CN107961771A - A kind of alumina support and preparation method thereof and Hydrobon catalyst and preparation method thereof - Google Patents
A kind of alumina support and preparation method thereof and Hydrobon catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN107961771A CN107961771A CN201610916357.3A CN201610916357A CN107961771A CN 107961771 A CN107961771 A CN 107961771A CN 201610916357 A CN201610916357 A CN 201610916357A CN 107961771 A CN107961771 A CN 107961771A
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- CN
- China
- Prior art keywords
- catalyst
- preparation
- alumina support
- carrier
- small
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 134
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 78
- 239000000843 powder Substances 0.000 claims abstract description 38
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 28
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 238000002803 maceration Methods 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000005416 organic matter Substances 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 37
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 239000011148 porous material Substances 0.000 description 23
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 229910052759 nickel Inorganic materials 0.000 description 19
- 229910052717 sulfur Inorganic materials 0.000 description 18
- 239000011593 sulfur Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- 229910017604 nitric acid Inorganic materials 0.000 description 15
- 238000007493 shaping process Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000009826 distribution Methods 0.000 description 12
- 229910052750 molybdenum Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 241000196324 Embryophyta Species 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 235000016768 molybdenum Nutrition 0.000 description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000011733 molybdenum Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 241000219782 Sesbania Species 0.000 description 8
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 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
- 238000001802 infusion Methods 0.000 description 6
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 6
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 101100422770 Caenorhabditis elegans sup-1 gene Proteins 0.000 description 3
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- -1 unlike Substances 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000010792 warming Methods 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—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
- B01J23/882—Molybdenum and cobalt
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- 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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- 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
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- 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
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- 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
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- 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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- 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
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Abstract
The preparation method and alumina support and Hydrobon catalyst as made from these methods of a kind of preparation method the present invention provides alumina support and the Hydrobon catalyst including this method.The preparation method of the alumina support include at 400 1000 DEG C roasting boehmite powder at least 1 15 it is small when, be then molded and dry.Method provided by the invention can improve the activity of Hydrobon catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of alumina support and alumina support obtained by this method and including
The preparation method of the Hydrobon catalyst of this method and Hydrobon catalyst obtained by this method.
Background technology
Hydrogenation is the mainstay in modern petroleum refining industry, it is producing clean fuel, raising product quality, is making full use of
Petroleum resources and pretreatment of raw material etc. play an important role.With economic, environmental protection and the development of society so that oil refining enterprise
Industry constantly puts forward higher requirements the activity and stability of hydrotreating catalyst, Hydrobon catalyst activity and selectivity
Need to be continuously improved.Wherein, hydrodesulfurization activity is an important indicator for weighing Hydrobon catalyst performance.
Usually, Hydrobon catalyst is using the sulfide of group vib metal (Mo and/or W) as main active component, and
Using the sulfide of group VIII metal (Co and/or Ni) as active component is helped, remaining component is carrier in catalyst.Study table
Bright, the carrier in catalyst plays an important role the performance of catalyst.Carrier not only should have larger specific surface area so that
Activated centre has higher dispersion degree, but also should have suitable pore passage structure to adapt to the diffusion of reactant, at the same time
Carrier can also have an impact the latent active at active phase center.Therefore, many patents and research have been directed to carrier
Exploitation and research.With the in poor quality of hydrogenating materials, the size reacted for molecule is incrementally increased, it is necessary to using bigger pore passage structure
Carrier can just better meet reactant diffusion demand.
It by boehmite be raw material that the preparation method of general alumina support, which is, add extrusion aid and adhesive progress into
Type, aluminium oxide is prepared after shaping by 100-200 DEG C of drying and 400-1000 DEG C of roasting.Increase the common methods master in aperture
Include the use of different boehmites mixing (such as CN1488441A), using expanding agent (such as CN1160602A, US4448896,
CN1055877C etc.) etc..For example, a water aluminium oxide is heat-treated by CN101450327A at a temperature of 150-300 DEG C, processing
Mediated after being mixed again with one or more in graphite, stearic acid, odium stearate, aluminum stearate afterwards uniformly, it is dry by 100-150 DEG C
Aluminium oxide is prepared by 700-1000 DEG C of roasting again after dry.Above expanding method, expanding agent mix not with boehmite
Uniformly cause reaming effect bad, the addition of expanding agent can also increase cost.
In addition, CN1087289A discloses a kind of method for preparing macropore alumina supporter.This method uses containing at room temperature
Boehmite moment is placed in high-temperature atmosphere, and high temperature range is 500-650 DEG C, and when constant temperature 2-4 is small at these elevated temperatures.This method
Reaming is carried out to carrier using the moisture of rapid evaporation under high temperature, but is needed using the activity of hydrogenation catalyst made from the carrier
Further improve.
The content of the invention
The purpose of the invention is to further improve the activity of Hydrobon catalyst, there is provided a kind of new carrying alumina
The preparation method of body and the preparation side of alumina support obtained by this method and the Hydrobon catalyst including this method
Method and Hydrobon catalyst obtained by this method.
The present invention provides a kind of preparation method of alumina support, this method is included boehmite in 400-1000
When roasting 1-15 is small at DEG C, then it is molded.
Present invention also offers the alumina support as made from the above method.
Present invention also offers a kind of preparation method of Hydrobon catalyst, this method includes preparing using the above method
Alumina support, impregnates the carrier with the maceration extract containing catalyst metal components afterwards.
Present invention also offers a kind of preparation method of Hydrobon catalyst, this method includes existing in boehmite powder
When roasting 1-15 is small at 400-1000 DEG C, then with the boehmite after the maceration extract impregnation-calcination containing catalyst metal components
Powder, is molded, is dry afterwards.
Present invention also offers the Hydrobon catalyst as made from the above method.
Hydrobon catalyst of the present invention, the catalyst employ new support preparation method, have carrier
Therefore more preferable pore passage structure, the catalyst have higher catalyst performance.
Usual alumina support is by the way that boehmite powder and peptizing agent and extrusion aid are passed through extruded moulding, Ran Houzai
Obtained by dry and roasting.Since hydrogenation reaction needs catalyst to have larger pore passage structure, and before roasting, general duct
Concentrate on 2-12nm, therefore, generally by by after shaping carrier carry out calcination process come improve the pore size of carrier so as to
The pore size of catalyst is improved, the duct of the carrier after roasting is generally concentrated at 2-20nm, and the average pore size of carrier increases, and
And it is generally acknowledged that calcination temperature is higher, pore size is bigger.However, with the increase of calcination temperature, the hole wall of carrier can occur
Cave in condensation.Although hole wall condensation can increase the average pore size of carrier, the hole wall of condensation can reduce the utilization of aluminium oxide
Rate, so as to reduce the catalytic activity of catalyst.The present invention, can by being roasted boehmite powder before extrusion molding
To improve the activity of Hydrobon catalyst.Speculate that reason there may be following three aspects.In a first aspect, heat treatment can be reduced
Hydroxyl quantity in boehmite powder, reduces the probability of duct condensation, increases the aperture of catalyst.Second aspect, shaping
Carrier afterwards need not be handled with higher temperature, and aluminium oxide hole wall need not carry out excessive condensation, improve oxidation
The utilization rate of aluminium.The third aspect, is before the forming heat-treated aluminium oxide, and part secondary can be also condensed, this meeting
Cause the size of aluminium oxide particles to tend to be single, duct more uniformly will be conducive to the diffusion of reactant in the carrier after shaping.
It is more more effective than conventional catalyst especially for heavier and more inferior oil product.
A preferred embodiment of the invention, in order to make active component reach preferably scattered, in maceration extract
Introduce the less organic matter of molecular weight, so can not only active component is preferably dissolved, but also can than molecular weight compared with
Big organic matter provides the space of more dissolving metals, further increases the quantity of active metal, there is provided number of active center
Mesh, promotes the raising of catalyst activity.
Specifically, in embodiment, use Hydrobon catalyst made from the method for the present invention to sulfur content for 9100ppm,
The distillate that nitrogen content is 532ppm carries out hydrotreating, and sulfur content can be reduced to below 10ppm, and nitrogen content is reduced to 5ppm
Hereinafter, desulfurization degree is up to more than 99.9%, and denitrification percent is up to more than 99.1%.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of preparation method of alumina support, and this method includes existing boehmite
When roasting 1-15 is small at 400-1000 DEG C, then it is molded.
The temperature of roasting is preferably 450-900 DEG C, when the time is preferably 3-8 small.
The shaping can be existing various forming methods, such as can be extruded moulding or roller forming.
The mode of the extruded moulding is referred to prior art progress, by after the boehmite of extruded moulding (after roasting) and glue
Solvent and extrusion aid are extruded into required shape, such as trifolium-shaped after mixing.
The extrusion aid and peptizing agent are referred to the prior art and make choice, for example, extrusion aid can be sesbania powder,
One or more in the material such as methylcellulose and starch, peptizing agent can be nitric acid, citric acid and acetic acid in one kind or
It is a variety of.
Boehmite powder after roasting：Water：Auxiliary agent squeezes：The amount ratio of peptizing agent is preferably 1:1.5-2.5:0.005-
0.06:0.005-0.05.Solid is based on quality (g) in aforementioned proportion, and liquid is based on volume (mL).Water and peptizing agent are usually with glue
The aqueous solution form of solvent uses.When peptizing agent is nitric acid, above-mentioned amount ratio uses gauge with commercially available concentrated nitric acid；Work as peptizing agent
For acetic acid when, above-mentioned amount ratio uses gauge with the pure acetic acid of commercially available analysis.
Preferably, it is dried again after extrusion, dry temperature can be 50-350 DEG C, be preferably 80-250 DEG C, more
Preferably 100-200 DEG C；When time can be 2-10 small, when being preferably 3-8 small, when more preferably 3-6 is small.
Present invention also offers the alumina support as made from the above method.The pore-size distribution of the carrier has following special
Sign：
On the basis of the total pore volume of carrier, aperture be 2-4nm account for 0-5 volumes %, 4-6nm account for 5-15 volumes %, 6-
8nm account for 10-40 volumes %, 8-10nm account for 20-35 volumes %, 10-20nm account for 20-35 volume %, more than accounting for for 20nm
Below 15 volume %.
In the present invention, the hole of the 2-4nm refers to that aperture is more than or equal to 2nm, and the hole less than 4nm, the hole of 4-6nm, is
Finger-hole footpath is more than or equal to the hole that 4nm is less than 6nm, and the hole of 6-8nm refers to that aperture is more than or equal to the hole that 6nm is less than or equal to 8nm, 8-
The hole of 10nm refers to that aperture is more than the hole that 8nm is less than 10nm, and the hole of 10-20nm refers to be more than or equal to 10nm less than or equal to 20nm's
Hole.
It is seen from the above data that using carrying alumina made from the method provided by the invention for first roasting reshaping
Body, more conventional to be first molded alumina support made from roasting method again, the hole of 2-8nm greatly reduces, and the Kong Ze of more than 8nm is significantly
Increase, so as to be more suitable for the processing of inferior distillate oil.
In the present invention, the pore size distribution of catalyst and carrier, aperture, pore volume using low-temperature nitrogen adsorption method measure (referring to《Stone
Oily chemical analysis method (RIPP test methods)》, Yang Cui surely compile by grade, and Science Press, nineteen ninety publishes).
Present invention also offers a kind of preparation method of Hydrobon catalyst, this method includes preparing using the above method
Shaping carrier, impregnates the shaping carrier with the maceration extract containing catalyst metal components afterwards.
A preferred embodiment of the invention, the preparation method of the Hydrobon catalyst include following step
Suddenly：
(1) maceration extract containing catalyst metal components is prepared；
(2) shaping carrier is prepared using the above method；
(3) maceration extract obtained using above-mentioned (1) impregnates the shaping carrier obtained by (2), then dries.
Present invention also offers the preparation method of another Hydrobon catalyst, this method is included boehmite powder
When roasting 1-15 is small at 400-1000 DEG C, then with the thin water aluminium of plan after the maceration extract impregnation-calcination containing catalyst metal components
Mountain flour, is molded afterwards.
A preferred embodiment of the invention, the preparation method of the Hydrobon catalyst include following step
Suddenly：
(a) maceration extract containing catalyst metal components is prepared；
(b) boehmite powder is roasted at 400-1000 DEG C 1-15 it is small when；
(c) maceration extract obtained using above-mentioned (a) impregnates the boehmite powder after the roasting obtained by (b), be then molded,
It is dry.
The main distinction of the preparation method of above two catalyst is to be molded different with the order of load.
The related operation of shaping and roasting has been described above, and any peptizing agent and auxiliary agent can be added without in shaping
Squeeze, details are not described herein for other operations.
Under preferable case, the maceration extract is also preferably less than 80 containing molecular weight except containing catalyst metal components
Organic matter no more than 75.Organic matter of its middle-molecular-weihydroxyethyl less than 80 can be that various molecular weight are less than 80 preferably no more than 75
And contain-OH ,-NH2, organic matters any one or more in-COOH, but it is preferably not included that the amide substance such as urea, tool
Body is preferably methanol, ethanol, propyl alcohol, isopropanol, butanol, isobutanol, ethylene glycol, formic acid, acetic acid, propionic acid, ethylenediamine, ethanol
One or more in amine, ethamine, propylamine, butylamine, amion acetic acid etc..Since itrogenous organic substance has certain toxicity, on
State the preferred alcohol and carboxylic acid of organic matter.
Organic matter of the molecular weight less than 80 and the molar ratio of group VIII metal atom are preferably 0.2-5, more preferably 0.5-
3。
The catalyst metal components are generally group VIII metal and vib metals element.
The content of catalyst metal components causes by the butt weight of catalyst and in terms of oxide in maceration extract, catalyst
The content of middle group VIII metallic element is 2-20 weight %, is preferably 2-15 weight %, more preferably 3-15 weight %, into one
Step is preferably 3-10 weight %；The content of vib metals element is 15-75 weight %, is preferably 15-60 weight %, more excellent
Elect 20-55 weight % as, more preferably 20-50 weight %.
In the present invention, butt weight is by the weight by sample when 600 DEG C of roastings 4 are small to measure.
A preferred embodiment of the invention, in solution processes are prepared first by the organic matter with containing the
Group vib metallic element and predecessor containing group VIII metal are added in the aqueous solution of phosphorus containg substances and/or ammonia, at 40-100 DEG C
1-8h is stirred, until whole dissolvings.Organic matter and phosphorus containg substances or ammonium hydroxide and the addition sequence of metal precursor can also be mutual
Mutually exchange.
In the present invention, the example of the group VIII metal element includes but not limited to one in iron, cobalt, nickel, ruthenium, rhodium and palladium
Kind is a variety of.The example of the group vib metallic element includes but not limited to the one or more in chromium, molybdenum and tungsten.It can pass through
Their presoma is added in maceration extract to obtain above-mentioned metal active constituent in the catalyst.The presoma of cobalt is included but not
The one or more being limited in cobalt nitrate, basic cobaltous carbonate, cobalt acetate and cobalt oxide, the presoma of Mo include but not limited to seven molybdenums
One or more in sour ammonium, ammonium molybdate, ammonium phosphomolybdate, molybdenum oxide, the presoma of Ni include but not limited to nickel nitrate, alkali formula carbon
One or more in sour nickel, nickel acetate and nickel oxide, the presoma of tungsten include but not limited to ammonium metatungstate, ethyl metatungstic acid
One or more in ammonium, tungsten oxide.
The method provided according to the present invention, preferably comprises phosphorus containg substances and/or ammonia, the phosphorus containg substances in the maceration extract
One or more including but not limited in phosphoric acid, hypophosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate.
The dosage of phosphorus containg substances causes on the basis of the butt weight of final catalyst, with P2O5The content of the P elements of meter
For 0.5-8 weight %.The concentration range of ammonium hydroxide is 10-25 weight %.The dosage of ammonium hydroxide, which is subject to, meets solvent needed for maceration extract.
Under preferable case, the preparation method of the catalyst is further included the carrier after dipping or the catalyst after shaping
It is dried.
Dry temperature can be 50-350 DEG C, be preferably 80-250 DEG C, and more preferably 100-200 DEG C, the time can be
When 2-10 is small, when being preferably 3-8 small, when more preferably 3-6 is small.
The present invention is not particularly limited impregnation method in the preparation method of the Hydrobon catalyst, can be according to
Well known to a person skilled in the art various modes to carry out.Such as dipping compound is born by modes such as infusion process, spray process
It is loaded in said catalyst carrier, detailed process is known to the skilled person, and therefore not to repeat here.Can soak in equal volume
Stain (i.e. hole saturation impregnates) can also be supersaturated dipping.
Present invention also offers the Hydrobon catalyst as made from the above method.Essence is hydrogenated with as made from the method for the present invention
Catalyst processed is oxidized catalyst, and hydrofining reaction is used for after vulcanization.
The conditions of vulcanization of catalyst of the present invention is 0.1-15MPa including sulfide stress, when volume space velocity is 0.5-20 small-1,
Hydrogen to oil volume ratio is 100-2000：1.Vulcanization is not particularly limited, and can be that dry pre-sulfiding or wet method vulcanizes.
Present invention also offers the sulphided state hydrogenation catalyst being prepared by the above method.
Present invention also offers application of the above-mentioned sulphided state hydrogenation catalyst in hydrodesulfurization reaction.
Preferably, the hydrodesulfurizationconditions conditions are 0.1-8MPa including pressure, and temperature is 260-410 DEG C, and volume space velocity is
When 0.5-10 is small-1, hydrogen to oil volume ratio 200-1000：1.
Catalyst provided by the invention can be when handling distillate with higher hydrodesulfurization performance.
The present invention is described further for the following examples.
In following embodiments, the hydrodesulfurization performance of catalyst is measured on 20mL high-pressure micro-devices, is directly adopted
Oxidized catalyst is converted into sulphided state catalyst with temperature programming vulcanization.Conditions of vulcanization is：Sulfide stress is 6.4MPa,
Sulfurized oil is containing CS2The kerosene of 2% weight, volume space velocity 2h-1, hydrogen-oil ratio 300v/v, first in 230 DEG C/h constant temperature 6h,
Then 360 DEG C of vulcanization 8h are warming up to again, and the heating rate in each stage is 10 DEG C/h.Switch reaction raw materials after vulcanization to be hydrogenated with
Desulphurizing activated test, reaction raw materials are the high nitrogen that sulfur content is 9100ppm, nitrogen content 532ppm, arene content are 55wt%
High aromatic fraction oil.Test condition is：Pressure is 6.4MPa, volume space velocity 1.5h-1, hydrogen-oil ratio 300v/v, reaction temperature
For 360 DEG C.7 days post analysis product sulfur levels of stable reaction.
The composition of catalyst is calculated according to inventory.The pore size distribution of catalyst and carrier, aperture, pore volume are using low
Warm determination of nitrogen adsorption (referring to《Petrochemical Engineering Analysis method (RIPP test methods)》, Yang Cui surely compile by grade, Science Press,
Nineteen ninety publishes), use the sulphur and nitrogen in sulphur blood urea/nitrogen analyzer (your silent winged generation of match produce, model TN/TS3000) analysis product
Mass fraction.
Comparative example 1
By boehmite (the PB90 powder of Chang Ling catalyst plant production, specific surface area 345m2/ g), sesbania powder according to
100g：3g ratios after mixing, add 105mL concentration and are the aqueous solution of nitric acid of 1.5wt%, and be again stirring for uniformly, then
By its extruded moulding.4h steps are roasted by the dry 5h at 120 DEG C and at 500 DEG C, it is the pure of 1.6mm that particle diameter, which is prepared,
Alumina support D1.The specific surface area of carrier D1 is 283m2/ g, pore volume 0.72mL/g, pore-size distribution are as shown in table 1.
Embodiment 1
By boehmite (the PB90 powder of Chang Ling catalyst plant production, specific surface area 345m2/ g) roasted at 500 DEG C
4h, powder and sesbania powder are according to 100g after roasting：3g ratios (for the dosage of powder in terms of the powder roasted, following embodiments are identical) mixing is equal
After even, 185mL aqueous solution of nitric acid is added, wherein nitric acid dosage is identical with the dosage of comparative example 1, and is again stirring for uniformly, then
By its extruded moulding.By the dry 5h at 120 DEG C, the pure alumina carrier S up1 that particle diameter is 1.6mm is prepared.Carrier
The specific surface area of Sup1 is 305m2/ g, pore volume 0.81mL/g, pore-size distribution are as shown in table 1.
Comparative example 2
By boehmite (the PB100 powder of Chang Ling catalyst plant production, specific surface area 330m2/ g), sesbania powder according to
100g：3.5g ratios after mixing, add 120mL concentration and are the aqueous solution of nitric acid of 1.5wt%, and be again stirring for uniform extrusion
Shaping.3h steps are roasted by the dry 4h at 150 DEG C and at 900 DEG C, the pure alumina that particle diameter is 1.6mm is prepared and carries
Body D2.The specific surface area of carrier D2 is 240m2/ g, pore volume 0.8mL/g, pore-size distribution are as shown in table 1.
Embodiment 2
By boehmite (the PB100 powder of Chang Ling catalyst plant production, specific surface area 330m2/ g) roasted at 900 DEG C
3h is burnt, powder and sesbania powder are according to 100g after roasting：3g ratios after mixing, add 195mL aqueous solution of nitric acid, and wherein nitric acid is used
Amount is identical with nitric acid dosage in comparative example 2, and is again stirring for uniformly, then by its extruded moulding.By dry at 150 DEG C
4h, is prepared the pure alumina carrier S up2 that particle diameter is 1.6mm.The specific surface area of carrier S up2 is 259m2/ g, pore volume are
0.91mL/g, pore-size distribution are as shown in table 1.
Comparative example 3
By boehmite (the PB110 powder of Chang Ling catalyst plant production, specific surface area 325m2/ g), sesbania powder according to
100g：2.5g ratios after mixing, add 120mL concentration and are the aqueous solution of nitric acid of 1.5wt%, and be again stirring for uniform extrusion
Shaping.4h steps are roasted by the dry 3h at 180 DEG C and at 700 DEG C, the pure alumina that particle diameter is 1.6mm is prepared and carries
Body D3.The specific surface area of carrier D3 is 264m2/ g, pore volume 0.75mL/g, pore-size distribution are as shown in table 1.
Embodiment 3
By boehmite (the PB110 powder of Chang Ling catalyst plant production, specific surface area 325m2/ g), roasted at 700 DEG C
4h is burnt, powder and sesbania powder are according to 100g after roasting：2.5g ratios after mixing, add 210mL aqueous solution of nitric acid, wherein nitric acid
Dosage is identical with nitric acid dosage in comparative example 3, and be again stirring for uniformly, then by its extruded moulding.By being done at 180 DEG C
Dry 3h, is prepared the pure alumina carrier S up3 that particle diameter is 1.6mm.The specific surface area of carrier S up3 is 275m2/ g, pore volume are
0.82mL/g, pore-size distribution are as shown in table 1.
Embodiment 4
By boehmite (the PB86 powder of Chang Ling catalyst plant production, specific surface area 375m2/ g), roasted at 450 DEG C
4h is burnt, with sesbania powder according to 100g after roasting：2.5g ratios after mixing, it is water-soluble for 1.5wt% nitric acid to add 185mL concentration
Liquid, and be again stirring for uniformly, then by its extruded moulding.By the dry 6h at 80 DEG C, it is the pure of 1.6mm that particle diameter, which is prepared,
Alumina support Sup4.The specific surface area of carrier is 305m2/ g, pore volume 0.63mL/g, pore-size distribution are as shown in table 1.
Comparative example 4
Method according to embodiment 4 prepares alumina support, unlike, the temperature of roasting is 350 DEG C, and grain is prepared
Footpath is the pure alumina carrier D4 of 1.6mm.The specific surface area of carrier D4 is 340m2/ g, pore volume 0.68mL/g, pore-size distribution is such as
Shown in table 1.
Table 1
The pore-size distribution that can be seen that alumina support made from method using the present invention from the data of table 1 has such as
Lower feature：
On the basis of the total pore volume of carrier, aperture be 2-4nm account for 0-5 volumes %, 4-6nm account for 5-15 volumes %, 6-
8nm account for 10-40 volumes %, 8-10nm account for 20-35 volumes %, 10-20nm account for 20-35 volume %, more than accounting for for 20nm
Below 15 volume %.
It is seen from the above data that using carrying alumina made from the method provided by the invention for first roasting reshaping
Body, more conventional to be first molded alumina support made from roasting method again, the hole of 2-8nm greatly reduces, and the Kong Ze of more than 8nm is significantly
Increase.
Embodiment 1-1
Under agitation, ethylenediamine, ammonium heptamolybdate and cobalt nitrate are added in the ammonium hydroxide that concentration is 18 weight %, in temperature
Spend to stir 4h at 80 DEG C, prepare maceration extract.Using hole saturation infusion process maceration extract impregnated carrier Sup1, then at 200 DEG C
When lower drying 5 is small, oxidized catalyst is obtained.On the basis of the butt weight of catalyst and in terms of oxide, molybdenum in catalyst
Content be 30.0%, the content of cobalt is 6.5%, and the molar ratio of ethylenediamine and cobalt atom is 2：1.Catalyst is through over cure and instead
After should testing, it is 9.5ppm, nitrogen content 3.4ppm to obtain sulfur content in product.
Comparative example 1-1
Method according to embodiment 1-1 prepares catalyst, unlike, carrier S up1 is replaced by carrier D1, is prepared into oxygen
Change state catalyst.For catalyst after over cure and reaction test, it is 31ppm, nitrogen content 7.8ppm to obtain sulfur content in product.
Embodiment 2-1
Under agitation, ethylene glycol, molybdenum oxide, basic nickel carbonate are added in phosphate aqueous solution, is 80 DEG C in temperature
Lower stirring 4h, prepares maceration extract.Using hole saturation infusion process maceration extract impregnated carrier Sup2, then drying 3 is small at 120 DEG C
When, obtain oxidized catalyst.On the basis of the butt weight of catalyst and in terms of oxide, molybdenum content is in catalyst
50%, nickel content 4%, P content 4%, the molar ratio of ethylene glycol and nickel is 3:1.Catalyst is through over cure and reaction test
Afterwards, it is 7.5ppm, nitrogen content 1ppm to obtain sulfur content in product.
Comparative example 2-1
Method according to embodiment 2-1 prepares catalyst, unlike, carrier S up2 is replaced by D2, obtains catalyst
Cat-D2.For catalyst after over cure and reaction test, it is 25ppm, nitrogen content 2.4ppm to obtain sulfur content in product.
Embodiment 3-1
Under agitation, propyl alcohol, molybdenum oxide, basic nickel carbonate are added in phosphorous acid aqueous solution, is 90 DEG C in temperature
Lower stirring 3h, prepares maceration extract.Using hole saturation infusion process maceration extract impregnated carrier Sup3, then drying 4 is small at 100 DEG C
When, obtain catalyst.On the basis of the butt weight of catalyst and in terms of oxide, molybdenum content is 30% in catalyst, and nickel contains
Measure as 5.5%, P content 4%, the molar ratio of propyl alcohol and nickel is 0.5:1.Catalyst obtains after over cure and reaction test
Sulfur content is 9.5ppm, nitrogen content 2.1ppm in product.
Comparative example 3-1
Method according to embodiment 3-1 prepares catalyst, unlike, carrier S up3 is replaced by D3, is prepared into oxidation state
Catalyst.For catalyst after over cure and reaction test, it is 28.6ppm, nitrogen content 3.2ppm to obtain sulfur content in product.
Embodiment 4-1
Under agitation, acetic acid, molybdenum oxide, basic nickel carbonate are added in phosphorous acid aqueous solution, is 90 DEG C in temperature
Lower stirring 3h, prepares maceration extract.Using hole saturation infusion process maceration extract impregnated carrier Sup4, then drying 4 is small at 100 DEG C
When, it is prepared into oxidized catalyst.On the basis of the butt weight of catalyst and in terms of oxide, molybdenum content is in catalyst
30%, nickel content 8.5%, P content 5%, the molar ratio of acetic acid and nickel is 3:1.Catalyst is through over cure and reaction test
Afterwards, it is 8.4ppm, nitrogen content 1.6ppm to obtain sulfur content in product.
Comparative example 4-1
Method according to embodiment 4-1 prepares catalyst, unlike, carrier S up4 is replaced by D4, is prepared into oxidation state
Catalyst.For catalyst after over cure and reaction test, it is 28.4ppm, nitrogen content 5.6ppm to obtain sulfur content in product.
Embodiment 5-1
Method according to embodiment 4-1 prepares catalyst, unlike, acetic acid is replaced by the monoethanolamine of identical weight, is obtained
To catalyst.For catalyst after over cure and reaction test, it is 9.3ppm, nitrogen content 2.1ppm to obtain sulfur content in product.
Embodiment 6-1
Method according to embodiment 4-1 prepares catalyst, unlike, acetic acid is replaced by the citric acid of identical weight, is obtained
To catalyst.For catalyst after over cure and reaction test, it is 18.3ppm, nitrogen content 3.1ppm to obtain sulfur content in product.
Embodiment 7-1
Method according to embodiment 4-1 prepares catalyst, unlike, propyl alcohol, molybdenum oxide, basic nickel carbonate are added sub-
It is changed to add phosphorous acid, molybdenum oxide, basic nickel carbonate in aqueous propanol solution in phosphate aqueous solution, the dosage of each material is identical,
Obtain catalyst.Catalyst is after over cure and reaction test, and it is 9.8ppm to obtain sulfur content in product, and nitrogen content is
2.5ppm。
Embodiment 8-1
Under agitation, ammonium metatungstate, molybdenum oxide, basic nickel carbonate and amion acetic acid are added in phosphate aqueous solution,
1h is stirred at being 80 DEG C in temperature, prepares maceration extract.Using hole saturation infusion process maceration extract impregnated carrier Sup1, Ran Hou
When drying 3 is small at 120 DEG C, oxidized catalyst is prepared into.On the basis of the butt weight of catalyst and in terms of oxide, catalysis
W content is 20% in agent, molybdenum content 6%, nickel content 4.1%, P content 5.6%, the atomic ratio of amion acetic acid and nickel
For 1.5:1.For catalyst after over cure and reaction test, it is 10.0ppm, nitrogen content 0.3ppm to obtain sulfur content in product.
Embodiment 9-1
By boehmite (the PB90 powder of Chang Ling catalyst plant production, specific surface area 345m2/ g) roasted at 600 DEG C
4h, the dipping solution containing ethylene glycol, Mo, Ni and phosphoric acid then prepared with the method described in embodiment 2-1 are mixed, powder
(quality, g)：Solution (volume, ml) 1:1, aftershaping and the dry 4h at 120 DEG C are uniformly mixed, it is urging for 1.6mm to obtain particle diameter
Agent.On the basis of the butt weight of catalyst and in terms of oxide, molybdenum content is 52% in catalyst, nickel content 5.5%,
P content is 4%, and the atomic ratio of ethylene glycol and nickel is 3:1.Catalyst obtains sulphur in product and contains after over cure and reaction test
Measure as 8ppm, nitrogen content 1.2ppm.
Embodiment 10-1
By boehmite (the PB110 powder of Chang Ling catalyst plant production, specific surface area 325m2/ g), roasted at 700 DEG C
4h is burnt, the dipping solution containing propyl alcohol, Mo, Ni and phosphoric acid then prepared with the method described in embodiment 3-1 is mixed, powder
(quality, g)：Solution (volume, ml) 1:2, it is uniformly mixed aftershaping and in 200 DEG C of dry 4h, obtains catalysis of the particle diameter for 1.6mm
Agent Cat10.On the basis of the butt weight of catalyst and in terms of oxide, molybdenum content is 35% in catalyst, and nickel content is
8.0%, P content 6%, the molar ratio of propyl alcohol and nickel is 3:1.Catalyst is obtained in product after over cure and reaction test
Sulfur content is 4.5ppm, nitrogen content 0.4ppm.
Embodiment 11-1
By boehmite (the PB110 powder of Chang Ling catalyst plant production, specific surface area 325m2/ g), roasted at 700 DEG C
4h is burnt, the dipping solution containing acetic acid, Mo, Ni and phosphoric acid then prepared with the method described in embodiment 4-1 is mixed, powder
(quality, g)：Solution (volume, ml) 1:0.6, it is uniformly mixed aftershaping and in 150 DEG C of dry 6h, obtains particle diameter urging for 1.6mm
Agent.On the basis of the butt weight of catalyst and in terms of oxide, molybdenum content is 42% in catalyst, nickel content 7%, P
Content is 6%, and the atomic ratio of acetic acid and nickel is 1:1.After over cure and reaction test, obtain sulfur content in product is catalyst
4.0ppm, nitrogen content 0.5ppm.
It can be seen that from embodiment 9-1 to embodiment 11-1 by will be mixed by burning rear oxidation aluminium with dipping solution
The catalyst that aftershaping obtains has good performance.
To sum up, the property of carrier can be changed using method provided by the invention, increase substantially Hydrobon catalyst
Performance, there is good prospects for commercial application.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (12)
1. a kind of preparation method of alumina support, this method includes at 400-1000 DEG C roasting boehmite powder at least
When 1-15 is small, then it is molded and dry.
2. according to the method described in claim 1, wherein, the roasting carried out at 450-900 DEG C 3-8 it is small when.
3. method according to claim 1 or 2, wherein, the molding mode is extruded moulding method, and dry temperature is
50-350 DEG C, when the time is 2-10 small.
4. the alumina support as made from the method described in any one in claim 1-3.
5. a kind of preparation method of Hydrobon catalyst, this method is included using in claim 1-3 described in any one
Method prepares alumina support, then uses the maceration extract containing hydrogenation active metal component to impregnate the alumina support, it
Carrier after dry dipping afterwards.
6. a kind of preparation method of Hydrobon catalyst, this method includes roasting boehmite powder at 400-1000 DEG C
When at least 1-15 is small, then use the maceration extract containing hydrogenation active metal component to impregnate, aftershaping and drying.
7. according to the method described in claim 6, wherein, the roasting carried out at 450-900 DEG C 3-8 it is small when.
8. according to the method described in any one in claim 5-7, wherein, at least one molecular weight is contained in the maceration extract
Organic matter, at least one group VIII metallic element, at least one vib metals element and phosphorus containg substances less than 80
And/or ammonia, organic matter of the molecular weight less than 80 contain at least one of-OH ,-NH ,-COOH group.
9. according to the method described in claim 8, wherein, organic matter of the molecular weight less than 80 is methanol, ethanol, propyl alcohol,
Isopropanol, butanol, isobutanol, ethylene glycol, formic acid, acetic acid, propionic acid, ethylenediamine, monoethanolamine, ethamine, propylamine, butylamine, amino second
At least one of acid.
10. method according to claim 8 or claim 9, wherein, organic matter of the molecular weight less than 80 and group VIII metal member
The molar ratio of element is 0.2-5, is preferably 0.5-3.
11. according to the method described in any one in claim 8-10, wherein, group VIII metallic element and at least one the
The dosage of group vib metallic element causes in gained catalyst, on the basis of the butt weight of catalyst and in terms of oxide, the
The content of group VIII metal element is 2-20%, is preferably 3-15%；The content of vib metals element is 15-75%, preferably
For 20-50%.
12. Hydrobon catalyst made from the method in claim 5-11 described in any one.
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| CN108671934A (en) * | 2018-05-28 | 2018-10-19 | 中化泉州石化有限公司 | A kind of preparation method of the Hydrobon catalyst of high mechanical properties |
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