtained solid material after CC14 extraction filtering, coextraction combining extraction liquid three times, simultaneously must with the method recycling design of distillation
To the elemental sulfur of crystallization, and extract liquor separates rear remaining solid and mixes with binder sesbania powder, and the useless agent of above-mentioned desulfurizing agent is made
Regrowth, wherein the dosage of binder sesbania powder be the solid masses 5%.
Embodiment 8
The embodiment of the invention provides a kind of mainly using FeOOH as the useless agent of the desulfurizing agent of active constituent, wherein described main
Using FeOOH as in the desulfurizing agent of active constituent, soluble ferric iron salt FeSO47H2O is 8g, EDETATE SODIUM 9g, sodium carbonate 2g, is gathered
Ethylene glycol 0.2g, D-sorbite 1g, amorphous FeOOH 7g and γ-FeOOH are 7g.
Sweetening process of the above-mentioned catalyst as coal pyrolysis gas, is summarized as follows:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and the air come with air pump is mixed into thick desulfurizing tower,
Using the process of bottom in and top out, to avoid there is liquid water to enter desulfurizing agent bed.It is herein to carry out thick removing hydrogen sulfide and take off
Except part R-SH and thiophene.
(2) gas heating after thick desulfurization is hydrolyzed to 110~125 DEG C, and most of COS and CS2 are hydrolyzed to H2S.
(3) gas after hydrolyzing is cooled to 20-~25 DEG C again, carries out H2S removing, herein to guarantee clean-up effect and make
The H2S that hydrolysis generates is totally removed using the form of double tower series-parallel operation with the service life, and is further removed remaining
R-SH and thiophene.It is totally removed by the remaining sulfide of this technical process, reaches final purification requirement total sulfur content and be less than
0.1ppm。
Desulfurizing agent becomes useless agent after being used for multiple times and deletes from desulfurizing agent bed, as in the application based on FeOOH
Want the useless agent of the desulfurizing agent of active constituent.
Above-mentioned desulfurizing agent give up agent regeneration method be,
After the useless agent of the desulfurizing agent is washed with water, the particle for being ground into 200 mesh with water in wet ball mill is given up
Agent powder；The useless agent powder is made into the water slurry that solid masses percentage composition is 7%, compressed air is passed through, when reacting one section
Between after inspection by sampling, when the sample of taking-up is reacted with hydrochloric acid does not generate H2S, then the iron sulfide in useless agent is fully converted to hydroxyl
Base iron oxide and elemental sulfur form the slurries containing the FeOOH and elemental sulfur, filter the slurries and obtain solid material,
The solid material is placed in flotation cell, water is added, then passes to air, elemental sulfur overflow due to it is with hydrophobicity
It out, then is the regrowth of the useless agent of above-mentioned desulfurizing agent after the sediment drying of lower vessel portion.
Embodiment 9 (application after the useless agent regeneration of desulfurizing agent)
As the catalyst of CO conversion reaction after giving up agent regeneration using desulfurizing agent collected by above-described embodiment 1-8, urged
The active testing of agent, while active survey is also applied to using the desulfurizing agent used in embodiment 2 and 8 as comparative example 1 and 2
Examination, active testing are as follows:
Unstripped gas group becomes 15vol%CO, 55vol%H2, 6vol%CO2, 24vol%N2, reaction steam-to-gas ratio be 1:1, it is empty
Speed is 4000h-1, it is 250~450 DEG C that catalyst activity, which tests warm area,；
The activity of catalyst indicates that calculation method is as follows with CO conversion ratio:
CO conversion ratio=(1-VCO'/VCO)/(1+VCO) × 100%
Wherein, VCO'For the percentage by volume of CO in reactor outlet gas, VCOFor the percentage by volume of CO in unstripped gas；
It is corresponding that test result is as follows shown in table 1:
CO conversion ratio under table 1, different test temperatures
7, the purposes of a kind of useless agent of desulfurizing agent containing FeOOH or useless agent regenerative agent in organic matter transformation technique.
Embodiment 1
A kind of biomass and hogwash fat cotransformation technique are present embodiments provided, is included the following steps:
The pretreatment of biomass:
Rice straw and reed straw are as biomass solid, with total restatement of the biomass, the moisture content of the biomass
It is 4%, the rice straw and reed straw is sent into micronizer and just crush, first smashed median is 100 μ
First smashed rice straw and reed straw are then sent into cuber and are carried out under 30 DEG C of temperature, the pressure of 3MPa by m
Compression, extrusion forming to its heap density are 0.8g/cm3, separating twice is carried out later, and the average particle size after separating twice is
3mm, it is spare；
Catalyst:
Catalyst is using FeOOH as the useless agent of the desulfurizing agent of active component, wherein described using FeOOH as active component
In desulfurizing agent, soluble ferric iron salt Fe (NO3)3·9H2O is 6g, molysite complexing agent triethanolamine 9g, amorphous FeOOH
15g；
Above-mentioned using FeOOH is the desulfurizing agent of active component for removing H in exhaust gas2The process of S is as follows: by H2S content is
5500mg/cm3Exhaust gas with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, is gone out in the desulfurization section
H in implication2When content≤0.01ppm of S, the waste in the desulfurization section is collected, as in the present embodiment is with FeOOH
The useless agent of the desulfurizing agent of active component.
The preparation of biomass slurry:
The biomass that pretreatment obtains is mixed to get mixture with above-mentioned catalyst, hogwash fat is added in said mixture
Middle stirring simultaneously grinds slurrying, forms slurries, and through detecting, the total content of rice straw and reed straw is 60wt% in the slurries,
The viscosity of the slurries is 500mPa ﹒ s (50 DEG C), and in above-mentioned slurries, the content of catalyst is 5wt%, the catalyst added
Average grain diameter be 5 μm；
Conversion reaction:
By CO and H2Gaseous mixture (CO accounting 60% and H2Accounting is that 40%) middle part is forced into 21MPa, is heated up to 350
It after DEG C, is passed through in the pipeline for conveying the slurries, after rest part is forced into 21MPa, is heated up to 500 DEG C, by slurry reactor
Device entrance injects in paste state bed reactor, while being passed through H2S into reactor and make the ferro element of reaction system and rubbing for element sulphur
, than being 1:5, the slurries generation cracking, carbonylation, transformation and hydrogenation reaction, the reaction pressure for controlling conversion reaction are for you
20MPa, reaction temperature are 380 DEG C, reaction time 60min, the CO and H2The volume ratio of gaseous mixture and the slurries be
Oil product is made in 3000:1.
Embodiment 2
A kind of biomass liquefying process is present embodiments provided, is included the following steps:
The pretreatment of biomass:
Wheat stalk and flax stalk are as biomass solid, with total restatement of the biomass, the moisture content of the biomass
It is 9%, the wheat stalk and flax stalk is sent into micronizer and just crush, first smashed median is 300 μ
First smashed wheat stalk and flax stalk are then sent into plodder and are carried out under 60 DEG C of temperature, the pressure of 3MPa by m
Compression, extrusion forming to its heap density are 1.1g/cm3, separating twice is carried out later, and the average particle size after separating twice is
2mm, it is spare；
Catalyst:
Catalyst is using FeOOH as the regrowth of the useless agent of the desulfurizing agent of active component, wherein is aoxidized with hydroxyl
Iron is the gross mass meter of the desulfurizing agent of active component, and alpha-feooh 30g, amorphous FeOOH is 20g, potassium oxide 8g, is glued
Tie agent kaolin 10g；
It is above-mentioned to be used in industry produce after middle coalite tar adds hydrogen upgrading using FeOOH as the desulfurizing agent of active component
The sweetening process of raw tail gas is as follows:
1) tail gas that coalite tar generates after fixed bed hydrogenation is catalyzed in collecting；
2) desulfurizing agent of the present embodiment is made to diameter is 1mm, length is 15mm cylindrical catalyst particle, and is filled in de-
In sulphur tower, desulfurization layer is formed；
3) by above-mentioned tail gas with 2000h-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer
Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as
The useless agent of the desulfurizing agent of active component in the application；
The regeneration method of above-mentioned useless agent, includes the following steps:
1) aqueous solution of above-mentioned useless agent and sodium hydroxide is stirred in slurry tank and is configured to slurries, maintain the pH value of slurries
It is 8.0, the solid content of the slurries is 4wt%；
2) it is passed through air in Xiang Shangshu slurries, and carries out oxidation reaction under 90 DEG C, 0.1MPa, with oxidation regeneration；
3) hydrogen sulfide is passed through into the slurries after oxidation again, and carries out vulcanization reaction under 10 DEG C, 5MPa；
4) it is passed through air into the slurries after vulcanization, and carries out oxidation reaction under 90 DEG C, 0.1MPa, to aoxidize again
It is raw；
5) step 3) and 4) once, the molar ratio of ferro element and element sulphur in the slurries after making the oxidation reaction are repeated
1:2；
6) slurries after the oxidation reaction are separated by solid-liquid separation, obtain the regenerative agent of above-mentioned useless agent.
The preparation of biomass slurry:
Biomass, sulphur powder and above-mentioned catalyst that pretreatment obtains are mixed to get mixture, by said mixture
Stirring pulping in the miscella of palm oil and petroleum base wax oil is added, forms slurries；Through detecting, wheat stalk and Asia in the slurries
The total content of numb stalk is 45wt%, and the molar ratio of ferro element and element sulphur is 1:2.5, and the viscosity of the slurries is 530mPa ﹒ s
(50 DEG C) by the content of the regrowth of the useless agent of the desulfurizing agent of active component of FeOOH are 0.3wt% in slurries, are thrown
Adding is 20 μm by the average grain diameter of the regrowth of the useless agent of the desulfurizing agent of active component of FeOOH；
Conversion reaction:
By CO and H2Gaseous mixture (CO accounting 80% and H2Accounting is that 20%) middle part is forced into 19.5MPa, is heated up to
It after 300 DEG C, is passed through in the pipeline for conveying the slurries, after rest part is forced into 19.3MPa, is heated up to 480 DEG C, by slurry bed system
In 3 inlets injection paste state bed reactor on reactor bottom and side wall, and split with into the slurries therein
Solution, carbonylation, transformation and hydrogenation reaction, control reaction pressure is 19MPa, reaction temperature is 390 DEG C, and the reaction time is
100min, the CO and H2Gaseous mixture and the slurries volume ratio be 800:1, be made oil product.
Embodiment 3
A kind of biomass liquefying process is present embodiments provided, is included the following steps:
The pretreatment of biomass:
Corn stover and ramie stalk stalk are as biomass solid, with total restatement of the biomass, the biomass it is aqueous
Rate is 20%, and the corn stover and ramie stalk are sent into micronizer and just crush, first smashed median particle size is
300 μm, first smashed corn stover and ramie stalk are then sent into temperature, the pressure of 2.5MPa in cuber at 50 DEG C
Under carry out compression extrusion forming to its heap density be 0.8g/cm3, separating twice is carried out later, the average grain after separating twice
Degree is 3mm, spare；
Catalyst:
Catalyst is using FeOOH as the useless agent of the desulfurizing agent of active component, wherein described using FeOOH as active component
In desulfurizing agent, amorphous FeOOH 70g, Co2O3It is 5g for 25g and NiO；
It is above-mentioned to remove H in exhaust gas by the desulfurizing agent of active component of FeOOH2The basic process of S, include the following steps: by
H2S content is 5500mg/cm3Exhaust gas with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, described
Desulfurization section is worked off one's feeling vent one's spleen middle H2When content≤0.01ppm of S, the waste in the desulfurization section is collected, as in the present embodiment
Using FeOOH as the useless agent of the desulfurizing agent of active component.
The preparation of biomass slurry:
Biomass, sulphur and above-mentioned catalyst that pretreatment obtains are mixed to get mixture, said mixture is added
Slurrying is emulsified into kitchen waste oil, forms slurries, through detecting, the total content of corn stover and ramie stalk is in the slurries
The molar ratio of 57wt%, ferro element and element sulphur is 1:3, and the viscosity of the slurries is 1130mPa ﹒ s (50 DEG C), in the slurries with
FeOOH is that the content of the useless agent of the desulfurizing agent of active component is 4wt%, added using FeOOH as the desulfurizing agent of active component
Useless agent average grain diameter be 120 μm；
Conversion reaction:
It after being partially forced into 18MPa in pure CO gas, being heated up to 250 DEG C, is passed through in the slurries, rest part pressurization
To 18MPa, be heated up to 500 DEG C after, by paste state bed reactor bottom and side wall 4 inlets inject paste state bed reactor
It is interior, while being passed through into reactor H2S and make the molar ratio 1:3 of ferro element and element sulphur in reaction system, the slurry cracking,
Carbonylation, transformation and hydrogenation reaction, control reaction pressure is 17MPa, reaction temperature is 400 DEG C, reaction time 40min, institute
The volume ratio for stating pure CO gas and the slurries is 950:1, and oil product is made.
Embodiment 4
A kind of biomass liquefying process is present embodiments provided, is included the following steps:
The pretreatment of biomass:
Pea stalk, broomcorn straw and rice straw are as biomass solid, with total restatement of the biomass, the biomass
Moisture content be 15%, by the pea stalk, broomcorn straw and rice straw be sent into micronizer carry out just crush, first powder
Median after broken is 250 μm, and first smashed pea stalk, broomcorn straw and rice straw are then sent into plodder
In carried out under 55 DEG C of temperature, the pressure of 1.5MPa compression extrusion forming to its heap density be 0.9g/cm3, two are carried out later
Secondary crushing, the average particle size after separating twice is 0.9mm, spare；
Catalyst:
Catalyst is used using FeOOH as the useless agent of the desulfurizing agent of active component, wherein using FeOOH as the desulfurization of active component
The gross mass meter of agent, described by the content of amorphous FeOOH in the desulfurizing agent of active component of FeOOH is 60%, carrier
The content of diatomite is 30%, and the content of binder fiber element powder is 10%；
The above-mentioned process using FeOOH as the desulfurizing agent of active component for removing H2S in exhaust gas is as follows: being by H2S content
The exhaust gas of 5500mg/cm3 is passed through desulfurization section with the air speed of 3000h-1, and desulphurization reaction is carried out at 30 DEG C, goes out in the desulfurization section
In implication when content≤0.01ppm of H2S, the waste in the desulfurization section is collected, as in the present embodiment is with FeOOH
The useless agent of the desulfurizing agent of active component.
The preparation of biomass slurry:
Biomass, sulphur and above-mentioned catalyst that pretreatment obtains are mixed to get mixture, said mixture is added
Homogeneous slurrying in the miscella of kitchen waste oil and rapeseed oil forms slurries, and wherein the molar ratio of ferro element and element sulphur is 1:4,
The subsequent kitchen waste oil and rapeseed oil with slurry used in the process can be replaced oil made from biomass liquefying process in the present embodiment
Product, through detecting, the total content of pea stalk, broomcorn straw and rice straw is 40wt% in the slurries, and the viscosity of the slurries is
820mPa ﹒ s (50 DEG C) by the content of the desulfurizing agent of active component of FeOOH is 8wt% in slurries, and what is added is with FeOOH
The average grain diameter of the desulfurizing agent of active component is 300 μm；
Liquefaction reaction:
By CO and H2Gaseous mixture (wherein in gaseous mixture CO volume accounting be 50%) be forced into 18MPa, be heated up to 380
After DEG C, by paste state bed reactor bottom and side wall 5 inlets injection paste state bed reactor in, and with enter institute therein
It states slurries and cracking, carbonylation, transformation and hydrogenation reaction occurs, control reaction pressure is 17MPa, reaction temperature is 420 DEG C, reaction
Time is 50min, the CO and H2Gaseous mixture and the slurries volume ratio be 900:1, be made oil product.
Embodiment 5
A kind of tar sand oil and hogwash fat cotransformation technique are present embodiments provided, is included the following steps:
Catalyst:
Catalyst is using FeOOH as the useless agent of the desulfurizing agent of active component, wherein described using FeOOH as active component
In desulfurizing agent, soluble ferric iron salt Fe (NO3)3·9H2O is 6g, molysite complexing agent triethanolamine 9g, amorphous FeOOH
15g；
Above-mentioned using FeOOH is the desulfurizing agent of active component for removing H in exhaust gas2The process of S is as follows: by H2S content is
5500mg/cm3Exhaust gas with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, is gone out in the desulfurization section
H in implication2When content≤0.01ppm of S, the waste in the desulfurization section is collected, as in the present embodiment is with FeOOH
The useless agent of the desulfurizing agent of active component；
The preparation of slurries:
Tar sand oil, hogwash fat, sulphur and above-mentioned catalyst are mixed to get mixture, and entered into mixture plus in right amount
Water, stirring pulping form slurries, and the average grain diameter of the catalyst added is 5 μm, and the molar ratio of ferro element and element sulphur is 1:
2；
Conversion reaction:
By CO and H2Gaseous mixture (CO accounting 60% and H2Accounting is that 40%) middle part is forced into 5.7MPa, is heated up to 500
It after DEG C, is passed through in the pipeline for conveying the slurries, after rest part is forced into 5.2MPa, is heated up to 500 DEG C, by slurry reactor
In device entrance injection paste state bed reactor, and cracking, carbonylation occurs, convert and adds hydrogen anti-with the slurries therein are entered
It answers, the reaction pressure for controlling conversion reaction is 5MPa, reaction temperature is 470 DEG C, reaction time 90min, the CO and H2's
The volume ratio of gaseous mixture and the slurries is 8000:1, and oil product is made.
Embodiment 6
The cotransformation technique for present embodiments providing a kind of dregs of fat, wheat stalk and kitchen waste oil, includes the following steps:
The pretreatment of the dregs of fat and wheat stalk:
The dregs of fat and wheat stalk are as biomass solid, and with total restatement of the biomass, the moisture content of the biomass is
5%, the dregs of fat and excrement are sent into micronizer and just crush, first smashed median is 200 μm, then will be first
The smashed dregs of fat and excrement are sent into plodder to be compressed under 55 DEG C of temperature, the pressure of 1.5MPa, and extrusion forming is extremely
Its heap density is 0.95g/cm3, separating twice is carried out later, and the average particle size after separating twice is 60 μm, spare；
Catalyst:
Catalyst is the regenerative agent of the useless agent of the desulfurizing agent containing FeOOH, wherein with total matter of the desulfurizing agent containing FeOOH
Meter, the content of γ-FeOOH is 45% in the desulfurizing agent containing FeOOH, and the content of alpha-feooh is 35%, carrier molecule
The content of sieve is 15%, and the content of binder sesbania powder is 5%；
H in above-mentioned catalyst removal exhaust gas2The basic process of S includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, collecting the waste in the desulfurization section is the useless agent of desulfurizing agent；
The regeneration method of the useless agent of above-mentioned desulfurizing agent are as follows: after the useless agent of the desulfurizing agent is washed with water, in wet ball mill
Useless agent powder is obtained with the particle that water is ground into 80 mesh；The useless agent powder is made into the aqueous suspension that solid masses percentage composition is 8%
Liquid is passed through compressed air, reacts inspection by sampling after a period of time, does not generate H when the sample of taking-up is reacted with hydrochloric acid2When S, then give up
Iron sulfide in agent is fully converted to FeOOH and elemental sulfur, forms the slurry containing the FeOOH and elemental sulfur
Liquid filters the slurries and obtains solid material, uses CC14The solid material obtained after extraction filtering, coextraction merge extraction three times
Liquid, the elemental sulfur crystallized simultaneously with the method recycling design of distillation, and extract liquor separates rear remaining solid and binder
The regrowth of the useless agent of above-mentioned desulfurizing agent is made in sesbania powder mixing, and wherein the dosage of binder sesbania powder is the solid masses
5%.
The preparation of slurries:
The dregs of fat and wheat stalk, carbon disulfide and above-mentioned catalyst that pretreatment obtains are mixed to get mixture, it will be upper
It states mixture and is added into kitchen waste oil and disperse slurrying, form slurries, through detecting, the total content of the dregs of fat and excrement is in the slurries
The molar ratio of 55wt%, ferro element and element sulphur is 1:2, and the viscosity of the slurries is 400mPa ﹒ s (50 DEG C), in above-mentioned slurries,
The content of catalyst is 10wt%, and the average grain diameter of the catalyst added is 5mm；
Conversion reaction:
By CO and H2Gaseous mixture (CO accounting 60% and H2Accounting is that 40%) middle part is forced into 16.8MPa, is heated up to
It after 250 DEG C, is passed through in the pipeline for conveying the slurries, after rest part is forced into 16.2MPa, is heated up to 550 DEG C, by ebullated bed
Reactor inlet injects in fluidized bed reactor, and cracking, carbonylation, transformation and plus hydrogen occurs with into the slurries therein
Reaction, the reaction pressure for controlling conversion reaction is 16MPa, reaction temperature is 420 DEG C, reaction time 60min, the CO and H2
Gaseous mixture and the slurries volume ratio be 5000:1, be made oil product.
Embodiment 7
The present embodiment is same as Example 2, and difference is only in that, the regeneration method for agent of giving up is different, gives up in the present embodiment
The regeneration method of agent is,
1) water vapour that pressure is 1MPa is passed through heating furnace, by steam heating to 400 DEG C；
2) water vapour after heating is passed into the desulfurizer for containing the useless agent of desulfurizing agent with the speed of 20m/s, heats desulfurization
Agent is given up agent；
3) guarantee desulfurizing agent give up agent bed temperature by steam heating to running 2h, steam consumption under conditions of 450 DEG C
For 8t/h；
4) analysis desulfurizer export pH, continuous 3 times be more than or equal to 7.5 when, a small amount of oven gas can be passed through into desulfurizer
It is restored；
5) being passed through level-one in fine de-sulfur process adds the oven gas after hydrogen to restore with 800m3/h to desulfurizing agent agent of giving up；
6) be passed through every primary inlet and outlet H2 concentration variation of 30min analysis after oven gas, when outlet H2 concentration stablize be greater than or
Equal to the regenerative agent that the useless agent of desulfurizing agent can be obtained in (3 analyses) after entrance H2 concentration.
Test example
The distribution of product prepared by the method using the embodiment of the present invention 1-7 is compared, the test method of product
It is as follows:
(there is solid remaining in gross mass-reaction product of SOLID ORGANIC matter transforming solid organic matter rate %=in raw material
Machine matter quality) gross mass of SOLID ORGANIC matter in/raw material, " SOLID ORGANIC matter " in the transforming solid organic matter rate refers both to nothing
Water, ash free basis (the same below)；
It under normal temperature and pressure is liquid phase oil product that transforming solid organic matter oil yield %=transforming solid organic matter, which is in product,
SOLID ORGANIC matter combined feed quality in quality/raw material；
Reaction generates water rate %=(total matter of the water quality of the reaction product-water that reaction starting is added or raw material is brought into
Amount)/raw material combined feed quality.As this value < 0, it is denoted as "None"；
Corresponding test result is as shown in Table 1 and Table 2:
1 transforming solid organic matter Contrast on effect of table
(liquid organic matter combined feed mid-boiling point is greater than in quality-product of 360 DEG C of materials liquid organic matter transformation rate %=
Oil product is greater than 360 DEG C of liquid oil gross mass)/liquid organic matter combined feed mid-boiling point is greater than the quality of 360 DEG C of materials；
In liquid organic matter transformation oil yield %=converted product there is quality/raw material liq of liquid phase oil product under normal temperature and pressure
Machine matter combined feed quality.
Product profiles versus after the conversion of 2 liquid organic matter material of table
From table 1 and 2 as can be seen that using the transforming solid organic matter oil yield > 50wt% of method of the invention, liquid
Organic matter transformation oil yield > 91%；The hair of the ideal fuels oil of 0.91 times of calorific value > of equal quality of organic matter transformation oil
Heat, organic matter transformation oil phase oxygen content < 4.8wt%；The generation water < 1.5wt% of raw material after reaction.
8, a kind of Fe21.333O32Desulfurizing agent gives up purposes of the agent as biomass hydrogenation liquefaction catalyst.
Embodiment 1
The embodiment of the invention provides a kind of Fe21.333O32Desulfurizing agent gives up agent, wherein with the Fe21.333O32Desulfurizing agent
Gross mass meter, the Fe21.333O32The content of magnetic iron oxide red is 75% in desulfurizing agent, and the content of binder attapulgite is
25%.
Sweetening process of the above-mentioned catalyst as coal pyrolysis gas, is summarized as follows:
(1) compressed coal pyrolysis gas is cooled to 25~40 DEG C, and the air come with air pump is mixed into thick desulfurizing tower,
Using the process of bottom in and top out, to avoid there is liquid water to enter desulfurizing agent bed.It is herein to carry out thick removing hydrogen sulfide and take off
Except part R-SH and thiophene.
(2) gas heating after thick desulfurization is hydrolyzed to 120~135 DEG C, by most of COS and CS2It is hydrolyzed to H2S。
(3) gas after hydrolyzing is cooled to 20~25 DEG C again, carries out H2S removing, herein to guarantee clean-up effect and to make
With service life, using the form of double tower series-parallel operation, the H that hydrolysis is generated2S is totally removed, and further removes remaining
R-SH and thiophene.It is totally removed by the remaining sulfide of this technical process, reaches final purification requirement total sulfur content and be less than
0.1ppm。
Desulfurizing agent becomes useless agent after being used for multiple times and deletes from desulfurizing agent bed, the as Fe in the application21.333O32Desulfurization
Agent is given up agent.
Embodiment 2
The embodiment of the invention provides a kind of Fe21.333O32Desulfurizing agent gives up agent, wherein with the Fe21.333O32Desulfurizing agent
Gross mass meter, the Fe21.333O32The content of magnetic iron oxide red is 89% in desulfurizing agent, and the bentonitic content of binder is
11%.For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
The as Fe of the application21.333O32Desulfurizing agent gives up agent.
Embodiment 3
The embodiment of the invention provides a kind of Fe21.333O32Desulfurizing agent gives up agent, wherein with the Fe21.333O32Desulfurizing agent
Gross mass meter, the Fe21.333O32Fe in desulfurizing agent21.333O32Content be 80%, carrier γ-Al2O3Content be 10%, glue
Tying the bentonitic content of agent is 10%.
H in above-mentioned catalyst removal exhaust gas2The matrix process of S, includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, the waste in the desulfurization section is collected, the catalyst as hydrogenation reaction.
Embodiment 4
The embodiment of the invention provides a kind of Fe21.333O32Desulfurizing agent gives up agent, wherein with the Fe21.333O32Desulfurizing agent
Gross mass meter, the Fe21.333O32Fe in desulfurizing agent21.333O32Content is 94%, and surplus is impurity and water.
For above-mentioned catalyst to the sweetening process of coke-stove gas, operating procedure is as follows:
By above-mentioned Fe21.333O32Desulfurizing agent and water are hybridly prepared into as desulfurizer slurry, FeOOH in the slurries
Total concentration be 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is
30 DEG C, the top of the desulfurizing tower carries out elution desulfurization to the coke-stove gas by the agent of nozzle injection desulfurization, after collecting desulfurization
Waste liquid it is dry be the application Fe21.333O32Desulfurizing agent gives up agent.
Embodiment 5
Using waste collected by the various embodiments described above as the catalyst of biomass liquefaction reaction, the work of catalyst is carried out
Property test, active testing is as follows: preparing the slurries containing corn stover and catalyst, above-mentioned slurries are delivered to slurry reactor
Hydrogenation liquefaction reaction is carried out in device, control reaction pressure is 20MPa, and temperature is 380 DEG C, wherein the additive amount of catalyst is jade
The distribution of the 2wt% of rice stalk additive amount, the product that the activity of catalyst is prepared with biomass liquefaction reaction indicate, such as the following table 1
It is shown:
1 embodiment 1-4 product profiles versus of table
As it can be seen from table 1 being reacted using the hydrogenation liquefaction that catalyst of the invention can effectively facilitate biomass.
9, one kind is with Fe21.333O32For main active desulfurizing agent useless agent as biomass hydrogenation liquefaction catalyst
Purposes.
Embodiment 1
The embodiment of the invention provides one kind mainly with Fe21.333O32For the useless agent of desulfurizing agent of active constituent, wherein described
Mainly with Fe21.333O32For in the desulfurizing agent of active constituent, magnetic iron oxide red Fe21.333O32For 55g, copper oxide 12g, carrier
Di-iron trioxide 21g；
Sweetening process of the above-mentioned catalyst as coal pyrolysis gas, is summarized as follows:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and the air come with air pump is mixed into thick desulfurizing tower,
Using the process of bottom in and top out, to avoid there is liquid water to enter desulfurizing agent bed.It is herein to carry out thick removing hydrogen sulfide and take off
Except part R-SH and thiophene.
(2) gas heating after thick desulfurization is hydrolyzed to 110~125 DEG C, and most of COS and CS2 are hydrolyzed to H2S.
(3) gas after hydrolyzing is cooled to 20-~25 DEG C again, carries out H2S removing, herein to guarantee clean-up effect and make
The H2S that hydrolysis generates is totally removed using the form of double tower series-parallel operation with the service life, and is further removed remaining
R-SH and thiophene.It is totally removed by the remaining sulfide of this technical process, reaches final purification requirement total sulfur content and be less than
0.1ppm。
Desulfurizing agent becomes useless agent after being used for multiple times and deletes from desulfurizing agent bed, as in the application with Fe21.333O32For
The useless agent of the desulfurizing agent of main active.
Embodiment 2
The embodiment of the invention provides one kind mainly with Fe21.333O32For the useless agent of desulfurizing agent of active constituent, wherein described
Mainly with Fe21.333O32For in the desulfurizing agent of active constituent, Fe21.333O32For 55g, Detitanium-ore-type Ti0222g, bentonite 15g；
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
As the application with Fe21.333O32For the useless agent of desulfurizing agent of main active.
Embodiment 3
The embodiment of the invention provides one kind mainly with Fe21.333O32For the useless agent of desulfurizing agent of active constituent, wherein described
Mainly with Fe21.333O32For in the desulfurizing agent of active constituent, Fe21.333O32For 55g, lead oxide 16g, manganese dioxide 20g, swelling
Native 15g；
H in above-mentioned catalyst removal exhaust gas2The matrix process of S, includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, the waste in the desulfurization section is collected, the catalyst as hydrogenation reaction.
Embodiment 4
The embodiment of the invention provides one kind mainly with Fe21.333O32For the useless agent of desulfurizing agent of active constituent, wherein described
Mainly with Fe21.333O32For in the desulfurizing agent of active constituent, Fe21.333O32For 47g, Detitanium-ore-type Ti0222g, bentonite 15g；
For above-mentioned catalyst to the sweetening process of coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into as desulfurizer slurry, the total concentration of FeOOH in the slurries
For 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, described
The top of desulfurizing tower carries out elution desulfurization to the coke-stove gas by the agent of nozzle injection desulfurization, and the waste liquid after collecting desulfurization is dry
As the application with Fe21.333O32For the useless agent of desulfurizing agent of main active.
Embodiment 5 (application of the useless agent of desulfurizing agent)
Using waste collected by the various embodiments described above as the catalyst of biomass liquefaction reaction, the work of catalyst is carried out
Property test, active testing is as follows: preparing the slurries containing corn stover and catalyst, above-mentioned slurries are delivered to slurry reactor
Hydrogenation liquefaction reaction is carried out in device, control reaction pressure is 20MPa, and temperature is 380 DEG C, wherein catalyst loading is corn
The distribution of the 2wt% of stalk additive amount, the product that the activity of catalyst is prepared with biomass liquefaction reaction indicate, such as the following table 1 institute
Show:
1 embodiment 1-4 product profiles versus of table
As it can be seen from table 1 being reacted using the hydrogenation liquefaction that catalyst of the invention can effectively facilitate biomass.
10, one kind contains Fe21.333O32Desulfurizing agent give up purposes as biomass hydrogenation liquefaction catalyst after agent regeneration.
Embodiment 1
The embodiment of the invention provides one kind to contain Fe21.333O32Desulfurizing agent give up agent regeneration method, wherein with described
Contain Fe21.333O32Desulfurizing agent gross mass meter, it is described to contain Fe21.333O32Desulfurizing agent in magnetic iron oxide red
Fe21.333O32For 55g, copper oxide 12g, carrier di-iron trioxide 21g；
Sweetening process of the above-mentioned catalyst as coal pyrolysis gas, is summarized as follows:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and the air come with air pump is mixed into thick desulfurizing tower,
Using the process of bottom in and top out, to avoid there is liquid water to enter desulfurizing agent bed.It is herein to carry out thick removing hydrogen sulfide and take off
Except part R-SH and thiophene.
(2) gas heating after thick desulfurization is hydrolyzed to 110~125 DEG C, and most of COS and CS2 are hydrolyzed to H2S.
(3) gas after hydrolyzing is cooled to 20-~25 DEG C again, carries out H2S removing, herein to guarantee clean-up effect and make
The H2S that hydrolysis generates is totally removed using the form of double tower series-parallel operation with the service life, and is further removed remaining
R-SH and thiophene.It is totally removed by the remaining sulfide of this technical process, reaches final purification requirement total sulfur content and be less than
0.1ppm。
Desulfurizing agent becomes useless agent after being used for multiple times and deletes from desulfurizing agent bed, as contains Fe in the application21.333O32
Desulfurizing agent give up agent.
It is above-mentioned to contain Fe21.333O32Desulfurizing agent give up agent regeneration method be,
Contain Fe for described21.333O32Desulfurizing agent give up agent be passed through in desulfurization reactor, then by O2/SO2Volume ratio is 1:
100 20mol%O2/SO2And 80mol%N2The regeneration gas of composition is passed through to the bottom inlet of above-mentioned desulfurization reactor, and is controlled
The temperature of desulfurization reactor processed is 800 DEG C, air speed 3000h-1, test desulfurization reactor import, outlet sulfur dioxide concentration, when
When import, outlet sulfur dioxide concentration are close, stop regeneration to get Fe is contained described in21.333O32Desulfurizing agent give up agent regeneration
Agent.
Embodiment 2
The embodiment of the invention provides one kind to contain Fe21.333O32Desulfurizing agent give up agent regeneration method, wherein with described
Contain Fe21.333O32Desulfurizing agent gross mass meter, it is described to contain Fe21.333O32Desulfurizing agent in Fe21.333O32For 55g, rutile titania
Mine type Ti0222g, bentonite 15g；
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
As contain Fe in the application21.333O32Desulfurizing agent give up agent.
It is above-mentioned to contain Fe21.333O32Desulfurizing agent give up agent regeneration method be,
Contain Fe for described21.333O32Desulfurizing agent give up agent be passed through in desulfurization reactor, then by O2/SO2Volume ratio is 1:
100 15mol%O2/SO2And 85mol%N2The regeneration gas of composition is passed through to the bottom inlet of above-mentioned desulfurization reactor, and is controlled
The temperature of desulfurization reactor processed is 800 DEG C, air speed 3000h-1, test desulfurization reactor import, outlet sulfur dioxide concentration, when
When import, outlet sulfur dioxide concentration are close, stop regeneration to get Fe is contained described in21.333O32Desulfurizing agent give up agent regeneration
Agent.
Embodiment 3
The embodiment of the invention provides one kind to contain Fe21.333O32Desulfurizing agent give up agent regeneration method, wherein with described
Contain Fe21.333O32Desulfurizing agent gross mass meter, it is described to contain Fe21.333O32Desulfurizing agent in Fe21.333O32For 55g, oxidation
Lead 16g, manganese dioxide 20g, bentonite 15g；
H in above-mentioned catalyst removal exhaust gas2The matrix process of S, includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, collecting the waste in the desulfurization section is to contain Fe in the application21.333O32Desulfurizing agent it is useless
Agent.
It is above-mentioned to contain Fe21.333O32Desulfurizing agent give up agent regeneration method be,
Contain Fe for described21.333O32Desulfurizing agent give up agent be passed through in desulfurization reactor, then by O2/SO2Volume ratio is 1:
100 28mol%O2/SO2And 72mol%N2The regeneration gas of composition is passed through to the bottom inlet of above-mentioned desulfurization reactor, and is controlled
The temperature of desulfurization reactor processed is 800 DEG C, air speed 3000h-1, test desulfurization reactor import, outlet sulfur dioxide concentration, when
When import, outlet sulfur dioxide concentration are close, stop regeneration to get Fe is contained described in21.333O32Desulfurizing agent give up agent regeneration
Agent.
Embodiment 4
The embodiment of the invention provides one kind to contain Fe21.333O32Desulfurizing agent give up agent regeneration method, wherein with described
Contain Fe21.333O32Desulfurizing agent gross mass meter, it is described to contain Fe21.333O32Desulfurizing agent in magnetic iron oxide red content
It is 96.2%, surplus is impurity and water；
For above-mentioned catalyst to the sweetening process of coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into as desulfurizer slurry, the total concentration of FeOOH in the slurries
For 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, described
The top of desulfurizing tower carries out elution desulfurization to the coke-stove gas by the agent of nozzle injection desulfurization, and the waste liquid after collecting desulfurization is dry
As contain Fe in the application21.333O32Desulfurizing agent give up agent.
It is above-mentioned to contain Fe21.333O32Desulfurizing agent give up agent regeneration method be,
(1) water vapour that pressure is 1.0MPa is passed through heating furnace, by steam heating to 420 DEG C；
(2) water vapour after heating is passed into the speed of 10m/s and is filled containing Fe21.333O32Desulfurizing agent give up agent
Desulfurizer contains Fe with heating21.333O32Desulfurizing agent give up agent；
(3) guarantee to contain Fe21.333O32Desulfurizing agent give up agent bed temperature by the item of steam heating to 400 DEG C or more
3h, steam consumption 7t/h are run under part；
(4) analysis desulfurizer export pH, continuous 3 times be more than or equal to 7.5 when, can be passed through into desulfurizer oven gas progress
Reduction；
(5) H is once imported and exported in every 30min analysis after being passed through oven gas2Concentration variation, as outlet H2Concentration stablize be greater than or
Equal to entrance H2After concentration (3 times analysis), that is, obtain described containing Fe21.333O32Desulfurizing agent give up agent regenerative agent.
Embodiment 5
Using the useless agent regenerative agent of desulfurizing agent collected by above-described embodiment 1-4 as the catalyst of biomass liquefaction reaction, together
When will contain Fe in embodiment 421.333O32Desulfurizing agent the catalyst of biomass liquefaction reaction is used in 1 as a comparison case；
The catalyst that biomass liquefaction reaction is used in above-described embodiment 1-4 and comparative example 1 is subjected to active testing, activity
It tests as follows: preparing the slurries containing corn stover and catalyst, above-mentioned slurries are delivered in paste state bed reactor and are added
Liquefaction of hydrogen reaction, control reaction pressure are 20MPa, and temperature is 380 DEG C, wherein the additive amount of catalyst is corn stover addition
The distribution of the 2wt% of amount, the product that the activity of catalyst is prepared with biomass liquefaction reaction indicate, as shown in table 1 below:
1 embodiment 1-4 product profiles versus of table
As it can be seen from table 1 being reacted using the hydrogenation liquefaction that catalyst of the invention can effectively facilitate biomass.
11、Fe21.333O32Desulfurizing agent purposes of the useless agent as CO transformation catalyst
Embodiment 1
The embodiment of the invention provides a kind of Fe21.333O32Desulfurizing agent useless agent, wherein with the Fe21.333O32Desulfurization
The gross mass meter of agent, the Fe21.333O32The content of magnetic iron oxide red is 70% in desulfurizing agent, the kaolinic content of binder
It is 30%；
Above-mentioned catalyst adds the sweetening process of the tail gas generated after hydrogen upgrading as follows for middle coalite tar in industry:
1) tail gas that coalite tar generates after fixed bed hydrogenation is catalyzed in collecting；
2) desulfurizing agent of the present embodiment is made to diameter is 1mm, length is 15mm cylindrical catalyst particle, and is filled in de-
In sulphur tower, desulfurization layer is formed；
3) by above-mentioned tail gas with 2000h-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer
Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as
Fe in the application21.333O32Desulfurizing agent useless agent.
Embodiment 2
The embodiment of the invention provides a kind of Fe21.333O32Desulfurizing agent useless agent, wherein with the Fe21.333O32Desulfurization
The gross mass meter of agent, the Fe21.333O32The content of magnetic iron oxide red is 75% in desulfurizing agent, and binder attapulgite contains
Amount is 25%；
Above-mentioned catalyst is as follows to the sweetening process of hydrogen sulfide containing coal pyrolysis gas:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and it is above-mentioned to be mixed into filling for next air with air pump
Mainly using iron oxide as in the desulfurizing tower of the desulfurizing agent of active constituent, using the process of bottom in and top out, to avoid have liquid water into
Enter desulfurizing agent bed removing hydrogen sulfide；
(2) above-mentioned desulfurizing agent becomes useless agent after being used for multiple times, and takes out from desulfurizing agent bed, as in the application
Fe21.333O32Desulfurizing agent useless agent.
Embodiment 3
The embodiment of the invention provides a kind of Fe21.333O32Desulfurizing agent useless agent, wherein with the Fe21.333O32Desulfurization
The gross mass meter of agent, the Fe21.333O32The content of magnetic iron oxide red is 96.2% in desulfurizing agent, and surplus is impurity and water；
Above-mentioned catalyst carries out sweetening process to the petroleum of hydrogen sulfide, and operating procedure is as follows:
(1) diameter is made in the desulfurizing agent of the present embodiment and is the catalyst granules of 1.5mm, and be filled in desulfurizing tower, shape
At desulfurization layer；
(2) petroleum for spraying hydrogen sulfide into desulfurization layer by nozzle from the top of desulfurizing tower, carries out elution desulfurization, collects
The useless agent of desulfurizing agent after desulfurization is the Fe in the application21.333O32Desulfurizing agent useless agent.
Embodiment 4
The embodiment of the invention provides a kind of Fe21.333O32Desulfurizing agent useless agent, wherein with the Fe21.333O32Desulfurization
The gross mass meter of agent, the Fe21.333O32The content of magnetic iron oxide red is 89% in desulfurizing agent, the bentonitic content of binder
It is 11%；
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make H2The gas water of S come into full contact with reacting with it, connects
Touch article part are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, the agent of giving up of catalyst after gas water desulfurization is
The Fe of the application21.333O32Desulfurizing agent useless agent.
Embodiment 5
The embodiment of the invention provides a kind of Fe21.333O32Desulfurizing agent useless agent, wherein with the Fe21.333O32Desulfurization
The gross mass meter of agent, the Fe21.333O32γ-Fe in desulfurizing agent21.333O32Content be 55%, β-Fe21.333O32Content be
25%, carrier γ-Al2O3Content be 10%, the bentonitic content of binder be 10%；
H in above-mentioned catalyst removal exhaust gas2The matrix process of S, includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, the waste in the desulfurization section is collected, the catalyst as CO conversion reaction.
Embodiment 6
The embodiment of the invention provides a kind of Fe21.333O32Desulfurizing agent useless agent, wherein with the Fe21.333O32Desulfurization
The gross mass meter of agent, the Fe21.333O32α-Fe in desulfurizing agent21.333O32Content is 49%, γ-Fe21.333O32Content is 45%,
Surplus is impurity and water；
For above-mentioned catalyst to the sweetening process of hydrogen sulfide containing coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into as desulfurizer slurry, solid content is 15wt% in the slurries,
Coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, the desulfurizing tower
Top sprays above-mentioned desulfurizing agent by nozzle and carries out elution desulfurization to the coke-stove gas, and the waste liquid drying after collecting desulfurization is
The Fe of the application21.333O32Desulfurizing agent give up agent.
Embodiment 7 (application of the useless agent of desulfurizing agent)
Agent is given up as the catalyst of CO conversion reaction using desulfurizing agent collected by above-described embodiment 1-6, carries out catalyst
Active testing, active testing are as follows:
Unstripped gas group becomes 15vol%CO, 55vol%H2, 6vol%CO2, 24vol%N2, reaction steam-to-gas ratio be 1:1, it is empty
Speed is 4000h-1, it is 250~450 DEG C that catalyst activity, which tests warm area,；
The activity of catalyst indicates that calculation method is as follows with CO conversion ratio:
CO conversion ratio=(1-VCO'/VCO)/(1+VCO) × 100%
Wherein, VCO'For the percentage by volume of CO in reactor outlet gas, VCOFor the percentage by volume of CO in unstripped gas；
It is corresponding that test result is as follows shown in table 1:
CO conversion ratio under table 1, different test temperatures
From table 1 it can be seen that: the application use Fe21.333O32Desulfurizing agent give up agent as CO transformation catalyst, can be effective
Catalysis CO changes reaction, improves the conversion ratio of CO.
12, contain Fe21.333O32Desulfurizing agent purposes of the useless agent as CO transformation catalyst.
Embodiment 1
The embodiment of the invention provides one kind to contain Fe21.333O32Desulfurizing agent useless agent, wherein it is described to contain
Fe21.333O32Desulfurizing agent in, magnetic iron oxide red Fe21.333O32For 50g, potassium oxide 8g, binder kaolin 10g；
Above-mentioned catalyst adds the sweetening process of the tail gas generated after hydrogen upgrading as follows for middle coalite tar in industry:
1) tail gas that coalite tar generates after fixed bed hydrogenation is catalyzed in collecting；
2) desulfurizing agent of the present embodiment is made to diameter is 1mm, length is 15mm cylindrical catalyst particle, and is filled in de-
In sulphur tower, desulfurization layer is formed；
3) by above-mentioned tail gas with 2000h-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer
Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as
Contain Fe in the application21.333O32Desulfurizing agent useless agent.
Embodiment 2
The embodiment of the invention provides one kind to contain Fe21.333O32Desulfurizing agent useless agent, wherein it is described to contain
Fe21.333O32Desulfurizing agent in, magnetic iron oxide red Fe21.333O32For 55g, copper oxide 12g, carrier di-iron trioxide 21g；
Above-mentioned catalyst is as follows to the sweetening process of hydrogen sulfide containing coal pyrolysis gas:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and it is above-mentioned to be mixed into filling for next air with air pump
Mainly using iron oxide as in the desulfurizing tower of the desulfurizing agent of active constituent, using the process of bottom in and top out, to avoid have liquid water into
Enter desulfurizing agent bed removing hydrogen sulfide；
(2) above-mentioned desulfurizing agent becomes useless agent after being used for multiple times, and takes out from desulfurizing agent bed, as containing in the application
Fe21.333O32Desulfurizing agent useless agent.
Embodiment 3
The embodiment of the invention provides one kind to contain Fe21.333O32Desulfurizing agent useless agent, wherein it is described to contain
Fe21.333O32Desulfurizing agent in, magnetic iron oxide red Fe21.333O32For 60g, zinc oxide 14g, binder kaolin 19g；
Above-mentioned catalyst carries out sweetening process to the petroleum containing hydrogen sulfide, and operating procedure is as follows:
(1) diameter is made in the desulfurizing agent of the present embodiment and is the catalyst granules of 1.5mm, and be filled in desulfurizing tower, shape
At desulfurization layer；
(2) petroleum containing hydrogen sulfide is sprayed into desulfurization layer from the top of desulfurizing tower by nozzle, carry out elution desulfurization,
The useless agent of desulfurizing agent after collecting desulfurization is to contain Fe in the application21.333O32Desulfurizing agent useless agent.
Embodiment 4
The embodiment of the invention provides one kind to contain Fe21.333O32Desulfurizing agent useless agent, wherein it is described to contain
Fe21.333O32Desulfurizing agent in, Fe21.333O32For 55g, Detitanium-ore-type Ti0222g, bentonite 15g；
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
As the application contains Fe21.333O32Desulfurizing agent useless agent.
Embodiment 5
The embodiment of the invention provides one kind to contain Fe21.333O32Desulfurizing agent useless agent, wherein it is described to contain
Fe21.333O32Desulfurizing agent in, Fe21.333O32For 60g, lead oxide 16g, manganese dioxide 20g, bentonite 15g；
H in above-mentioned catalyst removal exhaust gas2The matrix process of S, includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, the waste in the desulfurization section is collected, the catalyst as CO conversion reaction.
Embodiment 6
The embodiment of the invention provides one kind to contain Fe21.333O32Desulfurizing agent useless agent, wherein it is described to contain
Fe21.333O32Desulfurizing agent in, α-Fe21.333O32For 25g, β-Fe21.333O32For 22g, γ-Fe21.333O32For 20g, Detitanium-ore-type
Ti0222g, bentonite 15g；
For above-mentioned catalyst to the sweetening process of hydrogen sulfide containing coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into as desulfurizer slurry, solid content is 15wt% in the slurries,
Coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, the desulfurizing tower
Top sprays above-mentioned desulfurizing agent by nozzle and carries out elution desulfurization to the coke-stove gas, and the waste liquid drying after collecting desulfurization is
The application's contains Fe21.333O32Desulfurizing agent give up agent.
Embodiment 7 (application of the useless agent of desulfurizing agent)
Agent is given up as the catalyst of CO conversion reaction using desulfurizing agent collected by above-described embodiment 1-6, carries out catalyst
Active testing, active testing are as follows:
Unstripped gas group becomes 15vol%CO, 55vol%H2, 6vol%CO2, 24vol%N2, reaction steam-to-gas ratio be 1:1, it is empty
Speed is 4000h-1, it is 250~450 DEG C that catalyst activity, which tests warm area,；
The activity of catalyst indicates that calculation method is as follows with CO conversion ratio:
CO conversion ratio=(1-VCO'/VCO)/(1+VCO) × 100%
Wherein, VCO'For the percentage by volume of CO in reactor outlet gas, VCOFor the percentage by volume of CO in unstripped gas；
It is corresponding that test result is as follows shown in table 1:
CO conversion ratio under table 1, different test temperatures
From table 1 it can be seen that: the application use contain Fe21.333O32Desulfurizing agent give up agent as CO transformation catalyst, energy
Effectively catalysis CO changes reaction, improves the conversion ratio of CO.
13, contain Fe21.333O32Desulfurizing agent useless agent regeneration after purposes as CO transformation catalyst.
Embodiment 1
The embodiment of the invention provides one kind to contain Fe21.333O32Desulfurizing agent useless agent, wherein it is described to contain
Fe21.333O32Desulfurizing agent in, magnetic iron oxide red Fe21.333O32For 50g, potassium oxide 8g, binder kaolin 10g；
Above-mentioned catalyst adds the sweetening process of the tail gas generated after hydrogen upgrading as follows for middle coalite tar in industry:
1) tail gas that coalite tar generates after fixed bed hydrogenation is catalyzed in collecting；
2) desulfurizing agent of the present embodiment is made to diameter is 1mm, length is 15mm cylindrical catalyst particle, and is filled in de-
In sulphur tower, desulfurization layer is formed；
3) by above-mentioned tail gas with 2000h-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer
Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as
Contain Fe in the application21.333O32Desulfurizing agent useless agent；
It is above-mentioned to contain Fe21.333O32Desulfurizing agent useless agent regeneration method, include the following steps:
1) aqueous solution of above-mentioned useless agent and sodium hydroxide is stirred in slurry tank and is configured to slurries, maintain the pH value of slurries
It is 8.0, the solid content of the slurries is 4wt%；
2) it is passed through air in Xiang Shangshu slurries, and carries out oxidation reaction under 90 DEG C, 0.1MPa, with oxidation regeneration；
3) hydrogen sulfide is passed through into the slurries after oxidation again, and carries out vulcanization reaction under 10 DEG C, 5MPa；
4) it is passed through air into the slurries after vulcanization, and carries out oxidation reaction under 90 DEG C, 0.1MPa, to aoxidize again
It is raw；
5) step 3) and 4) twice, the molar ratio of ferro element and element sulphur in the slurries after making the oxidation reaction are repeated
1:4.5；
6) slurries after the oxidation reaction are separated by solid-liquid separation, obtain the regrowth of above-mentioned useless agent.
Embodiment 2
The embodiment of the invention provides one kind to contain Fe21.333O32Desulfurizing agent useless agent, wherein it is described to contain
Fe21.333O32Desulfurizing agent in, magnetic iron oxide red Fe21.333O32For 55g, copper oxide 12g, carrier di-iron trioxide 21g；
Above-mentioned catalyst is as follows to the sweetening process of hydrogen sulfide containing coal pyrolysis gas:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and it is above-mentioned to be mixed into filling for next air with air pump
Mainly using iron oxide as in the desulfurizing tower of the desulfurizing agent of active constituent, using the process of bottom in and top out, to avoid have liquid water into
Enter desulfurizing agent bed removing hydrogen sulfide；
(2) above-mentioned desulfurizing agent becomes useless agent after being used for multiple times, and takes out from desulfurizing agent bed, as containing in the application
Fe21.333O32Desulfurizing agent useless agent；
It is above-mentioned to contain Fe21.333O32Desulfurizing agent useless agent regeneration method, include the following steps:
1) above-mentioned useless agent is dispersed in water, forms slurries；
2) above-mentioned slurries are heated to 60 DEG C under normal pressure, hydrogen peroxide, flow are then added into slurries using peristaltic pump
Control is 500mL/min, and magnetic agitation is to promote reaction to carry out, reaction time 10min；
3) after the reaction was completed, filtering reacting liquid obtained precipitating is washed with water 2 times, natural airing, obtains above-mentioned useless agent
Regrowth.
Embodiment 3
The embodiment of the invention provides one kind to contain Fe21.333O32Desulfurizing agent useless agent, wherein it is described to contain
Fe21.333O32Desulfurizing agent in, magnetic iron oxide red Fe21.333O32For 60g, zinc oxide 14g, binder kaolin 19g；
Above-mentioned catalyst carries out sweetening process to the petroleum containing hydrogen sulfide, and operating procedure is as follows:
(1) diameter is made in the desulfurizing agent of the present embodiment and is the catalyst granules of 1.5mm, and be filled in desulfurizing tower, shape
At desulfurization layer；
(2) petroleum containing hydrogen sulfide is sprayed into desulfurization layer from the top of desulfurizing tower by nozzle, carry out elution desulfurization,
The useless agent of desulfurizing agent after collecting desulfurization is to contain Fe in the application21.333O32Desulfurizing agent useless agent；
It is above-mentioned to contain Fe21.333O32Desulfurizing agent useless agent regeneration method, include the following steps:
1) above-mentioned useless agent and water are stirred in slurry tank and is configured to slurries, the solid content of the slurries is 12wt%；
2) it is passed through sodium hypochlorite in Xiang Shangshu slurries, and carries out oxidation reaction under 60 DEG C, 1MPa, with oxidation regeneration；
3) Na is added into the slurries after oxidation again2S, and vulcanization reaction is carried out under 10 DEG C, 5MPa；
4) it is passed through hydrogen peroxide into the slurries after vulcanization, and carries out oxidation reaction under 30 DEG C, 1.1MPa, with oxidation
Regeneration；
5) step 3) and 4) four times are repeated, the molar ratio of ferro element and element sulphur in the slurries after making the oxidation reaction
1:5；
6) slurries after the oxidation reaction are separated by solid-liquid separation, obtain the regrowth of above-mentioned useless agent.
Embodiment 4
The embodiment of the invention provides one kind to contain Fe21.333O32Desulfurizing agent useless agent, wherein it is described to contain
Fe21.333O32Desulfurizing agent in, Fe21.333O32For 55g, Detitanium-ore-type Ti0222g, bentonite 15g；
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
As the application contains Fe21.333O32Desulfurizing agent useless agent；
It is above-mentioned to contain Fe21.333O32Desulfurizing agent useless agent regeneration method, include the following steps:
1) after above-mentioned useless agent being washed with water, the particle for being ground into 200 mesh with water in wet ball mill obtains useless agent powder；
2) the useless agent powder is made into the water slurry that solid masses percentage composition is 7%, is passed through compressed air, carried out anti-
It answers；
3) water slurry after reaction is filtered, the solid material is placed in flotation cell, water is added, then leads to
Enter air, is the regrowth of above-mentioned useless agent after the sediment drying of lower vessel portion.
Embodiment 5
The embodiment of the invention provides one kind to contain Fe21.333O32Desulfurizing agent useless agent, wherein it is described to contain
Fe21.333O32Desulfurizing agent in, Fe21.333O32For 60g, lead oxide 16g, manganese dioxide 20g, bentonite 15g；
H in above-mentioned catalyst removal exhaust gas2The matrix process of S, includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, the waste in the desulfurization section is collected, the catalyst as CO conversion reaction；
It is above-mentioned to contain Fe21.333O32Desulfurizing agent useless agent regeneration method, include the following steps:
1) above-mentioned useless agent is dispersed in water, forms slurries；
2) above-mentioned slurries are heated to 45 DEG C under normal pressure, hydrogen peroxide are then added into slurries using peristaltic pump, and lead to
Enter air, hydrogen peroxide flow control is 500mL/min, air flow control 100mL/min, magnetic agitation with promote to react into
Row, reaction time 5min；
3) after the reaction was completed, filtering reacting liquid obtained precipitating is washed with water 3 times, natural airing, obtains above-mentioned useless agent
Regrowth.
Embodiment 6
The embodiment of the invention provides one kind to contain Fe21.333O32Desulfurizing agent useless agent, wherein it is described to contain
Fe21.333O32Desulfurizing agent in, α-Fe21.333O32For 25g, β-Fe21.333O32For 22g, γ-Fe21.333O32For 20g, Detitanium-ore-type
Ti0222g, bentonite 15g；
For above-mentioned catalyst to the sweetening process of hydrogen sulfide containing coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into as desulfurizer slurry, solid content is 15wt% in the slurries,
Coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, the desulfurizing tower
Top sprays above-mentioned desulfurizing agent by nozzle and carries out elution desulfurization to the coke-stove gas, and the waste liquid drying after collecting desulfurization is
The application's contains Fe21.333O32Desulfurizing agent give up agent；
It is above-mentioned to contain Fe21.333O32Desulfurizing agent give up agent regeneration method, include the following steps:
1) aqueous solution of above-mentioned useless agent and potassium hydroxide is stirred in slurry tank and is configured to slurries, maintain the pH value of slurries
It is 8.0, the solid content of the slurries is 4wt%；
2) it is passed through in Xiang Shangshu slurries containing O2With O3Mixed gas, and oxidation reaction is carried out under 50 DEG C, 1MPa, with oxidation
Regeneration；
3) hydrogen sulfide is passed through into the slurries after oxidation again, and carries out vulcanization reaction under 10 DEG C, 5MPa；
4) it is passed through air into the slurries after vulcanization, and carries out oxidation reaction under 90 DEG C, 0.1MPa, to aoxidize again
It is raw；
5) step 3) and 4) three times, the molar ratio of ferro element and element sulphur in the slurries after making the oxidation reaction are repeated
1:4.9；
6) slurries after the oxidation reaction are separated by solid-liquid separation, obtain the regrowth of above-mentioned useless agent.
Embodiment 7 (application of the useless agent of desulfurizing agent)
To contain Fe in the regrowth of the useless agent of desulfurizing agent collected by above-described embodiment 1-6 and Examples 1 and 221.333O32
Catalyst of the desulfurizing agent as CO conversion reaction, carry out the active testing of catalyst, active testing is as follows:
Unstripped gas group becomes 15vol%CO, 55vol%H2, 6vol%CO2, 24vol%N2, reaction steam-to-gas ratio be 1:1, it is empty
Speed is 4000h-1, it is 250~450 DEG C that catalyst activity, which tests warm area,；
The activity of catalyst indicates that calculation method is as follows with CO conversion ratio:
CO conversion ratio=(1-VCO'/VCO)/(1+VCO) × 100%
Wherein, VCO'For the percentage by volume of CO in reactor outlet gas, VCOFor the percentage by volume of CO in unstripped gas；
It is corresponding that test result is as follows shown in table 1:
CO conversion ratio under table 1, different test temperatures
From table 1 it can be seen that: the application use contain Fe21.333O32Desulfurizing agent give up agent regrowth as CO convert urge
Agent can effectively be catalyzed CO and change reaction, improve the conversion ratio of CO.
14, one kind contains Fe21.333O32Desulfurizing agent use in organic matter transformation technique of useless agent or useless agent regenerative agent
On the way.
Embodiment 1
A kind of biomass liquefying process is present embodiments provided, is included the following steps:
The pretreatment of biomass:
Pea stalk, broomcorn straw and rice straw are as biomass solid, with total restatement of the biomass, the biomass
Moisture content be 15%, by the pea stalk, broomcorn straw and rice straw be sent into micronizer carry out just crush, first powder
Median after broken is 250 μm, and first smashed pea stalk, broomcorn straw and rice straw are then sent into plodder
In carried out under 55 DEG C of temperature, the pressure of 1.5MPa compression extrusion forming to its heap density be 0.9g/cm3, two are carried out later
Secondary crushing, the average particle size after separating twice is 0.9mm, spare；
Catalyst:
Catalyst is with Fe21.333O32For the regrowth of the useless agent of the desulfurizing agent of active component, wherein it is described with
Fe21.333O32For in the desulfurizing agent of active component, Fe21.333O32For 55g, Detitanium-ore-type Ti0222g, bentonite 15g；
It is above-mentioned with Fe21.333O32For the sweetening process of the desulfurizing agent of active component, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
As the application with Fe21.333O32For the useless agent of the desulfurizing agent of active component；
The regeneration method of above-mentioned useless agent, includes the following steps:
1) above-mentioned useless agent is dispersed in water, forms slurries；
2) above-mentioned slurries are heated to 45 DEG C under normal pressure, hydrogen peroxide are then added into slurries using peristaltic pump, and lead to
Enter air, hydrogen peroxide flow control is 500mL/min, air flow control 100mL/min, magnetic agitation with promote to react into
Row, reaction time 5min；
3) after the reaction was completed, filtering reacting liquid obtained precipitating is washed with water 3 times, natural airing, obtains above-mentioned useless agent
Regenerative agent.
The preparation of biomass slurry:
Biomass, sulphur and above-mentioned catalyst that pretreatment obtains are mixed to get mixture, said mixture is added
Homogeneous slurrying in the miscella of kitchen waste oil and rapeseed oil forms slurries, and the molar ratio of ferro element and element sulphur is 1 in slurries:
4, the subsequent kitchen waste oil and rapeseed oil with slurry used in the process can be replaced in the present embodiment made from biomass liquefying process
Oil product, through detecting, the total content of pea stalk, broomcorn straw and rice straw is 40wt%, the viscosity of the slurries in the slurries
For 820mPa ﹒ s (50 DEG C), with Fe in slurries21.333O32Content for the regrowth of the useless agent of the desulfurizing agent of active component is
8wt%, added with Fe21.333O32Average grain diameter for the regrowth of the useless agent of the desulfurizing agent of active component is 300 μm；
Liquefaction reaction:
By CO and H2Gaseous mixture (wherein in gaseous mixture CO volume accounting be 50%) be forced into 17.5MPa, be heated up to
It after 380 DEG C, is injected in paste state bed reactor by 5 inlets in paste state bed reactor bottom and side wall, and wherein with entrance
The slurries occur cracking, carbonylation, transformation and hydrogenation reaction, control reaction pressure be 17MPa, reaction temperature is 420 DEG C,
Reaction time is 50min, the CO and H2Gaseous mixture and the slurries volume ratio be 1500:1, be made oil product.
Embodiment 2
A kind of tar sand oil and palm oil cotransformation technique are present embodiments provided, is included the following steps:
Catalyst:
Catalyst is to contain Fe21.333O32Desulfurizing agent useless agent regrowth, wherein it is described to contain Fe21.333O32It is de-
In sulphur agent, magnetic iron oxide red Fe21.333O32For 55g, copper oxide 12g, carrier di-iron trioxide 21g；
Above-mentioned catalyst is as follows to the sweetening process of hydrogen sulfide containing coal pyrolysis gas:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and it is above-mentioned to be mixed into filling for next air with air pump
Mainly using iron oxide as in the desulfurizing tower of the desulfurizing agent of active constituent, using the process of bottom in and top out, to avoid have liquid water into
Enter desulfurizing agent bed removing hydrogen sulfide；
(2) above-mentioned desulfurizing agent becomes useless agent after being used for multiple times, and takes out from desulfurizing agent bed, as containing in the application
Fe21.333O32Desulfurizing agent useless agent；
It is above-mentioned to contain Fe21.333O32Desulfurizing agent useless agent regeneration method, include the following steps:
1) above-mentioned useless agent is dispersed in water, forms slurries；
2) above-mentioned slurries are heated to 60 DEG C under normal pressure, hydrogen peroxide, flow are then added into slurries using peristaltic pump
Control is 500mL/min, and magnetic agitation is to promote reaction to carry out, reaction time 10min；
3) after the reaction was completed, filtering reacting liquid obtained precipitating is washed with water 2 times, natural airing, obtains above-mentioned useless agent
Regenerative agent.
The preparation of slurries:
Tar sand oil, palm oil, sulphur and above-mentioned catalyst are mixed to get mixture, and entered into mixture plus in right amount
Water, stirring pulping form slurries, and the average grain diameter of the catalyst added is 300 μm, and ferro element and element sulphur rubs in slurries
You are than being 1:3；
Conversion reaction:
After being partially forced into 5.7MPa in pure CO, being heated up to 500 DEG C, it is passed through in the pipeline for conveying the slurries, remaining
Part be forced into 5.2MPa, be heated up to 500 DEG C after, by paste state bed reactor entrance injection paste state bed reactor in, and with entrance
Cracking, carbonylation, transformation and hydrogenation reaction occur for the slurries therein, in the conversion process, lead into paste state bed reactor
Enter hydrogen sulfide gas, to guarantee that the molar ratio of ferro element and element sulphur is 1:3 in reaction system, and controls the anti-of conversion reaction
Answering pressure is 5MPa, reaction temperature is 470 DEG C, reaction time 90min, the CO and H2Gaseous mixture and the slurries
Volume ratio is 3000:1, and oil product is made.
Embodiment 3
A kind of biomass and hogwash fat cotransformation technique are present embodiments provided, is included the following steps:
The pretreatment of biomass:
Rice straw and flax stalk are as biomass solid, with total restatement of the biomass, the moisture content of the biomass
It is 6%, the rice straw and reed straw is sent into micronizer and just crush, first smashed median is 150 μ
First smashed rice straw and reed straw are then sent into cuber and are carried out under 30 DEG C of temperature, the pressure of 3MPa by m
Compression, extrusion forming to its heap density are 0.8g/cm3, separating twice is carried out later, and the average particle size after separating twice is
3mm, it is spare；
Catalyst:
Catalyst is with Fe21.333O32For the useless agent of the desulfurizing agent of active component, wherein with the Fe21.333O32Desulfurizing agent
Gross mass meter, the Fe21.333O32The content of magnetic iron oxide red is 75% in desulfurizing agent, the content of binder attapulgite
It is 25%.
Sweetening process of the above-mentioned catalyst as coal pyrolysis gas, is summarized as follows:
(1) compressed coal pyrolysis gas is cooled to 25~40 DEG C, and the air come with air pump is mixed into thick desulfurizing tower,
Using the process of bottom in and top out, to avoid there is liquid water to enter desulfurizing agent bed.Thick removing hydrogen sulfide is only carried out herein.
(2) gas heating after thick desulfurization is hydrolyzed to 120~135 DEG C, by most of COS and CS2It is hydrolyzed to H2S。
(3) gas after hydrolyzing is cooled to 20~25 DEG C again, carries out H2S removing, herein to guarantee clean-up effect and to make
With service life, using the form of double tower series-parallel operation, the H that hydrolysis is generated2S is totally removed, and further removes remaining
R-SH and thiophene.It is totally removed by the remaining sulfide of this technical process, reaches final purification requirement total sulfur content and be less than
0.1ppm。
Desulfurizing agent becomes useless agent after being used for multiple times and deletes from desulfurizing agent bed, the as Fe in the application21.333O32Desulfurization
Agent is given up agent.
The preparation of biomass slurry:
React the pretreatment of procatalyst: with Fe in detection the present embodiment21.333O32For the useless agent of the desulfurizing agent of active component
The molar ratio of middle ferro element and element sulphur is mixed if the molar ratio of ferro element and element sulphur is not up to 1:5 into above-mentioned catalyst
Entering solid sulfur powder to the molar ratio of wherein ferro element and element sulphur is 1:5, to guarantee ferro element and sulphur in reaction system
The molar ratio of element is 1:5；
If the molar ratio of ferro element and element sulphur is greater than 1:5, by solvent extraction or the modes such as molten sulphur can be heated, taken off
Except extra sulphur；
The biomass that pretreatment obtains is mixed to get mixture with pretreated catalyst, said mixture addition is swilled
Slurrying is stirred and ground in water oil, forms slurries, through detecting, the total content of rice straw and reed straw is in the slurries
The viscosity of 60wt%, the slurries are 500mPa ﹒ s (50 DEG C), and in above-mentioned slurries, the content of catalyst is 5wt%, are added
The average grain diameter of catalyst is 5 μm；
Conversion reaction:
By CO and H2Gaseous mixture (CO accounting 60% and H2Accounting is that 40%) middle part is forced into 21MPa, is heated up to 350
It after DEG C, is passed through in the pipeline for conveying the slurries, after rest part is forced into 21MPa, is heated up to 500 DEG C, by slurry reactor
In device entrance injection paste state bed reactor, and cracking, carbonylation occurs, convert and adds hydrogen anti-with the slurries therein are entered
It answers, the reaction pressure for controlling conversion reaction is 20MPa, reaction temperature is 380 DEG C, reaction time 60min, the CO and H2's
The volume ratio of gaseous mixture and the slurries is 3000:1, and oil product is made.
Embodiment 4
A kind of biomass liquefying process is present embodiments provided, is included the following steps:
The pretreatment of biomass:
Wheat stalk and reed straw are as biomass solid, with total restatement of the biomass, the moisture content of the biomass
It is 8%, the wheat stalk and flax stalk is sent into micronizer and just crush, first smashed median is 100 μ
First smashed wheat stalk and flax stalk are then sent into plodder and are carried out under 60 DEG C of temperature, the pressure of 3MPa by m
Compression, extrusion forming to its heap density are 1.1g/cm3, separating twice is carried out later, and the average particle size after separating twice is
2mm, it is spare；
Catalyst:
Catalyst is using FeOOH as the useless agent of the desulfurizing agent of active component, wherein with the Fe21.333O32Desulfurization
The gross mass meter of agent, the Fe21.333O32The content of magnetic iron oxide red is 89% in desulfurizing agent, the bentonitic content of binder
It is 11%.For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, the gas water containing H2S is made come into full contact with instead with it
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, the catalyst after gas water desulfurization are useless
Agent is the Fe of the application21.333O32Desulfurizing agent gives up agent.
The preparation of biomass slurry:
Biomass, sulphur and above-mentioned catalyst that pretreatment obtains are mixed to get mixture, said mixture is added
Stirring pulping in the miscella of palm oil and petroleum base wax oil forms slurries；Through detecting, wheat stalk and flax straw in the slurries
The total content of stalk is 45wt%, and the molar ratio of ferro element and element sulphur is 1:2.5, and the viscosity of the slurries is 530mPa ﹒ s (50
DEG C), catalyst content is 0.3wt% in slurries, and average grain diameter is 20 μm.
Conversion reaction:
By CO and H2Gaseous mixture (CO accounting 80% and H2Accounting is that 20%) middle part is forced into 19.5MPa, is heated up to
It after 300 DEG C, is passed through in the pipeline for conveying the slurries, after rest part is forced into 19.3MPa, is heated up to 480 DEG C, by slurry bed system
In 3 inlets injection paste state bed reactor on reactor bottom and side wall, and split with into the slurries therein
Solution, carbonylation, transformation and hydrogenation reaction, control reaction pressure is 19MPa, reaction temperature is 390 DEG C, and the reaction time is
100min, the CO and H2Gaseous mixture and the slurries volume ratio be 800:1, be made oil product.
Embodiment 5
A kind of biomass liquefying process is present embodiments provided, is included the following steps:
The pretreatment of biomass:
Jowar stalk and ramie stalk stalk are as biomass solid, with total restatement of the biomass, the biomass it is aqueous
Rate is 15%, and the corn stover and ramie stalk are sent into micronizer and just crush, first smashed median particle size is
250 μm, first smashed corn stover and ramie stalk are then sent into temperature, the pressure of 1.5MPa in cuber at 50 DEG C
Under carry out compression extrusion forming to its heap density be 0.8g/cm3, separating twice is carried out later, the average grain after separating twice
Degree is 3mm, spare；
Catalyst:
The embodiment of the invention provides a kind of Fe21.333O32Desulfurizing agent gives up agent, wherein with the Fe21.333O32Desulfurizing agent
Gross mass meter, the Fe21.333O32Fe in desulfurizing agent21.333O32Content is 94%, and surplus is impurity and water.
For above-mentioned catalyst to the sweetening process of coke-stove gas, operating procedure is as follows:
By above-mentioned Fe21.333O32Desulfurizing agent and water are hybridly prepared into as desulfurizer slurry, FeOOH in the slurries
Total concentration be 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is
30 DEG C, the top of the desulfurizing tower carries out elution desulfurization to the coke-stove gas by the agent of nozzle injection desulfurization, after collecting desulfurization
Waste liquid it is dry be the application Fe21.333O32Desulfurizing agent gives up agent.
The preparation of biomass slurry:
Biomass, sulphur and above-mentioned catalyst that pretreatment obtains are mixed to get mixture, said mixture is added
Slurrying is emulsified into kitchen waste oil, forms slurries, through detecting, the total content of corn stover and ramie stalk is in the slurries
The molar ratio of 57wt%, ferro element and element sulphur is 1:3, and the viscosity of the slurries is 1130mPa ﹒ s (50 DEG C), in the slurries with
Fe21.333O32Content for the useless agent of the desulfurizing agent of active component is 4wt%, added with Fe21.333O32For active component
The average grain diameter of the useless agent of desulfurizing agent is 120 μm；
Conversion reaction:
It after being partially forced into 18MPa in pure CO gas, being heated up to 250 DEG C, is passed through in the slurries, rest part pressurization
To 18MPa, be heated up to 500 DEG C after, by paste state bed reactor bottom and side wall 4 inlets inject paste state bed reactor
It is interior, and with into the slurry cracking, carbonylation, transformation and hydrogenation reaction therein, control reaction pressure is 17MPa, reacts
Temperature is 400 DEG C, reaction time 40min, and the volume ratio of the pure CO gas and the slurries is 950:1, and oil product is made.
Embodiment 6
A kind of biomass liquefying process is present embodiments provided, is included the following steps:
The pretreatment of biomass:
Pea stalk, corn stover and rice straw are as biomass solid, with total restatement of the biomass, the biomass
Moisture content be 20%, by the pea stalk, broomcorn straw and rice straw be sent into micronizer carry out just crush, first powder
Median after broken is 300 μm, and first smashed pea stalk, broomcorn straw and rice straw are then sent into plodder
In carried out under 55 DEG C of temperature, the pressure of 2.5MPa compression extrusion forming to its heap density be 0.9g/cm3, two are carried out later
Secondary crushing, the average particle size after separating twice is 0.9mm, spare；
Catalyst:
Catalyst is used with Fe21.333O32For active component desulfurizing agent give up agent regenerative agent,
Wherein, contain Fe with described21.333O32Desulfurizing agent gross mass meter, it is described to contain Fe21.333O32Desulfurizing agent in
The content of magnetic iron oxide red is 96.2%, and surplus is impurity and water；
For above-mentioned catalyst to the sweetening process of coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into as desulfurizer slurry, the total concentration of FeOOH in the slurries
For 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, described
The top of desulfurizing tower carries out elution desulfurization to the coke-stove gas by the agent of nozzle injection desulfurization, and the waste liquid after collecting desulfurization is dry
As contain Fe in the application21.333O32Desulfurizing agent give up agent.
It is above-mentioned to contain Fe21.333O32Desulfurizing agent give up agent regeneration method be,
(1) water vapour that pressure is 1.0MPa is passed through heating furnace, by steam heating to 420 DEG C；
(2) water vapour after heating is passed into the speed of 10m/s and is filled containing Fe21.333O32Desulfurizing agent give up agent
Desulfurizer contains Fe with heating21.333O32Desulfurizing agent give up agent；
(3) guarantee to contain Fe21.333O32Desulfurizing agent give up agent bed temperature by the item of steam heating to 400 DEG C or more
3h, steam consumption 7t/h are run under part；
(4) analysis desulfurizer export pH, continuous 3 times be more than or equal to 7.5 when, can be passed through into desulfurizer oven gas progress
Reduction；
(5) every primary inlet and outlet H2 concentration of 30min analysis changes after being passed through oven gas, as outlet H2Concentration stablize be greater than or
Equal to entrance H2After concentration (3 times analysis), that is, obtain described containing Fe21.333O32Desulfurizing agent give up agent regenerative agent.
The preparation of biomass slurry:
Biomass, sulphur and above-mentioned catalyst that pretreatment obtains are mixed to get mixture, said mixture is added
Homogeneous slurrying in the miscella of kitchen waste oil and rapeseed oil, the molar ratio for forming ferro element and element sulphur is the slurries of 1:4, subsequent
The kitchen waste oil and rapeseed oil used during with slurry can be replaced oil product made from biomass liquefying process in the present embodiment, pass through
It detects, the total content of pea stalk, broomcorn straw and rice straw is 40wt% in the slurries, and the viscosity of the slurries is
820mPa ﹒ s (50 DEG C), with Fe in slurries21.333O32Content for the desulfurizing agent of active component is 8wt%, added with
Fe21.333O32Average grain diameter for the desulfurizing agent of active component is 300 μm；
Liquefaction reaction:
By CO and H2Gaseous mixture (wherein in gaseous mixture CO volume accounting be 50%) be forced into 18MPa, be heated up to 380
After DEG C, by paste state bed reactor bottom and side wall 5 inlets injection paste state bed reactor in, and with enter institute therein
It states slurries and cracking, carbonylation, transformation and hydrogenation reaction occurs, control reaction pressure is 17MPa, reaction temperature is 420 DEG C, reaction
Time is 50min, the CO and H2Gaseous mixture and the slurries volume ratio be 900:1, be made oil product.
Embodiment 7
The cotransformation technique for present embodiments providing a kind of dregs of fat, wheat stalk and kitchen waste oil, includes the following steps:
The pretreatment of the dregs of fat and wheat stalk:
The dregs of fat and wheat stalk are as biomass solid, and with total restatement of the biomass, the moisture content of the biomass is
7%, the dregs of fat and excrement are sent into micronizer and just crush, first smashed median is 250 μm, then will be first
The smashed dregs of fat and excrement are sent into plodder to be compressed under 50 DEG C of temperature, the pressure of 1.5MPa, and extrusion forming is extremely
Its heap density is 0.95g/cm3, separating twice is carried out later, and the average particle size after separating twice is 60 μm, spare；
Catalyst:
Catalyst is to contain Fe21.333O32Desulfurizing agent give up agent regenerative agent, wherein to contain Fe21.333O32Desulfurizing agent
Gross mass meter, it is described to contain Fe21.333O32Desulfurizing agent in Fe21.333O32Content be 80%, carrier molecule sieve content be
15%, the content of binder sesbania powder is 5%；
H in above-mentioned catalyst removal exhaust gas2The basic process of S includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, collecting the waste in the desulfurization section is the useless agent of desulfurizing agent；
The regeneration method of the useless agent of above-mentioned desulfurizing agent are as follows: after the useless agent of the desulfurizing agent is washed with water, in wet ball mill
Useless agent powder is obtained with the particle that water is ground into 80 mesh；The useless agent powder is made into the aqueous suspension that solid masses percentage composition is 8%
Liquid is passed through compressed air, reacts inspection by sampling after a period of time, does not generate H when the sample of taking-up is reacted with hydrochloric acid2When S, then give up
Iron sulfide in agent is fully converted to FeOOH and elemental sulfur, forms the slurry containing the FeOOH and elemental sulfur
Liquid filters the slurries and obtains solid material, uses CC14The solid material obtained after extraction filtering, coextraction merge extraction three times
Liquid, the elemental sulfur crystallized simultaneously with the method recycling design of distillation, and extract liquor separates rear remaining solid and binder
The regrowth of the useless agent of above-mentioned desulfurizing agent is made in sesbania powder mixing, and wherein the dosage of binder sesbania powder is the solid masses
5%.
The preparation of slurries:
The dregs of fat, wheat stalk, carbon disulfide and above-mentioned catalyst that pretreatment obtains are mixed to get mixture, it will be above-mentioned
Mixture, which is added into kitchen waste oil, disperses slurrying, forms slurries, through detecting, the total content of the dregs of fat and excrement is in the slurries
The molar ratio of 55wt%, ferro element and element sulphur is 1:2, and the viscosity of the slurries is 400mPa ﹒ s (50 DEG C), in above-mentioned slurries,
The content of catalyst is 10wt%, and the average grain diameter of the catalyst added is 5mm；
Conversion reaction:
By CO and H2Gaseous mixture (CO accounting 60% and H2Accounting is that 40%) middle part is forced into 16.8MPa, is heated up to
It after 250 DEG C, is passed through in the pipeline for conveying the slurries, after rest part is forced into 16.2MPa, is heated up to 550 DEG C, by ebullated bed
Reactor inlet injects in fluidized bed reactor, and cracking, carbonylation, transformation and plus hydrogen occurs with into the slurries therein
Reaction, the reaction pressure for controlling conversion reaction is 16MPa, reaction temperature is 420 DEG C, reaction time 60min, the CO and H2
Gaseous mixture and the slurries volume ratio be 5000:1, be made oil product.
Embodiment 8
The present embodiment is same as Example 6, and difference is only in that, the regeneration method for agent of giving up is different, gives up in the present embodiment
The regeneration method of agent is,
1) water vapour that pressure is 1MPa is passed through heating furnace, by steam heating to 400 DEG C；
2) water vapour after heating is passed into the desulfurizer for containing the useless agent of desulfurizing agent with the speed of 20m/s, heats desulfurization
Agent is given up agent；
3) guarantee desulfurizing agent give up agent bed temperature by steam heating to running 2h, steam consumption under conditions of 450 DEG C
For 8t/h；
4) analysis desulfurizer export pH, continuous 3 times be more than or equal to 7.5 when, a small amount of oven gas can be passed through into desulfurizer
It is restored；
5) being passed through level-one in fine de-sulfur process adds the oven gas after hydrogen to restore with 800m3/h to desulfurizing agent agent of giving up；
6) H is once imported and exported in every 30min analysis after being passed through oven gas2Concentration variation, as outlet H2Concentration stabilization is greater than or waits
In entrance H2The regenerative agent of the useless agent of desulfurizing agent can be obtained in (3 analyses) after concentration.
Test example
The distribution of product prepared by the method using the embodiment of the present invention 1-8 is compared, the test method of product
It is as follows:
(there is solid remaining in gross mass-reaction product of SOLID ORGANIC matter transforming solid organic matter rate %=in raw material
Machine matter quality) gross mass of SOLID ORGANIC matter in/raw material, " SOLID ORGANIC matter " in the transforming solid organic matter rate refers both to nothing
Water, ash free basis (the same below)；
It under normal temperature and pressure is liquid phase oil product that transforming solid organic matter oil yield %=transforming solid organic matter, which is in product,
SOLID ORGANIC matter combined feed quality in quality/raw material；
Reaction generates water rate %=(total matter of the water quality of the reaction product-water that reaction starting is added or raw material is brought into
Amount)/raw material combined feed quality.As this value < 0, it is denoted as "None"；
Corresponding test result is as shown in Table 1 and Table 2:
1 transforming solid organic matter Contrast on effect of table
(liquid organic matter combined feed mid-boiling point is greater than in quality-product of 360 DEG C of materials liquid organic matter transformation rate %=
Oil product is greater than 360 DEG C of liquid oil gross mass)/liquid organic matter combined feed mid-boiling point is greater than the quality of 360 DEG C of materials；
In liquid organic matter transformation oil yield %=converted product there is quality/raw material liq of liquid phase oil product under normal temperature and pressure
Machine matter combined feed quality.
Product profiles versus after the conversion of 2 liquid organic matter material of table
From table 1 and 2 as can be seen that using the transforming solid organic matter oil yield > 50wt% of method of the invention, liquid
Organic matter transformation oil yield > 91%；The hair of the ideal fuels oil of 0.91 times of calorific value > of equal quality of organic matter transformation oil
Heat, organic matter transformation oil phase oxygen content < 4.8wt%；The generation water < 1.5wt% of raw material after reaction.
15, purposes of the useless agent of ferric oxide desulfurizer as hydrogenation catalyst:
Embodiment 1 (tail gas)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, amorphous Fe in the ferric oxide desulfurizer2O3Content be 55%, carrier is that bentonitic content is 30%, bonding
The content of agent sesbania powder is 15%.
Above-mentioned catalyst adds the sweetening process of the tail gas generated after hydrogen upgrading as follows for middle coalite tar in industry:
1) tail gas that coalite tar generates after fixed bed hydrogenation is catalyzed in collecting；
2) desulfurizing agent of the present embodiment is made to diameter is 1mm, length is 15mm cylindrical catalyst particle, and is filled in de-
In sulphur tower, desulfurization layer is formed；
3) by above-mentioned tail gas with 2000h-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer
Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as
The useless agent of ferric oxide desulfurizer in the application.
Embodiment 2 (coal pyrolysis gas)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, γ-Fe in the ferric oxide desulfurizer2O3Content be 65%, the content of carrier natural zeolite is 30%, binder
The content of cellulose powder is 5%.
Above-mentioned catalyst is as follows to the sweetening process of hydrogen sulfide containing coal pyrolysis gas:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and it is above-mentioned to be mixed into filling for next air with air pump
Mainly using iron oxide as in the desulfurizing tower of the desulfurizing agent of active constituent, using the process of bottom in and top out, to avoid have liquid water into
Enter desulfurizing agent bed removing hydrogen sulfide；
(2) above-mentioned desulfurizing agent becomes useless agent after being used for multiple times, and takes out from desulfurizing agent bed, the as oxidation in the application
The useless agent of iron desulfurizing agent.
Embodiment 3 (petroleum)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, the content of the ferroso-ferric oxide of cubic system is 97.3% in the ferric oxide desulfurizer, and surplus is impurity and water；
Above-mentioned catalyst carries out sweetening process to the petroleum containing hydrogen sulfide, and operating procedure is as follows:
(1) diameter is made in the desulfurizing agent of the present embodiment and is the catalyst granules of 1.5mm, and be filled in desulfurizing tower, shape
At desulfurization layer；
(2) petroleum containing hydrogen sulfide is sprayed into desulfurization layer from the top of desulfurizing tower by nozzle, carry out elution desulfurization,
The useless agent of desulfurizing agent after collecting desulfurization is the useless agent of the ferric oxide desulfurizer in the application.
Embodiment 4 (gas water)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, amorphous Fe in the ferric oxide desulfurizer2O3.H2The content of O is 75%, and the content of carrier alundum is
10%, the content of binder sesbania powder is 15%；
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
The as useless agent of the ferric oxide desulfurizer of the application.
Embodiment 5 (exhaust gas)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, the content of the ferroso-ferric oxide of cubic system is 5% in the ferric oxide desulfurizer, amorphous Fe2O3Content be
25%, amorphous Fe2O3.H2The content of O is 60%, and the content of binder sesbania powder is 10%；
H in above-mentioned catalyst removal exhaust gas2The process of S includes the following steps: H2S content is 5500mg/cm3Exhaust gas
With 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2The content of S≤
When 0.01ppm, the waste in the desulfurization section is collected.
Embodiment 6 (coke-stove gas)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, γ-Fe in the ferric oxide desulfurizer2O3Content is 23%, and the ferroso-ferric oxide content of cubic system is 50%, is glued
Knot agent is that the content of sesbania powder is 27%；
For above-mentioned catalyst to the sweetening process of hydrogen sulfide containing coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into desulfurizer slurry, FeOOH is total dense in the desulfurizer slurry
Degree is 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, institute
The top for stating desulfurizing tower sprays above-mentioned desulfurizing agent by nozzle and carries out elution desulfurization to the coke-stove gas, useless after collecting desulfurization
The useless agent of the dry as ferric oxide desulfurizer of the application of liquid.
Embodiment 7 (application of the useless agent of desulfurizing agent)
Using the useless agent of desulfurizing agent collected by above-described embodiment 1-6 as the catalyst of corn stover liquefaction reaction, carry out
The active testing of catalyst, active testing are as follows: preparing the slurries containing corn stover and catalyst, above-mentioned slurries are delivered to
In paste state bed reactor, and it is passed through hydrogen into paste state bed reactor, carries out hydrogenation liquefaction reaction, control reaction pressure is
20MPa, temperature are 380 DEG C, wherein catalyst loading is the 2wt% of corn stover additive amount, the activity corn of catalyst
The distribution of the product of liquefaction of corn straw reaction preparation indicates, as shown in table 1 below:
1 product profiles versus of table
From table 1 it can be seen that: the application use ferric oxide desulfurizer useless agent as hydrogenation catalyst, can effectively be catalyzed
Hydrogenation reaction improves biomass conversion ratio.
It 16, is the useless agent of the desulfurizing agent of main active as the purposes of hydrogenation catalyst using iron oxide.
Embodiment 1 (tail gas)
The embodiment of the invention provides one kind mainly using iron oxide as the useless agent of the desulfurizing agent of active constituent, wherein described
Mainly using iron oxide as in the desulfurizing agent of active constituent, CuO 8g, molysite complexing agent triethanolamine 9g, amorphous Fe2O315g,
MnO2For 8g；
Above-mentioned catalyst adds the sweetening process of the tail gas generated after hydrogen upgrading as follows for middle coalite tar in industry:
1) tail gas that coalite tar generates after fixed bed hydrogenation is catalyzed in collecting；
2) desulfurizing agent of the present embodiment is made to diameter is 1mm, length is 15mm cylindrical catalyst particle, and is filled in de-
In sulphur tower, desulfurization layer is formed；
3) by above-mentioned tail gas with 2000h-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer
Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as
It is main using iron oxide as the useless agent of the desulfurizing agent of active constituent in the application.
Embodiment 2 (coal pyrolysis gas)
The embodiment of the invention provides one kind mainly using iron oxide as the useless agent of the desulfurizing agent of active constituent, wherein described
Mainly using iron oxide as in the desulfurizing agent of active constituent, calcium bicarbonate 10g, basic copper carbonate 12g, γ-Fe2O318g, MnO2
For 8g, NiO 5g；
Above-mentioned catalyst is as follows to the sweetening process of hydrogen sulfide containing coal pyrolysis gas:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and it is above-mentioned to be mixed into filling for next air with air pump
Mainly using iron oxide as in the desulfurizing tower of the desulfurizing agent of active constituent, using the process of bottom in and top out, to avoid have liquid water into
Enter desulfurizing agent bed removing hydrogen sulfide；
(2) above-mentioned desulfurizing agent becomes useless agent after being used for multiple times, and takes out from desulfurizing agent bed, as main in the application
Using iron oxide as the useless agent of the desulfurizing agent of active constituent.
Embodiment 3 (petroleum)
The embodiment of the invention provides one kind mainly using iron oxide as the useless agent of the desulfurizing agent of active constituent, wherein described
Mainly using iron oxide as in the desulfurizing agent of active constituent, ferroso-ferric oxide 50g, calcium sulphate dihydrate 12g, the alkali formula carbon of cubic system
Sour zinc 20g and sodium carboxymethylcellulose are 6g；
Above-mentioned catalyst carries out sweetening process to the petroleum containing hydrogen sulfide, and operating procedure is as follows:
(1) diameter is made in the desulfurizing agent of the present embodiment and is the catalyst granules of 1.5mm, and be filled in desulfurizing tower, shape
At desulfurization layer；
(2) petroleum containing hydrogen sulfide is sprayed into desulfurization layer from the top of desulfurizing tower by nozzle, carry out elution desulfurization,
The useless agent of desulfurizing agent after collecting desulfurization is main using iron oxide as the useless agent of the desulfurizing agent of active constituent in the application.
Embodiment 4 (gas water)
The embodiment of the invention provides one kind mainly using iron oxide as the useless agent of the desulfurizing agent of active constituent, wherein described
Mainly using iron oxide as in the desulfurizing agent of active constituent, amorphous Fe2O3.H2O 30g, bodied ferric sulfate 15g, basic copper carbonate
12g and sodium carboxymethylcellulose are 6g, amorphous Fe2O38g；
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
As the application's is main using iron oxide as the useless agent of the desulfurizing agent of active constituent.
Embodiment 5 (exhaust gas)
The embodiment of the invention provides one kind mainly using iron oxide as the useless agent of the desulfurizing agent of active constituent, wherein described
Mainly using iron oxide as in the desulfurizing agent of active constituent, ferroso-ferric oxide 12g, the amorphous Fe of cubic system2O324g, nothing are fixed
Shape Fe2O3.H2O 39g and NiO are 5g；
H in above-mentioned catalyst removal exhaust gas2The process of S includes the following steps: H2S content is 5500mg/cm3Exhaust gas
With 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2The content of S≤
When 0.01ppm, the waste in the desulfurization section is collected, the catalyst as hydrogenation reaction.
Embodiment 6 (coke-stove gas)
The embodiment of the invention provides one kind mainly using iron oxide as the useless agent of the desulfurizing agent of active constituent, wherein described
Mainly using iron oxide as in the desulfurizing agent of active constituent, γ-Fe2O323g, amorphous Fe2O324g, amorphous Fe2O3.H2O is
42g and MnO is 8g；
For above-mentioned catalyst to the sweetening process of hydrogen sulfide containing coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into desulfurizer slurry, FeOOH is total dense in the desulfurizer slurry
Degree is 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, institute
The top for stating desulfurizing tower sprays above-mentioned desulfurizing agent by nozzle and carries out elution desulfurization to the coke-stove gas, useless after collecting desulfurization
Dry liquid is the main using iron oxide as the useless agent of the desulfurizing agent of active constituent of the application.
Embodiment 7 (application of the useless agent of desulfurizing agent)
Using the useless agent of desulfurizing agent collected by above-described embodiment 1-6 as the catalyst of corn stover liquefaction reaction, carry out
The active testing of catalyst, active testing are as follows: preparing the slurries containing corn stover and catalyst, above-mentioned slurries are delivered to
In paste state bed reactor, and it is passed through hydrogen into paste state bed reactor, carries out hydrogenation liquefaction reaction, control reaction pressure is
20MPa, temperature are 380 DEG C, wherein catalyst loading is the 2wt% of corn stover additive amount, the activity corn of catalyst
The distribution of the product of liquefaction of corn straw reaction preparation indicates, as shown in table 1 below:
1 product profiles versus of table
From table 1 it can be seen that: the application use ferric oxide desulfurizer useless agent as hydrogenation catalyst, can effectively be catalyzed
Hydrogenation reaction improves biomass conversion ratio.
17, the purposes after the useless agent regeneration of ferric oxide desulfurizer as hydrogenation catalyst.
Embodiment 1 (tail gas)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, amorphous Fe in the ferric oxide desulfurizer2O3Content be 55%, carrier is that bentonitic content is 30%, bonding
The content of agent sesbania powder is 15%.
Above-mentioned catalyst adds the sweetening process of the tail gas generated after hydrogen upgrading as follows for middle coalite tar in industry:
1) tail gas that coalite tar generates after fixed bed hydrogenation is catalyzed in collecting；
2) desulfurizing agent of the present embodiment is made to diameter is 1mm, length is 15mm cylindrical catalyst particle, and is filled in de-
In sulphur tower, desulfurization layer is formed；
3) by above-mentioned tail gas with 2000h-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer
Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as
The useless agent of ferric oxide desulfurizer in the application；
The regeneration method of the useless agent of above-mentioned ferric oxide desulfurizer, includes the following steps:
1) weak acid water (containing dilute sulfuric acid) that the useless agent of ferric oxide desulfurizer is 4.0 with pH is dispersed, iron oxide desulfurization
The solid-to-liquid ratio of the useless agent of agent and weak acid water is 1: 4 (g/ml), and jitter time 30min obtains dispersion liquid；
2) above-mentioned dispersion liquid is heated to 60 DEG C under normal pressure, hydrogen peroxide is then added into dispersion liquid using peristaltic pump,
Flow control is 500mL/min, and hydrogen peroxide and the ferric oxide desulfurizer molar ratio of element sulphur in agent of giving up are 5: 1, magnetic agitation with
Reaction is promoted to carry out, reaction is simultaneously by vacuumizing the sulfur dioxide gas that transfer generates rapidly, reaction time 10min；
3) obtained precipitating is washed with water 2 times, then dries, obtain at 100 DEG C by after the reaction was completed, filtering reacting liquid
To the regenerative agent of the useless agent of above-mentioned ferric oxide desulfurizer, the filtrate being obtained by filtration then returns in dispersion step to be made as weak acid water circulation
With.
Embodiment 2 (coal pyrolysis gas)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, γ-Fe in the ferric oxide desulfurizer2O3Content be 65%, the content of carrier natural zeolite is 30%, binder
The content of cellulose powder is 5%.
Above-mentioned catalyst is as follows to the sweetening process of hydrogen sulfide containing coal pyrolysis gas:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and it is above-mentioned to be mixed into filling for next air with air pump
Mainly using iron oxide as in the desulfurizing tower of the desulfurizing agent of active constituent, using the process of bottom in and top out, to avoid have liquid water into
Enter desulfurizing agent bed removing hydrogen sulfide；
(2) above-mentioned desulfurizing agent becomes useless agent after being used for multiple times, and takes out from desulfurizing agent bed, the as oxidation in the application
The useless agent of iron desulfurizing agent；
The regeneration method of the useless agent of above-mentioned ferric oxide desulfurizer, includes the following steps:
1) the ferric oxide desulfurizer weak acid water (containing dilute hydrochloric acid) that agent is 5.0 with pH that gives up is dispersed, ferric oxide desulfurizer
The solid-to-liquid ratio of useless agent and weak acid water is 1: 6 (g/ml), and jitter time 30min obtains dispersion liquid；
2) above-mentioned dispersion liquid is heated to 60 DEG C under normal pressure, hydrogen peroxide is then added into dispersion liquid using peristaltic pump,
Flow control is 500mL/min, and hydrogen peroxide and the ferric oxide desulfurizer molar ratio of element sulphur in agent of giving up are 6: 1, magnetic agitation with
Reaction is promoted to carry out, reaction is simultaneously by vacuumizing the sulfur dioxide gas that transfer generates rapidly, reaction time 10min；
3) obtained precipitating is washed with water 2 times, then dries, obtain at 100 DEG C by after the reaction was completed, filtering reacting liquid
To the regenerative agent of the useless agent of above-mentioned ferric oxide desulfurizer, the filtrate being obtained by filtration then returns in dispersion step to be made as weak acid water circulation
With.
Embodiment 3 (petroleum)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, the content of the ferroso-ferric oxide of cubic system is 97.3% in the ferric oxide desulfurizer, and surplus is impurity and water；
Above-mentioned catalyst carries out sweetening process to the petroleum containing hydrogen sulfide, and operating procedure is as follows:
(1) diameter is made in the desulfurizing agent of the present embodiment and is the catalyst granules of 1.5mm, and be filled in desulfurizing tower, shape
At desulfurization layer；
(2) petroleum containing hydrogen sulfide is sprayed into desulfurization layer from the top of desulfurizing tower by nozzle, carry out elution desulfurization,
The useless agent of desulfurizing agent after collecting desulfurization is the useless agent of the ferric oxide desulfurizer in the application；
The regeneration method of the useless agent of above-mentioned ferric oxide desulfurizer, includes the following steps:
1) after the useless agent of the ferric oxide desulfurizer being washed with water, band water is ground into 300 purposes in wet ball mill
Grain obtains useless agent powder；
2) the useless agent powder is made into the water slurry that solid masses percentage composition is 15%, is passed through compressed air, reacted
Inspection by sampling after a period of time does not generate H when the sample of taking-up is reacted with hydrochloric acid2When S, the slurries containing elemental sulfur, filtering are formed
The slurries obtain solid material, and use CCl4Obtained solid material after extraction filtering, coextraction three times, combining extraction liquid,
The elemental sulfur crystallized simultaneously with the method recycling design of distillation, and extract liquor separates the rear namely regenerated object of remaining solid.
Embodiment 4 (gas water)
The embodiment of the invention provides after a kind of useless agent of ferric oxide desulfurizer regeneration, wherein with the iron oxide desulfurization
The gross mass meter of agent, amorphous Fe in the ferric oxide desulfurizer2O3.H2The content of O is 75%, and carrier alundum contains
Amount is 10%, and the content of binder sesbania powder is 15%；
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
As after the useless agent regeneration of the ferric oxide desulfurizer of the application；
The regeneration method of the useless agent of above-mentioned ferric oxide desulfurizer, includes the following steps:
1) after above-mentioned useless agent being washed with water, the particle for being ground into 200 mesh with water in wet ball mill obtains useless agent powder；
2) the useless agent powder is made into the water slurry that solid masses percentage composition is 7%, is passed through compressed air, carried out anti-
It answers；
3) water slurry after reaction is filtered, the solid material is placed in flotation cell, water is added, then leads to
Enter air, is the regrowth of above-mentioned useless agent after the sediment drying of lower vessel portion.
Embodiment 5 (exhaust gas)
The embodiment of the invention provides after a kind of useless agent of ferric oxide desulfurizer regeneration, wherein with the iron oxide desulfurization
The gross mass meter of agent, the content of the ferroso-ferric oxide of cubic system is 5% in the ferric oxide desulfurizer, amorphous Fe2O3Contain
Amount is 25%, amorphous Fe2O3.H2The content of O is 60%, and the content of binder sesbania powder is 10%；
H in above-mentioned catalyst removal exhaust gas2The process of S includes the following steps: H2S content is 5500mg/cm3Exhaust gas
With 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2The content of S≤
When 0.01ppm, the waste in the desulfurization section is collected；
The regeneration method of the useless agent of above-mentioned ferric oxide desulfurizer, includes the following steps:
1) water vapour that pressure is 1.0MPa is passed through heating furnace, by steam heating to 420 DEG C；
2) water vapour after heating is passed into the desulfurizer for filling the useless agent of ferric oxide desulfurizer with the speed of 10m/s, is added
Thermal oxide iron desulfurizing agent gives up agent；
3) guarantee ferric oxide desulfurizer give up agent bed temperature by steam heating to running under conditions of 400 DEG C or more
3h, steam consumption 7t/h；
4) analysis desulfurizer export pH, continuous 3 times be more than or equal to 7.5 when, a small amount of oven gas can be passed through into desulfurizer
It is restored；
5) being passed through level-one in fine de-sulfur process adds the oven gas after hydrogen with 900m3/ h goes back ferric oxide desulfurizer agent of giving up
It is former；
6) H is once imported and exported in every 30min analysis after being passed through oven gas2Concentration variation, as outlet H2Concentration stabilization is greater than or waits
In entrance H2Regrowth can be obtained in (3 analyses) after concentration.
Embodiment 6 (coke-stove gas)
The embodiment of the invention provides after a kind of useless agent of ferric oxide desulfurizer regeneration, wherein with the iron oxide desulfurization
The gross mass meter of agent, γ-Fe in the ferric oxide desulfurizer2O3Content is 23%, and the ferroso-ferric oxide content of cubic system is
50%, binder is that the content of sesbania powder is 27%；
For above-mentioned catalyst to the sweetening process of hydrogen sulfide containing coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into desulfurizer slurry, FeOOH is total dense in the desulfurizer slurry
Degree is 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, institute
The top for stating desulfurizing tower sprays above-mentioned desulfurizing agent by nozzle and carries out elution desulfurization to the coke-stove gas, useless after collecting desulfurization
After the useless agent regeneration of the dry as ferric oxide desulfurizer of the application of liquid；
The regeneration method of the useless agent of above-mentioned ferric oxide desulfurizer, includes the following steps:
1) water vapour that pressure is 1.5MPa is passed through heating furnace, by steam heating to 450 DEG C；
2) water vapour after heating is passed into the desulfurizer for filling the useless agent of ferric oxide desulfurizer with the speed of 15m/s, is added
Thermal oxide iron desulfurizing agent gives up agent；
3) guarantee ferric oxide desulfurizer give up agent bed temperature by steam heating to running under conditions of 400 DEG C or more
2h, steam consumption 6t/h；
4) analysis desulfurizer export pH, continuous 3 times be more than or equal to 7.5 when, a small amount of oven gas can be passed through into desulfurizer
It is restored；
5) being passed through level-one in fine de-sulfur process adds the oven gas after hydrogen with 800m3/ h goes back ferric oxide desulfurizer agent of giving up
It is former；
6) H is once imported and exported in every 30min analysis after being passed through oven gas2Concentration variation, as outlet H2Concentration stabilization is greater than or waits
In entrance H2Regrowth can be obtained in (3 analyses) after concentration.
Embodiment 7 (gas water)
The embodiment of the invention provides after a kind of useless agent of ferric oxide desulfurizer regeneration, wherein with the iron oxide desulfurization
The gross mass meter of agent, amorphous Fe in the ferric oxide desulfurizer2O3.H2The content of O is 75%, and carrier alundum contains
Amount is 10%, and the content of binder sesbania powder is 15%；
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
As after the useless agent regeneration of the ferric oxide desulfurizer of the application；
The regeneration method of the useless agent of above-mentioned ferric oxide desulfurizer, includes the following steps:
1) aqueous solution of above-mentioned useless agent and sodium hydroxide is stirred in slurry tank and is configured to slurries, maintain the pH value of slurries
It is 8.0, the solid content of the slurries is 4wt%；
2) it is passed through air in Xiang Shangshu slurries, and carries out oxidation reaction under 90 DEG C, 0.1MPa, with oxidation regeneration；
3) hydrogen sulfide is passed through into the slurries after oxidation again, and carries out vulcanization reaction under 10 DEG C, 5MPa；
4) it is passed through air into the slurries after vulcanization, and carries out oxidation reaction under 90 DEG C, 0.1MPa, to aoxidize again
It is raw；
5) step 3) and 4) twice, the molar ratio of ferro element and element sulphur in the slurries after making the oxidation reaction are repeated
1:4.5；
6) slurries after the oxidation reaction are separated by solid-liquid separation, obtain the regrowth of above-mentioned useless agent.
Comparative example 1
This comparative example provides a kind of ferric oxide desulfurizer, the iron oxide desulfurization in the ferric oxide desulfurizer and embodiment 1
Agent is same desulfurizing agent, wherein in terms of the gross mass of the ferric oxide desulfurizer, amorphous Fe in the ferric oxide desulfurizer2O3
Content be 55%, carrier is that bentonitic content is 30%, and the content of binder sesbania powder is 15%.
Comparative example 2
This comparative example provides a kind of ferric oxide desulfurizer, the iron oxide desulfurization in the ferric oxide desulfurizer and embodiment 5
Agent is same desulfurizing agent, wherein in terms of the gross mass of the ferric oxide desulfurizer, cubic system in the ferric oxide desulfurizer
The content of ferroso-ferric oxide is 5%, amorphous Fe2O3Content be 25%, amorphous Fe2O3.H2The content of O is 60%, bonding
The content of agent sesbania powder is 10%.
Embodiment 8 (application after the useless agent regeneration of desulfurizing agent)
With the oxidation in the regrowth and comparative example 1-2 after the useless agent regeneration of desulfurizing agent collected by above-described embodiment 1-7
Iron desulfurizing agent carries out the active testing of catalyst respectively as the catalyst of corn stover liquefaction reaction, and active testing is as follows: matching
The slurries containing corn stover and catalyst are made, above-mentioned slurries are delivered in paste state bed reactor, and to paste state bed reactor
It is inside passed through hydrogen, carries out hydrogenation liquefaction reaction, control reaction pressure is 20MPa, and temperature is 380 DEG C, wherein catalyst loading
For the 2wt% of corn stover additive amount, the distribution for the product that the activity of catalyst is prepared with corn stover liquefaction reaction is indicated, such as
Shown in the following table 1:
1 product profiles versus of table
From table 1 it can be seen that: the application use ferric oxide desulfurizer useless agent regeneration after be used as hydrogenation catalyst, can have
Catalytic hydrogenation reaction is imitated, biomass conversion ratio is improved.
18, the purposes after the useless agent regeneration of the desulfurizing agent containing iron oxide as hydrogenation catalyst.
Embodiment 1 (tail gas)
The embodiment of the invention provides a kind of useless agent of desulfurizing agent containing iron oxide, wherein described containing iron oxide
In desulfurizing agent, CuO 8g, molysite complexing agent triethanolamine 9g, amorphous Fe2O315g, MnO2For 8g；
Above-mentioned catalyst adds the sweetening process of the tail gas generated after hydrogen upgrading as follows for middle coalite tar in industry:
1) tail gas that coalite tar generates after fixed bed hydrogenation is catalyzed in collecting；
2) desulfurizing agent of the present embodiment is made to diameter is 1mm, length is 15mm cylindrical catalyst particle, and is filled in de-
In sulphur tower, desulfurization layer is formed；
3) by above-mentioned tail gas with 2000h-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer
Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as
The useless agent of the desulfurizing agent containing iron oxide in the application；
The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:
1) weak acid water (contain dilute sulfuric acid) that above-mentioned useless agent is 4.0 with pH is dispersed, ferric oxide desulfurizer give up agent with it is weak
The solid-to-liquid ratio of sour water is 1: 4 (g/ml), and jitter time 30min obtains dispersion liquid；
2) above-mentioned dispersion liquid is heated to 60 DEG C under normal pressure, hydrogen peroxide is then added into dispersion liquid using peristaltic pump,
Flow control is 500mL/min, and hydrogen peroxide and the ferric oxide desulfurizer molar ratio of element sulphur in agent of giving up are 5: 1, magnetic agitation with
Reaction is promoted to carry out, reaction is simultaneously by vacuumizing the sulfur dioxide gas that transfer generates rapidly, reaction time 10min；
3) obtained precipitating is washed with water 2 times, then dries, obtain at 100 DEG C by after the reaction was completed, filtering reacting liquid
To the regrowth of above-mentioned useless agent, the filtrate being obtained by filtration then returns in dispersion step and is recycled as weak acid water.
Embodiment 2 (coal pyrolysis gas)
The embodiment of the invention provides a kind of useless agent of desulfurizing agent containing iron oxide, wherein described containing iron oxide
In desulfurizing agent, calcium bicarbonate 10g, basic copper carbonate 12g, γ-Fe2O318g, MnO2For 8g, NiO 5g；
Above-mentioned catalyst is as follows to the sweetening process of hydrogen sulfide containing coal pyrolysis gas:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and it is above-mentioned to be mixed into filling for next air with air pump
In the desulfurizing tower of desulfurizing agent containing iron oxide, using the process of bottom in and top out, to avoid there is liquid water to enter desulfurizing agent bed
Remove hydrogen sulfide；
(2) above-mentioned desulfurizing agent becomes useless agent after being used for multiple times, and takes out from desulfurizing agent bed, as containing in the application
The useless agent of the desulfurizing agent of iron oxide.
The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:
1) weak acid water (contain dilute hydrochloric acid) that above-mentioned useless agent is 5.0 with pH is dispersed, ferric oxide desulfurizer give up agent with it is weak
The solid-to-liquid ratio of sour water is 1: 6 (g/ml), and jitter time 30min obtains dispersion liquid；
2) above-mentioned dispersion liquid is heated to 60 DEG C under normal pressure, hydrogen peroxide is then added into dispersion liquid using peristaltic pump,
Flow control is 500mL/min, and hydrogen peroxide and the ferric oxide desulfurizer molar ratio of element sulphur in agent of giving up are 6: 1, magnetic agitation with
Reaction is promoted to carry out, reaction is simultaneously by vacuumizing the sulfur dioxide gas that transfer generates rapidly, reaction time 10min；
3) obtained precipitating is washed with water 2 times, then dries, obtain at 100 DEG C by after the reaction was completed, filtering reacting liquid
To the regrowth of above-mentioned useless agent, the filtrate being obtained by filtration then returns in dispersion step and is recycled as weak acid water.
Embodiment 3 (petroleum)
The embodiment of the invention provides a kind of useless agent of desulfurizing agent containing iron oxide, wherein described containing iron oxide
In desulfurizing agent, ferroso-ferric oxide 50g, calcium sulphate dihydrate 12g, basic zinc carbonate 20g and the sodium carboxymethylcellulose of cubic system
For 6g；
Above-mentioned catalyst carries out sweetening process to the petroleum containing hydrogen sulfide, and operating procedure is as follows:
(1) diameter is made in the desulfurizing agent of the present embodiment and is the catalyst granules of 1.5mm, and be filled in desulfurizing tower, shape
At desulfurization layer；
(2) petroleum containing hydrogen sulfide is sprayed into desulfurization layer from the top of desulfurizing tower by nozzle, carry out elution desulfurization,
The useless agent of desulfurizing agent after collecting desulfurization is the useless agent of the desulfurizing agent containing iron oxide in the application；
The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:
1) after above-mentioned useless agent being washed with water, the particle of 300 mesh is ground into water in wet ball mill, obtains useless agent
Powder；
2) the useless agent powder is made into the water slurry that solid masses percentage composition is 15%, is passed through compressed air, reacted
Inspection by sampling after a period of time does not generate H when the sample of taking-up is reacted with hydrochloric acid2When S, the slurries containing elemental sulfur, filtering are formed
The slurries obtain solid material, and use CCl4Obtained solid material after extraction filtering, coextraction three times, combining extraction liquid,
The elemental sulfur crystallized simultaneously with the method recycling design of distillation, and extract liquor separates the rear namely regenerated object of remaining solid.
Embodiment 4 (gas water)
The embodiment of the invention provides a kind of useless agent of desulfurizing agent containing iron oxide, wherein described containing iron oxide
In desulfurizing agent, amorphous Fe2O3.H2O 30g, bodied ferric sulfate 15g, basic copper carbonate 12g and sodium carboxymethylcellulose be 6g,
Amorphous Fe2O38g；
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
The as useless agent of the desulfurizing agent containing iron oxide of the application；
The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:
1) after above-mentioned useless agent being washed with water, the particle for being ground into 200 mesh with water in wet ball mill obtains useless agent powder；
2) the useless agent powder is made into the water slurry that solid masses percentage composition is 7%, is passed through compressed air, carried out anti-
It answers；
3) water slurry after reaction is filtered, the solid material is placed in flotation cell, water is added, then leads to
Enter air, is the regrowth of above-mentioned useless agent after the sediment drying of lower vessel portion.
Embodiment 5 (exhaust gas)
The embodiment of the invention provides a kind of useless agent of desulfurizing agent containing iron oxide, wherein described containing iron oxide
In desulfurizing agent, ferroso-ferric oxide 12g, the amorphous Fe of cubic system2O324g, amorphous Fe2O3.H2O 39g and NiO are 5g；
H in above-mentioned catalyst removal exhaust gas2The process of S includes the following steps: H2S content is 5500mg/cm3Exhaust gas
With 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2The content of S≤
When 0.01ppm, the waste in the desulfurization section is collected；
The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:
1) above-mentioned useless agent is dispersed in water, forms slurries；
2) above-mentioned slurries are heated to 45 DEG C under normal pressure, hydrogen peroxide are then added into slurries using peristaltic pump, and lead to
Enter air, hydrogen peroxide flow control is 500mL/min, air flow control 100mL/min, magnetic agitation with promote to react into
Row, reaction time 5min；
3) after the reaction was completed, filtering reacting liquid obtained precipitating is washed with water 3 times, natural airing, obtains above-mentioned useless agent
Regrowth.
Embodiment 6 (coke-stove gas)
The embodiment of the invention provides a kind of useless agent of desulfurizing agent containing iron oxide, wherein described containing iron oxide
In desulfurizing agent, γ-Fe2O323g, amorphous Fe2O324g, amorphous Fe2O3.H2O is 42g and MnO is 8g；
For above-mentioned catalyst to the sweetening process of hydrogen sulfide containing coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into desulfurizer slurry, FeOOH is total dense in the desulfurizer slurry
Degree is 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, institute
The top for stating desulfurizing tower sprays above-mentioned desulfurizing agent by nozzle and carries out elution desulfurization to the coke-stove gas, useless after collecting desulfurization
The useless agent of the dry as desulfurizing agent containing iron oxide of the application of liquid；
The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:
1) water vapour that pressure is 1.5MPa is passed through heating furnace, by steam heating to 450 DEG C；
2) water vapour after heating is passed into the desulfurizer for filling above-mentioned useless agent with the speed of 15m/s, is heated above-mentioned useless
Agent；
3) guarantee the bed temperature of above-mentioned useless agent by steam heating to running 2h, steam use under conditions of 400 DEG C or more
Amount is 6t/h；
4) analysis desulfurizer export pH, continuous 3 times be more than or equal to 7.5 when, a small amount of oven gas can be passed through into desulfurizer
It is restored；
5) being passed through level-one in fine de-sulfur process adds the oven gas after hydrogen with 800m3/ h goes back ferric oxide desulfurizer agent of giving up
It is former；
6) H is once imported and exported in every 30min analysis after being passed through oven gas2Concentration variation, as outlet H2Concentration stabilization is greater than or waits
In entrance H2Regrowth can be obtained in (3 analyses) after concentration.
Embodiment 7 (gas water)
The embodiment of the invention provides a kind of useless agent of desulfurizing agent containing iron oxide, wherein described containing iron oxide
In desulfurizing agent, amorphous Fe2O3.H2O 30g, bodied ferric sulfate 15g, basic copper carbonate 12g and sodium carboxymethylcellulose be 6g,
Amorphous Fe2O38g；
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
The as useless agent of the desulfurizing agent containing iron oxide of the application；
The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:
1) aqueous solution of above-mentioned useless agent and sodium hydroxide is stirred in slurry tank and is configured to slurries, maintain the pH value of slurries
It is 8.0, the solid content of the slurries is 4wt%；
2) it is passed through air in Xiang Shangshu slurries, and carries out oxidation reaction under 90 DEG C, 0.1MPa, with oxidation regeneration；
3) hydrogen sulfide is passed through into the slurries after oxidation again, and carries out vulcanization reaction under 10 DEG C, 5MPa；
4) it is passed through air into the slurries after vulcanization, and carries out oxidation reaction under 90 DEG C, 0.1MPa, to aoxidize again
It is raw；
5) step 3) and 4) twice, the molar ratio of ferro element and element sulphur in the slurries after making the oxidation reaction are repeated
1:4.5；
6) slurries after the oxidation reaction are separated by solid-liquid separation, obtain the regrowth of above-mentioned useless agent.
Comparative example 1
This comparative example provides a kind of desulfurizing agent containing iron oxide, contains iron oxide in the desulfurizing agent and embodiment 1
Desulfurizing agent be same desulfurizing agent, wherein in the desulfurizing agent containing iron oxide, CuO 8g, molysite complexing agent triethanolamine
9g, amorphous Fe2O315g, MnO2For 8g.
Comparative example 2
This comparative example provides a kind of desulfurizing agent containing iron oxide, is somebody's turn to do in the desulfurizing agent containing iron oxide and embodiment 5
The desulfurizing agent containing iron oxide be same desulfurizing agent, wherein in the desulfurizing agent containing iron oxide, four oxygen of cubic system
Change three-iron 12g, amorphous Fe2O324g, amorphous Fe2O3.H2O 39g and NiO are 5g.
Embodiment 8 (application after useless agent regeneration)
With the regrowth after the useless agent regeneration of desulfurizing agent collected by above-described embodiment 1-7 and containing in comparative example 1 and 2
The desulfurizing agent of iron oxide carries out the active testing of catalyst, active testing respectively as the catalyst of corn stover liquefaction reaction
It is as follows: to prepare the slurries containing corn stover and catalyst, above-mentioned slurries are delivered in paste state bed reactor, and to slurry bed system
It is passed through hydrogen in reactor, carries out hydrogenation liquefaction reaction, control reaction pressure is 20MPa, and temperature is 380 DEG C, wherein catalyst
Additive amount is the 2wt% of corn stover additive amount, the distribution for the product that the activity of catalyst is prepared with corn stover liquefaction reaction
It indicates, as shown in table 1 below:
1 product profiles versus of table
From table 1 it can be seen that: the application use ferric oxide desulfurizer useless agent regeneration after be used as hydrogenation catalyst, can have
Catalytic hydrogenation reaction is imitated, biomass conversion ratio is improved.
19, purposes of the useless agent of ferric oxide desulfurizer as CO transformation catalyst.
Embodiment 1 (tail gas)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, amorphous Fe in the ferric oxide desulfurizer2O3Content be 55%, carrier is that bentonitic content is 30%, bonding
The content of agent sesbania powder is 15%.
Above-mentioned catalyst adds the sweetening process of the tail gas generated after hydrogen upgrading as follows for middle coalite tar in industry:
1) tail gas that coalite tar generates after fixed bed hydrogenation is catalyzed in collecting；
2) desulfurizing agent of the present embodiment is made to diameter is 1mm, length is 15mm cylindrical catalyst particle, and is filled in de-
In sulphur tower, desulfurization layer is formed；
3) by above-mentioned tail gas with 2000h-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer
Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as
The useless agent of ferric oxide desulfurizer in the application.
Embodiment 2 (coal pyrolysis gas)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, γ-Fe in the ferric oxide desulfurizer2O3Content be 65%, the content of carrier natural zeolite is 30%, binder
The content of cellulose powder is 5%.
Above-mentioned catalyst is as follows to the sweetening process of hydrogen sulfide containing coal pyrolysis gas:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and it is above-mentioned to be mixed into filling for next air with air pump
Mainly using iron oxide as in the desulfurizing tower of the desulfurizing agent of active constituent, using the process of bottom in and top out, to avoid have liquid water into
Enter desulfurizing agent bed removing hydrogen sulfide；
(2) above-mentioned desulfurizing agent becomes useless agent after being used for multiple times, and takes out from desulfurizing agent bed, the as oxidation in the application
The useless agent of iron desulfurizing agent.
Embodiment 3 (petroleum)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, the content of the ferroso-ferric oxide of cubic system is 97.3% in the ferric oxide desulfurizer, and surplus is impurity and water；
Above-mentioned catalyst carries out sweetening process to the petroleum containing hydrogen sulfide, and operating procedure is as follows:
(1) diameter is made in the desulfurizing agent of the present embodiment and is the catalyst granules of 1.5mm, and be filled in desulfurizing tower, shape
At desulfurization layer；
(2) petroleum containing hydrogen sulfide is sprayed into desulfurization layer from the top of desulfurizing tower by nozzle, carry out elution desulfurization,
The useless agent of desulfurizing agent after collecting desulfurization is the useless agent of the ferric oxide desulfurizer in the application.
Embodiment 4 (gas water)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, amorphous Fe in the ferric oxide desulfurizer2O3.H2The content of O is 75%, and the content of carrier alundum is
10%, the content of binder sesbania powder is 15%；
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
The as useless agent of the ferric oxide desulfurizer of the application.
Embodiment 5 (exhaust gas)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, the content of the ferroso-ferric oxide of cubic system is 5% in the ferric oxide desulfurizer, amorphous Fe2O3Content be
25%, amorphous Fe2O3.H2The content of O is 60%, and the content of binder sesbania powder is 10%；
H in above-mentioned catalyst removal exhaust gas2The process of S includes the following steps: H2S content is 5500mg/cm3Exhaust gas
With 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2The content of S≤
When 0.01ppm, the waste in the desulfurization section is collected, the catalyst as CO conversion reaction.
Embodiment 6 (coke-stove gas)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, γ-Fe in the ferric oxide desulfurizer2O3Content is 23%, and the ferroso-ferric oxide content of cubic system is 50%, is glued
Knot agent is that the content of sesbania powder is 27%；
For above-mentioned catalyst to the sweetening process of hydrogen sulfide containing coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into desulfurizer slurry, FeOOH is total dense in the desulfurizer slurry
Degree is 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, institute
The top for stating desulfurizing tower sprays above-mentioned desulfurizing agent by nozzle and carries out elution desulfurization to the coke-stove gas, useless after collecting desulfurization
The useless agent of the dry as ferric oxide desulfurizer of the application of liquid.
Embodiment 7 (application of the useless agent of desulfurizing agent)
Using the useless agent of desulfurizing agent collected by above-described embodiment 1-6 as the catalyst of CO conversion reaction, catalyst is carried out
Active testing, active testing is as follows:
Unstripped gas group becomes 15vol%CO, 55vol%H2, 6vol%CO2, 24vol%N2, reaction steam-to-gas ratio be 1:1, it is empty
Speed is 4000h-1, it is 250~450 DEG C that catalyst activity, which tests warm area,；
The activity of catalyst indicates that calculation method is as follows with CO conversion ratio:
CO conversion ratio=(1-VCO'/VCO)/(1+VCO) × 100%
Wherein, VCO'For the percentage by volume of CO in reactor outlet gas, VCOFor the percentage by volume of CO in unstripped gas；
It is corresponding that test result is as follows shown in table 1:
CO conversion ratio under table 1, different test temperatures
From table 1 it can be seen that: the application use ferric oxide desulfurizer useless agent as CO transformation catalyst, can effectively urge
Change CO to change reaction, improves the conversion ratio of CO.
It 20, is the useless agent of the desulfurizing agent of main active as the purposes of CO transformation catalyst using iron oxide.
Embodiment 1 (tail gas)
The embodiment of the invention provides one kind mainly using iron oxide as the useless agent of the desulfurizing agent of active constituent, wherein described
Mainly using iron oxide as in the desulfurizing agent of active constituent, CuO 8g, molysite complexing agent triethanolamine 9g, amorphous Fe2O315g,
MnO2For 8g；
Above-mentioned catalyst adds the sweetening process of the tail gas generated after hydrogen upgrading as follows for middle coalite tar in industry:
1) tail gas that coalite tar generates after fixed bed hydrogenation is catalyzed in collecting；
2) desulfurizing agent of the present embodiment is made to diameter is 1mm, length is 15mm cylindrical catalyst particle, and is filled in de-
In sulphur tower, desulfurization layer is formed；
3) by above-mentioned tail gas with 2000h-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer
Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as
It is main using iron oxide as the useless agent of the desulfurizing agent of active constituent in the application.
Embodiment 2 (coal pyrolysis gas)
The embodiment of the invention provides one kind mainly using iron oxide as the useless agent of the desulfurizing agent of active constituent, wherein described
Mainly using iron oxide as in the desulfurizing agent of active constituent, calcium bicarbonate 10g, basic copper carbonate 12g, γ-Fe2O318g, MnO2
For 8g, NiO 5g；
Above-mentioned catalyst is as follows to the sweetening process of hydrogen sulfide containing coal pyrolysis gas:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and it is above-mentioned to be mixed into filling for next air with air pump
Mainly using iron oxide as in the desulfurizing tower of the desulfurizing agent of active constituent, using the process of bottom in and top out, to avoid have liquid water into
Enter desulfurizing agent bed removing hydrogen sulfide；
(2) above-mentioned desulfurizing agent becomes useless agent after being used for multiple times, and takes out from desulfurizing agent bed, as main in the application
Using iron oxide as the useless agent of the desulfurizing agent of active constituent.
Embodiment 3 (petroleum)
The embodiment of the invention provides one kind mainly using iron oxide as the useless agent of the desulfurizing agent of active constituent, wherein described
Mainly using iron oxide as in the desulfurizing agent of active constituent, ferroso-ferric oxide 50g, calcium sulphate dihydrate 12g, the alkali formula carbon of cubic system
Sour zinc 20g and sodium carboxymethylcellulose are 6g；
Above-mentioned catalyst carries out sweetening process to the petroleum containing hydrogen sulfide, and operating procedure is as follows:
(1) diameter is made in the desulfurizing agent of the present embodiment and is the catalyst granules of 1.5mm, and be filled in desulfurizing tower, shape
At desulfurization layer；
(2) petroleum containing hydrogen sulfide is sprayed into desulfurization layer from the top of desulfurizing tower by nozzle, carry out elution desulfurization,
The useless agent of desulfurizing agent after collecting desulfurization is main using iron oxide as the useless agent of the desulfurizing agent of active constituent in the application.
Embodiment 4 (gas water)
The embodiment of the invention provides one kind mainly using iron oxide as the useless agent of the desulfurizing agent of active constituent, wherein described
Mainly using iron oxide as in the desulfurizing agent of active constituent, amorphous Fe2O3.H2O 30g, bodied ferric sulfate 15g, basic copper carbonate
12g and sodium carboxymethylcellulose are 6g, amorphous Fe2O38g；
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
As the application's is main using iron oxide as the useless agent of the desulfurizing agent of active constituent.
Embodiment 5 (exhaust gas)
The embodiment of the invention provides one kind mainly using iron oxide as the useless agent of the desulfurizing agent of active constituent, wherein described
Mainly using iron oxide as in the desulfurizing agent of active constituent, ferroso-ferric oxide 12g, the amorphous Fe of cubic system2O324g, nothing are fixed
Shape Fe2O3.H2O 39g and NiO are 5g；
H in above-mentioned catalyst removal exhaust gas2The process of S includes the following steps: H2S content is 5500mg/cm3Exhaust gas
With 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2The content of S≤
When 0.01ppm, the waste in the desulfurization section is collected, the catalyst as CO conversion reaction.
Embodiment 6 (coke-stove gas)
The embodiment of the invention provides one kind mainly using iron oxide as the useless agent of the desulfurizing agent of active constituent, wherein described
Mainly using iron oxide as in the desulfurizing agent of active constituent, γ-Fe2O323g, amorphous Fe2O324g, amorphous Fe2O3.H2O is
42g and MnO is 8g；
For above-mentioned catalyst to the sweetening process of hydrogen sulfide containing coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into desulfurizer slurry, FeOOH is total dense in the desulfurizer slurry
Degree is 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, institute
The top for stating desulfurizing tower sprays above-mentioned desulfurizing agent by nozzle and carries out elution desulfurization to the coke-stove gas, useless after collecting desulfurization
Dry liquid is the main using iron oxide as the useless agent of the desulfurizing agent of active constituent of the application.
Embodiment 7 (application of the useless agent of desulfurizing agent)
Using the useless agent of desulfurizing agent collected by above-described embodiment 1-6 as the catalyst of CO conversion reaction, catalyst is carried out
Active testing, active testing is as follows:
Unstripped gas group becomes 15vol%CO, 55vol%H2, 6vol%CO2, 24vol%N2, reaction steam-to-gas ratio be 1:1, it is empty
Speed is 4000h-1, it is 250~450 DEG C that catalyst activity, which tests warm area,；
The activity of catalyst indicates that calculation method is as follows with CO conversion ratio:
CO conversion ratio=(1-VCO'/VCO)/(1+VCO) × 100%
Wherein, VCO'For the percentage by volume of CO in reactor outlet gas, VCOFor the percentage by volume of CO in unstripped gas；
It is corresponding that test result is as follows shown in table 1:
CO conversion ratio under table 1, different test temperatures
From table 1 it can be seen that: the application use mainly using iron oxide as the useless agent of the desulfurizing agent of active constituent as CO convert
Catalyst can effectively be catalyzed CO and change reaction, improve the conversion ratio of CO.
21, the purposes after the useless agent regeneration of ferric oxide desulfurizer as CO transformation catalyst.
Embodiment 1 (tail gas)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, amorphous Fe in the ferric oxide desulfurizer2O3Content be 55%, carrier is that bentonitic content is 30%, bonding
The content of agent sesbania powder is 15%.
Above-mentioned catalyst adds the sweetening process of the tail gas generated after hydrogen upgrading as follows for middle coalite tar in industry:
1) tail gas that coalite tar generates after fixed bed hydrogenation is catalyzed in collecting；
2) desulfurizing agent of the present embodiment is made to diameter is 1mm, length is 15mm cylindrical catalyst particle, and is filled in de-
In sulphur tower, desulfurization layer is formed；
3) by above-mentioned tail gas with 2000h-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer
Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as
The useless agent of ferric oxide desulfurizer in the application；
The regeneration method of the useless agent of above-mentioned ferric oxide desulfurizer, includes the following steps:
1) aqueous solution of above-mentioned useless agent and sodium hydroxide is stirred in slurry tank and is configured to slurries, maintain the pH value of slurries
It is 8.0, the solid content of the slurries is 4wt%；
2) it is passed through air in Xiang Shangshu slurries, and carries out oxidation reaction under 90 DEG C, 0.1MPa, with oxidation regeneration；
3) hydrogen sulfide is passed through into the slurries after oxidation again, and carries out vulcanization reaction under 10 DEG C, 5MPa；
4) it is passed through air into the slurries after vulcanization, and carries out oxidation reaction under 90 DEG C, 0.1MPa, to aoxidize again
It is raw；
5) step 3) and 4) twice, the molar ratio of ferro element and element sulphur in the slurries after making the oxidation reaction are repeated
1:4.5；
6) slurries after the oxidation reaction are separated by solid-liquid separation, obtain the regrowth of above-mentioned useless agent.
Embodiment 2 (coal pyrolysis gas)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, γ-Fe in the ferric oxide desulfurizer2O3Content be 65%, the content of carrier natural zeolite is 30%, binder
The content of cellulose powder is 5%.
Above-mentioned catalyst is as follows to the sweetening process of hydrogen sulfide containing coal pyrolysis gas:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and it is above-mentioned to be mixed into filling for next air with air pump
Mainly using iron oxide as in the desulfurizing tower of the desulfurizing agent of active constituent, using the process of bottom in and top out, to avoid have liquid water into
Enter desulfurizing agent bed removing hydrogen sulfide；
(2) above-mentioned desulfurizing agent becomes useless agent after being used for multiple times, and takes out from desulfurizing agent bed, the as oxidation in the application
The useless agent of iron desulfurizing agent；
The regeneration method of the useless agent of above-mentioned ferric oxide desulfurizer, includes the following steps:
1) above-mentioned useless agent is dispersed in water, forms slurries；
2) above-mentioned slurries are heated to 60 DEG C under normal pressure, hydrogen peroxide, flow are then added into slurries using peristaltic pump
Control is 500mL/min, and magnetic agitation is to promote reaction to carry out, reaction time 10min；
3) after the reaction was completed, filtering reacting liquid obtained precipitating is washed with water 2 times, natural airing, obtains above-mentioned useless agent
Regrowth.
Embodiment 3 (petroleum)
The embodiment of the invention provides a kind of useless agent of ferric oxide desulfurizer, wherein with the total of the ferric oxide desulfurizer
Quality meter, the content of the ferroso-ferric oxide of cubic system is 97.3% in the ferric oxide desulfurizer, and surplus is impurity and water；
Above-mentioned catalyst carries out sweetening process to the petroleum containing hydrogen sulfide, and operating procedure is as follows:
(1) diameter is made in the desulfurizing agent of the present embodiment and is the catalyst granules of 1.5mm, and be filled in desulfurizing tower, shape
At desulfurization layer；
(2) petroleum containing hydrogen sulfide is sprayed into desulfurization layer from the top of desulfurizing tower by nozzle, carry out elution desulfurization,
The useless agent of desulfurizing agent after collecting desulfurization is the useless agent of the ferric oxide desulfurizer in the application；
The regeneration method of the useless agent of above-mentioned ferric oxide desulfurizer, includes the following steps:
1) above-mentioned useless agent and water are stirred in slurry tank and is configured to slurries, the solid content of the slurries is 12wt%；
2) it is passed through sodium hypochlorite in Xiang Shangshu slurries, and carries out oxidation reaction under 60 DEG C, 1MPa, with oxidation regeneration；
3) Na is added into the slurries after oxidation again2S, and vulcanization reaction is carried out under 10 DEG C, 5MPa；
4) it is passed through hydrogen peroxide into the slurries after vulcanization, and carries out oxidation reaction under 30 DEG C, 1.1MPa, with oxidation
Regeneration；
5) step 3) and 4) four times are repeated, the molar ratio of ferro element and element sulphur in the slurries after making the oxidation reaction
1:5；
6) slurries after the oxidation reaction are separated by solid-liquid separation, obtain the regrowth of above-mentioned useless agent.
Embodiment 4 (gas water)
The embodiment of the invention provides after a kind of useless agent of ferric oxide desulfurizer regeneration, wherein with the iron oxide desulfurization
The gross mass meter of agent, amorphous Fe in the ferric oxide desulfurizer2O3.H2The content of O is 75%, and carrier alundum contains
Amount is 10%, and the content of binder sesbania powder is 15%；
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
As after the useless agent regeneration of the ferric oxide desulfurizer of the application；
The regeneration method of the useless agent of above-mentioned ferric oxide desulfurizer, includes the following steps:
1) after above-mentioned useless agent being washed with water, the particle for being ground into 200 mesh with water in wet ball mill obtains useless agent powder；
2) the useless agent powder is made into the water slurry that solid masses percentage composition is 7%, is passed through compressed air, carried out anti-
It answers；
3) water slurry after reaction is filtered, the solid material is placed in flotation cell, water is added, then leads to
Enter air, is the regrowth of above-mentioned useless agent after the sediment drying of lower vessel portion.
Embodiment 5 (exhaust gas)
The embodiment of the invention provides after a kind of useless agent of ferric oxide desulfurizer regeneration, wherein with the iron oxide desulfurization
The gross mass meter of agent, the content of the ferroso-ferric oxide of cubic system is 5% in the ferric oxide desulfurizer, amorphous Fe2O3Contain
Amount is 25%, amorphous Fe2O3.H2The content of O is 60%, and the content of binder sesbania powder is 10%；
H in above-mentioned catalyst removal exhaust gas2The process of S includes the following steps: H2S content is 5500mg/cm3Exhaust gas
With 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2The content of S≤
When 0.01ppm, the waste in the desulfurization section is collected, the catalyst as CO conversion reaction；
The regeneration method of the useless agent of above-mentioned ferric oxide desulfurizer, includes the following steps:
1) above-mentioned useless agent is dispersed in water, forms slurries；
2) above-mentioned slurries are heated to 45 DEG C under normal pressure, hydrogen peroxide are then added into slurries using peristaltic pump, and lead to
Enter air, hydrogen peroxide flow control is 500mL/min, air flow control 100mL/min, magnetic agitation with promote to react into
Row, reaction time 5min；
3) after the reaction was completed, filtering reacting liquid obtained precipitating is washed with water 3 times, natural airing, obtains above-mentioned useless agent
Regrowth.
Embodiment 6 (coke-stove gas)
The embodiment of the invention provides after a kind of useless agent of ferric oxide desulfurizer regeneration, wherein with the iron oxide desulfurization
The gross mass meter of agent, γ-Fe in the ferric oxide desulfurizer2O3Content is 23%, and the ferroso-ferric oxide content of cubic system is
50%, binder is that the content of sesbania powder is 27%；
For above-mentioned catalyst to the sweetening process of hydrogen sulfide containing coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into desulfurizer slurry, FeOOH is total dense in the desulfurizer slurry
Degree is 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, institute
The top for stating desulfurizing tower sprays above-mentioned desulfurizing agent by nozzle and carries out elution desulfurization to the coke-stove gas, useless after collecting desulfurization
After the useless agent regeneration of the dry as ferric oxide desulfurizer of the application of liquid；
The regeneration method of the useless agent of above-mentioned ferric oxide desulfurizer, includes the following steps:
1) aqueous solution of above-mentioned useless agent and potassium hydroxide is stirred in slurry tank and is configured to slurries, maintain the pH value of slurries
It is 8.0, the solid content of the slurries is 4wt%；
2) it is passed through in Xiang Shangshu slurries containing O2With O3Mixed gas, and oxidation reaction is carried out under 50 DEG C, 1MPa, with oxidation
Regeneration；
3) hydrogen sulfide is passed through into the slurries after oxidation again, and carries out vulcanization reaction under 10 DEG C, 5MPa；
4) it is passed through air into the slurries after vulcanization, and carries out oxidation reaction under 90 DEG C, 0.1MPa, to aoxidize again
It is raw；
5) step 3) and 4) three times, the molar ratio of ferro element and element sulphur in the slurries after making the oxidation reaction are repeated
1:4.9；
6) slurries after the oxidation reaction are separated by solid-liquid separation, obtain the regrowth of above-mentioned useless agent.
Embodiment 7 (application after the useless agent regeneration of desulfurizing agent)
With the oxidation in the regrowth and embodiment 1-2 after the useless agent regeneration of desulfurizing agent collected by above-described embodiment 1-6
Catalyst of the iron desulfurizing agent as CO conversion reaction, carries out the active testing of catalyst, and active testing is as follows:
Unstripped gas group becomes 15vol%CO, 55vol%H2, 6vol%CO2, 24vol%N2, reaction steam-to-gas ratio be 1:1, it is empty
Speed is 4000h-1, it is 250~450 DEG C that catalyst activity, which tests warm area,；
The activity of catalyst indicates that calculation method is as follows with CO conversion ratio:
CO conversion ratio=(1-VCO'/VCO)/(1+VCO) × 100%
Wherein, VCO'For the percentage by volume of CO in reactor outlet gas, VCOFor the percentage by volume of CO in unstripped gas；
It is corresponding that test result is as follows shown in table 1:
CO conversion ratio under table 1, different test temperatures
From table 1 it can be seen that: the application use ferric oxide desulfurizer useless agent regeneration after be used as CO transformation catalyst, energy
Effectively catalysis CO changes reaction, improves the conversion ratio of CO.
22, the purposes after the useless agent regeneration of the desulfurizing agent containing iron oxide as CO transformation catalyst.
Embodiment 1 (tail gas)
The embodiment of the invention provides a kind of useless agent of desulfurizing agent containing iron oxide, wherein described containing iron oxide
In desulfurizing agent, CuO 8g, molysite complexing agent triethanolamine 9g, amorphous Fe2O315g, MnO2For 8g；
Above-mentioned catalyst adds the sweetening process of the tail gas generated after hydrogen upgrading as follows for middle coalite tar in industry:
1) tail gas that coalite tar generates after fixed bed hydrogenation is catalyzed in collecting；
2) desulfurizing agent of the present embodiment is made to diameter is 1mm, length is 15mm cylindrical catalyst particle, and is filled in de-
In sulphur tower, desulfurization layer is formed；
3) by above-mentioned tail gas with 2000h-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer
Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as
The useless agent of the desulfurizing agent containing iron oxide in the application；
The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:
1) aqueous solution of above-mentioned useless agent and sodium hydroxide is stirred in slurry tank and is configured to slurries, maintain the pH value of slurries
It is 8.0, the solid content of the slurries is 4wt%；
2) it is passed through air in Xiang Shangshu slurries, and carries out oxidation reaction under 90 DEG C, 0.1MPa, with oxidation regeneration；
3) hydrogen sulfide is passed through into the slurries after oxidation again, and carries out vulcanization reaction under 10 DEG C, 5MPa；
4) it is passed through air into the slurries after vulcanization, and carries out oxidation reaction under 90 DEG C, 0.1MPa, to aoxidize again
It is raw；
5) step 3) and 4) twice, the molar ratio of ferro element and element sulphur in the slurries after making the oxidation reaction are repeated
1:4.5；
6) slurries after the oxidation reaction are separated by solid-liquid separation, obtain the regrowth of above-mentioned useless agent.
Embodiment 2 (coal pyrolysis gas)
The embodiment of the invention provides a kind of useless agent of desulfurizing agent containing iron oxide, wherein described containing iron oxide
In desulfurizing agent, calcium bicarbonate 10g, basic copper carbonate 12g, γ-Fe2O318g, MnO2For 8g, NiO 5g；
Above-mentioned catalyst is as follows to the sweetening process of hydrogen sulfide containing coal pyrolysis gas:
(1) compressed coal pyrolysis gas is cooled to 30~35 DEG C, and it is above-mentioned to be mixed into filling for next air with air pump
In the desulfurizing tower of desulfurizing agent containing iron oxide, using the process of bottom in and top out, to avoid there is liquid water to enter desulfurizing agent bed
Remove hydrogen sulfide；
(2) above-mentioned desulfurizing agent becomes useless agent after being used for multiple times, and takes out from desulfurizing agent bed, as containing in the application
The useless agent of the desulfurizing agent of iron oxide.
The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:
1) above-mentioned useless agent is dispersed in water, forms slurries；
2) above-mentioned slurries are heated to 60 DEG C under normal pressure, hydrogen peroxide, flow are then added into slurries using peristaltic pump
Control is 500mL/min, and magnetic agitation is to promote reaction to carry out, reaction time 10min；
3) after the reaction was completed, filtering reacting liquid obtained precipitating is washed with water 2 times, natural airing, obtains above-mentioned useless agent
Regrowth.
Embodiment 3 (petroleum)
The embodiment of the invention provides a kind of useless agent of desulfurizing agent containing iron oxide, wherein described containing iron oxide
In desulfurizing agent, ferroso-ferric oxide 50g, calcium sulphate dihydrate 12g, basic zinc carbonate 20g and the sodium carboxymethylcellulose of cubic system
For 6g；
Above-mentioned catalyst carries out sweetening process to the petroleum containing hydrogen sulfide, and operating procedure is as follows:
(1) diameter is made in the desulfurizing agent of the present embodiment and is the catalyst granules of 1.5mm, and be filled in desulfurizing tower, shape
At desulfurization layer；
(2) petroleum containing hydrogen sulfide is sprayed into desulfurization layer from the top of desulfurizing tower by nozzle, carry out elution desulfurization,
The useless agent of desulfurizing agent after collecting desulfurization is the useless agent of the desulfurizing agent containing iron oxide in the application；
The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:
1) above-mentioned useless agent and water are stirred in slurry tank and is configured to slurries, the solid content of the slurries is 12wt%；
2) it is passed through sodium hypochlorite in Xiang Shangshu slurries, and carries out oxidation reaction under 60 DEG C, 1MPa, with oxidation regeneration；
3) Na is added into the slurries after oxidation again2S, and vulcanization reaction is carried out under 10 DEG C, 5MPa；
4) it is passed through hydrogen peroxide into the slurries after vulcanization, and carries out oxidation reaction under 30 DEG C, 1.1MPa, with oxidation
Regeneration；
5) step 3) and 4) four times are repeated, the molar ratio of ferro element and element sulphur in the slurries after making the oxidation reaction
1:5；
6) slurries after the oxidation reaction are separated by solid-liquid separation, obtain the regrowth of above-mentioned useless agent.
Embodiment 4 (gas water)
The embodiment of the invention provides a kind of useless agent of desulfurizing agent containing iron oxide, wherein described containing iron oxide
In desulfurizing agent, amorphous Fe2O3.H2O 30g, bodied ferric sulfate 15g, basic copper carbonate 12g and sodium carboxymethylcellulose be 6g,
Amorphous Fe2O38g；
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
The as useless agent of the desulfurizing agent containing iron oxide of the application；
The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:
1) after above-mentioned useless agent being washed with water, the particle for being ground into 200 mesh with water in wet ball mill obtains useless agent powder；
2) the useless agent powder is made into the water slurry that solid masses percentage composition is 7%, is passed through compressed air, carried out anti-
It answers；
3) water slurry after reaction is filtered, the solid material is placed in flotation cell, water is added, then leads to
Enter air, is the regrowth of above-mentioned useless agent after the sediment drying of lower vessel portion.
Embodiment 5 (exhaust gas)
The embodiment of the invention provides a kind of useless agent of desulfurizing agent containing iron oxide, wherein described containing iron oxide
In desulfurizing agent, ferroso-ferric oxide 12g, the amorphous Fe of cubic system2O324g, amorphous Fe2O3.H2O 39g and NiO are 5g；
H in above-mentioned catalyst removal exhaust gas2The process of S includes the following steps: H2S content is 5500mg/cm3Exhaust gas
With 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2The content of S≤
When 0.01ppm, the waste in the desulfurization section is collected, the catalyst as CO conversion reaction；
The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:
1) above-mentioned useless agent is dispersed in water, forms slurries；
2) above-mentioned slurries are heated to 45 DEG C under normal pressure, hydrogen peroxide are then added into slurries using peristaltic pump, and lead to
Enter air, hydrogen peroxide flow control is 500mL/min, air flow control 100mL/min, magnetic agitation with promote to react into
Row, reaction time 5min；
3) after the reaction was completed, filtering reacting liquid obtained precipitating is washed with water 3 times, natural airing, obtains above-mentioned useless agent
Regrowth.
Embodiment 6 (coke-stove gas)
The embodiment of the invention provides a kind of useless agent of desulfurizing agent containing iron oxide, wherein described containing iron oxide
In desulfurizing agent, γ-Fe2O323g, amorphous Fe2O324g, amorphous Fe2O3.H2O is 42g and MnO is 8g；
For above-mentioned catalyst to the sweetening process of hydrogen sulfide containing coke-stove gas, operating procedure is as follows:
Above-mentioned desulfurizing agent and water are hybridly prepared into desulfurizer slurry, FeOOH is total dense in the desulfurizer slurry
Degree is 10wt%, the coke-stove gas after deamination is passed through desulfurizing tower from bottom, the temperature of the desulfurizing tower tower reactor is 30 DEG C, institute
The top for stating desulfurizing tower sprays above-mentioned desulfurizing agent by nozzle and carries out elution desulfurization to the coke-stove gas, useless after collecting desulfurization
The useless agent of the dry as desulfurizing agent containing iron oxide of the application of liquid；
The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:
1) aqueous solution of above-mentioned useless agent and potassium hydroxide is stirred in slurry tank and is configured to slurries, maintain the pH value of slurries
It is 8.0, the solid content of the slurries is 4wt%；
2) it is passed through in Xiang Shangshu slurries containing O2With O3Mixed gas, and oxidation reaction is carried out under 50 DEG C, 1MPa, with oxidation
Regeneration；
3) hydrogen sulfide is passed through into the slurries after oxidation again, and carries out vulcanization reaction under 10 DEG C, 5MPa；
4) it is passed through air into the slurries after vulcanization, and carries out oxidation reaction under 90 DEG C, 0.1MPa, to aoxidize again
It is raw；
5) step 3) and 4) three times, the molar ratio of ferro element and element sulphur in the slurries after making the oxidation reaction are repeated
1:4.9；
6) slurries after the oxidation reaction are separated by solid-liquid separation, obtain the regrowth of above-mentioned useless agent.
Comparative example 1
This comparative example provides a kind of desulfurizing agent containing iron oxide, contains iron oxide in the desulfurizing agent and embodiment 1
Desulfurizing agent be same desulfurizing agent, wherein in the desulfurizing agent containing iron oxide, CuO 8g, molysite complexing agent triethanolamine
9g, amorphous Fe2O315g, MnO2For 8g.
Comparative example 2
This comparative example provides a kind of desulfurizing agent containing iron oxide, is somebody's turn to do in the desulfurizing agent containing iron oxide and embodiment 5
The desulfurizing agent containing iron oxide be same desulfurizing agent, wherein in the desulfurizing agent containing iron oxide, four oxygen of cubic system
Change three-iron 12g, amorphous Fe2O324g, amorphous Fe2O3.H2O 39g and NiO are 5g.
Embodiment 7 (application of the useless agent of desulfurizing agent)
With the regrowth of the useless agent of desulfurizing agent collected by above-described embodiment 1-6 and comparative example 1-2 containing iron oxide
Catalyst of the desulfurizing agent as CO conversion reaction, carries out the active testing of catalyst, and active testing is as follows:
Unstripped gas group becomes 15vol%CO, 55vol%H2, 6vol%CO2, 24vol%N2, reaction steam-to-gas ratio be 1:1, it is empty
Speed is 4000h-1, it is 250~450 DEG C that catalyst activity, which tests warm area,；
The activity of catalyst indicates that calculation method is as follows with CO conversion ratio:
CO conversion ratio=(1-VCO'/VCO)/(1+VCO) × 100%
Wherein, VCO'For the percentage by volume of CO in reactor outlet gas, VCOFor the percentage by volume of CO in unstripped gas；
It is corresponding that test result is as follows shown in table 1:
CO conversion ratio under table 1, different test temperatures
From table 1 it can be seen that: the application using the desulfurizing agent containing iron oxide useless agent regeneration after be used as CO transformation catalyst,
It can effectively be catalyzed CO and change reaction, improve the conversion ratio of CO.
23, the purposes of the useless agent of the desulfurizing agent containing iron oxide or useless agent regenerative agent in organic matter transformation technique.
Embodiment 1
A kind of biomass and hogwash fat cotransformation technique are present embodiments provided, is included the following steps:
The pretreatment of biomass:
Rice straw and reed straw are as biomass solid, with total restatement of the biomass, the moisture content of the biomass
It is 4%, the rice straw and reed straw is sent into micronizer and just crush, first smashed median is 100 μ
First smashed rice straw and reed straw are then sent into cuber and are carried out under 30 DEG C of temperature, the pressure of 3MPa by m
Compression, extrusion forming to its heap density are 0.8g/cm3, separating twice is carried out later, and the average particle size after separating twice is
3mm, it is spare；
Catalyst:
Catalyst is the regenerative agent of the useless agent of the desulfurizing agent containing iron oxide, wherein the desulfurizing agent containing iron oxide
In, CuO 8g, molysite complexing agent triethanolamine 9g, amorphous Fe2O315g, MnO2For 8g；
Above-mentioned catalyst adds the sweetening process of the tail gas generated after hydrogen upgrading as follows for middle coalite tar in industry:
1) tail gas that coalite tar generates after fixed bed hydrogenation is catalyzed in collecting；
2) desulfurizing agent of the present embodiment is made to diameter is 1mm, length is 15mm cylindrical catalyst particle, and is filled in de-
In sulphur tower, desulfurization layer is formed；
3) by above-mentioned tail gas with 2000h-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer
Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as
The useless agent of the desulfurizing agent containing iron oxide in the application；
The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:
1) weak acid water (contain dilute sulfuric acid) that above-mentioned useless agent is 4.0 with pH is dispersed, ferric oxide desulfurizer give up agent with it is weak
The solid-to-liquid ratio of sour water is 1: 4 (g/ml), and jitter time 30min obtains dispersion liquid；
2) above-mentioned dispersion liquid is heated to 60 DEG C under normal pressure, hydrogen peroxide is then added into dispersion liquid using peristaltic pump,
Flow control is 500mL/min, and hydrogen peroxide and the ferric oxide desulfurizer molar ratio of element sulphur in agent of giving up are 5: 1, magnetic agitation with
Reaction is promoted to carry out, reaction is simultaneously by vacuumizing the sulfur dioxide gas that transfer generates rapidly, reaction time 10min；
3) obtained precipitating is washed with water 2 times, then dries, obtain at 100 DEG C by after the reaction was completed, filtering reacting liquid
To the regrowth of above-mentioned useless agent, the filtrate being obtained by filtration then returns in dispersion step and is recycled as weak acid water；
The preparation of biomass slurry:
Biomass, sulphur and above-mentioned catalyst that pretreatment obtains are mixed to get mixture, said mixture is added
Slurrying is stirred and ground in hogwash fat, forms slurries, through detecting, the total content of rice straw and reed straw is in the slurries
The molar ratio of 60wt%, ferro element and element sulphur is 1:5, and the viscosity of the slurries is 500mPa ﹒ s (50 DEG C), in above-mentioned slurries,
The content of catalyst is 5wt%, and the average grain diameter of the catalyst added is 5 μm；
Conversion reaction:
By CO and H2Gaseous mixture (CO accounting 60% and H2Accounting is that 40%) middle part is forced into 21MPa, is heated up to 350
It after DEG C, is passed through in the pipeline for conveying the slurries, after rest part is forced into 21MPa, is heated up to 500 DEG C, by slurry reactor
In device entrance injection paste state bed reactor, and cracking, carbonylation occurs, convert and adds hydrogen anti-with the slurries therein are entered
It answers, the reaction pressure for controlling conversion reaction is 20MPa, reaction temperature is 360 DEG C, reaction time 65min, the CO and H2's
The volume ratio of gaseous mixture and the slurries is 3000:1, and oil product is made.
Embodiment 2
A kind of biomass and palm oil cotransformation technique are present embodiments provided, is included the following steps:
The pretreatment of biomass:
Wheat stalk and corn stover are as biomass solid, with total restatement of the biomass, the moisture content of the biomass
It is 10%, the wheat stalk and corn stover is sent into micronizer and just crush, first smashed median is 300
μm, then first smashed wheat stalk and corn stover are sent into cuber under 60 DEG C of temperature, the pressure of 0.5MPa
Carrying out compression extrusion forming to its heap density is 0.9g/cm3, separating twice, the average particle size after separating twice are carried out later
It is spare for 5mm；
Catalyst:
Catalyst is using iron oxide as the useless agent of the desulfurizing agent of active component, wherein described using iron oxide as active component
Desulfurizing agent in, calcium bicarbonate 10g, basic copper carbonate 12g, γ-Fe2O318g, MnO2For 8g, NiO 5g；
It is above-mentioned using iron oxide as the sweetening process of the desulfurizing agent of active component, be summarized as follows:
1) tail gas that coalite tar generates after fixed bed hydrogenation is catalyzed in collecting；
2) desulfurizing agent of the present embodiment is made to diameter is 1mm, length is 15mm cylindrical catalyst particle, and is filled in de-
In sulphur tower, desulfurization layer is formed；
3) by above-mentioned tail gas with 2000h-1Air speed by desulfurization layer, and occur at 50 DEG C with the desulfurizing agent in desulfurization layer
Desulphurization reaction removes hydrogen sulfide in tail gas, and to the end of reacting, the useless agent of the desulfurizing agent after taking out reaction is cooled to room temperature, as
In the application using iron oxide as the useless agent of the desulfurizing agent of active component；
The preparation of biomass slurry:
Biomass, sulphur and above-mentioned catalyst that pretreatment obtains are mixed to get mixture, said mixture is added
It is dispersed with stirring slurrying in palm oil, forms slurries, through detecting, wheat stalk and the total content of corn stover are in the slurries
The molar ratio of 50wt%, ferro element and element sulphur is 1:1, and the viscosity of the slurries is 1400mPa ﹒ s (50 DEG C), in above-mentioned slurries
In, the content of catalyst is 1wt%, and the average grain diameter of the catalyst added is 10 μm；
Conversion reaction:
By CO and H2Gaseous mixture (CO accounting 60% and H2Accounting is that 40%) middle part is forced into 16MPa, is heated up to 400
It after DEG C, is passed through in the pipeline for conveying the slurries, after rest part is forced into 16MPa, is heated up to 520 DEG C, is reacted by suspension bed
Entrance injects in suspended-bed reactor, and cracking, carbonylation, transformation and hydrogenation reaction occurs with the slurries therein are entered,
The reaction pressure for controlling conversion reaction is 15MPa, reaction temperature is 420 DEG C, reaction time 30min, the CO and H2It is mixed
The volume ratio for closing gas and the slurries is 2000:1, and oil product is made.
Embodiment 3
A kind of biomass and rapeseed oil cotransformation technique are present embodiments provided, is included the following steps:
The pretreatment of biomass:
Sawdust and soybean stalk are as biomass solid, and with total restatement of the biomass, the moisture content of the biomass is
2%, the sawdust and soybean stalk are sent into micronizer and just crush, first smashed median is 150 μm, then
First smashed sawdust and soybean stalk are sent into cuber to carry out compressing under 50 DEG C of temperature, the pressure of 1MPa and are squeezed into
Type to its heap density is 1g/cm3, separating twice is carried out later, and the average particle size after separating twice is 4mm, spare；
Catalyst:
Catalyst is using iron oxide as the regrowth of the useless agent of the desulfurizing agent of active component, wherein described to be with iron oxide
In the desulfurizing agent of active component, ferroso-ferric oxide 50g, calcium sulphate dihydrate 12g, basic zinc carbonate 20g and the carboxylic first of cubic system
Base sodium cellulosate is 6g；
Above-mentioned catalyst carries out sweetening process to the petroleum containing hydrogen sulfide, and operating procedure is as follows:
(1) diameter is made in the desulfurizing agent of the present embodiment and is the catalyst granules of 1.5mm, and be filled in desulfurizing tower, shape
At desulfurization layer；
(2) petroleum containing hydrogen sulfide is sprayed into desulfurization layer from the top of desulfurizing tower by nozzle, carry out elution desulfurization,
The useless agent of desulfurizing agent after collecting desulfurization is the useless agent of the desulfurizing agent containing iron oxide in the application；
The regeneration method of the useless agent of the above-mentioned desulfurizing agent containing iron oxide, includes the following steps:
1) above-mentioned useless agent and water are stirred in slurry tank and is configured to slurries, the solid content of the slurries is 12wt%；
2) it is passed through sodium hypochlorite in Xiang Shangshu slurries, and carries out oxidation reaction under 60 DEG C, 1MPa, with oxidation regeneration；
3) Na is added into the slurries after oxidation again2S, and vulcanization reaction is carried out under 10 DEG C, 5MPa；
4) it is passed through hydrogen peroxide into the slurries after vulcanization, and carries out oxidation reaction under 30 DEG C, 1.1MPa, with oxidation
Regeneration；
5) step 3) and 4) once, the molar ratio of ferro element and element sulphur in the slurries after making the oxidation reaction are repeated
1:1.8；
6) slurries after the oxidation reaction are separated by solid-liquid separation, obtain the regrowth of above-mentioned useless agent；
The preparation of biomass slurry:
Biomass, sulphur and above-mentioned catalyst that pretreatment obtains are mixed to get mixture, said mixture is added
Slurrying is sheared in rapeseed oil and forms slurries, and through detecting, the total content of sawdust and soybean stalk is 40wt%, ferro element in the slurries
It is 1:2 with the molar ratio of element sulphur, the viscosity of the slurries is 1000mPa ﹒ s (50 DEG C), using iron oxide as active component in slurries
Desulfurizing agent useless agent regrowth content be 2wt%, added using iron oxide as the useless agent of the desulfurizing agent of active component
The average grain diameter of regrowth is 400 μm；
Conversion reaction:
After being forced into 18.2MPa by synthesis gas (wherein the volume accounting of CO is 20%), be heated up to 450 DEG C, by bubbling bed
In 4 inlets injection bubbling bed reactor in sidewall of reactor and bottom, and split with into the slurries therein
Solution, carbonylation, transformation and hydrogenation reaction, the reaction pressure for controlling conversion reaction is 18MPa, reaction temperature is 380 DEG C, when reaction
Between be 100min, the volume ratio of the synthesis gas and the slurries is 950:1, and oil product is made.
Embodiment 4
A kind of biomass liquefying process is present embodiments provided, is included the following steps:
The pretreatment of biomass:
Rice straw and broad bean stalk are as biomass solid, with total restatement of the biomass, the moisture content of the biomass
It is 10%, the rice straw and broad bean stalk is sent into micronizer and just crush, first smashed median particle size is 100
μm, then first smashed rice straw and broad bean stalk are sent into cuber under 30 DEG C of temperature, the pressure of 0.5MPa
It is compressed, extrusion forming to its heap density is 1.0g/cm3, separating twice, the average particle size after separating twice are carried out later
It is spare for 1mm；
Catalyst:
Catalyst is using iron oxide as the regrowth of the useless agent of the desulfurizing agent of active component, wherein described to be with iron oxide
In the desulfurizing agent of active component, ferroso-ferric oxide 12g, the amorphous Fe of cubic system2O324g, amorphous Fe2O3.H2O 39g
It is 5g with NiO；
H in above-mentioned desulfurizing agent removing exhaust gas2The matrix process of S, includes the following steps: H2S content is 5500mg/cm3's
Exhaust gas is with 3000h-1Air speed be passed through desulfurization section, desulphurization reaction is carried out at 30 DEG C, the H in the desulfurization section is worked off one's feeling vent one's spleen2S's
When content≤0.01ppm, the waste in the desulfurization section is collected；
It is above-mentioned using iron oxide as the regeneration method of the useless agent of the desulfurizing agent of active component, include the following steps:
The regeneration method of above-mentioned useless agent, includes the following steps:
1) after above-mentioned useless agent being washed with water, the particle for being ground into 200 mesh with water in wet ball mill obtains useless agent powder；
2) the useless agent powder is made into the water slurry that solid masses percentage composition is 7%, is passed through compressed air, carried out anti-
It answers；
3) water slurry after reaction is filtered, the solid material is placed in flotation cell, water is added, then leads to
Enter air, is the regrowth of above-mentioned useless agent after the sediment drying of lower vessel portion；
The preparation of biomass slurry:
Biomass, carbon disulfide and above-mentioned catalyst that pretreatment obtains are mixed to get mixture, which added
Enter and disperse slurrying in coal tar, forms slurries, through detecting, rice straw and the total content of broad bean stalk are in the slurries
The molar ratio of 55wt%, ferro element and element sulphur is 1:0.9, and the viscosity of the slurries is 510mPa ﹒ s (50 DEG C), is urged in the slurries
The content of agent is 0.2wt%, and the average grain diameter of the catalyst added is 2 μm；
Conversion reaction:
By CO and H2Gaseous mixture (CO accounting 60% and H2Accounting be 40%) pressurize 20.4MPa, be heated up to 500 DEG C after, by
In 3 inlets injection paste state bed reactor on paste state bed reactor side wall, and split with into the slurries therein
Solution, carbonylation, transformation and hydrogenation reaction, control reaction pressure is 20MPa, reaction temperature is 410 DEG C, and the reaction time is
110min, the CO and H2Gaseous mixture and the slurries volume ratio be 650:1, be made oil product.
Embodiment 5
The cotransformation technique for present embodiments providing a kind of biomass and petroleum base wax oil, includes the following steps:
The pretreatment of biomass:
Cotton stalk is as biomass solid, and with total restatement of the biomass, the moisture content of the biomass is 1%, by this
Cotton stalk is sent into micronizer and just crush, and first smashed median is 200 μm, then will first smashed cotton
It is 0.9g/ that chopped straw stalk, which is sent into plodder and carries out compression extrusion forming to its heap density under 40 DEG C of temperature, the pressure of 2MPa,
cm3, separating twice is carried out later, and the average particle size after separating twice is 1mm, spare；
Catalyst:
Catalyst is the useless agent of the desulfurizing agent containing iron oxide, amorphous in the desulfurizing agent containing iron oxide
Fe2O3.H2O 30g, bodied ferric sulfate 15g, basic copper carbonate 12g and sodium carboxymethylcellulose are 6g, amorphous Fe2O38g；
For above-mentioned catalyst to the sweetening process of gas water, operating procedure is as follows:
By above-mentioned Catalyst packing in fixed bed reactors, make containing H2The gas water of S come into full contact with it anti-
It answers, contact conditions are as follows: temperature is 35 DEG C, pressure 0.2MPa and volume space velocity 10000h-1, catalyst after gas water desulfurization gives up agent
The as useless agent of the desulfurizing agent containing iron oxide of the application.
The preparation of biomass slurry:
The biomass that pretreatment obtains is mixed to get mixture with above-mentioned catalyst, said mixture is added to petroleum
Disperse slurrying in base wax oil, form slurries, through detecting, the total content of cotton stalk is 50wt% in the slurries, which glues
Degree is 400mPa ﹒ s (50 DEG C), and in above-mentioned slurries, the content of catalyst is 1wt%, the average grain diameter of the catalyst added
It is 10 μm；
Conversion reaction:
By CO and H2Gaseous mixture (CO accounting 60% and H2Accounting is that 40%) middle part is forced into 17MPa, is heated up to 250
It after DEG C, is passed through in the pipeline for conveying the slurries, after rest part is forced into 17MPa, is heated up to 550 DEG C, by ebullating bed reactor
Device entrance injects in fluidized bed reactor, and hydrogen sulfide ferro element and sulphur member into reaction system are passed through into fluidized bed reactor
The molar ratio of element is 1:2, and cracking, carbonylation, transformation and hydrogenation reaction, control conversion occurs with the slurries therein are entered
The reaction pressure of reaction is 16MPa, reaction temperature is 420 DEG C, reaction time 40min, the CO and H2Gaseous mixture and institute
The volume ratio for stating slurries is 1000:1, and oil product is made.
Embodiment 6
A kind of biomass and rapeseed oil cotransformation technique are present embodiments provided, it is same as Example 3, unique difference
Place, the regeneration method of the useless agent of the desulfurizing agent containing iron oxide in the present embodiment include the following steps: 1) to be 1.5MPa by pressure
Water vapour be passed through heating furnace, by steam heating to 450 DEG C；
2) water vapour after heating is passed into the desulfurizer for filling above-mentioned useless agent with the speed of 15m/s, is heated above-mentioned useless
Agent；
3) guarantee the bed temperature of above-mentioned useless agent by steam heating to running 2h, steam use under conditions of 400 DEG C or more
Amount is 6t/h；
4) analysis desulfurizer export pH, continuous 3 times be more than or equal to 7.5 when, a small amount of oven gas can be passed through into desulfurizer
It is restored；
5) being passed through level-one in fine de-sulfur process adds the oven gas after hydrogen to go back with 800m3/h to ferric oxide desulfurizer agent of giving up
It is former；
6) be passed through every primary inlet and outlet H2 concentration variation of 30min analysis after oven gas, when outlet H2 concentration stablize be greater than or
Regenerative agent can be obtained equal to (3 analyses) after entrance H2 concentration.
Comparative example 1
This comparative example provides a kind of biomass and rapeseed oil cotransformation technique, and conversion process is same as Example 3, no
Be with place: sawdust and soybean stalk are as biomass solid in this comparative example, with total restatement of the biomass, the biomass
Moisture content be 80ppm；The molar ratio of ferro element and element sulphur is 1:0.1 in reaction system.
Test example 1
The distribution for the product that method using the embodiment of the present invention 1-6 is prepared with comparative example 1 is compared, product
Test method is as follows:
(there is solid remaining in gross mass-reaction product of SOLID ORGANIC matter transforming solid organic matter rate %=in raw material
Machine matter quality) gross mass of SOLID ORGANIC matter in/raw material, " SOLID ORGANIC matter " in the transforming solid organic matter rate refers both to nothing
Water, ash free basis (the same below)；
It under normal temperature and pressure is liquid phase oil product that transforming solid organic matter oil yield %=transforming solid organic matter, which is in product,
SOLID ORGANIC matter combined feed quality in quality/raw material；
Reaction generates water rate %=(total matter of the water quality of the reaction product-water that reaction starting is added or raw material is brought into
Amount)/raw material combined feed quality.As this value < 0, it is denoted as "None"；
Corresponding test result is as shown in table 1:
1 transforming solid organic matter Contrast on effect of table
From table 1 it can be seen that: the reaction of conversion process of the present invention generates water rate and is not more than 1.6wt%；And in the prior art often
Rule in the hydrogenation technique under pure hydrogen, reaction generate water rate 25wt% or more.
It 24, is the useless agent of the hydrogenation catalyst of main active as the purposes of CO transformation catalyst using Ni-Mo.
Embodiment 1
Present embodiments provide a kind of using Ni-Mo as the useless agent of the hydrogenation catalyst of main active, wherein it is described with
Ni-Mo is in the hydrogenation catalyst of main active, with the total restatement of hydrogenation catalyst, MoO330%, NiO 7%, TiO2
3%, P2O52.5%, surplus is γ-Al2O3；
Above-mentioned hydrogenation catalyst adds hydrogen for cracked diesel oil, wherein density (the d of cracked diesel oil4 20) it is 0.893g/cm3,
Sulfur content are as follows: 6154 μ g/g, nitrogen content are as follows: 1035 μ g/g, aniline point are 49.0 DEG C, Cetane number 35.8, boiling range 171-
362℃；
Corresponding hydrogenation process is as follows: 100g catalyst being fitted into fixed bed, hydrogen is passed through, adjustment system pressure is
Reactor is warming up to 120 DEG C with the heating rate of 35 DEG C/h, makes to urge within constant temperature 2 hours by 6.0MPa, amounts of hydrogen 800ml/min
Agent dehydration.Start to be pumped into presulfurization oil after dehydration: presulfurization oil is the aviation kerosine for being added to 3% carbon disulfide, into
Material speed is 100ml/h.Then the temperature of reactor is risen to by 200 DEG C, 240 DEG C, 280 DEG C, 320 with the heating rate of 40 DEG C/h
DEG C, and at each temperature spot constant temperature 1 hour；340 DEG C are finally warming up to, is kept for 12 hours, starts to be pumped into after completing presulfurization
Cracked diesel oil feedstock oil is stated, and in 350 DEG C of temperature, pressure 6.0MPa, liquid air speed 1.0h-1, hydrogen to oil volume ratio is under 480V/V
Carry out plus hydrogen, after adding hydrogen, collect useless agent, as in the present embodiment using Ni-Mo as the hydrogenation catalyst of main active
The useless agent of agent.
Embodiment 2
Present embodiments provide a kind of using Ni-Mo as the useless agent of the hydrogenation catalyst of main active, wherein it is described with
Ni-Mo is in the hydrogenation catalyst of main active, with the total restatement of hydrogenation catalyst, MoO330%, NiO 10%, carboxylic first
Base cellulose 8%, chromium 1.5%, tungsten oxide 5%, surplus are silica/alumina complex carrier；
Above-mentioned hydrogenation catalyst adds hydrogen for Petropols, and corresponding hydrogenation process is as follows: using loaded catalyst
It for the fixed bed reactors of 50-100ml, will be first crushed by the hydrogenation catalyst of main active of Ni-Mo, take the granularity to be
The catalyst 50ml of 1mm or so is fitted into reactor, and by pumping the Petropols solution that will be dissolved with solvent, (Petropols contain
40%) amount is delivered to reactor from top together with hydrogen (hydrogen purity is greater than 90%) and carries out adding hydrogen by catalyst bed
Reaction.The Hydrogen Vapor Pressure of catalysis reaction is 10.0Mpa, and reaction temperature is 260 DEG C, and the mass space velocity of Petropols is 0.3g/h-1,
The volume ratio (hydrogen-oil ratio) of hydrogen and resin is 1000, after adding hydrogen, collects useless agent, as in the present embodiment with Ni-Mo
For the useless agent of the hydrogenation catalyst of main active.
Embodiment 3
Present embodiments provide a kind of using Ni-Mo as the useless agent of the hydrogenation catalyst of main active, wherein it is described with
Ni-Mo is in the hydrogenation catalyst of main active, with the total restatement of hydrogenation catalyst, MoO310%, NiO 40%, chromium
1.5%, amorphous silicon aluminium 6%, zeolite 2%, chrome green 5%, zirconium 1.3%, surplus are titanium dioxide；
Above-mentioned hydrogenation catalyst is used for poor oil-residual hydrogenation, and corresponding hydrogenation process is as follows:
1) firstly, being obtained to being the hydrogenation catalyst of main active in 250 DEG C of fluidization processing 30min using Ni-Mo
Fluidize state hydrogenation catalyst；
2) again by 60g poor oil-residual oil (as feedstock oil), the above-mentioned fluidisation state hydrogenation catalyst of 1.85g and 0.586g liter
Magnificent sulphur stirs evenly in high-speed homogenization machine, obtains mixture；
3) it then, takes 44g said mixture to be added in autoclave, is first passed through hydrogen into autoclave, makes
Pressure reaches 24MPa and hunts leak in kettle, while air in kettle is discharged；Being re-filled with hydrogen makes to reach initial hydrogen pressure in kettle
12.5MPa is warming up to 450 DEG C of reaction temperature, at stirring rate 500r/min, after being stirred to react 90min, stops heating and stirs
It mixes, uses water-cooling pattern that temperature in the kettle is rapidly decreased to room temperature to terminate reaction, after adding hydrogen, collect useless agent, as this reality
Apply in example using Ni-Mo as the useless agent of the hydrogenation catalyst of main active.
Embodiment 4
Present embodiments provide a kind of using Ni-Mo as the useless agent of the hydrogenation catalyst of main active, wherein it is described with
Ni-Mo is in the hydrogenation catalyst of main active, with the total restatement of hydrogenation catalyst, MoO350%, NiO 10%, tungsten
3%, molecular sieve 12%, boron 2%, tungsten oxide 2%, chrome green 5%, zirconium 1.3%, surplus are active carbon；
Above-mentioned hydrogenation catalyst adds hydrogen for coalite tar, and corresponding hydrogenation process is as follows:
(1) true boiling point distillation instrument is used, 1kg coal tar is subjected to fractionation cutting, obtains the first component and heavy constituent,
In, the cutting temperature for being fractionated cutting is 300 DEG C；Using on the basis of the total amount as the coal tar of raw material, the content of heavy constituent is 60
Weight %；
(2) heavy constituent that step (1) obtains is mixed with pentane by the weight ratio of 1:6 and carries out extraction and separation, extracted
Take phase and raffinate phase.Wherein, it is 50 DEG C that the condition of extraction, which includes: temperature, and pressure is atmospheric pressure.Obtained extraction phase is carried out
Normal pressure fractionation, isolates pentane, obtains deasphalted oil；
(3) by as hydrogenating materials obtain first group of the deasphalted oil and step (1) that the step of (2) obtains is distributed into
In the fixed bed reactors (filling is using Ni-Mo as the hydrogenation catalyst of main active in fixed bed reactors) of 200mL, into
Row hydrogenation process；Wherein, the loadings of hydrocracking catalyst are 100mL.Hydrogen partial pressure in fixed bed reactors is 14.7MPa
(in terms of absolute pressure), hydrogen to oil volume ratio 1500；Mean temperature in Hydrobon catalyst bed is 390 DEG C, is hydrocracked and urges
Mean temperature in agent bed is 400 DEG C；Weight (hourly) space velocity (WHSV) of the hydrogenating materials in fixed bed reactors is 0.15h-1.Add
After hydrogen, collect useless agent, as in the present embodiment using Ni-Mo as the useless agent of the hydrogenation catalyst of main active.
Embodiment 5
Present embodiments provide a kind of using Ni-Mo as the useless agent of the hydrogenation catalyst of main active, wherein it is described with
Ni-Mo is in the hydrogenation catalyst of main active, with the total restatement of hydrogenation catalyst, MoO310%, NiO 35%, palladium
3%, tungsten 5%, manganese 5%, cobalt oxide 2%, tungsten oxide 2%, chrome green 5%, zirconium 1.3%, surplus are active carbon；
Above-mentioned hydrogenation catalyst adds hydrogen for reduced crude, and corresponding hydrogenation process is as follows: flowing in single hose fixed bed
In formula residual hydrogenation reactor, top is packed intoBall-type using Ni-Mo as the hydrogenation catalyst of main active
300ml；Bottom is packed intoCeramic ring filler 50ml；Resid feed distributed area is set between catalyst bed and packing layer
Domain, 150 DEG C of feed residue and hydrogen enter reactor here, and raw material selects the normal pressure slag of Saudi Arabia's middle matter crude oil
Oil；Residue settling zone is provided under packing layer, reactor provides reaction temperature using two-part electric heating constant temperature salt bath.Continuous
In operation process, operating condition are as follows: in hydrogenation zone, 388 DEG C of mean temperature, pressure 14.4Mpa, volume of the hydrogen to raw material
Than being 800: 1, the air speed of feed residue is 0.55h-1；In solvent extraction region, stagnation pressure 14.4Mpa, mean temperature 365
DEG C, agent oil quality ratio is 7: 100.With the mixing of raw material injection 7.0m% (relative to feed residue flow) gasoline and aviation kerosine
Oil (gasoline/diesel mass ratio is 4: 1), quantitatively releases the residue oil of 10m% in reactor bottom, after adding hydrogen, collects useless
Agent, as in the present embodiment using Ni-Mo as the useless agent of the hydrogenation catalyst of main active.
Embodiment 6
Present embodiments provide a kind of using Ni-Mo as the useless agent of the hydrogenation catalyst of main active, wherein it is described with
Ni-Mo is in the hydrogenation catalyst of main active, with the total restatement of hydrogenation catalyst, MoO323%, NiO 35%, zinc
1.9%, phosphorus pentoxide 5.8%, silicon 11%, cobalt oxide 2%, tungsten oxide 2%, chrome green 5%, surplus be silica/
Alumina composite carrier；
Above-mentioned hydrogenation catalyst is used for residual hydrogenation, and corresponding hydrogenation process is as follows: the residual oil raw material in head tank is through pumping
It mixes after pressurization with High Pressure Hydrogen and is entered from reactor bottom equipped with adding using Ni-Mo as main active in the form of upper feeding
The fluidized bed reactor of hydrogen catalyst makes catalyst keep boiling-like, the part material and catalyst pumped from head tank and raw material
Aqueous solution is sufficiently mixed uniformly in multistage shearing tank, is dispersed type catalyst transport pump and is entered fluidized bed reactor without catalyst
Liquid phase region, under defined reaction condition, the heavy resid raw material entered from reactor bottom successively be main living with Ni-Mo
Property ingredient hydrogenation catalyst contact, carry out catalytic hydrogenation reaction, hydrogenation temperature is 425 DEG C, reaction pressure 15Mpa, when liquid
Volume space velocity is 0.5h-1, hydrogen to oil volume ratio 600:1 after adding hydrogen, collects useless agent, as in the present embodiment with Ni-Mo
For the useless agent of the hydrogenation catalyst of main active.
Embodiment 7 (application of the useless agent of hydrogenation catalyst)
Using Ni-Mo to be the useless agent of the hydrogenation catalyst of main active as CO collected by above-described embodiment 1-6
The catalyst of conversion reaction carries out the active testing of catalyst, and active testing is as follows:
Unstripped gas group becomes 15vol%CO, 55vol%H2, 6vol%CO2, 24vol%N2, reaction steam-to-gas ratio be 1:1, it is empty
Speed is 4000h-1, it is 250~450 DEG C that catalyst activity, which tests warm area,；
The activity of catalyst indicates that calculation method is as follows with CO conversion ratio:
CO conversion ratio=(1-VCO'/VCO)/(1+VCO) × 100%
Wherein, VCO'For the percentage by volume of CO in reactor outlet gas, VCOFor the percentage by volume of CO in unstripped gas；
It is corresponding that test result is as follows shown in table 1:
CO conversion ratio under table 1, different test temperatures
From table 1 it can be seen that: the present invention in using Ni-Mo be the useless agent of the hydrogenation catalyst of main active have it is excellent
CO converts catalytic effect, can effectively improve CO conversion ratio.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
- Agent, Fe 1. a kind of FeOOH gives up21.333O32Useless agent, iron oxide give up agent, the useless agent of Ni-Mo as hydrogenation liquefaction catalyst, conduct CO transformation catalyst, the purposes in organic matter transformation technique；The FeOOH give up agent be FeOOH desulfurizing agent give up agent, using FeOOH as the useless agent of the desulfurizing agent of main active, contain Regrowth after the useless agent regeneration of the desulfurizing agent of FeOOH；The Fe21.333O32Useless agent is Fe21.333O32Desulfurizing agent useless agent, with Fe21.333O32For the desulfurization of main active The useless agent of agent contains Fe21.333O32Desulfurizing agent give up agent regeneration after regrowth；The iron oxide give up agent be ferric oxide desulfurizer useless agent, using iron oxide as the useless agent of the desulfurizing agent of main active, Regrowth after the useless agent regeneration of desulfurizing agent containing iron oxide；The Ni-Mo gives up agent as using Ni-Mo as the useless agent of the hydrogenation catalyst of main active.
- 2. purposes according to claim 1, which is characterized in that FeOOH is One or more of with amorphous FeOOH；FeOOH desulfurizing agent gives up agent as the useless agent generated after sulfur-bearing ingredient in the desulfurizing agent removing coke-stove gas of FeOOH；FeOOH desulfurizing agent gives up agent as the useless agent generated after sulfur-bearing ingredient in the desulfurizing agent removing waste water of FeOOH；FeOOH desulfurizing agent gives up agent as the sulfur-bearing ingredient generation in the desulfurizing agent removing coal pyrolysis gas and/or calcium carbide stove exhaust of FeOOH Exhaust gas.
- 3. purposes according to claim 1 or 2, which is characterized in that also wrapped by the desulfurizing agent of main active of FeOOH Include molysite chelating agent, bodied ferric sulfate, basic copper carbonate, calcium bicarbonate, zinc oxide, calcium sulphate dihydrate, the oxide of nickel, cobalt One or more of oxide, oxide of nickel；Desulfurizing agent containing FeOOH gives up agent as the useless agent generated after H2S in the desulfurizing agent removing gas containing FeOOH；Or,The desulfurizing agent containing FeOOH gives up agent to generate after sulfur-bearing ingredient in the desulfurizing agent removing coke-stove gas containing FeOOH Useless agent；Or,It is useless to generate after sulfur-bearing ingredient in the desulfurizing agent removing waste water containing FeOOH that the desulfurizing agent containing FeOOH gives up agent Agent；Or,The desulfurizing agent containing FeOOH gives up agent as in desulfurizing agent removing coal pyrolysis gas and/or calcium carbide stove exhaust containing FeOOH Sulfur-bearing ingredient generate exhaust gas.
- 4. purposes according to any one of claim 1-3, which is characterized in that the useless agent regeneration of the desulfurizing agent containing FeOOH Purposes as biomass hydrogenation liquefaction catalyst afterwards, the desulfurizing agent containing FeOOH give up agent regeneration method be,(1) the useless agent of the desulfurizing agent containing FeOOH is ground into particle, obtains useless agent powder；(2) the useless agent powder is made into suspension, being passed through oxygenous gas and aoxidize vulcanizes the iron in the suspension Object conversion, forms the slurries containing amorphous FeOOH and elemental sulfur；(3) slurries are filtered and obtains solid material, the elemental sulfur in the solid material described in solvent extraction is remaining after extraction Solid is the regrowth containing the useless agent of FeOOH desulfurizing agent；The purposes alternatively, desulfurizing agent containing FeOOH gives up after agent regeneration as biomass hydrogenation liquefaction catalyst, described contains The give up regeneration method of agent of the desulfurizing agent of FeOOH is,(1) the useless agent of the desulfurizing agent containing FeOOH is ground into particle, obtains useless agent powder；(2) the useless agent powder is made into suspension, being passed through oxygenous gas and aoxidize vulcanizes the iron in the suspension Object conversion, forms the slurries containing amorphous FeOOH and elemental sulfur；(3) it is placed in container by the slurries or by the solid material obtained after slurries filtering, being passed through air makes the list Matter sulphur floats, and the sediment of lower vessel portion is the regrowth containing the useless agent of FeOOH desulfurizing agent；Purposes after the useless agent regeneration of the above-mentioned desulfurizing agent containing FeOOH as biomass hydrogenation liquefaction catalyst, regeneration method In further include the steps that by it is described containing FeOOH desulfurizing agent give up agent regrowth mixed with organic binder；The purposes alternatively, desulfurizing agent containing FeOOH gives up after agent regeneration as biomass hydrogenation liquefaction catalyst, described contains The give up regeneration method of agent of the desulfurizing agent of FeOOH is,(1) by the useless agent weak acid water dispersion of the desulfurizing agent containing FeOOH, dispersion liquid is formed；(2) dispersion liquid is heated, then oxidant is added into the dispersion liquid after heating and is reacted, reaction turns rapidly simultaneously Innidiation at sulfur dioxide gas；(3) after the reaction was completed, obtained precipitating is washed, is dried by filtering reacting liquid, obtains described containing FeOOH desulfurization The regrowth of the useless agent of agent.
- 5. purposes described in any one of -4 according to claim 1, which is characterized in that the useless agent of the desulfurizing agent containing FeOOH or On the way, the useless agent regeneration preparation of the desulfurizing agent containing FeOOH is useless for use of the useless agent regenerative agent in organic matter transformation technique The method of agent regenerative agent include but is not limited to it is following several, a kind of method for preparing useless agent regenerative agent provided is, A1, by institute The useless agent for stating the desulfurizing agent containing FeOOH is ground into particle, obtains useless agent powder；A2, the useless agent powder is made into suspension, be passed through Oxygenous gas, which carries out oxidation, converts the iron sulfide in the suspension, is formed and contains amorphous FeOOH and simple substance The slurries of sulphur；A3, the filtering slurries obtain solid material, the elemental sulfur in the solid material described in solvent extraction, after extraction Remaining solid is the regenerative agent of the useless agent containing FeOOH desulfurizing agent.Its useless agent regenerative agent of another preparation provided Method be that the useless agent of the desulfurizing agent containing FeOOH B1, is ground into particle, obtain useless agent powder；B2, by the useless agent Powder is made into suspension, and being passed through oxygenous gas and aoxidize converts the iron sulfide in the suspension, is formed containing without fixed The slurries of shape FeOOH and elemental sulfur；B3, it is placed in by the slurries or by the solid material obtained after slurries filtering In container, being passed through air makes the elemental sulfur float, and the sediment of lower vessel portion is described containing the useless agent of FeOOH desulfurizing agent Regenerative agent.Its another method for preparing useless agent regenerative agent provided is that C1, agent that the desulfurizing agent containing FeOOH gives up are used Weak acid water dispersion forms dispersion liquid；C2, the dispersion liquid is heated, then oxidant is added into the dispersion liquid after heating and carries out Reaction, the reaction sulfur dioxide gas that transfer generates rapidly simultaneously；C3, after the reaction was completed, filtering reacting liquid, the precipitating that will be obtained It washed, dried, obtain the regenerative agent containing the useless agent of FeOOH desulfurizing agent.Its useless agent regeneration of another preparation provided The method of agent is that the regenerative agent of the useless agent of the desulfurizing agent containing FeOOH is by slurry method to the desulfurizing agent containing FeOOH Useless agent aoxidized, vulcanized and aoxidized after obtained regenerative agent.Its provide also a kind of method for preparing useless agent regenerative agent be, The useless agent of desulfurizing agent containing FeOOH is mixed with water or aqueous slkali, is configured to slurries；Oxidant is added into the slurries, Once oxidation reaction occurs；Vulcanizing agent is added into the slurries after the oxidation reaction, and vulcanization reaction occurs；It is anti-to the vulcanization Oxidant is added in slurries after answering, and secondary oxidation reaction occurs；Circulation carries out the vulcanization reaction and the secondary oxidation is anti- It answers；Slurries after secondary oxidation reaction are separated by solid-liquid separation, the regeneration of the useless agent of the desulfurizing agent containing FeOOH is obtained Agent；Alternatively,The regenerative agent and organic matter of useless agent and/or the useless agent of desulfurizing agent containing FeOOH are prepared to form slurries, by the slurries with Pure CO or gas mixing containing CO carry out conversion reaction.Preferably, further include the steps that sulfur-containing compound is added, make iron in slurries The molar ratio of element and element sulphur is 1:(0.5 ~ 5).
- 6. purposes according to any one of claims 1-5, which is characterized in that the useless agent of the desulfurizing agent containing FeOOH or On the way, the reaction pressure of the conversion reaction is 5-22MPa, reaction temperature to use of the useless agent regenerative agent in organic matter transformation technique Degree is 200-470 DEG C；In the slurries, the regeneration agent content of useless agent and/or the useless agent of the desulfurizing agent containing FeOOH is 0.1 ~ 10wt%, is put down Equal partial size is 0.1 μm of -5mm；The volume content of CO is not less than 15%, preferably not less than 50% in gas containing CO, is most preferably not less than 90%.
- 7. purposes according to claim 1 to 6, which is characterized in that the Fe21.333O32Desulfurizing agent give up agent be Fe21.333O32Desulfurizing agent removes H in gas2The useless agent generated after S；Alternatively,Fe21.333O32Desulfurizing agent gives up purposes of the agent as biomass hydrogenation liquefaction catalyst, the Fe21.333O32Desulfurizing agent give up agent be Fe21.333O32Desulfurizing agent removing coke-stove gas in the useless agent that generates after sulfur-bearing ingredient；Alternatively,Fe21.333O32Desulfurizing agent gives up purposes of the agent as biomass hydrogenation liquefaction catalyst, the Fe21.333O32Desulfurizing agent give up agent be Fe21.333O32Desulfurizing agent removing waste water in the useless agent that generates after sulfur-bearing ingredient；Alternatively,Fe21.333O32Desulfurizing agent gives up purposes of the agent as biomass hydrogenation liquefaction catalyst, the Fe21.333O32Desulfurizing agent give up agent be Fe21.333O32Desulfurizing agent removing coal pyrolysis gas and/or calcium carbide stove exhaust in sulfur-bearing ingredient generate exhaust gas.
- 8. purposes described in any one of -7 according to claim 1, which is characterized in that Fe21.333O32For main active Purposes of the useless agent of desulfurizing agent as biomass hydrogenation liquefaction catalyst, it is described with Fe21.333O32For the desulfurization of main active Agent further includes potassium oxide, Detitanium-ore-type Ti02, copper oxide, lead oxide, zinc oxide, one or more of manganese dioxide；Alternatively,With Fe21.333O32It is described for purposes of the useless agent as biomass hydrogenation liquefaction catalyst of the desulfurizing agent of main active With Fe21.333O32Useless agent for the desulfurizing agent of main active is H in the desulfurizing agent removing gas2The useless agent generated after S； Alternatively,With Fe21.333O32It is described for purposes of the useless agent as biomass hydrogenation liquefaction catalyst of the desulfurizing agent of main active With Fe21.333O32Useless agent for the desulfurizing agent of main active is to produce after sulfur-bearing ingredient in the desulfurizing agent removing coke-stove gas Raw useless agent；Alternatively,With Fe21.333O32It is described for purposes of the useless agent as biomass hydrogenation liquefaction catalyst of the desulfurizing agent of main active With Fe21.333O32To be generated after sulfur-bearing ingredient in the useless agent desulfurizing agent removing waste water of the desulfurizing agent of main active Useless agent；Alternatively,With Fe21.333O32It is described for purposes of the useless agent as biomass hydrogenation liquefaction catalyst of the desulfurizing agent of main active With Fe21.333O32Useless agent for the desulfurizing agent of main active is the desulfurizing agent removing coal pyrolysis gas and/or calcium carbide stove exhaust In sulfur-bearing ingredient generate exhaust gas.
- 9. purposes according to claim 1 to 8, which is characterized in that state in ferric oxide desulfurizer activity at It is divided into di-iron trioxide and/or ferroso-ferric oxide.
- 10. purposes according to claim 9, which is characterized in that the di-iron trioxide is α-Fe2O3, α- Fe2O3.H2O, γ-Fe2O3, γ-Fe2O3.H2O, amorphous Fe2O3, amorphous Fe2O3.H2At least one of O；The ferroso-ferric oxide is the ferroso-ferric oxide of cubic system.
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