CN107303484B - A kind of preparation method and hydrotreating catalyst of siliceous macropore alumina supporter - Google Patents
A kind of preparation method and hydrotreating catalyst of siliceous macropore alumina supporter Download PDFInfo
- Publication number
- CN107303484B CN107303484B CN201610252534.2A CN201610252534A CN107303484B CN 107303484 B CN107303484 B CN 107303484B CN 201610252534 A CN201610252534 A CN 201610252534A CN 107303484 B CN107303484 B CN 107303484B
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- Prior art keywords
- acid
- boehmite
- siliceous
- hours
- carbon black
- Prior art date
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Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 73
- 239000000843 powder Substances 0.000 claims abstract description 59
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 45
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000006229 carbon black Substances 0.000 claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 35
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000007598 dipping method Methods 0.000 claims abstract description 16
- 239000003292 glue Substances 0.000 claims abstract description 15
- 238000004898 kneading Methods 0.000 claims abstract description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 14
- 238000001125 extrusion Methods 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 9
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- 239000004202 carbamide Substances 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910001868 water Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 8
- 238000007781 pre-processing Methods 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 6
- 241001502050 Acis Species 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 235000010447 xylitol Nutrition 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 4
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 claims description 4
- 229930091371 Fructose Natural products 0.000 claims description 4
- 239000005715 Fructose Substances 0.000 claims description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 4
- 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 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229930195725 Mannitol Natural products 0.000 claims description 4
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 claims description 4
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 4
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 239000000594 mannitol Substances 0.000 claims description 4
- 235000010355 mannitol Nutrition 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000811 xylitol Substances 0.000 claims description 4
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 4
- 229960002675 xylitol Drugs 0.000 claims description 4
- 238000010009 beating Methods 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000000274 adsorptive effect Effects 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- -1 sorbierite Chemical compound 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000000465 moulding Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- 241000772415 Neovison vison Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910018551 Ni—NH Inorganic materials 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WCJJSOKIRDOTGW-UHFFFAOYSA-N C(C)O.[Si](OC)(O)(O)O Chemical compound C(C)O.[Si](OC)(O)(O)O WCJJSOKIRDOTGW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 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 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007324 demetalation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UUYKGYZJARXSGB-UHFFFAOYSA-N ethanol;ethoxy(trihydroxy)silane Chemical compound CCO.CCO[Si](O)(O)O UUYKGYZJARXSGB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- C10G45/06—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 nickel or cobalt metal, or compounds thereof
- C10G45/08—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 nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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Abstract
The present invention provides the preparation method and hydrotreating catalyst of a kind of siliceous macropore alumina supporter, and carrier preparation includes: that (1) with the aqueous solution containing polyalcohol and/or glucide impregnates boehmite dry glue powder, and the material after dipping carries out hydro-thermal charing process；(2) carbon black powder is impregnated with siliceous solution, carbon black powder and step (1) boehmite, extrusion aid, peptizing agent kneading are at plastic after dipping, first in a nitrogen atmosphere then roasting roasts material after extrusion, drying, drying in air atmosphere, and silica containing alumina support is made.The hydrotreating catalyst includes above-mentioned carrier and hydrogenation active component.The alumina support of this method preparation mechanical strength with higher while having large hole appearance with aperture, the carrier are suitable for the fields such as preparation weight, residuum hydrogenating and metal-eliminating catalyst.
Description
Technical field
The invention belongs to field of hydrogenation, and the preparation method and one kind more particularly to a kind of siliceous macropore alumina supporter add
Hydrogen handles catalyst.
Background technique
Currently, in the production process of mink cell focus hydrodemetallization, since feedstock oil contains a certain amount of vanadium, sulphur, arsenic, nickel
Equal impurity, easily form deposition, so that the duct of blocking catalyst, causes catalyst activity to decline rapidly, or even inactivation, influence
Industrial application.Hold with large hole and the catalyst of larger bore dia holds metal and appearance coke formation is strong, catalyst can be slowed down
The operation cycle for inactivating, making catalyst extends.The pore structure of catalyst is determined that therefore, preparation has by the carrier for constituting catalyst
Large hole is held and the carrier of larger bore dia is to prepare residual oil, especially prepare and add for the higher decompression residuum of tenor
The key of hydrogen catalyst for demetalation.
CN1160602A disclose a kind of macropore alumina supporter for being suitable as Hydrodemetalation catalyst carrier and its
Preparation method.The preparation method of the macropore alumina supporter includes that boehmite dry glue powder is mixed with water or aqueous solution,
It is kneaded into plastic, obtained plastic is extruded into bar on banded extruder, drying simultaneously roasts to obtain product, its main feature is that,
It is additionally added carbon black powder in above process as physics expanding agent and chemical action can occur with boehmite or aluminium oxide
The chemical enlargement agent of phosphorous, silicon or boron compound.Wherein carbon black powder dosage is 3-10 weight %(on the basis of the weight of aluminium oxide).
Alumina support obtained can be used for preparing mink cell focus especially residuum hydrogenating and metal-eliminating and/or Hydrobon catalyst.
US4448896 is proposed using carbon black as expanding agent.Expanding agent is uniformly mixed with boehmite dry glue powder, to
Aqueous solution of nitric acid kneading 30 minutes that mass fraction is 4.3% are added in said mixture, it is 2.1% that mass fraction, which is then added,
Ammonia spirit kneading 25 minutes, kneading uniformly after extruded moulding, carrier after molding, which is fired, is made final alumina support.Its
The additional amount of middle carbon black powder is preferably greater than the 20% of activated alumina or its precursor weight.
CN102441436A discloses a kind of preparation method of alumina support.This method prepares the step of alumina support such as
Under: (1) boehmite dry glue powder and extrusion aid be uniformly mixed, and is then added and has dissolved physics expanding agent and chemical enlargement agent
Aqueous solution；(2) step (1) resulting material is uniformly mixed, the extruded moulding on banded extruder；(3) step (2) resulting material is dry
Final alumina support is made in dry, roasting.
In conclusion usually using physics expanding agent and chemical enlargement during prior art preparation macropore alumina supporter
Agent improves the aperture of carrier, and the addition of expanding agent can be such that alumina support macropore content increases really.But in alumina support
Forming process, need to be by kneadings such as boehmite dry glue powder, extrusion aid, peptizing agents at plastic, then extruded moulding, due to squeezing
The presence of the larger pressure of process can make the macropore of alumina powder itself that part occur to collapse, to make the Kong Rong of final carrier
And macropore content substantially reduces.In addition, the mechanical strength of the alumina support of existing method preparation needs to be further increased.
Summary of the invention
Aiming at the shortcomings of the prior art, the present invention provides a kind of preparation method of siliceous macropore alumina supporter, this method
The alumina support of preparation mechanical strength with higher while having large hole appearance with aperture, present invention simultaneously provides one kind
Hydrotreating catalyst, the catalyst are suitable for preparation weight, residuum hydrogenating and metal-eliminating field.
The preparation method of siliceous macropore alumina supporter of the invention, comprises the following processes:
(1) impregnate boehmite dry glue powder with the aqueous solution containing polyalcohol and/or glucide, the material after dipping into
Row hydro-thermal charing process；
(2) carbon black powder is impregnated with siliceous solution, carbon black powder and step (1) boehmite, extrusion aid, peptizing agent after dipping
Kneading is at plastic, and first in a nitrogen atmosphere then roasting roasts the material after extrusion, drying, drying in air atmosphere, makes
Obtain silica containing alumina support.
In the method for the present invention, polyalcohol described in step (1) is in xylitol, sorbierite, mannitol or arabite
It is one or more of；The carbohydrate is the mixing of one or more of glucose, ribose or fructose etc.；Containing polyalcohol and/or sugar
The mass concentration of the aqueous solution of substance is 20%-40%.The dosage of aqueous solution containing polyalcohol and/or glucide is thin for that will intend
Diaspore dry glue powder is totally submerged, and dip time is 3-5 hours.
In the method for the present invention, hydro-thermal charing process described in step (1) is the heat treatment carried out in sealing device, preferably
Autoclave can be dynamic response kettle or static reaction kettle, preferably static reaction kettle；The hydro-thermal charing process temperature
It is 120-160 DEG C, the processing time is 8-16 hours.
In the method for the present invention, preferably the boehmite in step (1) is pre-processed, preprocessing process is as follows: will
Boehmite is mixed with beating with deionized water, and the mixed acid solution of appropriate organic acid and inorganic acid is added in Xiang Shangshu slurries,
The pH value for controlling slurries is 2-5, carries out being heated to reflux processing；Appropriate urea is added into above-mentioned slurries and carries out hydro-thermal process, water
Slurries after heat treatment are washed, dry.
Wherein, the described process that is mixed with beating is carried out using conventional method in that art, boehmite and deionized water
Mass ratio is preferably 1:3-1:10；The organic acid is the mixing of one or more of acetic acid, oxalic acid or citric acid, described
Inorganic acid is the mixing of one or more of sulfuric acid, nitric acid or hydrochloric acid；The substance of organic acid and inorganic acid in mixed acid solution
Amount ratio be 1:3-1:6, the concentration of the mixed acid solution is calculated as 3-6mol/L with inorganic acid；It is described to be heated to reflux treatment temperature
It is 30-60 DEG C, being heated to reflux the time is 1-5 hours；The mass ratio of the amount of urea and boehmite is 1:5-1:10；
Borate preferably is added simultaneously while urea is added, the borate can be metaborate, ortho-borate and more boron
The mixing of one or more of hydrochlorate, the additional amount of borate is 0.5:100- with the mass ratio of boehmite in terms of boron oxide
1.5:100；The hydro-thermal process is the heat treatment under the self-generated pressure of autoclave, and treatment temperature is 120-160 DEG C,
Handling the time is 4-8 hours；The drying temperature is 100-120 DEG C, and drying time is 6-10 hours.
In the method for the present invention, siliceous solution described in step (2) is the ethanol solution containing esters of silicon acis, and wherein esters of silicon acis is selected from
One or more of methyl orthosilicate, ethyl orthosilicate or butyl silicate.
In the method for the present invention, in siliceous solution described in step (2), silicone content is calculated as final vehicle weight with silica
2wt%-6wt%, the dosage of siliceous solution is the 30%-50% of carbon black powder saturated water adsorptive value.
In the method for the present invention, the dosage of carbon black powder described in step (2) is the 20%- of boehmite dry glue powder weight
40%。
In the method for the present invention, extrusion aid described in step (2) is one of sesbania powder, starch or methylcellulose or several
Kind, preferably sesbania powder, extrusion aid additional amount are the 3%-5% of boehmite dry glue powder weight.
In the method for the present invention, peptizing agent described in step (2) is one of formic acid, acetic acid, citric acid or nitric acid or several
Kind mixing, additional amount is the 3%-10% of boehmite dry glue powder weight, depending on last molding effect.
In the method for the present invention, step (2) drying condition is 1-10 hours dry at 100-130 DEG C.
In the method for the present invention, 350-450 DEG C of maturing temperature under step (2) described nitrogen atmosphere, calcining time is that 4-6 is small
When, the maturing temperature under the air atmosphere is 450-550 DEG C, and calcining time is 4-8 hours.Process baked above is in tube furnace
Middle progress, before roasting, calcination atmosphere need to be full of entire tube furnace, also can choose other and be suitably able to carry out baking operation
Equipment.
Present invention simultaneously provides a kind of hydrotreating catalyst, which includes hydrogenation active component and carrier, wherein
The carrier is the siliceous macropore alumina supporter of the method for the present invention preparation.Hydrogen can will be added living using technology well known in the art
Property component loads on carrier, such as infusion process, the routine techniques such as kneading method.
For boehmite dry glue powder through hydro-thermal charing process, it is intercrystalline that the carbons substance of formation is filled in boehmite
In duct, when extruded moulding, due to the presence of carbon particle, good supporting role can be played, effectively prevents and intends thin water
The collapsing of aluminium stone macropore, the hole for improving carrier holds and macropore content.The oxygen of silica and surface when being roasted under nitrogen atmosphere
Change aluminium effect, in conjunction with composite oxides are formed, when roasting under air atmosphere, carbon black powder oxidation is removed, silica shell is formed,
Due to the presence of silica, play the role of good skeletal support, it is therefore prevented that the collapsing of macropore, corresponding duct are conducive to slag
The mass transfer of oil molecule and diffusion.In addition, silica exists, the acidity of carrier at corresponding macropore is reduced, improves and accordingly urges
The anti-carbon of agent and anti-caking power increase the service life of catalyst.The gas that carbon black powder oxidation thing is formed can rise
To good reaming effect, the content of the carrier macropore of raising.
The method of the present invention simultaneously preferably pre-processes boehmite, first with mixed acid solution to boehmite into
Row processing is dissolved amorphous since mixed acid and boehmite effect are more moderate when can both overcome exclusive use organic acid
The halfway deficiency of phase hydrated alumina, and boehmite duct can be damaged to avoid being used alone when inorganic acid,
The dissolution of amorphous phase hydrated alumina is removed while guaranteeing boehmite pore structure.Dissolved aluminium salt is retained in slurry
In liquid, then urea is added into slurries and when sealing hydro-thermal process, urea is decomposed into NH under high temperature environment3And CO2, NH3With
CO2NH is generated in the presence of water vapour4 +And HCO3 -Ion, NH4 +And HCO3 -Ion at high temperature under high pressure, makes to intend thin water
Aluminium stone crystal grain regrows and crystallization, and boehmite crystal grain is made to grow up, and changes the accumulation mode of crystal grain, improves macropore
Content, while dissolve Al3+Following reaction: Al occurs3++NH3.H2O Al(OH)3+NH4 +, Al (OH)3+ NH4 ++HCO3 -
NH4Al(OH)2CO3, NH4Al(OH)2CO3Gas is generated when roasting can play good reaming effect.Boron when borate is added
Double hydrolysis occur for hydrochlorate and aluminium salt, and the boron oxide precipitating load of formation is in oxidation aluminium surface, while improving carrier aperture
The surface nature of modulation carrier.
Specific embodiment
The effect and effect of the method for the present invention are further illustrated below with reference to embodiment, but are not limited to following implementation
Example.
Using N2Physics suction-desorption characterization embodiment and comparative example carrier pore structure, concrete operations are as follows: using ASAP-
2420 type N2Physics is inhaled-is desorbed instrument and characterizes to catalyst sample pore structure.Take a small amount of sample be vacuum-treated 3 at 300 DEG C ~
Product is finally placed under the conditions of liquid nitrogen cryogenics (- 200 DEG C) and carries out nitrogen suction-desorption test by 4 h.Wherein surface area is according to BET
Equation obtains, and pore-size distribution and pore volume are obtained according to BJH model.
It is as follows using XRF characterization embodiment and comparative example carrier components, concrete operations: to use RIGAKU company, Japan ZSX-
100e type Xray fluorescence spectrometer, performance indicator: X-ray tube Be window thickness: 30 μm；Power: 4kW；Output voltage: 20-60kV；
Export electric current: 2-150mA；2 0.0001 ° of the angle θ reproducibilities；2 0.0002 ° of the angle θ accuracys.
Hydrogenation active component is loaded to in embodiment using infusion process the siliceous macroporous aluminium oxide of the method for the present invention preparation
On.The hydrogenation active component maceration extract is to form to calculate according to final catalyst to prepare.In hydrogenation active component maceration extract,
Vib metals content is calculated as 7-15g/100ml with oxide, and group VIII tenor is calculated as 0.8-3g/ with oxide
100ml, can use volume impregnation, incipient impregnation or spray impregnating mode, and dip time is 1-5 hours.After dipping
Carrier through drying, roasting obtain hydrotreating catalyst.Wherein the drying condition is the dry 6-10 at 80-120 DEG C
Hour；The roasting condition is to roast 3-6 hours at 400-600 DEG C.
Embodiment 1
It weighs boehmite (production of Shandong Aluminum Co., Ltd. Co., Ltd) 200g to be placed in a beaker, 400mL is added into beaker
The xylose alcohol solution that mass concentration is 25% impregnates 4 hours.Through filtering, filter cake is transferred in autoclave material after dipping
Charing process is carried out, treatment temperature is 140 DEG C, and the processing time is 10 hours.
Weigh 25 grams of carbon black powder be placed in spray rolling pot in, under rotary state, with atomizing type to rolling pot in carbon black powder
Unsaturation sprays the ethanol solution 7.5ml containing 2 grams of silica of ethyl orthosilicate.Carbon black powder after dipping and 150 grams it is above-mentioned
Boehmite, 2g sesbania powder are sufficiently mixed, be added in Xiang Shangshu material it is uniform dissolved with the aqueous solution kneading of 2g acetic acid in right amount, squeeze
Item molding.Wet stock after molding is 8 hours dry in 110 DEG C.Material after drying is placed in tube furnace, is passed through into tube furnace
Nitrogen makes nitrogen full of entire burner hearth, roasts 6 hours in 400 DEG C, and then nitrogen leak is passed through air, roasts 6 hours in 500 DEG C
Silicon-containing alumina carrier A1 is made, the property of carrier is shown in Table 1.
Embodiment 2
With embodiment 1, the mixing of the sorbierite and mannitol that are only 1:1 with the mass ratio that mass concentration is 40% is water-soluble
Liquid impregnates boehmite 3 hours.Charing process temperature is 130 DEG C, is handled the time 14 hours.The additional amount of carbon black powder is 20
Gram, when spraying carbon black powder is ethanol solution of the 7ml containing 3 grams of silica of methyl orthosilicate.Roasting under nitrogen atmosphere
Temperature is 350 DEG C.Alumina support A2 of the present invention is made, the property of carrier is shown in Table 1.
Embodiment 3
With embodiment 1, the mixed aqueous solution of the glucose and ribose that are only 1:1 with the mass ratio that mass concentration is 30%
Dipping boehmite 5 hours.Charing process temperature is 120 DEG C, and the charing process time is 16 hours.The additional amount of carbon black powder is
35 grams, when spraying carbon black powder is ethanol solution of the 14ml containing 5 grams of silica of butyl silicate, the roasting under nitrogen atmosphere
Burning temperature is 450 DEG C.Alumina support A3 of the present invention is made, the property of carrier is shown in Table 1.
Embodiment 4
With embodiment 1, the mixing water of the arabite and fructose that are only 1:1 with the mass ratio that mass concentration is 20%
Solution impregnates boehmite 4 hours.Charing process temperature is 150 DEG C, and the charing process time is 12 hours.The addition of carbon black powder
Amount is 30 grams, and when spraying carbon black powder is ethanol solution of the 13.5ml containing 4 grams of silica of methyl orthosilicate, nitrogen atmosphere
Under maturing temperature be 350 DEG C.Alumina support A4 of the present invention is made, the property of carrier is shown in Table 1.
Embodiment 5
With embodiment 1, only impregnated boehmite 5 hours with the sorbitol aqueous solution that mass concentration is 35%.At charing
Managing temperature is 160 DEG C, and the charing process time is 8 hours.The additional amount of carbon black powder is 40 grams, and that when spraying carbon black powder is 25ml
The ethanol solution of 6 grams of the ethyl orthosilicate containing silica, the maturing temperature under nitrogen atmosphere are 450 DEG C.Oxygen of the present invention is made
Change alumina supporter A5, the property of carrier is shown in Table 1.
Embodiment 6
With embodiment 1, only boehmite is pre-processed, process is as follows: weighing 200g boehmite dry glue
Powder (production of Shandong Aluminum Co., Ltd. Co., Ltd) is set in a round bottom flask, 600 grams of deionized water mashing is added into flask, to above-mentioned slurry
It is 3mol/L that appropriate nitric acid molar concentration is added in liquid, and acetic acid molar concentration is the mixed acid solution of 1mol/L, controls slurries
PH value is 3 and is heated to reflux 3 hours in 40 DEG C.Above-mentioned slurries are transferred in autoclave, 20 grams of urea are added into mixed material
And it is heat-treated 6 hours after sealing autoclave in 140 DEG C.Mixed serum is filtered after being cooled to room temperature, is washed, 120 DEG C of dryings 8
Hour obtained boehmite.
It weighs above-mentioned boehmite 200g to be placed in a beaker, the xylose that 400mL mass concentration is 25% is added into beaker
Alcohol solution impregnates 4 hours.For material after dipping through filtering, filter cake, which is transferred in autoclave, carries out charing process, processing temperature
Degree is 140 DEG C, and the processing time is 10 hours.Treated dry materials.
Weigh 25 grams of carbon black powder be placed in spray rolling pot in, under rotary state, with atomizing type to rolling pot in carbon black powder
Unsaturation sprays the ethanol solution 7.5ml containing 2 grams of silica of ethyl orthosilicate.Carbon black powder after dipping and 150 grams it is above-mentioned
Boehmite, 4g sesbania powder are sufficiently mixed, be added in Xiang Shangshu material it is uniform dissolved with the aqueous solution kneading of 5g acetic acid in right amount, squeeze
Item molding.Wet stock after molding is 8 hours dry in 110 DEG C.Material after drying is placed in tube furnace, is passed through into tube furnace
Nitrogen makes nitrogen full of entire burner hearth, roasts 6 hours in 400 DEG C, and then nitrogen leak is passed through air, roasts 6 hours in 500 DEG C
Alumina support is made.
It weighs 100 grams of above-mentioned alumina support to be placed in a beaker, 150mlMo-Ni-NH is added3Solution (contains
MoO312.0wt%, NiO3.0 wt%) dipping 2 hours, redundant solution is filtered off, 120 DEG C dry, then in 550 DEG C of roasting temperatures 5
Hour, catalyst C1 is made, the property of the catalyst is shown in Table 1.
Embodiment 7
With embodiment 6
The difference is that: in preprocessing process, the additional amount of deionized water is 1400 grams.Mixed acid is dissolved with 4 mol
The mixed acid of sulfuric acid and 1mol oxalic acid, the pH value for controlling slurries is 2, and the temperature being heated to reflux is 30 DEG C, is flowed back 5 hours.Urea
Additional amount be 30 grams, hydro-thermal process temperature be 120 DEG C, hydro-thermal process 8 hours；
The mixed aqueous solution dipping of the sorbierite and mannitol that are 1:1 with the mass ratio that mass concentration is 40% intends thin water aluminium
Stone 3 hours.Charing process temperature is 130 DEG C, is handled the time 14 hours；
The additional amount of carbon black powder is 20 grams, and that when spraying carbon black powder is 7ml containing 3 grams of silica of methyl orthosilicate
Ethanol solution；
Maturing temperature under nitrogen atmosphere is 350 DEG C, and catalyst C2 is made, and the property of the catalyst is shown in Table 1.
Embodiment 8
With embodiment 6
The difference is that: in preprocessing process, only the additional amount of deionized water is 2000 grams.Mixed acid be dissolved with
The mixed acid of 6mol/L sulfuric acid and 1mol/L citric acid, the pH value for controlling slurries is 5, and being heated to reflux temperature is 60 DEG C, when reflux
Between 1 hour.Urea additional amount is 40 grams, and 160 DEG C of hydro-thermal process temperature, hydrothermal conditions are 4 hours；
The mixed aqueous solution of the glucose and ribose that are 1:1 with the mass ratio that mass concentration is 30% impregnates boehmite 5
Hour.Charing process temperature is 120 DEG C, and the charing process time is 16 hours；
The additional amount of carbon black powder is 35 grams, and that when spraying carbon black powder is 14ml containing 5 grams of silica of butyl silicate
Ethanol solution；
Maturing temperature under nitrogen atmosphere is 450 DEG C, and catalyst C3 is made, and the property of the catalyst is shown in Table 1.
Embodiment 9
With embodiment 6
The difference is that: in preprocessing process, 3.0 gram of four boron is added into mixed material while urea is only added
Sour sodium.
The mixed aqueous solution dipping of the arabite and fructose that are 1:1 with the mass ratio that mass concentration is 20% intends thin water
Aluminium stone 4 hours, charing process temperature was 150 DEG C, and the charing process time is 12 hours；
The additional amount of carbon black powder is 30 grams, and that when spraying carbon black powder is 13.5ml containing 4 grams of silica of positive silicic acid first
The ethanol solution of ester；
Maturing temperature under nitrogen atmosphere is 350 DEG C, and catalyst C4 is made, and the property of the catalyst is shown in Table 1.
Embodiment 10
With embodiment 6
The difference is that: it is only impregnated boehmite 5 hours with the sorbitol aqueous solution that mass concentration is 35%, charcoal
Changing treatment temperature is 160 DEG C, and the charing process time is 8 hours；
The additional amount of carbon black powder is 40 grams, and that when spraying carbon black powder is 25ml containing 6 grams of silica of ethyl orthosilicate
Ethanol solution；
Maturing temperature under nitrogen atmosphere is 450 DEG C, and catalyst C5 is made, and the property of the catalyst is shown in Table 1.
Comparative example 1
With example 1, only esters of silicon acis is unsupported on carbon black powder, but is added when kneading, and comparative example oxygen is made
Change alumina supporter A6, the property of carrier is shown in Table 1.
Comparative example 2
With example 1,25 grams of xylitols are added in the form of kneading when carrier is formed only, comparative example aluminium oxide is made
The property of carrier A7, carrier are shown in Table 1.
Comparative example 3
With embodiment 6, only boehmite is not impregnated with xylitol and hydro-thermal process, but by the xylitol of phase homogenous quantities
It is added in carrier in a manner of kneading in carrier molding, comparative example catalyst C6 is made, the property of catalyst is shown in Table 2.
Comparative example 4
With embodiment 6, only esters of silicon acis is unsupported on carbon black powder, but is added when kneading, and comparative example is made
The property of catalyst C7, catalyst are shown in Table 2.
1 carrying alumina volume property of table.
Pore size distribution refers to that the Kong Rong of certain diameter range inner hole in carrier accounts for the percentage of total pore volume.
2 catalyst property of table.
Pore size distribution refers to that the Kong Rong of certain diameter range inner hole in catalyst accounts for the percentage of total pore volume.
Table 1 the result shows that, using the method for the present invention prepare macropore alumina supporter, have larger aperture while have
There are biggish Kong Rong, the pore size distribution of concentration, higher mechanical strength.The alumina support of this method preparation is suitable for weight, residual oil
Hydrodemetallization field.
Hydrodemetalation catalyst will be prepared with above-mentioned A1-A7 carrier.Process is as follows: it is each to weigh A1-A7 carrier respectively
100 grams, 150mlMo-Ni-NH is added3Solution (contains MoO312.0wt%, NiO3.0 wt%) dipping 2 hours, redundant solution is filtered off,
120 DEG C drying, then 550 DEG C roasting temperature 5 hours, obtain Hydrodemetalation catalyst C8-C14.
Embodiment 11
Using feedstock oil listed by table 3 as raw material, the catalytic performance of C1-C14 is evaluated on 200 milliliters of hydrogenation reaction device,
The item that catalyst is long 2 ~ 3 millimeters, catalyst loading are 100 milliliters, and reaction temperature is 375 DEG C, hydrogen partial pressure 13MPa, when liquid
Air speed is 1.0 hours-1, hydrogen to oil volume ratio 1000, measurement generates the content of each impurity in oil after reaction 200 hours, calculates gold
Symbolic animal of the birth year is shown in Table 3 to removal efficiency, evaluation result.
3 raw material oil nature of table
4 catalyst hydrogenation performance comparison of table
It can be seen from 4 data of table compared with comparing alumina support, the catalysis that is prepared using aluminium oxide of the present invention as carrier
Agent hydrodemetallization activity with higher.
Claims (9)
1. a kind of preparation method of siliceous macropore alumina supporter, it is characterised in that include the following: (1) with containing polyalcohol and/or
The aqueous solution of glucide impregnates boehmite dry glue powder, and the material after dipping carries out hydro-thermal charing process；(2) with siliceous molten
Liquid impregnates carbon black powder, carbon black powder and step (1) boehmite after dipping, extrusion aid, peptizing agent kneading at plastic, extrusion,
First in a nitrogen atmosphere then roasting roasts material after dry, dry in air atmosphere, and silica containing oxidation is made
Alumina supporter；Polyalcohol described in step (1) is one or more of xylitol, sorbierite, mannitol or arabite；It is described
Carbohydrate be the mixing of one or more of glucose, ribose or fructose；The matter of aqueous solution containing polyalcohol and/or glucide
Amount concentration is 20%-40%；The dosage of aqueous solution containing polyalcohol and/or glucide is to soak boehmite dry glue powder completely
Not yet, dip time is 3-5 hours；Hydro-thermal charing process described in step (1) is the heat treatment carried out in sealing device, described
Hydro-thermal charing process temperature be 120-160 DEG C, processing the time be 8-16 hours；Siliceous solution described in step (2) is siliceous
The ethanol solution of acid esters, wherein esters of silicon acis is selected from one or more of methyl orthosilicate, ethyl orthosilicate or butyl silicate；
350-450 DEG C of maturing temperature under step (2) described nitrogen atmosphere, calcining time is 4-6 hours；Step (2) the air gas
Maturing temperature under atmosphere is 450-550 DEG C, and calcining time is 4-8 hours.
2. according to the method for claim 1, it is characterised in that: pre-process the boehmite in step (1), in advance
Treatment process is as follows: boehmite and deionized water being mixed with beating, appropriate organic acid and inorganic is added in Xiang Shangshu slurries
The mixed acid solution of acid, the pH value for controlling slurries is 2-5, carries out being heated to reflux processing；Appropriate urea is added into above-mentioned slurries
Hydro-thermal process is carried out, the slurries after hydro-thermal process are washed, dry.
3. according to the method for claim 2, it is characterised in that: in preprocessing process, the organic acid is acetic acid, oxalic acid
Or the mixing of one or more of citric acid, the inorganic acid are the mixing of one or more of sulfuric acid, nitric acid or hydrochloric acid；It is mixed
The mass ratio of the material for closing organic acid and inorganic acid in acid solution is 1:3-1:6, and the concentration of the mixed acid solution is with inorganic acid
It is calculated as 3-6mol/L；The treatment temperature that is heated to reflux is 30-60 DEG C, and being heated to reflux the time is 1-5 hours.
4. according to the method for claim 2, it is characterised in that: in preprocessing process, the amount of urea and intend thin water
The mass ratio of aluminium stone is 1:5-1:10.
5. according to the method for claim 2, it is characterised in that: in preprocessing process, boron is added while urea is added
Hydrochlorate, the borate are the mixing of one or more of metaborate, ortho-borate and multi-borate, the addition of borate
Amount is 0.5:100-1.5:100 with the mass ratio of boehmite in terms of boron oxide.
6. according to the method for claim 2, it is characterised in that: in preprocessing process, the hydro-thermal process is in high pressure
Heat treatment under the self-generated pressure of reaction kettle, treatment temperature are 120-160 DEG C, and the processing time is 4-8 hours.
7. according to the method for claim 1, it is characterised in that: in siliceous solution described in step (2), silicone content is with dioxy
SiClx is calculated as the 2wt%-6wt% of final vehicle weight, and the dosage of siliceous solution is the 30%-50% of carbon black powder saturated water adsorptive value.
8. according to the method for claim 1, it is characterised in that: the dosage of carbon black powder described in step (2) is to intend thin water aluminium
The 20%-40% of stone dry glue powder weight.
9. a kind of hydrotreating catalyst, which includes hydrogenation active component and carrier, it is characterised in that: the carrier is
The siliceous macropore alumina supporter of claim 1 ~ 8 any claim the method preparation.
Priority Applications (1)
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| CN113694913B (en) * | 2020-05-22 | 2024-03-08 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN112237908A (en) * | 2020-09-30 | 2021-01-19 | 山东公泉化工股份有限公司 | Catalyst carrier, hydrotreating catalyst, preparation method and application |
| CN114505067B (en) * | 2020-10-29 | 2023-09-01 | 中国石油化工股份有限公司 | Carbon-coated aluminum composite material and preparation method and application thereof |
| CN114425455B (en) * | 2020-10-29 | 2023-09-01 | 中国石油化工股份有限公司 | Catalytic carrier material, catalytic material, preparation method and application |
| CN116408138A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气集团有限公司 | Catalyst for synthesizing aromatic hydrocarbon and preparation method and application thereof |
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