CN1272103C - Selective hydrogenation catalyst for alkadiene - Google Patents
Selective hydrogenation catalyst for alkadiene Download PDFInfo
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- CN1272103C CN1272103C CN 200310121167 CN200310121167A CN1272103C CN 1272103 C CN1272103 C CN 1272103C CN 200310121167 CN200310121167 CN 200310121167 CN 200310121167 A CN200310121167 A CN 200310121167A CN 1272103 C CN1272103 C CN 1272103C
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- catalyst
- nickel
- weight
- molybdenum
- cobalt
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 150000001993 dienes Chemical class 0.000 title claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 59
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 23
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011733 molybdenum Substances 0.000 claims abstract description 22
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 15
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 15
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010937 tungsten Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- 239000003921 oil Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 206010013786 Dry skin Diseases 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 9
- 229910052794 bromium Inorganic materials 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 8
- 229910001950 potassium oxide Inorganic materials 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 235000011118 potassium hydroxide Nutrition 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 6
- 239000011609 ammonium molybdate Substances 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 229940010552 ammonium molybdate Drugs 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 238000002803 maceration Methods 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000003223 protective agent Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052776 Thorium Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- -1 molybdate compound Chemical class 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 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
- 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 2
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000002872 contrast media Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- DANMWBNOPFBJSZ-UHFFFAOYSA-N 1-iodo-2,3-dimethylbenzene Chemical group CC1=CC=CC(I)=C1C DANMWBNOPFBJSZ-UHFFFAOYSA-N 0.000 description 1
- 241000640882 Condea Species 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
- ZGRBQKWGELDHSV-UHFFFAOYSA-N N.[W+4] Chemical compound N.[W+4] ZGRBQKWGELDHSV-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 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
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 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
- 235000009566 rice Nutrition 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention relates to a catalyst for selectively hydrogenating diolefin. The present invention contains alumina supporters, cobalt and/or nickel selected from the VIII group, molybdenum and/or tungsten selected from the VIB group and alkali metals, wherein the cobalt and/or nickel, the molybdenum and/or tungsten are loaded on the alumina supporters. The present invention is characterized in that the present invention contains the components in the form of oxide adopting the catalyst weight as the reference: 0.5 to 8 wt% of the cobalt and/or nickel selected from the VIII group, 2 to 15 wt% of the molybdenum and/or tungsten selected from the VIB group, more than 2 to 8 wt% of the alkali metals and an equilibrium amount of the alumina supporters. Compared with the existing catalyst, when the catalyst for selectively hydrogenating diolefin, which is provided by the present invention, is used for hydrogenating gasoline distillate oil, the hydrogenation activity and the selectivity of diolefin are high.
Description
Technical field
The invention relates to a kind of Hydrobon catalyst, more specifically say so about a kind of alkadienes selective hydrocatalyst.
Background technology
Contain more alkadienes in the catalytically cracked gasoline, under the certain reaction temperature, alkadienes also reacts together with other hydro carbons in the catalytically cracked gasoline except that polymerization own, generates colloid and other coking precursor.Normally adopt the method for hydrogenation optionally it to be removed.
US6,084,140 discloses a kind of preparation method to height unsaturated hydrocarbons selective hydrocatalyst in the olefine fraction.This catalyst is made up of aluminium oxide and the Metal Palladium that loads on this aluminium oxide.The content of Metal Palladium is 0.02-3.0 weight %.This catalyst can effectively remove the height unsaturated hydrocarbons in the olefine fraction.
US6,255,548 disclose a kind of preparation method to unsaturated hydro carbons such as alkynes and alkadienes selective hydrocatalyst.This catalyst is loaded on the carrier by at least a VIII family's metal and at least a promoter metal M and makes.This VIII family metal can be in nickel, palladium, platinum, rhodium, ruthenium, the iridium one or more, preferred palladium, and nickel, platinum, last weight range 0.01-50 weight % is if the preferred 0.05-1 weight of noble metal %, if this metal is nickel then preferred 5-30 weight %.Metal M is selected from one or more in germanium, tin, the gold, silver, weight range 0.01-10 weight % on the metal M, preferred 0.02-5 weight %.This catalyst also can contain alkalinous metal such as potassium or sodium and/or the 0.01-2.0 weight % elementary sulfur of 0.1-3 weight %.
US6,388,162 disclose a kind of method that removes alkadienes in olefin feedstock.This method is that carbon number is made with extra care at 10 to 20 the raw material that is rich in alkene, removes alkadienes wherein.The catalyst that this method is used is made up of alumina support and the Metal Palladium that loads on this alumina support, amount 0.05-0.2 weight % on the metal, and preferred 0.2 weight %, wherein the aluminium oxide specific area is not more than 15 meters
2/ gram, preferred 2-5 rice
2/ gram.
Adopt noble metal catalyst to carry out selective hydrogenation, can well the alkadienes in the feedstock oil be removed.But for sulphur, higher full cut or the heavy distillat catalytically cracked gasoline of nitrogen content, the easy inactivation of noble metal is restricted the use of this class catalyst.
Generally speaking, under the hydrofinishing condition alkene particularly the hydrogenation of alkadienes carry out easily.But, adopting the non-noble metal hydrogenation catalyst for refining optionally during the alkadienes in the hydrogenation and removing feedstock oil, the problem that exists is how when guaranteeing to remove alkadienes, avoid or reduce olefinic polymerization, monoolefin hydrogenation is saturated, to improve the selectivity of hydrogenation reaction.
Alkali-metal existence is favourable to suppressing the catalyst surface carbon distribution, so prior art is when preparation is used for the Hydrobon catalyst of the higher feedstock oil of olefin(e) centent, and the Chang Zuowei adjuvant component is introduced alkali metal.
CN 1113829A discloses a kind of preparation method who contains the Hydrobon catalyst of molybdenum, nickel, potassium metal component, its main feature is preformed transition state of alumina carrier, single-steeping contains molybdenum, nickel, the potassium solution of ammonia, and drying, roasting make catalyst.Transition state of alumina comprises η, γ, θ aluminium oxide, preferred gama-alumina.This catalyst metal components content is MoO
310.0～24.0%, NiO 2.6～8.8%, K 0.3～1.5%.This catalyst can be used for containing the hydrodesulfurization of the light oil distillate or the gas of organic sulfur, is specially adapted to the hydrodesulfurization of naphtha and coking dry gas.
CN 1302849A discloses a kind of hydrogenation activity protective agent and preparation method thereof, contains gama-alumina and δ-aluminium oxide in the protective agent used carrier simultaneously; Contain group vib metal oxide 3～22% and VIII family metal oxide 0.5～5m% in the protective agent, contain the element 0～2m% of IA family, contain the element 0～3m% of VA family, specific surface 100～250m
2/ g.Pore volume 0.4～0.8ml/g.The group vib metal oxide is the oxide of Mo, W in this protective agent, and the group VIII metal oxide is the oxide of Fe, Co, Ni, and VA family element is P, As, Sb, Bi element.The protective agent that this catalyst is suitable for catalyst for hydroprocessing of heavy oil uses.
The Hydrobon catalyst of this class alkali metal containing component can be used for the alkadienes selective hydrogenation of gasoline fraction, but active low.
Summary of the invention
The objective of the invention is to overcome existing Hydrobon catalyst active low shortcoming when being used for the alkadienes selective hydrogenation, a kind of new active higher alkadienes selective hydrocatalyst is provided.
The present inventor's discovery, in the Hydrobon catalyst of the alkali metal containing component that prior art provides, alkali-metal content low (less than 2 weight %), this is to cause the active low major reason of this class catalyst alkadienes selective hydrogenation.
Alkadienes selective hydrocatalyst provided by the invention contains a kind of alumina support and loads on the cobalt that is selected from group VIII on this carrier and/or molybdenum and/or the tungsten and the alkaline components of nickel, group vib, it is characterized in that, in oxide and with the catalyst is benchmark, this catalyst contain the molybdenum that is selected from group vib of the cobalt that is selected from group VIII of 0.5-8 weight % and/or nickel, 2-15 weight % and/or tungsten,＞alkali metal of 2-8 weight % and the alumina support of aequum.
Compare with existing catalyst, catalyst provided by the invention has higher diene hydrogenation activity when being used for the hydrofinishing of gasoline fraction oil.
For example, under identical reaction condition, be 1.6gI. (100g) to a kind of diene value
-1, bromine valency 37.1gBr. (100ml)
-1The catalytically cracked gasoline heavy distillate carry out hydrogenation and take off diene, when adopting catalyst provided by the invention (content of nickel oxide is that the content of 1.4 weight %, molybdenum oxide is that the content of 4.5 weight %, potassium oxide is 2.1 weight %), the diene value that generates oil is reduced to 0.3gI. (100g)
-1, the bromine valency be 36.1gBr. (100ml)-
1;And during Comparative Examples catalyst (carrier is identical with preceding agent, and the content of nickel oxide is that the content of 1.4 weight %, molybdenum oxide is that the content of 4.6 weight %, potassium oxide is 1.4 weight %), the diene value that generates oil is reduced to 0.5gI. (100g)
-1, the bromine valency is 34.7gBr. (100ml)
-1
The specific embodiment
According to catalyst provided by the invention, in oxide and with the catalyst is benchmark, preferably contains the molybdenum that is selected from group vib and/or tungsten, the alkali metal of 2.5-6 weight % and the alumina support of aequum of the cobalt that is selected from group VIII of 1-6 weight % and/or nickel, 4-12 weight %.Wherein, the atomic ratio of group VIII metal component and group vib metal component is 0.5-2, is preferably 0.7-1.5.
Described group VIII metal component is preferably nickel, and alkali metal is preferably potassium.
Described alumina support is the transition aluminas that is selected among γ, η, θ, δ and the χ one or more, also can be to contain one or more to be selected among silicon, titanium, magnesium, boron, zirconium, thorium, niobium, the rare earth among one or more γ, η, θ, δ and χ that dose component one or more transition aluminas, be preferably gama-alumina and contain one or more that one or more dose the gama-alumina of component among being selected from silicon, titanium, magnesium, boron, zirconium, thorium, niobium, rare earth.
Described aluminium oxide can be that commercially available commodity also can be by any one method preparation in the prior art.For example, can be by one or more the mixture that is selected among hibbsite, monohydrate alumina and the amorphous hydroted alumina, or one or more the mixture among hibbsite, monohydrate alumina and the amorphous hydroted alumina of siliceous, titanium, magnesium, boron, zirconium, thorium, niobium, rare earth make after moulding and roasting.
Preparation of catalysts method provided by the invention is included in to be enough to belong under the condition that is deposited on the described alumina support being selected from the molybdenum of the cobalt of group VIII and/or nickel, group vib and/or tungsten and alkaline components, with alumina support with contain the cobalt and/or nickel, the molybdenum of group vib and/or the solution of tungsten and alkali-metal compound that are selected from group VIII and contact, for example pass through methods such as dipping, co-precipitation, preferred infusion process.Wherein, being selected from the molybdenum of the cobalt of group VIII and/or nickel, group vib and/or tungsten and alkali metal can also can be incorporated in the alumina support respectively simultaneously.
Described molybdate compound is selected from one or more in the soluble compound that contains molybdenum, as in molybdenum oxide, molybdate, the paramolybdate one or more, and preferred molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein.
Described Tungstenic compound is selected from one or more in the soluble compound of tungstenic, as in tungstates, metatungstate, the ethyl metatungstate one or more, and the preferred inclined to one side tungsten ammonium of ammonium metatungstate, ethyl wherein.
Described cobalt compound is selected from one or more in the soluble compound that contains cobalt, as in the soluble complexes of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobalt one or more, is preferably cobalt nitrate, basic cobaltous carbonate.
Described nickeliferous compound is selected from one or more in the nickel metal soluble compound, as in the soluble complexes of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel one or more, is preferably nickel nitrate, basic nickel carbonate.
The compound of described alkali metal containing, preferred hydroxide, in the inorganic or acylate one or more wherein.For example be selected from potassium hydroxide, potassium nitrate, potassium chloride, potassium acetate, potassium phosphate, potassium hydrogen phosphate and the potassium dihydrogen phosphate in the potassium-containing compound one or more.
According to catalyst provided by the invention, look the article shaped that various objectives or requirement can be made into various easy operatings, for example microballoon, sphere, tablet or bar shaped etc.Moulding can be carried out according to a conventional method, all can as methods such as compressing tablet, spin, extrusions.
According to the conventional method in this area, catalyst provided by the invention can carry out presulfurization with the sulfur-bearing raw material usually under 140-370 ℃ temperature in the presence of hydrogen before using, this presulfurization can be carried out also can original position vulcanizing in device outside device, is translated into sulfide type.
Catalyst provided by the invention has higher hydrogenation activity and selectivity to the alkadienes in the gasoline fraction oil, be particularly suitable for containing alkadienes gasoline fraction oil be the hydrofinishing of purpose with the hydrogenation dialkene removal.Described gasoline fraction can be catalytically cracked gasoline, coker gasoline, direct steaming gasoline, pressure gasoline etc.
The following examples will the invention will be further described.
Example 1
This example illustrates Catalysts and its preparation method provided by the invention.
Take by weighing dry glue powder 800 grams that Chang Ling oil plant catalyst plant is produced, be extruded into circumscribed circle diameter and be 1.4 millimeters trilobal bar, 120 ℃ of oven dry, roasting obtained 584 gram carrier Z in 3 hours under 630 ℃ of air atmospheres.
Take by weighing nickel nitrate 4 gram, ammonium molybdate 6 grams, potassium hydroxide (KOH content 82%, Beijing chemical reagent factory product, down with) 3.3 grams, adopt the NH of 16 weight %
3Aqueous solution dissolving is made into 90 milliliters of maceration extracts.With this solution impregnation 100 gram carriers Z4 hour,, reduce to after the room temperature with 80 milliliters of the aqueous solution that contain 2 gram nickel nitrates dipping once more, and, obtain catalyst C1 in 4 hours, 420 ℃ roastings of 120 ℃ of dryings 4 hours in 4 hours, 420 ℃ roastings of 120 ℃ of dryings 4 hours.Nickel, molybdenum, potassium oxide content are listed in the table 1 among the catalyst C1.
Nickel, molybdenum, potassium content adopt the x ray fluorescence spectrometry method to measure (down together).
Comparative Examples 1
This Comparative Examples explanation Comparative Examples Catalysts and its preparation method.
Take by weighing nickel nitrate 4.0 grams, ammonium molybdate 6 grams, potassium hydroxide 2.2 grams adopt 16 weight %NH
3Aqueous solution dissolving, be made into 90 milliliters of maceration extracts.With this solution impregnation 100 gram carrier Z 4 hours, then 120 ℃ of dryings 4 hours, 420 ℃ of roastings 4 hours obtained catalyst B 1.Nickel, molybdenum, potassium oxide content are listed in the table 1 in the catalyst B 1.
Comparative Examples 2
This Comparative Examples explanation Comparative Examples Catalysts and its preparation method.
Take by weighing nickel nitrate 4 grams, ammonium molybdate 6 grams, potassium hydroxide 2.2 restrains, and adopts the NH of 16 weight %
3Aqueous solution dissolving is made into 90 milliliters of maceration extracts.With this solution impregnation 100 gram carrier Z 4 hours,, flood once more for 80 milliliters with containing the nickel nitrate 2 gram aqueous solution after reducing to room temperature, and, obtain catalyst B 2 in 4 hours, 420 ℃ roastings of 120 ℃ of dryings 4 hours in 4 hours, 420 ℃ roastings of 120 ℃ of dryings 4 hours.Nickel, molybdenum, potassium oxide content are listed in the table 1 in the catalyst B 2.
Example 2
This example illustrates Catalysts and its preparation method provided by the invention.
Take by weighing nickel nitrate 4 grams, ammonium molybdate 6 grams, potassium hydroxide 9 restrains, and adopts the NH of 16 weight %
3Aqueous solution dissolving is made into 90 milliliters of maceration extracts.With this solution impregnation 100 gram carrier Z 4 hours, in 4 hours, 420 ℃ roastings of 120 ℃ of dryings 4 hours, reduce to after the room temperature with 80 milliliters of the aqueous solution that contain 10 gram nickel nitrates dipping once more, open in 4 hours, 420 ℃ roastings of 120 ℃ of dryings 4 hours, obtain catalyst C2.Nickel, molybdenum, potassium oxide content are listed in the table 1 among the catalyst C2.
Example 3
This example illustrates Catalysts and its preparation method provided by the invention.
Take by weighing nickel nitrate 10 grams, ammonium molybdate 14 grams, potassium hydroxide 6.5 restrains, and adopts the NH of 16 weight %
3Aqueous solution dissolving is made into 90 milliliters of maceration extracts.With this solution impregnation 100 gram carrier Z 4 hours,, reduce to after the room temperature with 80 milliliters of the aqueous solution that contain 14 gram nickel nitrates dipping once more, and, obtain catalyst C3 in 4 hours, 420 ℃ roastings of 120 ℃ of dryings 4 hours in 4 hours, 420 ℃ roastings of 120 ℃ of dryings 4 hours.Nickel, molybdenum, potassium oxide content are listed in the table 1 among the catalyst C3.
Example 4
This example illustrates Catalysts and its preparation method provided by the invention.
Take by weighing SB aluminium hydrate powder 800 grams that German CONDEA company produces, and contain magnesium nitrate [Mg (NO
3)
26H
2O] aqueous solution of 115 grams mix for 750 milliliters, are extruded into circumscribed circle diameter and are 1.4 millimeters trilobal bar, 120 ℃ of oven dry, roasting obtained the alumina support Z2 that 602 grams contain magnesia 3.1 weight % in 2 hours under 550 ℃ of air atmospheres.
Take by weighing nickel nitrate 7.5 grams, 11 milliliters of ammonium metatungstate solutions (79.3 gram tungstic acid/100 ml solns), potassium nitrate 11.8 restrains, and adopts the NH of 16 weight %
3Aqueous solution dissolving is made into 90 milliliters of co-impregnated solutions.With this solution impregnation 100 gram carriers Z24 hour, then 120 ℃ of dryings 4 hours, 420 ℃ of roastings 4 hours obtained catalyst C4.Nickel, tungsten, potassium oxide content are listed in the table 1 among the catalyst C4.
Table 1
| Example | The catalyst numbering | Content, heavy % | Nickel/molybdenum or tungsten (atom) | |||
| Nickel oxide | Molybdenum oxide | Tungsten oxide | Potassium oxide | |||
| 1 | C1 | 1.4 | 4.5 | 2.1 | 0.6 | |
| Comparative Examples 1 | B1 | 0.9 | 4.6 | 1.4 | 0.4 | |
| Comparative Examples 2 | B2 | 1.4 | 4.6 | 1.4 | 0.6 | |
| 2 | C2 | 3.1 | 4.3 | - | 5.4 | 1.4 |
| 3 | C3 | 5.5 | 10.5 | - | 4.1 | 1.0 |
| 4 | C4 | 1.7 | - | 7.9 | 5.0 | 0.7 |
Example 5-8
The explanation of this example the invention provides the alkadienes selective hydrogenation performance that catalyst is used for gasoline fraction oil.
With the catalytically cracked gasoline heavy distillate is raw material (its character sees Table 2), evaluate catalysts C1, C2, C3, C4 on the 50ml fixed-bed reactor.Before formal charging, with the direct steaming gasoline that contains 2 heavy % carbon disulfide catalyst is vulcanized earlier, conditions of vulcanization is: hydrogen dividing potential drop 1.6 MPas, 290 ℃ of temperature, liquid hourly space velocity (LHSV) 2h
-1, hydrogen to oil volume ratio 300, cure time 9 hours, cut raw material afterwards and react, reaction temperature is 240 ℃, the hydrogen dividing potential drop is 1.6 MPas, volume space velocity 20 hours
-1, hydrogen-oil ratio (volume) 100 reacts sample analysis after 100 hours, the results are shown in table 3.
The assay method of diene value: accurately draw 5 milliliters of samples in the ground conical flask with pipette, accurately add 20 milliliters of benzene-anhydrous maleic acid anhydride solutions (containing 30 gram anhydrous maleic acid acid anhydrides in every liter of benzene) and 0.2 milliliter of iodo-xylene solution (0.1N) with pipette again, replace sample to do blank test with 10 milliliters of benzene simultaneously.Conical flask is loaded onto spherical reflux condenser, put into 80 ℃ of waters bath with thermostatic control and refluxed 30 minutes,, continue to reflux 30 minutes, make the abundant hydrolysis of residue maleic anhydride again from condenser adding 5 ml deionized water suitable for reading.Be cooled to room temperature, with 5 milliliters of ether, 20 ml deionized water flushing condenser, unload conical flask then respectively.Mixture in the bottle poured in 250 milliliters of separatory funnels separate.With the aqueous solution after the sodium hydroxide solution titration separation of 0.5N, record consumes volume at last.
L * the d of diene value=12.692 * N * (B-A)
In the formula: the N-NaOH concentration of standard solution
The volume of the NaOH solution that the B-blank test is consumed, milliliter
The volume of the NaOH solution that the A-sample is consumed, milliliter
The L-volume of sample, milliliter
20 ℃ of density of d-sample, grams per milliliter
The assay method of bromine valency is RIPP 66-90.
Comparative Examples 3-4
This Comparative Examples explanation reference catalyst is used for the hydrofinishing performance of gasoline fraction oil.
Adopt with example 4 same procedure evaluations and estimate Comparative Examples catalyst B 1, B2, reaction result sees Table 3.
Table 2
| The oil product title | Catalytically cracked gasoline heavy distillat |
| Density (20 ℃), g/cm 3Sulphur, ppm diene value, gI 2/ 100g bromine valency; GBr/100g boiling range D-86, ℃ initial boiling point 10% 50% 90% 95% is done | 0.7855 1680 1.6 37.1 92 112 135 165 174 190 |
Table 3
| Example | 5 | Contrast medium 3 | Contrast medium 4 | 6 | 7 | 8 |
| Catalyst | C1 | B1 | B2 | C2 | C3* | C4 |
| The product characteristics diene value, gI 2/ 100g bromine valency, gBr/100g | 0.3 36.1 | 0.6 33.9 | 0.5 34.7 | ＜0.2 36.3 | ＜0.2 36.4 | ＜0.2 35.4 |
* the C3 reaction temperature is 230 ℃
The result of table 3 can illustrate, compares with existing catalyst, and catalyst provided by the invention has higher diene hydrogenation activity when being used for the hydrofinishing of gasoline fraction oil.
The bromine valency of feedstock oil is 37.1gBr/100ml, and the generation oil bromine valency behind the hydrogenation all decreases.But from the result of table 3 as can be seen, adopt when the invention provides catalyst, generate the degree that oily bromine valency reduces and be lower than existing catalyst, illustrate that the invention provides catalyst has selectivity preferably.
Claims (6)
1, a kind of alkadienes selective hydrocatalyst, this catalyst contains a kind of alumina support and loads on the cobalt that is selected from group VIII on this carrier and/or molybdenum and/or the tungsten and the alkaline components of nickel, group vib, it is characterized in that, in oxide and with the catalyst is benchmark, this catalyst contain the molybdenum that is selected from group vib of the cobalt that is selected from group VIII of 0.5-8 weight % and/or nickel, 2-15 weight % and/or tungsten,＞alkali metal of 2-8 weight % and the alumina support of aequum.
2, catalyst according to claim 1, it is characterized in that, in oxide and with the catalyst is benchmark, and this catalyst contains the molybdenum that is selected from group vib and/or tungsten, the alkali metal of 2.5-6 weight % and the alumina support of aequum of the cobalt that is selected from group VIII of 1-6 weight % and/or nickel, 4-12 weight %.
3, catalyst according to claim 1 and 2 is characterized in that, described group VIII metal component is a nickel.
4, catalyst according to claim 1 and 2 is characterized in that, described alkali metal is potassium.
5, catalyst according to claim 1 is characterized in that, the atomic ratio of described group VIII metal component and group vib metal component is 0.5-2.
6, catalyst according to claim 5 is characterized in that, the atomic ratio of described group VIII metal component and group vib metal component is 0.7-1.5.
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| CN 200310121167 CN1272103C (en) | 2003-12-22 | 2003-12-22 | Selective hydrogenation catalyst for alkadiene |
| US11/016,986 US7745372B2 (en) | 2003-12-22 | 2004-12-21 | Catalyst for selective hydrogenation of olefins and its preparation as well as use |
| FR0413779A FR2864102B1 (en) | 2003-12-22 | 2004-12-22 | SELECTIVE HYDROGENATION CATALYST OF OLEFINS AND ITS PREPARATION AND USE |
| KR1020040110202A KR101122209B1 (en) | 2003-12-22 | 2004-12-22 | A catalyst for selective hydrogenation of olefins and its preparation as well as use |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2811194C1 (en) * | 2023-06-02 | 2024-01-11 | Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" | Catalyst for selective hydrogenation of dienes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100448951C (en) * | 2005-08-09 | 2009-01-07 | 中国石油化工股份有限公司 | Method of producing catalytic reforming raw material |
| CN1916121B (en) * | 2005-08-17 | 2010-04-21 | 中国石油天然气集团公司 | Method for preparing diene selective hydrotreating catalyst for gasoline |
| FR2937566B1 (en) * | 2008-10-24 | 2014-07-18 | Arkema France | HYDROGENATION CATALYST, IN PARTICULAR CARBON SULPHIDE |
| CN103084193A (en) * | 2011-10-28 | 2013-05-08 | 江苏佳誉信实业有限公司 | Cracking gasoline and catalytic gasoline selective hydrogenation diene removal catalyst and method |
| CN103145516B (en) * | 2011-12-06 | 2015-01-21 | 中国石油天然气股份有限公司 | Method for selective hydrogenation of unsaturated compound |
| CN104437523B (en) * | 2013-09-22 | 2016-08-24 | 中国石油化工股份有限公司 | A kind of alkadienes selective hydrocatalyst and preparation thereof and application |
| CN106362758B (en) * | 2015-07-21 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of alkadienes selective hydrocatalyst and its application |
| CN106268848A (en) * | 2016-07-22 | 2017-01-04 | 西安向阳航天材料股份有限公司 | A kind of coke-stove gas Hydrobon catalyst and preparation method thereof |
| CN110496611B (en) * | 2018-05-16 | 2022-07-08 | 湖南长岭石化科技开发有限公司 | Alumina carrier and preparation method thereof, catalyst and preparation method thereof, and method for reducing content of diolefin in hydrocarbon oil |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2811194C1 (en) * | 2023-06-02 | 2024-01-11 | Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" | Catalyst for selective hydrogenation of dienes |
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