CN107189812B - A method of cracking C6-C8 fraction selective hydrogenation - Google Patents
A method of cracking C6-C8 fraction selective hydrogenation Download PDFInfo
- Publication number
- CN107189812B CN107189812B CN201710409059.XA CN201710409059A CN107189812B CN 107189812 B CN107189812 B CN 107189812B CN 201710409059 A CN201710409059 A CN 201710409059A CN 107189812 B CN107189812 B CN 107189812B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- acid
- alumina
- alumina support
- 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.)
- Expired - Fee Related
Links
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 63
- 238000005336 cracking Methods 0.000 title claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 227
- 239000003054 catalyst Substances 0.000 claims abstract description 113
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 91
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 45
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011777 magnesium Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011574 phosphorus Substances 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000002671 adjuvant Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 68
- 238000002360 preparation method Methods 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 46
- 229920001661 Chitosan Polymers 0.000 claims description 41
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 33
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 26
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 20
- 229910052684 Cerium Inorganic materials 0.000 claims description 19
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000395 magnesium oxide Substances 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 238000009826 distribution Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 17
- 229910001593 boehmite Inorganic materials 0.000 claims description 16
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 10
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 8
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 235000011054 acetic acid Nutrition 0.000 claims description 5
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 230000009514 concussion Effects 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 abstract description 17
- 229910052785 arsenic Inorganic materials 0.000 abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 14
- 239000011593 sulfur Substances 0.000 abstract description 14
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 8
- 239000003921 oil Substances 0.000 description 46
- 150000001993 dienes Chemical class 0.000 description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 229910052782 aluminium Inorganic materials 0.000 description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 34
- 239000000463 material Substances 0.000 description 31
- 239000011148 porous material Substances 0.000 description 30
- 239000002131 composite material Substances 0.000 description 20
- 239000004411 aluminium Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 17
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 16
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 16
- 229910052794 bromium Inorganic materials 0.000 description 16
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 15
- 239000004793 Polystyrene Substances 0.000 description 15
- 229910052740 iodine Inorganic materials 0.000 description 15
- 239000011630 iodine Substances 0.000 description 15
- 239000012071 phase Substances 0.000 description 15
- 229920002223 polystyrene Polymers 0.000 description 15
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 12
- 238000000197 pyrolysis Methods 0.000 description 12
- 239000002202 Polyethylene glycol Substances 0.000 description 11
- 239000003292 glue Substances 0.000 description 11
- 229920001223 polyethylene glycol Polymers 0.000 description 11
- -1 ethylene, propylene Chemical group 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- 239000000084 colloidal system Substances 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 239000004005 microsphere Substances 0.000 description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000004939 coking Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 5
- 239000004964 aerogel Substances 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- IOGARICUVYSYGI-UHFFFAOYSA-K azanium (4-oxo-1,3,2-dioxalumetan-2-yl) carbonate Chemical compound [NH4+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O IOGARICUVYSYGI-UHFFFAOYSA-K 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000006210 lotion Substances 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 150000001345 alkine derivatives Chemical class 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000002941 palladium compounds Chemical class 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000009415 formwork Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000007524 organic acids Chemical group 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000012687 aluminium precursor Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- FOJJCOHOLNJIHE-UHFFFAOYSA-N aluminum;azane Chemical compound N.[Al+3] FOJJCOHOLNJIHE-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000005312 bioglass Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000007144 microwave assisted synthesis reaction Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- PZKNFJIOIKQCPA-UHFFFAOYSA-N oxalic acid palladium Chemical compound [Pd].OC(=O)C(O)=O PZKNFJIOIKQCPA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000010187 selection method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002893 slag Substances 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
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/651—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/10—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/52—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The present invention relates to a kind of methods for cracking the selective hydrogenation of C6-C8 fraction, catalyst includes the alumina support with macroporous structure and the metal active component palladium being carried on carrier, total weight of the content of palladium based on the catalyst is 0.2-0.35wt%, contain adjuvant component phosphorus and magnesium in alumina support with macroporous structure, it is respectively P that the content of adjuvant component phosphorus and magnesium, which accounts for the percentage composition of carrier quality,2O50.1-2.5wt%, MgO 0.1-2.5wt%；Hydrogenation process conditions: reaction inlet temperature≤45 DEG C, reaction pressure 2.5-4.5MPa, hydrogen to oil volume ratio 60-450；Liquid volume air speed 3.0-5.5h‑1.Catalyst is strong to the drippolene adaptability to raw material of different arsenic contents, different sulfur contents, and catalyst low-temperature activity is good.
Description
Technical field
The present invention relates to a kind of selection method of hydrotreating for petroleum hydrocarbon product, are especially adapted for use in one section of drippolene
Selective hydrogenation is a kind of method for cracking the selective hydrogenation of C6-C8 fraction.
Background technique
Drippolene is the important by-product of steam cracking industrial production ethylene, propylene, including C5-C10 fraction.Drippolene
It forms very complicated, mainly there is benzene,toluene,xylene, monoolefine, diolefin, linear paraffin, cycloalkane and nitrogen, sulphur, oxygen, chlorine
With the organic compound of heavy metal etc., a component more than totally 200, wherein benzene,toluene,xylene (being referred to as BTX) about 50-90%, no
Saturated hydrocarbons 25-30%.It is the characteristics of according to a large amount of aromatic hydrocarbons are contained in drippolene, widely used, it both can be used as the tune of gasoline
And component, high-octane gasoline is produced, separation production aromatic hydrocarbons etc. can also be passed through.
Since drippolene complicated composition, thermal stability are poor, in general, first removing alkadienes and benzene through one-stage selective hydrogenation
Ethylene after Secondary hydrodesulfurization, is mainly used for Aromatics Extractive Project.Industrial catalyst for selective hydrogenation of cracked gasoline is mainly at present
(C5 hydrocarbon-does the hydrocarbon for 204 DEG C for Pd system or Ni series catalysts, midbarrel (C6-C8 hydrocarbon compound fraction) plus hydrogen or full fraction
Compound fraction) hydrogenation technique.Due to the difference of each ethylene unit cracking stock and cracking condition, each device drippolene raw material
Composition difference is larger, and especially (polymerization reaction occurs for the unsaturation component such as alkadienes and styrene for the diene of drippolene, colloid
The high molecular polymer of generation) and As, content of beary metal there are larger differences；Some device raw pyrolysis gasoline dienes, colloid
Height, and the toxic contents such as colloid and As, heavy metal are higher in some device raw pyrolysis gasoline raw materials, individual device raw pyrolysis gasoline
The toxic contents such as diene, colloid and As, heavy metal are high.
Alkadienes and alkynes in drippolene are easy polymerization collagen at high temperature, are deposited on catalyst surface, Yi Zao
At catalyst inactivation, it is necessary to frequently activation and regeneration.Pyrolysis gasoline hydrogenation catalyst mainly has Pd/Al2O3And Ni/Al2O3
Two kinds of catalyst.The advantages that Pd series catalysts have initial temperature low, and hydrogenation activity is big, and adaptation air speed is high, long service life,
The catalyst mode for having industrial application includes Pd-Cr/Al2O3, Pd/Al2O3。
Usual pyrolysis gasoline hydrogenation catalyst is using the metal salt of active component or the solution dipping of organo-metallic compound
The carrier, it is then by processes such as dry, roastings that active component is oxide carried to carrier surface, logical hydrogen is needed before use
Pyrolysis gasoline hydrogenation reaction could be used for after gas reduction.Common carrying alumina body aperture is too small, when colloid, arsenic contain in raw material
When amount, sulfur content are exceeded, the easy coking and blocking in hole on catalyst influences catalyst activity and stabilized hydrogenation.
Macroporous oxide is due to using extensively with biggish cellular structure, higher specific surface area, good thermal stability
In fields such as heterogeneous catalyst, catalyst carrier, adsorption and separation material, chromatograph packing material, electrode material, acoustic resistance and thermal resistance materials.
The carrier of aluminium oxide with macroporous structure is relatively more.CN03126434.4 discloses a kind of macropore alumina supporter,
Containing aluminium oxide, also contain a kind of halogen, on the basis of carrier total amount, which contains the aluminium oxide of 95-99 weight %, with member
Element meter, the halogen of 0.1-5 weight %, acid amount is less than 0.2 mM/gram.The preparation method of macropore alumina supporter includes will
A kind of precursor of aluminium oxide is formed and is roasted, and before molding and roasting, the precursor of aluminium oxide and a kind of expanding agent are mixed
It closes, the expanding agent includes a kind of organic expanding agent and a kind of halide, and maturing temperature is 600-850 DEG C, calcining time 1-10
Hour, the dosage of each component contains final alumina support, on the basis of carrier total amount, the aluminium oxide of 95-99 weight %,
Based on the element, the halogen of 0.1-5 weight %.Organic expanding agent is in starch, synthetic cellulose, polymeric alcohol, surfactant
One or more.Synthetic cellulose is in carboxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxylated cellulose
It is one or more of.Polymeric alcohol is selected from one or more of polyethylene glycol, poly- propyl alcohol, polyvinyl alcohol, and surfactant is selected from rouge
Fat alcohol polyoxyethylene ether, fatty alkanol amide, molecular weight are the acrylic copolymer of 200-10000, in maleic acid copolymer
It is one or more of.CN201110410339.5 provides a kind of high temperature-resistant active aluminum oxide material and preparation method thereof, the oxygen
Change aluminum material to be made by following steps: after macropore boehmite, high viscous boehmite are mixed with additive with water, turn
Speed is to stir evenly under 100-1000r/min, adds the dilute nitric acid reaction that concentration is 30%, until pH is the peptization of 2.0-5.5
When state, it is aged 3-6h in the case where 80 DEG C of -100 DEG C of temperature stir, pore creating material is added at room temperature and stirs evenly, is slurrying, spraying, dry
It is dry, it is roasted at 900 DEG C and aluminium oxide is made.The alumina material has many advantages, such as convenient for batch production and high-ratio surface.?
Specific surface can be kept in 110m for a long time at a temperature of 1000-1100 DEG C2/ g or more；The work of the alumina material preparation method
Skill process is simple, low in cost.Wherein the sky agent of making is selected from polyvinyl alcohol, polyethylene glycol, polyacrylamide or methyl fibre
One of element is tieed up, dosage is the 0-40% of oxide total weight in alumina material." Zhongshan University's journal " (2002,41
(2): 121-122 the method) introduced is as follows: the polystyrene colloidal crystal microballoon that diameter is 600nm is placed on a buchner funnel, so
The ethanol solution of aluminum nitrate and citric acid is added drop-wise to afterwards on glue crystalline substance under suction filtration, is allowed in its fully penetrated gap into microballoon,
Through dry and roasting, polystyrene moulding is removed, macroporous aluminium oxide is obtained." Acta PhySico-Chimica Sinica " (2006,22 (7): 831-
835) method that granular formwork method prepares three-dimensional ordered macroporous alumina is described, this method is as follows: first using emulsion polymerization
Method obtains polystyrene microsphere, and alumina sol is made in aluminum nitrate plus weak aqua ammonia, then stirs the two by a certain percentage mixed
It closes, ultrasonic treatment, then through dry and roasting, obtains macroporous aluminium oxide.CN201010221302.3 (CN102311134A) is open
A kind of spherical integral macroporous alumina and preparation method thereof.Method includes the following steps: by polymer microballoon lotion, oxidation
Aluminum sol and coagulant are mixed in a certain proportion uniformly, which is scattered in oily phase, form w/o type drop, then again
Above-mentioned mixed phase system is heated, makes the alumina sol gelling balling-up in water phase, it is micro- to isolate molding gel from oily phase later
Ball, then the spherical integral macroporous alumina is obtained after aged, dry and roasting in aqueous ammonia medium.The aluminium oxide
Macropore diameter is uniform controllable in the range of less than 1 μm, and the size of spheric granules is controllable, and mechanical strength is higher, forms
Journey is simple and easy to do, convenient for being prepared on a large scale.Polymer microballoon diameter 50-1000nm, the type of polymer microballoon are polystyrene
The esters microballoons such as microballoon, polyaerylic acid N-butyl microballoon, polyacrylate.Coagulant is hexamethylenetetramine, urea.Oil is mutually
Organic hydrocarbon.The invention mainly prepares Integral macroporous alumina, and macropore diameter is uniform controllable.Preparation process uses
Lipid microballoon and coagulant etc..Preparation process is complicated, and reagent raw material used is relatively more.Due to polymer microballoon make
Alumina support internal gutter structure is blind bore, that is to say, that alumina support internal gutter does not have connectivity.
CN201010221297.6 discloses a kind of preparation method of Integral macroporous alumina.Method includes the following steps: aluminium
Source, polyethylene glycol and after being uniformly mixed selected from low-carbon alcohol and water at least one, will low-carbon epoxyalkane be added it is described mixed
It closes in object, obtains Integral macroporous alumina through aging, immersion, drying and roasting.Of the invention preparation method is simple, ring
Border pollution is small, its aperture of gained Integral macroporous alumina is controllable at 0.05-10 μm.Monoblock type macropore oxidation provided by the invention
Object can be applied to the fields such as macromolecular heterogeneous catalysis, adsorption and separation material, chromatograph packing material, electrode material, acoustic resistance and thermal resistance material.
CN201410347665.X disclose a kind of macropore hold, the preparation method of high-strength alumina, by the way that polyacrylamide, poly- is added
The expanding agents such as vinyl alcohol, alkylcellulose, sesbania powder, starch are obtained containing eurypyloue alumina support, the dosage of expanding agent
The 10-30% of aluminium oxide is accounted for, but not publicly specific pore diameter range.The although available preferable macropore oxidation of hard mould agent method
Alumina supporter, but the dosage of its template causes processing cost to greatly improve more preferably greater than 20%, the decomposition of a large amount of templates
The demand for development of low-carbon environment-friendly is not met.CN201010509425.7 discloses the side of a kind of hydro-thermal and the common reaming of template
Method is acted on, the dosage of template can be reduced with preparing the alumina support containing macroporous structure by the complementary reaming of hydro-thermal
To 3-10%, but hydro-thermal is assisted to cause the raising of energy consumption.CN200310103035.X discloses a kind of macroporous aluminium oxide
Preparation method carries out reaming using polyvinyl alcohol, poly- propyl alcohol, polyethylene glycol soft template, by the way that 1% polyethylene glycol is added,
Kong Rong of the aperture greater than 100nm accounts for the 26.2% of total pore volume.Soft template has the advantages that dosage is low, reaming effect is good, still
The solubility property of the alcohols soft template of higher molecular weight in water is poor, causes it to be used to expand super large porous aluminum oxide and is limited
System.CN200910204238.5 (CN102040235) discloses a kind of three-dimensional ordered macroporous alumina and preparation method thereof.The party
Then method fills certain party legal system the following steps are included: monodispersed polymer microballoon is assembled into glue crystal template into template
Standby alumina sol most obtains macroporous aluminium oxide through dry and roasting afterwards.This method can be good at control Aluminum sol and
The recombination process of Aluminum sol and polymer microballoon does not destroy the network structure of alumina gel as far as possible, makes prepared oxidation
Aluminium not only has the macropore duct of three-dimensional order but also specific surface area with higher.The invention is burnt by the appropriateness to template
The small fenestra tied and formed, makes the macropore in material be connected with the macropore of surrounding by 12 small fenestras.The oxidation of the invention
Aluminium is suitable for use as the adsorption and separation material of mink cell focus catalyst carrier and organic macromolecule.Have in catalyst carrier material application
Conducive to the mass transfer ability of material in the catalyst is improved, be conducive to the activity and selectivity for improving catalyst.
CN201410148773.4 discloses a kind of preparation method of aluminum oxide porous microballoon, comprising the following steps: 1) by surface-active
Agent is dissolved in deionized water, stirring, as water phase；2) chelating agent, alumina precursor and n-octyl alcohol are mixed, is stirred, as
Oily phase；3) Span80 and pore-foaming agent, stirring are added in oily phase；4) clear oil obtained by step 3) is mutually poured into water phase
Continue stirring and emulsifying；5) step 4) gains are filtered by vacuum, it is dry after gained Washing of Filter Cake, obtain aluminum oxide porous microballoon.It should
Microballoon has internal closing macroporous structure, and Microsphere Size is 1 μm -100 μm, and the invention is solidifying using the colloidal sol in pore-foaming agent and lotion
Glue process obtains the metal porous microballoon with internal closing macroporous structure.Porous microsphere is prepared using phase separation principle.It is internal
Closing aperture is 50nm-5 μm.Inside closing aperture is 50nm-5 μm.Aperture is closed inside the aluminum oxide porous microballoon,
That is alumina support internal gutter does not have connectivity.Pore-foaming agent is polyvinylpyrrolidone, polyacrylamide or poly- third
Olefin(e) acid.The invention has used a large amount of surfactant, chelating agent, pore-foaming agent, and it is more to prepare raw material, and synthesis technology is complicated.
The above macroporous aluminium oxide mainly uses cellulose, polymeric alcohol, polystyrene etc. to prepare macropore oxygen as expanding agent
Change aluminium.
Alumina support with macropore and mesoporous i.e. composite pore structural also compares more.CN101200297A discloses whole
The preparation method of figure macroporous aluminium oxide: use reversed concentrated emulsions method big as monomer preparation monoblock type using styrene and divinylbenzene
Hole organic formwork；Al is prepared using aluminium isopropoxide or boehmite as predecessor2O3The hydrosol；By Al2O3The hydrosol is filled into whole
In body formula macropore organic formwork；Filled monolithic devices organic/inorganic composite is removed through drying in 600 DEG C of -900 DEG C of roastings
Template obtains integral macroporous alumina.The advantages of this method is that preparation process is simple and easy, monoblock type macropore oxygen obtained
Change the macropore duct that there is aluminium micron order to interconnect, aperture is 1-50 μm.It is simple that this method prepares Integral macroporous alumina
It is easy, but the volume fraction of water phase accounts for 75%-90% in this method, and correspondingly the volume fraction of organic monomer is relatively low, this
For method while reducing organic monomer consumption, the preparation efficiency of prepared template is relatively low, is unfavorable for subsequent step macropore
It is prepared by the batch of aluminium oxide.A kind of preparation method of the alumina support of composite pore structural of CN201110032234.0, including will
Closing containing calorize selected from least one of aluminium isopropoxide, aluminium secondary butylate, aluminum nitrate, aluminium chloride, Aluminum sol and boehmite powder
Object and composite mould plate agent are mixed and are roasted, the composite mould plate agent be mesoporous template and macroporous granules template, it is described mesoporous
Template is selected from polyethylene glycol propylene glycol-polyethylene glycol triblock polymer, polyethylene glycol, lauryl amine, cetyl
At least one of trimethylammonium bromide, lauric acid, stearic acid and fatty alcohol polyoxyethylene ether, the macroporous granules template are selected from
Partial size is residual greater than the polystyrene microsphere of 50nm, poly (methyl methacrylate) micro-sphere, particles of bioglass, pitch particle or heavy oil
Slag；The weight ratio of the mesoporous template, macroporous granules template and aluminum contained compound is 0.1-2:0.1-0.7:1, wherein institute
The weight of aluminum contained compound is stated in terms of aluminium oxide.The invention also discloses have mesopore orbit while preparation by the above method
With the alumina support in macropore duct, intermediary hole accounts for the 40%-90% of total pore volume, and macropore accounts for the 10%-60% of total pore volume.
CN201210328824.2 discloses a kind of method for preparing solid phase of gradient distribution hole gama-alumina.This method is anti-by solid phase
Precursor aluminium carbonate ammonium should be obtained, the gamma oxidation that a kind of high specific surface area, gradient distribution hole and large hole are held is obtained after roasting
Aluminium.The present invention is the most outstanding to be technically characterized in that using raw material solid phase reactive synthesis technique, as obtained by synthesis condition control
The property of gama-alumina.Meanwhile the method for the present invention is simple, and it is easily operated, addition expanding agent is not needed, save the cost is suitble to work
Industryization batch production.The preparation process of alumina support of the present invention the following steps are included: (1) aluminum nitrate, ammonium hydrogen carbonate and table
Face activating agent is fully ground uniformly, and ageing certain time obtains precursor aluminium carbonate ammonium in the closed container of specific temperature；(2)
It will form after mixing after the drying of precursor aluminium carbonate ammonium obtained by (1) with peptizing agent, can generally be squeezed using banded extruder
Item molding；(3) (2) are obtained that final alumina support is made in molding drying, aerobic roasting.Step lures described in (1)
The polyethylene glycol that agent is liquid form is led, additional amount is equivalent to the 0.1-10.0% of aluminum nitrate weight.Carbonic acid described in step (2)
The drying process of aluminium ammonium is 1-20 hours dry generally at 50-180 DEG C.Roasting process described in step (3) is in 350-900
It is roasted 1-10 hours at DEG C.The invention prepares gama-alumina using the decomposition at a certain temperature of precursor aluminium carbonate ammonium.Aluminium carbonate
Ammonium generates gas, such as NH in decomposable process3And CO2, the generation and evolution of these gases can manufacture some macropores.Simultaneous oxidation
The pattern of aluminium is transformed by the pattern topology of aluminium carbonate ammonium.Slower heating rate is conducive to gas object in roasting process
Matter slowly escapes, and does not easily cause carrier to collapse.Method is simple, does not need to add any physics expanding agent.
CN201310097588.2 discloses a kind of gama-alumina particle and preparation method thereof: 1) aluminum soluble salt being dissolved in by acid
In aqueous solution of the pH value of acidification less than or equal to 3, the amount that the aluminum soluble salt is added makes obtained containing aluminium in aluminum water solution
The molar concentration of ion is 0.01-5mol/L；2) obtained containing alkaline precipitating agent, the alkali is added in aluminum water solution to step 1)
Property precipitating reagent be added amount make reaction after solution ph between 5-12；3) the mixed sediment solution that step 2) obtains is existed
At room temperature stir 0.1-3h after, be put into water-bath or water heating kettle, 50-150 DEG C at a temperature of be aged 6-24h；4) by step
3) solution after being aged is after mixing evenly, dry using spray drying process, and control inlet air temperature is 150-400 when spray drying
DEG C, leaving air temp is 60-110 DEG C, and the thermal efficiency of spray drying is 50% or more；5) oxidation after the drying for obtaining step 4)
Aluminium precursor powder is heated to 250 DEG C -350 DEG C at room temperature with first rate of heat addition, is then heated to second rate of heat addition
400 DEG C -800 DEG C, heat preservation 0.5-20h obtains final product gama-alumina particle；Wherein, first rate of heat addition is less than
Two rates of heat addition, and first rate of heat addition and second rate of heat addition are in the range of 0.1-10 DEG C/min.It is obtained
Gama-alumina is experiments verify that test, and specific surface area is in 180m2/g-260m2In/g range, there is high-specific surface area.It is made
Gama-alumina particle observed under scanning electron microscope have hollow foam shape pattern, and have micropore-mesopore-macropore it is compound
Aperture structure.In this way, when gama-alumina is as catalyst carrier, hollow foam shape pattern can be effectively in dispersed catalyst
Active component.And hollow foam shape pattern and composite bore diameter structure, be conducive to the mass transfer in catalytic process, to accelerate
Rate of catalysis reaction.The composite bore diameter structure refers to not only include micropore of the aperture less than 2nm, but also including aperture in 2nm-50nm
Between it is mesoporous, further include aperture be greater than 50nm macropore.It further include making to obtained containing being added in aluminum water solution in step 1)
Hole agent, the amount that the pore creating material is added that the molar concentration of pore creating material in rear solution is added to be aluminum ions molar concentration
0.01-5 times.The pore creating material is cetyl trimethylammonium bromide (CTAB), neopelex (SDBS), polyethylene
One or more of alcohol (PVA), polyethylene glycol (PEG) and calgon.CN101863499A
(201010187094.X) provides a kind of preparation method of macroporous-mesoporous alumina.The following steps are included: a. first helps reaction
Agent and aluminium salt are dissolved in organic solvent solution, reaction promoter: two kinds of material mol ratios of aluminium ion are 3-5:1, then by template
Above-mentioned solution is added and dissolves, aluminium ion and template molar ratio are 1:0.015-0.025, and the pH value control of final solution exists
3.5-6.0；B. the solution by a step preparation carries out aging process, so that it is gradually removed organic solvent and moisture in system and obtains greatly
Hole-meso-porous alumina presoma；C. macroporous-mesoporous alumina powder is obtained through 400-800 DEG C of calcination process.Present invention process letter
Single, duct rule, pore-size distribution is concentrated and can realize controllable adjustment according to concrete application situation, thus more in petrochemical industry
Mutually catalysis, adsorbing separation and have important application value as catalyst carrier, energy and material etc..It makes full use of anti-
The space frame effect and coordination and intermediary's organic polymer, reaction promoter for answering auxiliary agent and template are to inorganic ions
Complexing, so that a step prepares the adjustable macroporous-mesoporous alumina material in aperture.Prepared foramen magnum-mesoporous oxidation
The specific surface area of aluminum material is up to 250-320m2/ g, duct rule, pore-size distribution in mesoporous 5-40nm, macropore 50-150nm, and
Adjusting can be realized according to the actual situation.Reaction promoter is organic acid, and aluminium salt is inorganic aluminate.Template is triblock copolymer.
Organic solvent is anhydrous alcohols, ethers or ketones solvent.Organic acid is citric acid or lauric acid.Triblock copolymer is
P123 or F127.Tie-Zhen Ren etc. (Langmuir, 2004,20:1531-1534) uses nonionic surfactant
56 aluminium secondary butylate of Brij uses hydro-thermal method and Microwave-assisted synthesis macroporous-mesoporous alumina in acid condition, synthesis it is porous
0.8-2 μm of alumina powder macropore diameter, mesoporous pore size 5-8nm, 0.4-1.4 μm of hole wall of aluminium oxide.Its deficiency is aluminium-alcohol salt
Expensive, the macroporous-mesoporous alumina hole appearance of synthesis is small, duct is irregular, pore-size distribution is excessive and cannot achieve pore structure
Effective adjusting thus have significant limitation in using effect and range.Jean-Philippe Dacquin etc.
It using P123 is template in mixed solution that (J.Am.Chem.Soc., 2009,131:12896-12897), which uses sol-gel method,
It is middle to be introduced into the polystyrene droplet with single dispersed phase to realize the formation of macropore in macroporous-mesoporous alumina.Deficiency
Place is that macropore diameter size (300nm or 400nm) is determined by the secondary size for introducing polystyrene drop completely, i.e. macropore diameter
Size depends on polystyrene droplet size.Organic molecule in the change of the part to solution itself component and system can not be passed through
It interacts to realize the adjustment in aperture.Huining Li et al. (Inorganic Chemistry, 2009,48:4421) is equally adopted
The polymethyl methacrylate with single dispersed phase is introduced in mixed solution with sol-gel method by template of F127
(PMMA) droplet realizes the formation of macropore in macroporous-mesoporous alumina, shortcoming be macropore diameter size also completely by
Secondary introducing polymethyl methacrylate droplet size determines, can not be changed by the part to solution system itself component come real
The adjustment in existing aperture also cannot achieve the controllable of foramen magnum-mesoporous aperture to realize the formation of foramen magnum-mesoporous composite pore structural
Adjust, in use, in particular for complicated ingredient bulky molecular catalysis during by significant limitation.
The above composite holes alumina support generally uses organic polymer such as polyvinyl alcohol, polymethylacrylic acid etc. as mould
Plate agent either expanding agent.So that the preparation of composite holes and macroporous aluminium oxide material there are the monomer of template have certain toxicity,
The problems such as template consumption is larger, preparation cost is higher, preparation process is cumbersome.Meanwhile there is also the discharges in roasting process
The problem of object environmental pollution.Also there is the patent that saccharide compound is added in polymer microballoon lotion.
CN201310142454.8 discloses a kind of preparation method of alumina hollow ball, and it is water-soluble to prepare chitosan-acetic acid-
Liquid；By polystyrene spheres: chitosan-acetic acid-aqueous solution be 5:1-10:1 mass ratio, press polystyrene spheres: alpha-alumina
Body is that the mass ratio of 1:5-1:15 takes each raw material；Polystyrene spheres and chitosan-acetic acid-aqueous solution are mixed, polyphenyl is made
Ethylene ball surface uniformly coats one layer of chitosan-acetic acid-aqueous solution；It is coated with chitosan-acetic acid-aqueous solution polyphenyl second again
In alkene ball and alpha-alumina powder investment ball-milling device, with the revolving speed rotation cladding 2-24h of 5-30r/s, obtained core-shell structure copolymer ball；It will
After the calcining of core-shell structure copolymer ball warp, the alumina hollow ball that diameter is 0.2-2mm, wall thickness is 20-100 μm is obtained.
CN201110170283.0 discloses a kind of three-dimensional ordered macroporous alumina and preparation method thereof.The three-dimensional ordered macroporous oxidation
Aluminium, diameter macropores 50-1000nm, grain diameter 1-50mm, mechanical strength 80-280g/mm.This method includes following step
It is rapid: saccharide compound and the concentrated sulfuric acid will to be added into monodisperse polymer micro-sphere lotion, obtain polymer-modified microballoon glue crystalline substance mould
Plate is subsequently filled alumina sol, then through aging and roasting, obtains three-dimensional ordered macroporous alumina.The polymer microballoon
Diameter is 50-1000nm, can be used polystyrene microsphere, poly (methyl methacrylate) micro-sphere, polyacrylic acid N-butyl microballoon and
One of different monooctyl ester microballoon of polyacrylic acid is a variety of, preferably polystyrene microsphere.The monodisperse refers to polymer microballoon
The standard deviation of diameter is not more than 10%.The carbohydrate organic matter be one of Soluble Monosaccharide and polysaccharide or a variety of, preferably
For one of sucrose, glucose, chitosan or a variety of.This method can increase substantially the adhesion amount of aluminium oxide precursor, increase
The strong mechanical strength of material, it is subtle powder that when removing template is removed in high-temperature roasting, large pore material is not easily broken, can still be protected
Hold higher integrity degree.Chitosan is in ceramic coating adsorbent material field using more." mesoporous chitosan-aluminium hydroxide is compound
Material Study on adsorption properties " (author: Peng Shaohua] University Of Suzhou, " Suzhou Institute of Science and Technology journal: natural science edition " 2013 30
Rolled up for 4 phases): with chitosan and AlCl3For raw material, it is prepared for chitosan and α-Al (OH)3Composite material.With X-ray powder diffraction,
Transmission electron microscope, infrared, thermogravimetric and specific surface instrument characterization has been carried out to it the result shows that: α-Al (OH)3It is in chitosan complexes
Now typical mesoporous characteristic, BET specific surface area 55.4m2·g-1, BJH average pore size is 3.3nm；Specifically the preparation method comprises the following steps: claiming
It takes 2.0g Aluminium chloride hexahydrate to be dissolved in the hydrochloric acid that 5.0mL pH value is 1,2.0g chitosan, then plus 10.0mL distilled water is added
Stirring, and the pH value of solution is adjusted to 1 with dilute hydrochloric acid.Still aging 30min (solution becomes paste), the NaOH for being 14 with pH value
Solution adjusts the pH value of solution to 8, has white flock precipitate generation, filters, wash away remaining NaOH with distilled water, be put into baking
Case obtains product after 120 DEG C of heat preservation 5h.Step as above, prepare chitosan respectively and aluminium chloride mass ratio be respectively 1:2,1:3,
The product of 2:1,3:1.
" preparation and characterization of chitosan/oxidized aluminium composite aerogel " (Chang Xinhong；The chemicalization engineering of Luoyang Normal College
Institute, " Luoyang Normal College's journal ", 11 phases of volume 31 in 2012): with chitosan and inorganic aluminate AlCl3.6H2O is raw material, is passed through
Sol-gel process uses CO respectively2Supercritical drying means and freeze-drying means are prepared for novel chitosan/oxidized aluminium
Composite aerogel.The result shows that the content of chitosan influences the properties such as specific surface area and the pore volume of composite aerogel, with shell
The increase of glycan content, the specific surface area for mixing aeroge are gradually reduced.Ratio table of the different drying means to composite aerogel
The properties such as area also have apparent influence.Composite aerogel contains micropore and mesoporous.CN201110022814.1 one kind has super
The ordered mesoporous metal oxide material of large aperture, it is characterised in that utilize the amphipathic block with ultrahigh molecular weight hydrophobic section
Copolymer is as structure directing agent, according to the principle of ligand assisted self assembling, before making mesoporous material during solvent volatilization
It drives and is acted between body and structure directing agent, and microphase-separated is differently formed according to hydrophilic and hydrophobic, ultimately form orderly to be situated between and see knot
Structure；After removing structure directing agent again, the ordered mesoporous metal oxide material with ultra-large aperture is formed；Wherein, block copolymerization
The molecular weight of the hydrophobic block of object is greater than 10000g/mol；The ordered mesoporous metal oxide material mesoporous pore size is in 10-50nm
Between, mesoporous wall thickness of material is between 4-20nm.The hydrophilic block of the block copolymer is polyoxyethylene blocks；Institute
The hydrophobic block for stating block copolymer is polystyrene or derivatives thereof, polyacrylate or derivatives thereof, polymethylacrylic acid
The copolymer of ester or derivatives thereof, one kind of polylactic acid pole or derivative or two or more polymer described above.The invention system
Standby is meso-porous alumina, similar also CN101153051A, CN1631796A, CN101134567A, CN101823706A,
CN101863499A.CN201310258011.5 is related to a kind of tooth spherical alumina support, tooth ball-aluminium oxide hydrotreating is urged
Agent and preparation method thereof, including following components: peptizing agent, 0.5-4 parts by weight；Lubricant, 0.2-2 parts by weight；Dispersing agent,
0.2-3 parts by weight；Expanding agent, 0.3-4 parts by weight；Aluminium hydroxide, 100 parts by weight.Expanding agent is polyvinyl alcohol, polyacrylic acid
One of sodium, starch derivatives or carbon black or mixture.The invention, which is added to anionic surfactant, reduces various help
Specific surface area increases 246m while agent ingredient additive amount2/ g, expanding agent Sodium Polyacrylate.The oxidation of tooth spherical shape described in the invention
Alumina supporter, since the wherein groups such as various auxiliary agents such as peptizing agent, expanding agent, dispersing agent, anionic surfactant are greatly lowered
The content divided, has not only saved cost, has also had many advantages, such as large specific surface area, high mechanical strength.The invention has used peptizing agent,
Lubricant, dispersing agent, the reagents such as expanding agent, obtained alumina support are unimodal pore size distributions.CN201110116418.5 is mentioned
It has supplied a kind of mesoporous sphere aluminium oxide and has been oriented to the method for preparing the mesoporous sphere aluminium oxide using template.Using oil column at
The template with guide function is added in type method during preparing Aluminum sol into Aluminum sol, and Aluminum sol is in molding and aging
In the process, since the presence of the template with guide function makes to produce a large amount of meso-hole structure in alumina balls.Template
For organic monomer or linear polymer, organic monomer is one of acrylic acid, ammonium acrylate, acrylamide, allyl alcohol.Jie
Hole ball-aluminium oxide specific surface is 150-300m2/ g, particle diameter 0.1-5mm, pore volume 0.7-1.5ml/g, bore dia are
The hole of 2-40nm is greater than 97%, and heap density is 0.30-0.80g/cm3, crushing strength is 70-250N/.The invention utilizes template
The mesoporous sphere alumina pore diameter of agent preparation compares concentration, this kind of mesoporous sphere aluminium oxide can be used for petrochemical industry and fining
Work is catalyst or catalyst carrier.
Macroporous aluminium oxide and compound porous aluminum oxide have different journeys to activity, selectivity and the stability aspect of catalyst
The improvement result of degree.The solubility of polyvinyl alcohol template in water is influenced by the degree of polymerization, it is caused to be used for super big hole oxygen
Change and is also subject to certain restrictions in the preparation of aluminium.
CN201010622227.1 is related to a kind of catalyst for selective hydrogenation of cracked gasoline, and it includes as carrier
Magnesia-titania-alumina composite oxide, and the Metal Palladium active component being carried on the composite oxide carrier
And Group IIA and/or IIIB race metal promoter metal, wherein metal palladium content is 0.25-0.35 weight %, and promoter metal content is
0.2-3 weight %, and the content based on oxidation aluminium magnesia in carrier is 0.1-3 weight % and the content of titanium oxide is 5-20
Weight %.The catalyst can be used for selective hydrogenation of cracked gasoline, and low temperature active is high, and selectivity is high, anti-As, S, O, N impurity energy
Power is strong, and charging capacity is greatly and activity stabilized under long-term operation.Moreover, it relates to the preparation of the catalyst and select
Application in hydrocracking gasoline.Finally, preparing composite oxides used using co-precipitation method the invention further relates to a kind of
The method of carrier.CN201310379189.5 discloses a kind of pyrolysis gasoline selective hydrogenation catalyst, including carrier and is carried on
Metal active constituent on carrier, the active component containing high molecular polymer water phase without the micro- of cosurfactant
It is prepared in lotion law system；The carrier be selected from aluminium oxide, titanium oxide, magnesia, zinc oxide, diatomite, molecular sieve,
At least one of kaolin, cordierite；The active component is main active component and helps active component, wherein main active group
It is divided into palladium, content is the 0.01wt%-1.0wt% of carrier gross weight, and the high molecular polymer is water-soluble polyphosphazene polymer
Close object.The activity of the catalyst in the reaction is higher, and selectivity is more preferable, and appearance glue ability is more preferable, and preparation process is easy, catalyst
Particle shape can be controlled well.CN201110089806.9 is related to a kind of for drippolene or its fraction selective hydrogenation
Palladium-silver/alumina-silica titanium catalyst, which includes the aluminium oxide-titanium oxide compound as carrier, and negative
The active component Pd and Ag being loaded on the carrier, wherein the content of Pd is based on the total catalyst weight as 0.15-0.5 weight
% is measured, it is 0.8-4.5 weight % that the content of Ag, which is based on the total catalyst weight,.Compared with similar catalyst, present invention catalysis
Agent can be used for drippolene or its fraction plus hydrogen, low temperature hydrogenation selectivity is high, and anti-As impurity ability is strong, and charging capacity is big, and
It is activity stabilized.Moreover, it relates to the preparation method of aforementioned catalytic agent.Catalyst of the present invention can also be used for other petroleum hydrocarbons
The selective hydrogenation of the alkynes and/or diolefin of class.CN200610029962.5 is related to a kind of for full-cut fraction pyrolysis gasoline choosing
Selecting property adds the method for hydrogen, mainly solves to exist in the prior art to be difficult to the full-cut fraction pyrolysis gasoline high to colloid and free water content
The technical issues of carrying out selective hydrogenation.The present invention is by using with C5Hydrocarbon-does the cracking of the hydrocarbon compound fraction for 204 DEG C
Gasoline and hydrogen are raw material, are 30-80 DEG C, reaction pressure 2.0-3.0MPa in reaction temperature, green oil air speed is 2.5-5.0
Hour- 1, under conditions of hydrogen/oil volume ratio is 60-120:1, raw material is contacted with catalyst, is reacted, and the diene in raw material is made
Hydrocarbon and alkylene aromatic component are converted to monoolefine and alkylaromatic hydrocarbon, and wherein catalyst includes alumina support, active group parting
Belong to palladium or its oxide, the element of at least one IA in the periodic table of elements or IIA or its oxide, at least one selected from member
The element of IVA or VA or its oxide in plain periodic table, carrier specific surface area are 40-160 meters2/ gram, total pore volume 0.3-1.2
Ml/g, and carrier has the technical solution of compound pore size distribution, preferably solves the problems, such as this, can be used for full fraction cracking vapour
In the industrial production of oily selective hydrogenation.The preparation method of catalyst of the present invention is identical as common lamella catalyst dipping technique:
Carrier first can be presoaked with liquid that maceration extract dissolves each other with a kind of, then with salt solution impregnation containing palladium, the carrier after dipping is through washing
Wash, dry, in air 300-600 DEG C roast up to oxidative catalyst finished product.Finished catalyst need to only lead in the reactor
Hydrogen reducing can be used.The catalyst that the present invention uses has a composite pore structural, it is biggish can several apertures, and rich in abundant
It is mesoporous.Catalyst of the invention has good low temperature active, selection when being used for full-cut fraction pyrolysis gasoline selective hydrogenation
Property and stability, and have good anti-interference, resistance to high colloid and high-content free water performance.40 DEG C of inlet temperature,
Reaction pressure 2.7Mpa, hydrogen/oil volume ratio 80:1, green oil air speed 3.8 hours-1Under the conditions of, to gum level be 150 milligrams/
Full fraction (the hydrocarbon compound fraction that C5 hydrocarbon-is done as the 204 DEG C) drippolene that 100 grams of oil, free water content are 1000ppm into
Row selective hydrogenation reaction, outlet diene average value are 0.0 gram of iodine/100 gram oil, and diolefin hydrogenation rate is 100%, are achieved preferably
Technical effect.The preparation method of the invention carrier includes mixing aluminium oxide and modifying agent, peptizing agent, water in the desired amount, squeezing
It is first 1-24 hours dry at 50-120 DEG C after item molding, it is then roasted 1-10 hours at 800-1150 DEG C, obtains aluminium oxide
Carrier.Modifying agent, peptizing agent is not expressly recited in the invention, and polyvinyl alcohol has been used in embodiment 1, thus knows that the invention has
The carrier of compound pore size distribution is obtained with polyvinyl alcohol.It mainly solves to exist in the prior art and is difficult to colloid and dissociates
The technical issues of high full-cut fraction pyrolysis gasoline of water content carries out selective hydrogenation.It is similar there are also CN200610029963.X with
And CN200610029961.0.CN02111016.6 is related to a kind of catalyst for one-stage selective hydrogenation of gasoline splitting.It is main
When solving in conventional art using one-component Metal Palladium, the selectively lower problem of diolefin hydrogenation.The present invention is by using in δ
Phase alumina supported on carriers palladium, it is 0.6-0.9 mls/g that wherein carrier hole, which holds, and specific surface area is 140-170 meters2/ gram, it urges
Agent shell thickness is that 0.03-0.09 millimeters of technical solution preferably solves the problems, such as this, can be used for one section of drippolene choosing
Selecting property adds in the industrial production of hydrogen.The selectively lower disadvantage of the invention diolefin hydrogenation provides a kind of new for drippolene
The catalyst of one-stage selective hydrogenation.The catalyst has hydrogenation activity moderate, and diolefin hydrogenation selectivity is high, has stronger anti-
Poisoning capability, the good feature of operational stability.Invention uses the cylindrical body carrier containing at least one hole, carrier due to carrier
Geometrical surface is larger, and reaction bed pressure drop is enable to reduce, and is conducive to react cooling, while bed temperature can be made more uniform, have
Conducive to the selectivity for improving purpose product, high-speed operating is adapted to；The dispersion for being conducive to palladium simultaneously, reduces the content of palladium.Carrier
Hole hold it is larger, the appearance coke ability of catalyst can be improved.By the control of Metal Palladium shell thickness at 0.03-0.09 millimeters, a side
Face is conducive to inhibit the side reaction of deep hydrogenation, is on the other hand also beneficial to the evenly dispersed of Metal Palladium, improves the utilization rate of palladium,
Help to achieve the purpose that improve selectivity.Catalyst produced by the present invention, tests prove that, diolefin hydrogenation is selectively reachable
38% or more, while there is preferable stability, achieve preferable technical effect.A kind of cracking vapour of CN200810102240.7
Oil distillate section selective hydrogenation method provides use after catalyst reduction, it is characterised in that add using palladium series hydrocatalyst
Hydrogen process conditions are as follows: liquid volume air speed≤5h-1,28-120 DEG C of reactor inlet temperature, reaction pressure >=2.4MPa, hydrogen oil
Volume ratio 50-500；Palladium series hydrocatalyst used, θ, α mixing crystal form carrying alumina with θ type aluminium oxide or based on θ type
Body in terms of catalyst weight 100%, contains active component Pd 0.2-0.5wt%, auxiliary agent 2- using Metal Palladium as active component
8wt% lanthanum and/or cerium, 2-8wt% alkali earth metal；It remains to provide use by regeneration after catalyst coking and deactivation.Herein
Under application method and process conditions, catalyst have good Hydrogenation, especially when in hydrogenating materials have minor amount of water, colloid
When, still there is good hydrogenation activity and stability.CN200310124229.8 one kind is used for drippolene C5-C9 fraction,
The especially C8-C9 double distilled component selections catalyst that is hydrogenated into alkene, including as carrier aluminium oxide, be covered in the carrier table
Alkaline-earth metal or its oxide on face and it is carried on metal Pd and Mo or Pd and W on the carrier as active component,
The content that wherein content of alkaline-earth metal is based on that the total catalyst weight is 1-3 ω %, Pd is based on the total catalyst weight
It is 1:0.5-2.5 for the weight ratio of 0.24-0.35 ω %, Pd and Mo or Pd and W.Catalyst crushing strength of the present invention is greater than 18N/
mm.The catalyst can be used for drippolene C5-C9 fraction, especially C8-C9 heavy fractioning hydrogenation, and low temperature active is high, anti-As,
S, O, N impurity ability are strong, and charging capacity is big and activity stabilized.The invention alumina catalyst carrier introduces alkaline-earth metal and is changed
Property, it can also be used to the selection of the alkynes or diolefin of other petroleum hydrocarbons adds hydrogen.A kind of unsaturated hydrocarbons of CN200810114744.0
Selective hydrogenation catalyst and preparation method thereof.The catalyst includes on the basis of the total weight of catalyst using aluminium oxide as carrier
Following components: using palladium as active component, palladium content 0.1-1.0%, rare earth metal content 0.3-8.0%, alkaline-earth metal contain
Amount is 0.1-5.0%, in addition can also contain fluorine, fluorine content 0-3.0%.Catalyst carrier is θ or mixes crystal form Al2O3, with θ
Based on crystal form.The palladium catalyst is distributed preferably in the secondary outer layer of catalyst；The catalyst has certain anti-impurity and anti-coking
Energy；The catalyst is suitable for full-cut fraction pyrolysis gasoline one-stage selective hydrogenation process, is also applied in other distillates unsaturated
Hydrocarbon-selective hydrogenation process.
The prior art changes support chemistry composition and type, and addition coagent mainly to promote catalyst performance
Energy.Since the impurity such as As, S, O, N and gum level are higher in drippolene, catalyst is set to be easy inactivation, it is therefore desirable to crack vapour
Oily catalyst has appearance glue ability good, anti-arsenic, sulfur resistive, the characteristic for inhibiting coking ability strong.
Summary of the invention
The present invention provides a kind of method for cracking the selective hydrogenation of C6-C8 fraction, is particularly suitable for drippolene C8 fraction
Selective hydrogenation.The process uses load type palladium catalyst, and carrier is the alumina support with macroporous structure, macropore oxygen
Change the characteristics of aluminium is adjustable with pore size, and macropore ratio can be controlled effectively.The activity of the catalyst in the reaction is higher,
Selectivity is more preferable, and appearance glue ability is more preferable, and anti-arsenic, inhibits coking ability strong at sulfur resistive, splits to different arsenic contents, different sulfur contents
Solution gasoline stocks are adaptable, and catalyst low-temperature activity is good.
A method of cracking C6-C8 fraction selective hydrogenation, catalyst includes the alumina support with macroporous structure
With the metal active component palladium being carried on carrier, the content of palladium is 0.2-0.35wt% based on the total weight of the catalyst, excellent
0.25-0.3wt% is selected, alumina support is using chitosan as expanding agent；Contain adjuvant component phosphorus and magnesium, auxiliary agent group in carrier
Dividing the content of phosphorus and magnesium to account for the percentage composition of carrier quality is respectively P2O50.1-2.5wt%, MgO 0.1-2.5wt%, aperture
It is distributed 60-180nm, preferably 65-150nm, macropore ratio 2-75%, preferably 5-65%, hole holds 0.8-2.0ml/g, preferably 0.8-
1.3ml/g or preferred 1.6-2.0ml/g, specific surface area 250-300m2/g；
Hydrogenation process conditions: reaction inlet temperature≤45 DEG C, reaction pressure 2.5-4.5MPa, hydrogen to oil volume ratio 60-450；
Liquid volume air speed 3.0-5.5h-1。
Preferably, the hydrogenation process conditions: liquid volume air speed 3.0-4.5h-1, react inlet temperature≤40 DEG C, reaction
Pressure 2.5-4.0MPa, hydrogen to oil volume ratio 60-300.
Also contain adjuvant component cerium in the alumina support with macroporous structure, the content of adjuvant component cerium oxide accounts for
The percentage composition of carrier quality is 0.1-2.5wt%.
The preparation method of the catalyst by active component palladium dipping, can spray to load using the methods of dipping, spraying
On body, then catalyst is dried, roasts and obtains the catalyst.Such as catalyst can be prepared according to the following steps:
Prepare palladium-containing solution dipping have macroporous structure alumina support, through 110-160 DEG C drying 3-9 hours, 400-650 DEG C roast
4-9 hours, finally obtain catalyst prod.
In the preparation method of catalyst of the present invention, palladium compound used can be any one disclosed in prior art
Suitable for the palladium compound of palladium catalyst processed, such as palladium chloride, palladium nitrate, palladium sulfate, tetrachloro-palladium acid aluminium, four cyano palladium acid aluminium, four nitre
Base palladium acid sodium, acylate such as oxalic acid palladium of palladium etc..To prepare solvent used in palladium compound solution do not have it is any specifically limited,
As long as it can dissolve used palladium compound.Preferred solvent be for example water, dilute hydrochloric acid, dust technology, dilute sulfuric acid or
Their mixed liquor.
Alumina support of the present invention with macroporous structure, aperture can by change expanding agent additional amount and
The molecular size range of expanding agent is adjusted.Pore-size distribution can change between 60-180nm, such as 60-90nm, 100-
The ranges such as 160nm, 120-180nm.Macropore ratio is 2-75%, can be tuned as 5-30%, the models such as 35-50%, 55-75%
It encloses.
The present invention also provides a kind of preparation methods of alumina support with macroporous structure, firstly, being acidified with acid solution
Chitosan, then by boehmite and sesbania powder be added in kneader be uniformly mixed, add phosphoric acid, magnesium nitrate mixing it is molten
The acid solution of chitosan-containing is finally added in boehmite powder and mediates the uniformly addition of the acid solution containing expanding agent by liquid
Amount is 0.1-8wt%, the preferably 0.2-5.0wt% of boehmite, by extrusion-molding-drying-roasting, obtains having big
The alumina support of pore structure.
The preparation method of alumina support with macroporous structure may be incorporated into cerium, such as by cerous nitrate and magnesium nitrate one
It plays mixing to be added in carrier, obtains the alumina support of phosphorous, magnesium, cerium.
The process of the acid solution acidified chitosan is as follows: first by chitosan expanding agent be added to 30-95 DEG C go from
In sub- water, acid is added dropwise later, until chitosan dissolution is completely, obtains the acid solution containing expanding agent.The acid can be inorganic acid
Or organic acid, preferably acetic acid, formic acid, malic acid, lactic acid etc..The additional amount of acid is advisable with that can be completely dissolved chitosan.It can also
To select water soluble chitosan, such as carboxyl chitosan, chitosan salt, sulfated chitosan etc..Chitosan acid solution is best
With ultrasonic oscillation or magnetic agitation.Ultrasonic oscillation 10min or more, magnetic agitation 0.5-2h.Ultrasound is carried out to expanding agent
Wave concussion or magnetic agitation, expanding agent good dispersion, alumina support is more prone to produce macropore, and pore-size distribution more collects
In, pore-size distribution is in 70-180nm.The additional amount of the sesbania powder is the 0.1-7wt% of boehmite.
It mediates or extrusion technique is that the configured acid solution containing expanding agent is added in sesbania powder and boehmite
Be uniformly mixed, later extrusion, molding, by 100-160 DEG C drying 3-9 hours, 650-800 DEG C roasting 4-8 hours, finally obtain
Alumina support with macroporous structure.
Alumina support of the present invention uses chitosan for expanding agent, and the alumina support of preparation contains macroporous structure,
Also contain meso-hole structure simultaneously, macropore range is a kind of big containing Jie-in 2-50nm, mesoporous ratio 15-75%, preferably 15-50%
The alumina support in hole.And aperture is not uniform aperture structure.
The alumina support with macroporous structure obtained using preparation method of the present invention can also utilize phosphorus and magnesium
Carrier surface is modified, the concentration of phosphorus and magnesium is unsuitable excessively high, and preferably configuration concentration is lower than phosphorus when preparing complex carrier
Acid and magnesium nitrate aqueous solution spray carrier surface, preferably carry out carrier surface modification as follows: configuration phosphoric acid and nitre
The aqueous solution spray of sour magnesium has the alumina support of macroporous structure, obtains used additives phosphorus through drying, roasting and magnesium carries out surface
Modified alumina support, control is with phosphorus pentoxide in the alumina support of macroporous structure and content of magnesia in 0.1-
In the range of 2.5wt%, and the content of carrier surface phosphorus pentoxide and magnesia is made to be internal phosphorus pentoxide and magnesia
1.1-1.6 times of content.
The above-mentioned alumina support containing adjuvant component phosphorus, magnesium and cerium, can also using phosphorus, magnesium and cerium to carrier surface into
Row is modified, and the aqueous solution of configuration phosphoric acid, magnesium nitrate and cerous nitrate sprays carrier surface, preferably carries out carrier as follows
Surface is modified: the aqueous solution spray of configuration phosphoric acid, magnesium nitrate and cerous nitrate has the alumina support of macroporous structure, through dry
Dry, roasting obtains used additives phosphorus, magnesium and cerium and carries out the modified alumina support in surface, controls the carrying alumina with macroporous structure
The content of phosphorus pentoxide, magnesia and cerium oxide is all in the range of 0.1-2.5wt% in body, and aoxidizes carrier surface five
The content of two phosphorus, magnesia and cerium oxide is 1.1-1.6 times of internal phosphorus pentoxide, magnesia and cerium-oxide contents.
Compared with prior art, the invention has the following advantages that
1, for catalyst carrier of the present invention using chitosan as expanding agent, expanding agent chitosan is cheap, and environmental protection
It is nontoxic, it is suitble to industrialized production.The obtained alumina support with macroporous structure, pore size is adjustable, and macropore ratio can
Effectively to control.And carrier also contains mesoporous, is a kind of Jie-macropore alumina supporter.Catalyst carrier has macroporous structure,
It is good to hold glue ability, inhibits coking ability strong, anti-arsenic, sulfur resistive effect are good.
2, the present invention can also in alumina support and carrier surface introduce cerium, make carrier surface cerium content be higher than carry
Internal portion, there is the alumina support of macroporous structure to be prepared into one-stage selective hydrogenation of gasoline splitting catalyst, be able to suppress for this
Olefinic polymerization improves diolefin hydrogenation selectivity.
3, the alumina support with macroporous structure that the present invention obtains is big to having using phosphorus and magnesium or phosphorus, magnesium and cerium
The alumina carrier surface of pore structure is modified, and make carrier surface phosphorus pentoxide, magnesia, cerium oxide content be interior
Portion's phosphorus pentoxide, magnesia, 1.1-1.6 times of cerium-oxide contents.Carrier surface is modified by the way of spray, energy
The partial pore of enough effective peptization carrier surfaces, advantageously reduces the micropore ratio of carrier surface in this way, improves carrier surface Jie-
Macropore ratio promotes carrier surface to produce more active sites load centres, effectively improves the utilization rate of palladium, improves cracking vapour
Oily selective hydrogenation activity.And concentration of component different structure inside and outside this carrier, so that alkynes and alkadienes is not easily accessed hole
Polymerization reaction occurs inside road and blocks duct.Dipping method should not be used to the improvement of carrier surface, impregnated carrier surface can make greatly
Amount moisture enters carrier, is not achieved and improves carrier surface Jie-macropore ratio purpose.
Detailed description of the invention
Fig. 1 is the graph of pore diameter distribution of the alumina support with macroporous structure prepared by embodiment 3.
Specific embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as to limit of the invention
System.
Prepare primary raw material source used in catalyst: source chemicals used in the present invention are commercial product.
Embodiment 1
8.0g water soluble chitosan expanding agent is added in 50 DEG C of deionized water first, acetic acid is added dropwise later, until
Chitosan dissolution completely, obtains the acid solution containing expanding agent.Phosphatase 11 .46g, magnesium nitrate 7.35g are weighed respectively, by phosphoric acid and nitre
Sour magnesium, which is dissolved completely in 70g distilled water, is made into phosphorous, magnesium aqueous solution.Weigh 350g boehmite powder and the field 20.0g
Cyanines powder is added in kneader, and is uniformly mixed, and the mixed solution of phosphoric acid and magnesium nitrate is added, finally by the acid of chitosan-containing
Solution, which is added in boehmite, to be mediated uniformly, is clover shape by kneading-extruded moulding.It is small in 120 DEG C of dryings 8
When, 700 DEG C roast 4 hours, obtain phosphorous and magnesium alumina support 1.Phosphorus pentoxide 0.5wt%, magnesia in carrier 1
0.8wt%.Alumina support specific surface area and pore-size distribution with macroporous structure are shown in Table 1.
150ml water is added in palladium chloride, is added and is diluted to 1L with ionized water again after dissolving with hydrochloric acid and is made into palladium solution, according to
Required shell thickness adjusts pH value；Carrier is presoaked with ionized water again, palladium solution impregnating carrier is used after being filtered dry moisture, after being filtered dry moisture
130 DEG C of drying, 450 DEG C roast 5 hours, obtain catalyst 1.1 palladium content of catalyst is 0.27wt%.
Embodiment 2
8.0g water soluble chitosan expanding agent is added in 50 DEG C of deionized water, acetic acid is added dropwise later, until shell is poly-
Sugar dissolution completely, obtains the acid solution containing expanding agent.Phosphatase 11 .09g, magnesium nitrate 9.12g are weighed respectively, by phosphoric acid and magnesium nitrate
It is dissolved completely in 70g distilled water and is made into phosphorous, magnesium aqueous solution.Weigh 350g boehmite powder and 20.0g sesbania powder
It is added in kneader, and is uniformly mixed, add the mixed solution of phosphoric acid and magnesium nitrate, finally by the acid solution of chitosan-containing
It is added in boehmite and mediates uniformly, be clover shape by kneading-extruded moulding.It is 8 hours dry at 120 DEG C, 700
DEG C roasting 4 hours, obtain phosphorous and magnesium alumina support 1.It recycles phosphorus and magnesium to be modified carrier surface, configures phosphorous
The aqueous solution of acid and magnesium nitrate spray has the alumina support 1 of macroporous structure, and 8 hours dry through 120 DEG C, 700 DEG C of roastings 4 are small
When obtain used additives phosphorus and magnesium and carry out the modified alumina support 2 in surface, the content of carrier surface phosphorus pentoxide and magnesia
It is 1.2 times of internal phosphorus pentoxide and content of magnesia.Alumina support specific surface area and aperture point with macroporous structure
Cloth is shown in Table 1.
Palladium solution impregnation of alumina carrier 2 is configured, 6 hours dry at 120 DEG C, 500 DEG C roast 5 hours, are catalyzed
Agent 2.2 palladium content of catalyst is 0.31wt%.
Embodiment 3
The preparation method of carrier is carried out according to embodiment 1.The difference is that adjuvant component also contains cerium in carrier, by water
Soluble chitosan expanding agent is changed to water-insoluble chitosan expanding agent, and chitosan formic acid liquid magnetic stirrer 30 is divided
Clock obtains the alumina support 3 with macroporous structure.The content of adjuvant component phosphorus, magnesium and cerium accounts for the hundred of carrier quality in carrier
Point content is respectively 1.8wt%, 2.0wt%, 0.6wt%.Its specific surface area and pore-size distribution are shown in Table 1.
Palladium solution impregnation of alumina carrier 3 is configured, 6 hours dry at 120 DEG C, 500 DEG C roast 5 hours, are catalyzed
Agent 3.3 palladium content of catalyst is 0.29wt%.
Embodiment 4
The preparation method of carrier is carried out according to embodiment 3.The difference is that water soluble chitosan expanding agent is changed to
Water-insoluble chitosan expanding agent, chitosan acetic acid solution was with ultrasonic oscillation 15 minutes.Obtain the aluminium oxide with macroporous structure
Carrier.In carrier the content of adjuvant component phosphorus, magnesium and cerium account for the percentage composition of carrier quality be respectively 1.6wt%, 1.6wt%,
0.6wt%.It recycles phosphorus, magnesium and cerium to be modified carrier surface, obtains carrier 4,4 surface phosphorus pentoxide of carrier, oxidation
The content of cerium and magnesia is 1.5 times of internal phosphorus pentoxide, cerium oxide and content of magnesia.Oxidation with macroporous structure
4 specific surface area of alumina supporter and pore-size distribution are shown in Table 1.
Palladium solution impregnation of alumina carrier 4 is configured, 7 hours dry at 125 DEG C, 480 DEG C roast 6 hours, are catalyzed
Agent 4.4 palladium content of catalyst is 0.30wt%.
Catalyst 1-4 is respectively charged into 100ml insulation bed reaction device, at 120 DEG C of temperature, the body of hydrogen and catalyst
Product cools to 40 DEG C of laggard feedstock oils, drippolene C8 fraction diene content is 19.13g than restoring 7 hours under the conditions of 200:1
Iodine/100g oil, gum level are 208mg/100ml oil, bromine valency is 38.94g bromine/100g oil, sulfur content is 103ppm and arsenic contains
Amount is 190ppb；Reaction process condition are as follows: 40 DEG C of inlet temperature, hydrogen to oil volume ratio 110:1, reaction pressure 2.8MPa, green oil
Air speed 6.0h-1；The average diene for operating 1 hydrogenated products of 180h catalyst is 0.52 gram of iodine/100 gram oil, and bromine valency is 20.83 grams
Bromine/100 gram oil, diolefin hydrogenation rate 97.1%；The average diene for operating 2 hydrogenated products of 180h catalyst is 0.35 gram of iodine/100 gram
Oil, bromine valency are 19.21 grams of bromine/100 gram oil, diolefin hydrogenation rate 98.2%.The average diene of 3 hydrogenated products of catalyst is 0.41 gram
Iodine/100 gram oil, bromine valency are 19.52 grams of bromine/100 gram oil, diolefin hydrogenation rate 97.5%.The average diene of 4 hydrogenated products of catalyst
For 0.31 gram of iodine/100 gram oil, bromine valency is 19.04 grams of bromine/100 gram oil, diolefin hydrogenation rate 98.5%.
Under the conditions of feedstock oil gum level is 208mg/100ml oil, sulfur content is 103ppm and arsenic content is 190ppb,
0.52 gram of iodine/100 gram of average diene oil left and right of hydrogenated products, 97.1% or more diolefin hydrogenation rate, catalyst activity is higher, choosing
Selecting property is more preferable, and appearance glue ability is more preferable, and anti-arsenic, inhibits coking ability strong at sulfur resistive.
After catalyst 1-4 operates 450h, the average diene of 1 hydrogenated products of catalyst is 0.89 gram of iodine/100 gram oil, diene
Hydrogenation rate 96.7%；The average diene of 2 hydrogenated products of catalyst is 0.42 gram of iodine/100 gram oil, diolefin hydrogenation rate 97.9%.It urges
The average diene of 3 hydrogenated products of agent is 0.61 gram of iodine/100 gram oil, diolefin hydrogenation rate 97.3%.4 hydrogenated products of catalyst
Average diene is 0.33 gram of iodine/100 gram oil, diolefin hydrogenation rate 98.4%.Catalyst appearance glue ability is good, and anti-arsenic, inhibits knot at sulfur resistive
Burnt ability is strong, catalyst performance stabilised.
Catalyst 3 and 4 is respectively charged into 100ml insulation bed reaction device, at 120 DEG C of temperature, hydrogen and catalyst
It is restored 7 hours under the conditions of volume ratio 200:1, cools to 40 DEG C of laggard feedstock oils, drippolene C6-C8Fraction, diene content are
17.24g iodine/100g oil, bromine valency are 28.03g bromine/100g oil, gum level is 34mg/100ml oil, sulfur content be 142ppm and
Arsenic content is 143ppb；Reaction process condition are as follows: 45 DEG C of inlet temperature, hydrogen to oil volume ratio 250:1, reaction pressure 3.0MPa, newly
Fresh oil air speed 3.0h-1；The average diene for operating 3 hydrogenated products of 180h catalyst is 0.40 gram of iodine/100 gram oil, bromine valency 16.31
Gram bromine/100 gram.The average diene for operating 4 hydrogenated products of 180h catalyst is 0.32 gram of iodine/100 gram oil, and bromine valency is 16.12 grams
Bromine/100 gram oil.It is that 34mg/100ml is oily, sulfur content is 142ppm and arsenic content is 143ppb condition in feedstock oil gum level
Under, 0.40 gram of iodine/100 gram of average diene oil left and right of hydrogenated products, catalyst appearance glue ability is good, and anti-arsenic, inhibits coking at sulfur resistive
Ability is strong, and catalyst is adaptable to the feedstock oil of different sulfur contents, gum level, arsenic content.
The alumina support specific surface area and pore-size distribution of 1 macropore of table
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (4)
1. a kind of method for cracking the selective hydrogenation of C6-C8 fraction, it is characterised in that:
Catalyst includes the alumina support with macroporous structure and the metal active component palladium being carried on carrier, the content of palladium
Total weight based on the catalyst is 0.20-0.30wt%, and alumina support, as expanding agent, has macropore knot using chitosan
Contain adjuvant component phosphorus, magnesium and cerium in the alumina support of structure, the percentage that the content of adjuvant component phosphorus and magnesium accounts for carrier quality contains
Amount is respectively P2O5The content of 0.1-2.5wt%, MgO 0.1-2.5wt%, adjuvant component cerium oxide account for the percentage of carrier quality
Content is 0.10-2.5wt%, pore-size distribution 60-180nm, macropore ratio 2-75%, and hole holds 0.8-2.0ml/g, specific surface area
250-300m2/g；
The preparation method of the alumina support with macroporous structure includes the following steps: firstly, poly- with acid solution acidification shell
Then boehmite and sesbania powder are added in kneader and are uniformly mixed, add phosphoric acid, magnesium nitrate and cerous nitrate by sugar
The acid solution of chitosan-containing is finally added in boehmite and mediates uniformly by mixed solution, the acid solution containing expanding agent
Additional amount is that the 0.1-8wt% of boehmite obtains the oxidation with macroporous structure by extrusion-molding-drying-roasting
Alumina supporter；
To the obtained alumina support with macroporous structure, be modified using phosphorus, magnesium and cerium to carrier surface: configuration is phosphorous
The aqueous solution spray of acid, magnesium nitrate and cerous nitrate has the alumina support of macroporous structure, obtains used additives through drying, roasting
Phosphorus, magnesium and cerium carry out the modified alumina support in surface, control phosphorus pentoxide, oxygen in the alumina support with macroporous structure
Change the content of magnesium and cerium oxide all in the range of 0.1-2.5wt%, and makes carrier surface phosphorus pentoxide, magnesia and oxidation
The content of cerium is 1.1-1.6 times of internal phosphorus pentoxide, magnesia and cerium-oxide contents；
The hydrogenation process conditions: reaction inlet temperature≤45 DEG C, reaction pressure 2.5-4.5MPa, hydrogen to oil volume ratio 60-
450；Liquid volume air speed 3.0-5.5h-1。
2. a kind of method for cracking the selective hydrogenation of C6-C8 fraction according to claim 1, it is characterised in that: described to add
Hydrogen process conditions are as follows: liquid volume air speed 3.0-4.5h-1, react inlet temperature≤40 DEG C, reaction pressure 2.5-4.0MPa, hydrogen oil
Volume ratio 60-300.
3. a kind of method for cracking the selective hydrogenation of C6-C8 fraction according to claim 1, it is characterised in that: the oxygen
Change alumina supporter and also contain meso-hole structure simultaneously, macropore range is in 2-50nm, mesoporous ratio 15-75%.
4. a kind of method for cracking the selective hydrogenation of C6-C8 fraction according to claim 1, it is characterised in that: the use
Acid solution acidified chitosan, acid are one or more of acetic acid, formic acid, malic acid or lactic acid, chitosan acid solution ultrasound
Wave concussion or magnetic agitation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710409059.XA CN107189812B (en) | 2017-06-02 | 2017-06-02 | A method of cracking C6-C8 fraction selective hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710409059.XA CN107189812B (en) | 2017-06-02 | 2017-06-02 | A method of cracking C6-C8 fraction selective hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107189812A CN107189812A (en) | 2017-09-22 |
| CN107189812B true CN107189812B (en) | 2019-01-25 |
Family
ID=59877760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710409059.XA Expired - Fee Related CN107189812B (en) | 2017-06-02 | 2017-06-02 | A method of cracking C6-C8 fraction selective hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107189812B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3988210A4 (en) * | 2019-06-21 | 2023-07-05 | Heesung Catalysts Corporation | Catalyst for synthesis of hydrogen peroxide and recovery, and method of preparing same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429890A (en) * | 2001-12-31 | 2003-07-16 | 北京燕山石油化工公司研究院 | Catalyst used for cracking gusoline selective hydrogenation, its preparation method and use |
| CN101121899A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Selectivity hydrogenation method for whole fraction crack petroleum |
| CN101433841A (en) * | 2007-12-13 | 2009-05-20 | 中国石油天然气股份有限公司 | Selectively hydrogenating catalyst and preparation method thereof |
| CN102728351A (en) * | 2011-04-11 | 2012-10-17 | 中国石油化工股份有限公司 | Pd-Ag/Al2O3-TiO2 catalyst for selective hydrogenation of cracked gasoline or its fractions, and preparation method thereof |
| CN103706408A (en) * | 2013-12-18 | 2014-04-09 | 宁波金远东工业科技有限公司 | Protective agent of coal tar hydrogenation catalyst and preparation method of protective agent |
-
2017
- 2017-06-02 CN CN201710409059.XA patent/CN107189812B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429890A (en) * | 2001-12-31 | 2003-07-16 | 北京燕山石油化工公司研究院 | Catalyst used for cracking gusoline selective hydrogenation, its preparation method and use |
| CN101121899A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Selectivity hydrogenation method for whole fraction crack petroleum |
| CN101433841A (en) * | 2007-12-13 | 2009-05-20 | 中国石油天然气股份有限公司 | Selectively hydrogenating catalyst and preparation method thereof |
| CN102728351A (en) * | 2011-04-11 | 2012-10-17 | 中国石油化工股份有限公司 | Pd-Ag/Al2O3-TiO2 catalyst for selective hydrogenation of cracked gasoline or its fractions, and preparation method thereof |
| CN103706408A (en) * | 2013-12-18 | 2014-04-09 | 宁波金远东工业科技有限公司 | Protective agent of coal tar hydrogenation catalyst and preparation method of protective agent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3988210A4 (en) * | 2019-06-21 | 2023-07-05 | Heesung Catalysts Corporation | Catalyst for synthesis of hydrogen peroxide and recovery, and method of preparing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107189812A (en) | 2017-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107159283B (en) | A kind of method of cracking c5-C9 fraction selective hydrogenation | |
| CN107185567B (en) | A kind of nickel system selective hydrocatalyst and preparation method thereof | |
| CN107096552B (en) | A kind of catalyst and preparation method for FCC gasoline removal of mercaptans | |
| CN106994361B (en) | A kind of alumina support and preparation method with macroporous structure | |
| CN107081155B (en) | A kind of catalyst and preparation method for catalytic gasoline hydrogenation desulfurization | |
| CN107159279B (en) | A kind of one-stage selective hydrogenation of gasoline splitting catalyst and preparation method thereof | |
| CN107177371B (en) | A kind of hydrodesulfurizationprocess process of catalytically cracked gasoline | |
| CN104646050B (en) | A kind of hydrogenation catalyst and its preparation and application | |
| CN106747591B (en) | A kind of macropore holds the preparation method of alumina support | |
| CN105440168B (en) | The composite mesoporous carrier of spherical montmorillonite and support type polyethylene catalysts and its preparation method and application | |
| CN107057757B (en) | A kind of method of one-stage selective hydrogenation of gasoline splitting | |
| CN106179474B (en) | A kind of Hydrobon catalyst and its preparation method | |
| CN109894122A (en) | A kind of FCC gasoline Hydrobon catalyst and preparation method thereof | |
| CN108160103A (en) | The preparation of high dispersive transition metal nanoparticles support type porous zeotile aggregation | |
| CN107177370B (en) | A method of being used for FCC gasoline removal of mercaptans | |
| CN107189812B (en) | A method of cracking C6-C8 fraction selective hydrogenation | |
| CN104891539A (en) | Chambering method for spherical aluminum oxide particles | |
| CN107189811B (en) | A kind of full-cut fraction pyrolysis gasoline section selective hydrogenation method | |
| CN103638968B (en) | Preparation method and application method of non-noble metal reforming catalyst | |
| CN108452839B (en) | Mesoporous-microporous composite molecular sieve, catalyst, preparation method and application thereof | |
| Liang et al. | Borax-assisted hydrothermal carbonization to fabricate monodisperse carbon spheres with high thermostability | |
| CN106179382B (en) | A kind of preparation method of body phase hydrotreating catalyst | |
| CN108786833A (en) | A kind of heavy-oil hydrogenation catalyst and preparation method thereof | |
| CN103771475B (en) | A kind of gama-alumina raw powder's production technology | |
| CN107344105B (en) | Hydrocracking catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190125 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |