CN112742409A - Catalyst for reducing mercaptan, preparation method and application thereof, and method for reducing mercaptan in gasoline - Google Patents
Catalyst for reducing mercaptan, preparation method and application thereof, and method for reducing mercaptan in gasoline Download PDFInfo
- Publication number
- CN112742409A CN112742409A CN201911055366.8A CN201911055366A CN112742409A CN 112742409 A CN112742409 A CN 112742409A CN 201911055366 A CN201911055366 A CN 201911055366A CN 112742409 A CN112742409 A CN 112742409A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acid
- active component
- silica
- molybdenum
- 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
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 36
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 35
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011733 molybdenum Substances 0.000 claims abstract description 34
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 37
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- -1 organic acid ammonium salts Chemical class 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 235000015165 citric acid Nutrition 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- FCKYPQBAHLOOJQ-UWVGGRQHSA-N 2-[[(1s,2s)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)[C@H]1CCCC[C@@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UWVGGRQHSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 34
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 34
- 239000000243 solution Substances 0.000 description 31
- 239000000047 product Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 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 17
- 239000000843 powder Substances 0.000 description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 description 15
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 14
- 238000007598 dipping method Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000002336 sorption--desorption measurement Methods 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 229910001593 boehmite Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- AUTNMGCKBXKHNV-UHFFFAOYSA-P diazanium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [NH4+].[NH4+].O1B([O-])OB2OB([O-])OB1O2 AUTNMGCKBXKHNV-UHFFFAOYSA-P 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000005416 organic matter Substances 0.000 description 2
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
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- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
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- 238000010521 absorption reaction Methods 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
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- 230000002378 acidificating effect Effects 0.000 description 1
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- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
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- 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
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 1
- 229960001633 lanthanum carbonate Drugs 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 150000002815 nickel Chemical class 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
- 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
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of catalysts, and discloses a catalyst for reducing mercaptan, a preparation method and application thereof, and a method for reducing mercaptan in gasoline. The catalyst comprises a carrier and an active component nickel and optionally an active component molybdenum which are loaded on the carrier, wherein the content of the active component nickel is 1-15 wt% and the content of the active component molybdenum is 0-12 wt% in terms of oxides based on the total amount of the catalyst; the molybdenum equilibrium adsorption capacity of the carrier is MoO3Calculated as 8-20 percent, the specific surface area is 200-350m2Per g, pore volume of 0.65-1.2cm3(ii) in terms of/g. When the catalyst provided by the invention is used for reducing the gasoline mercaptan and the diolefin, the catalyst has higher activity and selectivity.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a catalyst for reducing mercaptan, a preparation method and application thereof, and a method for reducing mercaptan in gasoline.
Background
The increasing awareness of environmental protection and stricter regulations of environmental protection force the oil refining world to pay more attention to the development of clean fuel production technology, and how to economically and reasonably produce ultra-low sulfur oil products becomes one of the problems to be solved in the oil refining world at present and in a certain period in the future.
Diolefins in the catalytically cracked gasoline are easy to polymerize and coke on a catalyst, so that the catalyst is deactivated and the bed pressure drop is increased, so that the diolefins are required to be selectively removed by hydrogenation. The olefin in the gasoline is mainly enriched in the light fraction section of the gasoline, and the sulfur in the light gasoline is mainly mercaptan with the carbon number of 4 and below 4. In order to produce clean gasoline, the research on a hydrodesulfurization catalyst with excellent performance is dedicated at home and abroad, but olefins in the catalytic cracking gasoline are easily saturated under the hydrodesulfurization reaction condition, so that the octane number loss and the hydrogen consumption are increased. In order to reduce the mercaptan in gasoline, especially in light gasoline, it is necessary to design and construct a catalyst with high activity and high selectivity for reducing the mercaptan in gasoline.
Therefore, a catalyst for reducing mercaptans is needed.
Disclosure of Invention
The invention aims to provide a novel catalyst for reducing mercaptan, a preparation method and application thereof, and a method for reducing mercaptan in gasoline.
In order to achieve the above object, the first aspect of the present invention provides a catalyst for reducing mercaptan, the catalyst comprising a carrier and an active component nickel and optionally an active component molybdenum, which are supported on the carrier, wherein the content of the active component nickel is 1-15 wt% and the content of the active component molybdenum is 0-12 wt% in terms of oxide, based on the total amount of the catalyst; the molybdenum equilibrium adsorption capacity of the carrier is MoO3Calculated as 8-20 percent, the specific surface area is 200-350m2Per g, pore volume of 0.65-1.2cm3/g。
Preferably, the content of the active component nickel is 3-15 wt% and the content of the active component molybdenum is 1-11 wt% calculated by oxide based on the total amount of the catalyst.
Preferably, the atomic ratio of the active component nickel to the sum of the active component nickel and the active component molybdenum is 0.3 or more, and more preferably 0.4 to 0.8.
In a second aspect, the present invention provides a method for preparing the above catalyst, which comprises: the support is impregnated with a solution containing a nickel-containing compound and optionally a molybdenum-containing compound, followed by drying and optionally calcining.
Preferably, the solution further contains a complexing agent, and the complexing agent is selected from at least one of organic acid and/or ammonium salt thereof.
In a third aspect, the invention provides a use of the above catalyst for reducing mercaptans in gasoline.
Preferably, the catalyst provided by the invention is suitable for reducing mercaptan in gasoline, and is particularly suitable for reducing mercaptan in light gasoline, so that the requirement of clean gasoline production is met.
In a fourth aspect, the present invention provides a method for reducing mercaptans in gasoline, the method comprising: the gasoline fraction is contacted with the above-mentioned catalyst under the condition of removing mercaptan.
Preferably, the mercaptan removal conditions comprise: the temperature is 80-200 ℃, the pressure is 0.5-3MPa, and the volume ratio of hydrogen to oil is 1-200Nm3/m3The volume space velocity is 0.5-10h-1。
Through the technical scheme, the activity and the selectivity of the catalyst for gasoline sweetening can be remarkably improved through the matching of the catalyst carrier with specific properties (with specific molybdenum equilibrium adsorption capacity, specific surface area and pore volume) and the active components of nickel and molybdenum with specific contents. According to the test example, the evaluation result under the same conditions of using full range gasoline (mercaptan sulfur content is 49 mug/g, diene iodine value is 1.8gI/100g) as raw material finds that the mercaptan sulfur content in the product obtained by using the reference agent is 16 mug/g, and the diene iodine value is 0.6gI/100 g; the mercaptan sulfur content in the product obtained by the catalyst provided by the invention can be as low as 5 mu g/g, and the diene iodine value can be as low as less than 0.2gI/100 g. Compared with the prior art, the catalyst provided by the invention can obviously reduce the contents of mercaptan and diene in gasoline, and has higher activity and selectivity.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a catalyst for reducing mercaptan, which comprises a carrier and an active component nickel and optionally an active component molybdenum which are loaded on the carrier, wherein the content of the active component nickel is 1-15 wt% and the content of the active component molybdenum is 0-12 wt% calculated by oxides based on the total amount of the catalyst; the molybdenum equilibrium adsorption capacity of the carrier is MoO3Calculated as 8-20 percent, the specific surface area is 200-350m2Per g, pore volume of 0.65-1.2cm3/g。
In the present invention, unless otherwise specified, the method for measuring the equilibrium adsorption amount of molybdenum is as follows: adding 180g ammonium heptamolybdate and 7000mL deionized water into a stainless steel belt reaction kettle with a stirring and polytetrafluoroethylene lining, stirring, dissolving and clarifying, adding 100g ground carrier powder (the particle size is less than 200 meshes)) After stirring for 24 hours, pouring all the slurry into a Buchner funnel, and carrying out suction filtration and washing with deionized water for 6 times, wherein the deionized water used for washing each time is 7000 mL; the filter cake after 6 times of washing is dried at 120 ℃ for 12h and then roasted at 420 ℃ for 4 h. Determining MoO of the roasted sample by adopting an X fluorescence method3The percentage content is as follows.
According to the invention, preferably, the content of the active component nickel is 3-15 wt% and the content of the active component molybdenum is 1-11 wt% calculated by oxide based on the total amount of the catalyst. Specifically, the active component nickel is present in an amount of 3 wt.%, 8 wt.%, 10 wt.%, 12 wt.% and 15 wt.%, and intermediate values therebetween; the active component molybdenum is present in an amount of 1 wt.%, 3 wt.%, 5 wt.%, 7 wt.%, 9 wt.% and 11 wt.%, and any intermediate value therebetween.
According to the present invention, the atomic ratio of the active component nickel to the sum of the active component nickel and the active component molybdenum is preferably 0.3 or more, and more preferably 0.4 to 0.8. The preferable limiting ratio of the invention is more beneficial to improving the activity and the selectivity of the catalyst.
According to a preferred embodiment of the invention, the molybdenum equilibrium adsorption quantity of the support is MoO3Calculated as 8-16%, and the specific surface area is 200-300m2Per g, pore volume of 0.65-1cm3/g。
In the present invention, the carrier is not particularly limited. Specifically, the carrier is selected from one or more of alumina, silica, alumina-silica, titania, alumina-titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia, preferably at least one of alumina, silica and titania, more preferably alumina.
According to the present invention, the above-mentioned carrier can be obtained commercially or can be prepared by a conventional method.
According to a preferred embodiment of the present invention, the method for preparing the carrier comprises: sequentially carrying out first drying, forming and first roasting on a carrier precursor, wherein the preparation method of the carrier precursor comprises the following steps:
(1) mixing pseudo-boehmite containing or not containing an auxiliary agent and a solution containing an inorganic aluminum-containing compound to obtain a first slurry;
(2) adjusting the pH of the slurry to 7-10 to obtain a second slurry;
(3) aging the second slurry.
The inventor of the invention finds that the carrier prepared by the specific method has obviously better catalytic performance when being used in the mercaptan removal process by matching with the active component.
The invention has wide selection of the kind of the inorganic aluminum-containing compound, and preferably, the inorganic aluminum-containing compound is selected from at least one of aluminum sulfate, sodium metaaluminate, aluminum nitrate and aluminum trichloride.
The concentration of the solution containing the inorganic aluminum-containing compound is selected in a wide range, for example, every 1000mL of the solution containing the inorganic aluminum-containing compound is mixed with Al2O3The inorganic aluminium-containing compound may be present in an amount of 1 to 100g, for example 3 to 65 g. The solvent of the solution containing the inorganic aluminum-containing compound may be water.
Preferably, the solution containing the inorganic aluminum-containing compound further contains an organic substance, and the organic substance is one or more selected from organic acids, organic acid ammonium salts and organic alcohols.
The organic acid is preferably selected from one or more of trans-1, 2-cyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, tartaric acid and malic acid. The organic acid ammonium salt can be selected from the corresponding organic acid ammonium salts, and the invention is not described herein again.
The organic alcohol is preferably selected from one or more of glycerol, ethylene glycol, polyethylene glycol, trimethylolethane, pentaerythritol, xylitol and sorbitol.
The invention has wide selection range of the dosage of the organic matter, and preferably, the organic matter and Al are used2O3The mass ratio of the inorganic aluminum-containing compound is 0.1-20: 1, preferably 0.5 to 10: 1.
the invention has wide selection range of the dosage ratio of the inorganic aluminum-containing compound to the pseudo-boehmite containing or not containing the auxiliary agent, and preferably, Al is used2O3The mass ratio of the inorganic aluminum-containing compound to the pseudo-boehmite containing or not containing the auxiliary agent on a dry basis is 0.1-30: 100, preferably 1 to 20: 100, more preferably 5 to 15: 100.
specifically, the mixing in step (1) is carried out under stirring.
According to the present invention, in the step (2), the pH of the slurry may be adjusted with an acid or a base.
The types of the acid and the alkali are not particularly limited, as long as the function of adjusting the pH is achieved, the alkali can be hydroxide or salt which is hydrolyzed in an aqueous medium to make an aqueous solution alkaline, and the hydroxide is preferably one or more selected from urea, ammonia water, sodium hydroxide and potassium hydroxide; preferably, the salt is selected from one or more of ammonium bicarbonate, ammonium carbonate, sodium bicarbonate, sodium carbonate, potassium bicarbonate and potassium carbonate; the acid can be protonic acid or oxide which is acidic in an aqueous medium, preferably the protonic acid is one or more selected from nitric acid, sulfuric acid and hydrochloric acid, and preferably the oxide is carbon dioxide.
According to a preferred embodiment of the present invention, in the step (2), the pH of the slurry is adjusted to 8.5 to 10.
According to a preferred embodiment of the invention, the aging conditions comprise: the temperature is 25-90 ℃ and the time is 0.2-12 hours.
According to the present invention, the conditions of the first drying are not particularly limited, and for example, the drying may be performed at 80 to 150 ℃ for 1 to 24 hours.
According to the present invention, specifically, the method for preparing the carrier further comprises subjecting the carrier precursor to filtration washing before the first drying. The specific operation of the filtration washing in the present invention is not particularly limited, and may be carried out according to a conventional technique in the art.
The dry basis in the present invention means, unless otherwise specified: the alumina hydrate was raised to 600 ℃ in a muffle furnace under air atmosphere at a rate of 4 ℃/min and then kept at 600 ℃ for 4 hours, the percentage of the weight of the product after calcination to the weight of the alumina hydrate before calcination being dry-basis ÷ the weight of the product after calcination ÷ the weight of the alumina hydrate before calcination × 100%.
The pseudoboehmite according to the present invention may or may not contain an auxiliary agent, and the present invention is not particularly limited thereto. The auxiliary agent can be one or more elements selected from IIIA, IVA, VA, VIIA, IIA, IIB, IIIB and IVB groups, and preferably one or more elements selected from fluorine, phosphorus, boron, silicon, magnesium, zinc, lanthanum, cerium, titanium and zirconium. Preferably, the content of the assistant is 0.1 to 10% by weight, preferably 0.3 to 5% by weight, and more preferably 0.3 to 4% by weight in terms of element, based on the total amount of the assistant-containing pseudoboehmite on a dry basis.
The introduction mode of the auxiliary agent can be that the pseudo-boehmite is impregnated by the solution containing the auxiliary agent, and can also be introduced in the process of synthesizing the pseudo-boehmite, and preferably introduced in the process of synthesizing the pseudo-boehmite.
The auxiliaries may be introduced in the form of an auxiliary-containing compound. The adjuvant-containing compound is preferably a water-soluble compound of the adjuvant, and examples of the water-soluble compound of the adjuvant include, but are not limited to: hydrofluoric acid, ammonium fluoride, ammonium hydrofluoride, fluorosilicic acid, ammonium fluorosilicate, boric acid, ammonium borate, ammonium metaborate, ammonium tetraborate, phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, boric acid, ammonium tetraborate, silica sol, silicon tetrachloride, ammonium fluorosilicate, and ethyl orthosilicate, magnesium nitrate, magnesium acetate, magnesium sulfate, basic magnesium carbonate, magnesium chloride, zinc nitrate, zinc acetate, zinc sulfate, zinc hydroxycarbonate, zinc chloride, lanthanum nitrate, lanthanum carbonate, lanthanum chloride, cerium nitrate, cerium carbonate, cerium chloride, titanium sulfate, titanium tetrachloride, titanium trichloride, tetrabutyl titanate, zirconium nitrate, zirconyl nitrate, and zirconium oxychloride.
The molding method of the present invention is not particularly limited, and various molding methods conventionally used in the art may be employed, and specifically, the molding method may include: grinding the product obtained by the first drying, kneading the ground product with water, an optional extrusion aid and an optional binder, and forming the product in a strip extruder. The shape of the molded article is not particularly limited in the present invention, and may be any shape applicable to carriers in the art, for example, a spherical shape or a multi-lobal shape. The specific operation of the molding is not described herein again.
The conditions for the first calcination are selected in a wide range, and the calcination can be carried out at 400-700 ℃ for 1-10 hours. The present invention is exemplified by the examples of 600 ℃ and 4 hours in the examples of the present invention, and the present invention is not limited thereto.
In a second aspect, the present invention provides a method for preparing the above catalyst, which comprises: the support is impregnated with a solution containing a nickel-containing compound and optionally a molybdenum-containing compound, followed by drying and optionally calcining.
According to one embodiment of the invention, the support is impregnated with a solution containing a nickel-containing compound, followed by drying and optionally calcination.
According to one embodiment of the invention, the support is impregnated with a solution containing a nickel-containing compound and a molybdenum-containing compound, and then dried and optionally calcined.
In the present invention, the nickel-containing compound is not particularly limited. Specifically, the nickel-containing compound is a soluble nickel salt, is selected from at least one of nickel nitrate, nickel acetate, basic nickel carbonate and nickel chloride, and is preferably basic nickel carbonate. Basic nickel carbonate is used in the examples of the present invention, but the present invention is not limited thereto.
In the present invention, the molybdenum-containing compound is not particularly limited. Specifically, the molybdenum-containing compound is a soluble molybdenum salt selected from at least one of molybdate, paramolybdate, ammonium dimolybdate, ammonium tetramolybdate and ammonium heptamolybdate, and preferably ammonium heptamolybdate. Ammonium heptamolybdate is used in the examples of the present invention, but the present invention is not limited thereto.
According to a preferred embodiment of the present invention, in the above-described method for preparing a catalyst, the solution further contains a complexing agent selected from at least one of an organic acid and/or an ammonium salt thereof. Impregnation of the support with said solution containing the complexing agent is more advantageous for a uniform loading of the nickel containing compound and optionally the molybdenum containing compound on the support.
In the present invention, the organic acid and/or the ammonium salt thereof is not particularly limited. In particular, the organic acid and/or its ammonium salt is selected from an organic acid, an organic acid ammonium salt or a mixture of an organic acid and its ammonium salt. Preferably, the organic acid is at least one selected from the group consisting of trans-1, 2-cyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, tartaric acid and malic acid, and more preferably citric acid. The organic acid ammonium salt corresponds to the organic acid ammonium salt, and the description of the invention is omitted.
Preferably, the molar ratio of the complexing agent to the nickel-containing compound calculated as the active component nickel is 0.3-2: 1.
in the present invention, the impregnation is not particularly limited. In particular, the impregnation is selected from saturation impregnation or excess impregnation, when excess impregnation is employed, filtration is required to remove excess solvent before drying and optionally calcining.
The concentration of the solution is selected from a wide range, and a person skilled in the art can appropriately select the concentration according to the water absorption of the carrier and the amount of the target metal, and the invention is not described in detail herein.
In the present invention, the drying conditions are not particularly limited. Specifically, the drying conditions include: the temperature is 60-180 ℃, preferably 80-150 ℃; the time is 0.5-24h, preferably 3-12 h.
In the present invention, the conditions for the calcination are not particularly limited. Specifically, the roasting conditions include: the temperature is 300-550 ℃, and preferably 400-500 ℃; the time is 0.5-15h, preferably 2-10 h.
In a third aspect, the invention provides a use of the above catalyst for reducing mercaptans in gasoline.
In a fourth aspect, the present invention provides a method for reducing mercaptans in gasoline, the method comprising: the gasoline fraction is contacted with the above-mentioned catalyst under the condition of removing mercaptan.
The catalyst is preferably presulfided prior to use using methods conventional in the art. In general, the conditions of the prevulcanisation may include: presulfiding with one or more of sulfur, hydrogen sulfide, carbon disulfide, dimethyl disulfide or polysulfide in the presence of hydrogen at a temperature of 140-. The pre-vulcanization can be carried out outside the hydrogenation reactor or can be carried out in situ in the hydrogenation reactor.
According to the present invention, preferably, the mercaptan removal conditions comprise: the temperature is 80-200 ℃, the pressure is 0.5-3MPa, and the volume ratio of hydrogen to oil is 1-200Nm3/m3The volume space velocity is 0.5-10h-1(ii) a Further preferably, the temperature is 80-180 ℃, the pressure is 1-3MPa, and the volume ratio of hydrogen to oil is 6-50Nm3/m3The volume space velocity is 0.5-6h-1。
In the present invention, the gasoline fraction is not particularly limited. Specifically, the mercaptan content in the gasoline fraction is 4-87 mu g/g.
The present invention will be described in detail below by way of specific examples.
In the following examples and comparative examples, the equilibrium adsorption amount of molybdenum was measured by: adding 180g of ammonium heptamolybdate and 7000mL of deionized water into a stainless steel strip reaction kettle with a stirring and polytetrafluoroethylene lining, stirring, dissolving and clarifying, adding 100g of ground carrier powder (the granularity is less than 200 meshes), continuously stirring for 24h, pouring all the slurry into a Buchner funnel, and carrying out suction filtration and washing with deionized water for 6 times, wherein the deionized water used in each washing is 7000 mL; the filter cake after 6 times of washing is dried at 120 ℃ for 12h and then roasted at 420 ℃ for 4 h. Determining MoO of the roasted sample by adopting an X fluorescence method3The percentage content is as follows.
The pseudoboehmite used in the following examples includes the following four: pseudo-boehmite powder (dried)70% by weight of base), 3% by weight of P2O5Pseudo boehmite powder (73 wt% on a dry basis) containing 5 wt% SiO2Pseudo-boehmite powder (75 wt% on a dry basis) containing 1 wt% of MgO (71 wt% on a dry basis) was obtained from catalyst division of petrochemical Co., Ltd.
The contents of the carrier and the active components Ni and Mo in the catalyst and the atomic ratio of the active component nickel to the sum of the active component nickel and the active component molybdenum are all shown in Table 1, wherein the atomic ratio of the active component nickel to the sum of the active component nickel and the active component molybdenum is calculated by the charging amount.
Example 1
Preparing aluminum sulfate aqueous solution (using Al) in a reaction kettle with a stirrer2O3Measured, contains 3 g of Al2O3) 1000ml of (1), and keeping the temperature at 35 ℃; adding 25 g of glycerol, stirring uniformly, adding 500 g of pseudo-boehmite powder (dry basis is 70 wt%), stirring uniformly, adding concentrated ammonia water (25 wt%), adjusting the pH value to 9.5, and keeping for 12 hours. The filter cake was dried at 120 ℃ for 8 hours. The dried product was ground to a size of 100 mesh and then extruded into clover-shaped strips having a circumscribed circle diameter of 1.6 mm by a bar extruder (manufacturer: general scientific and technical works of south China university, type: F-26 (III)). After the wet strip was dried at 120 ℃ for 4 hours, it was kept at 600 ℃ in a muffle furnace under an air atmosphere for 4 hours to obtain an alumina support S1. By N2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
88.26g of ammonium citrate is weighed, 80mL of deionized water and 20mL of strong ammonia water are added and heated to be dissolved, 51.9g of basic nickel carbonate is added, after the basic nickel carbonate is dissolved and clarified, 24.5g of ammonium heptamolybdate is added, and the volume is 190mL after the basic nickel carbonate is dissolved and clarified. The solution was impregnated with 200g of alumina support S1; the dipping time is 2h, then the dipped product is dried for 4h at 120 ℃, and is roasted for 3h at 450 ℃, and the catalyst C1 is obtained.
Example 2
Preparing aluminum sulfate aqueous solution (using Al) in a reaction kettle with a stirrer2O3Calculated, containing 62 g Al2O3) 1000ml of (1), and keeping the temperature at 90 ℃;adding 66 g of glycerol, stirring uniformly, and then adding 500 g of P with 3 weight percent2O5Pseudo-boehmite powder (73 wt% on a dry basis) was stirred uniformly, then concentrated ammonia (25 wt%) was added dropwise, the pH was adjusted to 9.6, and the mixture was kept for 3 hours. The filter cake was dried at 120 ℃ for 8 hours. The dried product was ground to a size of 100 mesh and then extruded into clover-shaped strips having a circumscribed circle diameter of 1.6 mm by a bar extruder (manufacturer: general scientific and technical works of south China university, type: F-26 (III)). After the wet strip was dried at 120 ℃ for 4 hours, it was kept at 600 ℃ in a muffle furnace under an air atmosphere for 4 hours to obtain an alumina support S2. By N2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
88.26g of ammonium citrate is weighed, 80mL of deionized water and 20mL of strong ammonia water are added and heated to be dissolved, 51.9g of basic nickel carbonate is added, after the basic nickel carbonate is dissolved and clarified, 24.5g of ammonium heptamolybdate is added, and the volume is determined to be 200mL after the basic nickel carbonate is dissolved and clarified. The solution was impregnated with 200g of alumina support S2; the dipping time is 2h, then the dipped product is dried for 4h at 120 ℃, and is roasted for 3h at 450 ℃, and the catalyst C2 is obtained.
Example 3
Preparing aluminum sulfate aqueous solution (using Al) in a reaction kettle with a stirrer2O3Calculated, containing 62 g Al2O3) 1000ml of (1), and keeping the temperature at 90 ℃; 500 g of a 3% by weight P solution are added2O5Pseudo-boehmite powder (73 wt% on a dry basis) was stirred uniformly, then concentrated ammonia (25 wt%) was added dropwise, the pH was adjusted to 9.6, and the mixture was kept for 3 hours. The filter cake was dried at 120 ℃ for 8 hours. The dried product was ground to a size of 100 mesh and then extruded into clover-shaped strips having a circumscribed circle diameter of 1.6 mm by a bar extruder (manufacturer: general scientific and technical works of south China university, type: F-26 (III)). After the wet strip was dried at 120 ℃ for 4 hours, it was kept at 600 ℃ in a muffle furnace under an air atmosphere for 4 hours to obtain an alumina support S3. By N2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
88.26g of ammonium citrate is weighed, 80mL of deionized water and 20mL of strong ammonia water are added and heated to be dissolved, 51.9g of basic nickel carbonate is added, after the basic nickel carbonate is dissolved and clarified, 24.5g of ammonium heptamolybdate is added, and the volume is determined to be 200mL after the basic nickel carbonate is dissolved and clarified. The solution was impregnated with 200g of alumina support S3; the dipping time is 2h, then the dipped product is dried for 4h at 120 ℃, and is roasted for 3h at 450 ℃, and the catalyst C3 is obtained.
Example 4
Preparing aluminum sulfate aqueous solution (using Al) in a reaction kettle with a stirrer2O3Measured, contains 31 g of Al2O3) 1000ml of (1), and keeping the temperature at 80 ℃; adding 128 g of glycerol, stirring uniformly, and then adding 500 g of SiO with the content of 5 weight percent2Pseudo-boehmite powder (75 wt% on a dry basis) was stirred uniformly, then concentrated ammonia (25 wt%) was added dropwise, the pH was adjusted to 9.4, and the mixture was kept for 3 hours. The filter cake was dried at 120 ℃ for 8 hours. The dried product was ground to a size of 100 mesh and then extruded into clover-shaped strips having a circumscribed circle diameter of 1.6 mm by a bar extruder (manufacturer: general scientific and technical works of south China university, type: F-26 (III)). After the wet strip was dried at 120 ℃ for 4 hours, it was kept at 600 ℃ in a muffle furnace under an air atmosphere for 4 hours to obtain an alumina support S4. By N2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
88.26g of ammonium citrate is weighed, 80mL of deionized water and 20mL of strong ammonia water are added and heated to be dissolved, 51.9g of basic nickel carbonate is added, after the basic nickel carbonate is dissolved and clarified, 24.5g of ammonium heptamolybdate is added, and the volume is 198mL after the basic nickel carbonate is dissolved and clarified. The solution was impregnated with 200g of alumina support S4; the dipping time is 2h, then the dipped product is dried for 4h at 120 ℃, and is roasted for 3h at 450 ℃, and the catalyst C4 is obtained.
Example 5
Preparing sodium metaaluminate aqueous solution (using Al) in a reaction kettle with a stirrer2O3Measured, 78 g of Al2O3) 1000ml of (1), and keeping the temperature at 85 ℃; adding 12 g of glycerol, 18 g of ethylene glycol, 5g of polyethylene glycol 200, 1g of citric acid and 2g of ammonium citrate, stirring uniformly, adding 500 g of pseudo-boehmite powder (dry basis 71 wt%) containing 1 wt% of MgO, stirring uniformly, adding dilute nitric acid (5 wt%), adjusting the pH value to 9.3, and keeping for 3 hours. The filter cake was dried at 120 ℃ for 8 hours. Will be driedThe resultant was ground to a fine powder and sieved with a 100-mesh sieve, and then extruded into clover-shaped strips having a circumscribed circle diameter of 1.6 mm by a bar extruder (manufacturer: general scientific and industrial plant, model: F-26 (III)). After the wet strip was dried at 120 ℃ for 4 hours, it was kept at 600 ℃ in a muffle furnace under an air atmosphere for 4 hours to obtain an alumina support S5. By N2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
88.26g of ammonium citrate is weighed, 80mL of deionized water and 20mL of strong ammonia water are added and heated to be dissolved, 51.9g of basic nickel carbonate is added, after the basic nickel carbonate is dissolved and clarified, 24.5g of ammonium heptamolybdate is added, and the volume is 198mL after the basic nickel carbonate is dissolved and clarified. The solution was impregnated with 200g of alumina support S5; the dipping time is 2h, then the dipped product is dried for 4h at 120 ℃, and is roasted for 3h at 450 ℃, and the catalyst C5 is obtained.
Example 6
500 g of pseudo-boehmite powder (70 wt% on a dry basis) was weighed and extruded into clover-shaped strips having a circumscribed circle diameter of 1.6 mm by a strip extruder (manufacturer: general plant of science and technology industries of southern China university, type: F-26 (III)). After the wet strip was dried at 120 ℃ for 4 hours, it was kept at 600 ℃ in a muffle furnace under an air atmosphere for 4 hours to obtain an alumina support S6. By N2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
88.26g of ammonium citrate is weighed, 80mL of deionized water and 20mL of strong ammonia water are added and heated to be dissolved, 51.9g of basic nickel carbonate is added, after the basic nickel carbonate is dissolved and clarified, 24.5g of ammonium heptamolybdate is added, and the volume is 198mL after the basic nickel carbonate is dissolved and clarified. The solution was impregnated with 200g of alumina support S6; the dipping time is 2h, then the dipped product is dried for 4h at 120 ℃, and is roasted for 3h at 450 ℃, and the catalyst C6 is obtained.
Example 7
500 g of P3% by weight are weighed2O5The pseudo-boehmite powder (dry basis: 73 wt%) was extruded into clover-shaped strips having a circumscribed circle diameter of 1.6 mm by means of a bar extruder (manufacturer: general scientific and technical industries of university of south China, type: F-26 (III)). After the wet strip was dried at 120 ℃ for 4 hours, it was kept at 600 ℃ in a muffle furnace under an air atmosphere for 4 hours to obtain an alumina support S7. By N2Adsorption/desorption determination ratio tableArea and pore volume, the results are listed in table 1.
88.26g of ammonium citrate is weighed, 80mL of deionized water and 20mL of strong ammonia water are added and heated to be dissolved, 51.9g of basic nickel carbonate is added, after the basic nickel carbonate is dissolved and clarified, 24.5g of ammonium heptamolybdate is added, and the volume is 198mL after the basic nickel carbonate is dissolved and clarified. The solution was impregnated with 200g of alumina support S7; the dipping time is 2h, then the dipped product is dried for 4h at 120 ℃, and is roasted for 3h at 450 ℃, and the catalyst C7 is obtained.
Example 8
500 g of a mixture containing 5% by weight of SiO are weighed2The pseudo-boehmite powder (dry basis: 75 wt%) was extruded into clover-shaped strips having a circumscribed circle diameter of 1.6 mm by means of a bar extruder (manufacturer: general scientific and technical works of south China university, type: F-26 (III)). After the wet strip was dried at 120 ℃ for 4 hours, it was kept at 600 ℃ in a muffle furnace under an air atmosphere for 4 hours to obtain an alumina support S8. By N2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
88.26g of ammonium citrate is weighed, 80mL of deionized water and 20mL of strong ammonia water are added and heated to be dissolved, 51.9g of basic nickel carbonate is added, after the basic nickel carbonate is dissolved and clarified, 24.5g of ammonium heptamolybdate is added, and the volume is 198mL after the basic nickel carbonate is dissolved and clarified. The solution was impregnated with 200g of alumina support S8; the dipping time is 2h, then the dipped product is dried for 4h at 120 ℃, and is roasted for 3h at 450 ℃, and the catalyst C8 is obtained.
Example 9
500 g of pseudo-boehmite powder containing 1 wt% of MgO (71 wt% on a dry basis) was weighed and extruded into clover-shaped strips having a circumscribed circle diameter of 1.6 mm by a strip extruder (manufacturer: general plant of science and technology industries of south China university, type: F-26 (III)). After the wet strip was dried at 120 ℃ for 4 hours, it was kept at 600 ℃ in a muffle furnace under an air atmosphere for 4 hours to obtain an alumina support S9. By N2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1.
88.26g of ammonium citrate is weighed, 80mL of deionized water and 20mL of strong ammonia water are added and heated to be dissolved, 51.9g of basic nickel carbonate is added, after the basic nickel carbonate is dissolved and clarified, 24.5g of ammonium heptamolybdate is added, and the volume is 198mL after the basic nickel carbonate is dissolved and clarified. The solution was impregnated with 200g of alumina support S9; the dipping time is 2h, then the dipped product is dried for 4h at 120 ℃, and is roasted for 3h at 450 ℃, and the catalyst C9 is obtained.
Example 10
Weighing 78.26g of ammonium citrate and 18.36g of citric acid, adding 80mL of deionized water and 30mL of concentrated ammonia water, heating for dissolving, then adding 69.2g of basic nickel carbonate, dissolving and clarifying, then adding 24.5g of ammonium heptamolybdate, dissolving and clarifying, and fixing the volume to 198 mL. The solution was impregnated with 200g of alumina support S1; the dipping time is 2h, then the dipped product is dried for 4h at 120 ℃, and is roasted for 3h at 450 ℃, and the catalyst C10 is obtained.
Example 11
Weighing 23.26g of ammonium citrate and 20.35g of citric acid, adding 80mL of deionized water and 20mL of concentrated ammonia water, heating for dissolving, then adding 18.4g of basic nickel carbonate, dissolving and clarifying, then adding 32.2g of ammonium heptamolybdate, dissolving and clarifying, and fixing the volume to 198 mL. The solution was impregnated with 200g of alumina support S1; the dipping time is 2h, then the dipped product is dried for 4h at 120 ℃, and is roasted for 3h at 450 ℃, and the catalyst C11 is obtained.
Example 12
42.15g of ammonium citrate and 12.36g of citric acid are weighed, 80mL of deionized water and 20mL of strong ammonia water are added and heated to be dissolved, 33.6g of basic nickel carbonate is added, 36.1g of ammonium heptamolybdate is added after dissolution and clarification, and the volume is 198mL after dissolution and clarification. The solution was impregnated with 200g of alumina support S1; the dipping time is 2h, then the dipped product is dried for 4h at 120 ℃, and is roasted for 3h at 450 ℃, and the catalyst C12 is obtained.
Example 13
101.56g of ammonium citrate is weighed, 80mL of deionized water and 20mL of concentrated ammonia water are added and heated to be dissolved, then 69.5g of basic nickel carbonate is added, and the volume is 198mL after dissolution and clarification. The solution was impregnated with 200g of alumina support S1; the dipping time is 2h, then the dipped product is dried for 4h at 120 ℃, and is roasted for 3h at 450 ℃, and the catalyst C13 is obtained.
Comparative example 1
A catalyst was prepared according to the method of example 6, except that commercial SB powder was used, and an aqueous ammonium fluoride solution was added to the extrudate so that the alumina support DT-1 contained 1.51 wt.% F (calculated as element) by passing N through2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1. To obtain catalystReagent D1.
Comparative example 2
A catalyst was prepared as in example 6, except that commercial SB powder was used and an aqueous ammonium fluoride solution was added to the extrudate so that the alumina support DT-2 contained 0.73 wt.% F (on an elemental basis) as measured by N2The specific surface area and pore volume were measured by adsorption/desorption, and the results are shown in Table 1. Catalyst D2 was obtained.
TABLE 1
Note: in table 1, the Ni content and the Mo content are both calculated as oxides.
Test example
The catalysts C1-C13 and D1-D2 were crushed into 20-30 mesh particles, and the catalyst particles were charged into the constant temperature zones of a 20mL hydrogenation test unit reactor, respectively.
Before the catalyst is used, carrying out vulcanization, wherein the vulcanization conditions comprise: the vulcanized oil adopts 2w percent of carbon disulfide/straight-run gasoline, and the volume space velocity is 2h-1The volume ratio of standard hydrogen to oil is 150Nm3/m3And vulcanizing at constant temperature of 320 ℃ for 4 h. After the vulcanization is finished, the reaction conditions are adjusted as follows: the reaction temperature is 120 ℃, the pressure is 1.6MPa, and the volume ratio of standard hydrogen to oil is 6Nm3/m3Volume space velocity of 2h-1Evaluation was carried out using a full-range gasoline (mercaptan sulfur mass fraction of 49. mu.g/g, diene iodine value of 1.8gI/100g) as a raw material. The results of the analyses of the mercaptan content and the iodine value of the diolefins of the products after 8 days of reaction are shown in Table 2.
TABLE 2
The results in table 1 show that the catalyst provided by the invention can significantly reduce the contents of mercaptan and diene in gasoline, and has high activity and selectivity.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A catalyst for reducing mercaptan comprises a carrier and an active component nickel and optionally an active component molybdenum which are loaded on the carrier, wherein the content of the active component nickel is 1-15 wt% and the content of the active component molybdenum is 0-12 wt% calculated by oxides based on the total amount of the catalyst; the molybdenum equilibrium adsorption capacity of the carrier is MoO3Calculated as 8-20 percent, the specific surface area is 200-350m2Per g, pore volume of 0.65-1.2cm3/g。
2. The catalyst of claim 1, wherein the content of the active component nickel is 3-15 wt% and the content of the active component molybdenum is 1-11 wt% calculated by oxide based on the total amount of the catalyst;
preferably, the atomic ratio of the active component nickel to the sum of the active component nickel and the active component molybdenum is 0.3 or more, and more preferably 0.4 to 0.8.
3. The catalyst of claim 1 or 2, wherein the equilibrium adsorption amount of molybdenum of the support is in MoO3Calculated as 8-16%, and the specific surface area is 200-300m2Per g, pore volume of 0.65-1cm3/g。
4. A catalyst according to any one of claims 1 to 3, wherein the support is selected from one or more of alumina, silica, alumina-silica, titania, alumina-titania, magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-zirconia, titania-zirconia, silica-alumina-thoria, silica-alumina-titania, silica-alumina-magnesia and silica-alumina-zirconia, preferably at least one of alumina, silica and titania;
preferably, the preparation method of the carrier comprises the following steps: sequentially carrying out first drying, forming and first roasting on a carrier precursor, wherein the preparation method of the carrier precursor comprises the following steps:
(1) mixing pseudo-boehmite containing or not containing an auxiliary agent and a solution containing an inorganic aluminum-containing compound to obtain a first slurry;
(2) adjusting the pH of the slurry to 7-10, preferably 8.5-10, to obtain a second slurry;
(3) aging the second slurry, preferably under conditions comprising: the temperature is 25-90 ℃ and the time is 0.2-12 hours;
preferably, the solution containing the inorganic aluminum-containing compound in the step (1) further contains an organic substance, and the organic substance is one or more selected from organic acids, organic acid ammonium salts and organic alcohols.
5. The catalyst according to claim 4, wherein Al is used2O3The mass ratio of the inorganic aluminum-containing compound to the pseudo-boehmite containing or not containing the auxiliary agent on a dry basis is 0.1-30: 100, preferably 1 to 20: 100, more preferably 5 to 15: 100, respectively;
preferably, the organic substance is mixed with Al2O3The mass ratio of the inorganic aluminum-containing compound is 0.1-20: 1, preferably 0.5 to 10: 1;
preferably, the inorganic aluminum-containing compound is selected from at least one of aluminum sulfate, sodium metaaluminate, aluminum nitrate and aluminum trichloride.
6. A process for preparing a catalyst as claimed in any one of claims 1 to 5, which process comprises: impregnating the support with a solution containing a nickel-containing compound and optionally a molybdenum-containing compound, followed by drying and optionally calcining;
preferably, the solution also contains a complexing agent, and the complexing agent is selected from at least one of organic acid and/or ammonium salt thereof;
preferably, the organic acid is selected from at least one of trans-1, 2-cyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, tartaric acid, and malic acid;
preferably, the molar ratio of the complexing agent to the nickel-containing compound calculated as the active component nickel is 0.3-2: 1.
7. the production method according to claim 6, wherein the drying conditions include: the temperature is 60-180 ℃, preferably 80-150 ℃; the time is 0.5 to 24 hours, preferably 3 to 12 hours;
preferably, the conditions of the calcination include: the temperature is 300-550 ℃, and preferably 400-500 ℃; the time is 0.5-15h, preferably 2-10 h.
8. Use of a catalyst according to any one of claims 1 to 5 for the reduction of mercaptans in gasoline.
9. A method for reducing mercaptans in gasoline, the method comprising: contacting the gasoline fraction with a catalyst according to any one of claims 1 to 5 under mercaptan removal conditions;
preferably, the mercaptan removal conditions comprise: the temperature is 80-200 ℃, the pressure is 0.5-3MPa, and the volume ratio of hydrogen to oil is 1-200Nm3/m3The volume space velocity is 0.5-10h-1。
10. A process according to claim 9, wherein the mercaptan content of said gasoline fraction is between 4 and 87 μ g/g.
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