CN113856770A - Preparation method of sulfurized hydrogenation catalyst, sulfurized hydrogenation catalyst and application - Google Patents
Preparation method of sulfurized hydrogenation catalyst, sulfurized hydrogenation catalyst and application Download PDFInfo
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- CN113856770A CN113856770A CN202010618961.4A CN202010618961A CN113856770A CN 113856770 A CN113856770 A CN 113856770A CN 202010618961 A CN202010618961 A CN 202010618961A CN 113856770 A CN113856770 A CN 113856770A
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- Prior art keywords
- catalyst
- oil
- temperature
- hydrogen
- pressure
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- 239000003054 catalyst Substances 0.000 title claims abstract description 152
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 61
- 238000011282 treatment Methods 0.000 claims abstract description 29
- 238000002161 passivation Methods 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000007654 immersion Methods 0.000 claims abstract description 7
- 239000003921 oil Substances 0.000 claims description 51
- 235000019198 oils Nutrition 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 239000007789 gas Substances 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- 239000001257 hydrogen Substances 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 230000003647 oxidation Effects 0.000 claims description 28
- 238000007254 oxidation reaction Methods 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 239000011261 inert gas Substances 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 19
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 15
- 239000002283 diesel fuel Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010926 purge Methods 0.000 claims description 6
- 238000005486 sulfidation Methods 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- -1 carbon disulfide, mercaptans Chemical class 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 5
- 239000008158 vegetable oil Substances 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000010775 animal oil Substances 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- 238000004939 coking Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims 2
- 239000003209 petroleum derivative Substances 0.000 claims 2
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical class S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 238000004523 catalytic cracking Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 239000002480 mineral oil Substances 0.000 claims 1
- 235000010446 mineral oil Nutrition 0.000 claims 1
- 239000005416 organic matter Substances 0.000 claims 1
- 238000000197 pyrolysis Methods 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 description 19
- 230000003197 catalytic effect Effects 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 10
- 238000005987 sulfurization reaction Methods 0.000 description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 9
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052976 metal sulfide Inorganic materials 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- SHMVRUMGFMGYGG-UHFFFAOYSA-N [Mo].S=O Chemical compound [Mo].S=O SHMVRUMGFMGYGG-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 235000005687 corn oil Nutrition 0.000 description 2
- 239000002285 corn oil Substances 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 2
- 229910003452 thorium oxide Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 150000004684 trihydrates Chemical class 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 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 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
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- 239000002594 sorbent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
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Abstract
The invention relates to a preparation method of a vulcanized hydrogenation catalyst, which comprises the steps of sequentially carrying out first heat treatment on an oxidized catalyst in the presence of a vulcanizing agent and immersion oil, second heat treatment under the atmosphere of first reducing gas, third heat treatment under the atmosphere of second reducing gas and passivation treatment; wherein, the temperature of the three heat treatments is increased in sequence. Compared with the prior art, the preparation method provided by the invention is simpler and more effective, the vulcanized hydrogenation catalyst obtained by the preparation method has better performance, and when the vulcanized hydrogenation catalyst provided by the invention is applied, the startup time of a hydrogenation device can be greatly shortened, and the startup risk is reduced.
Description
Technical Field
The invention belongs to the field of hydrogenation catalysts, and particularly relates to a preparation method of a sulfurized hydrogenation catalyst, a catalyst prepared by the method and application of the catalyst.
Background
With the heavy crude oil resource, hydrocracking becomes the main technical means for producing clean gasoline and diesel oil and high-quality chemical raw materials. The catalyst used in the hydrogenation process takes VIB group metals such as molybdenum and/or tungsten, VIII group metals such as nickel and/or cobalt as active components, and acidic materials such as alumina silica or molecular sieves and the like as carriers. At present, after the oil refinery is shut down and overhauled, in order to create economic benefits for completing production tasks, the oil refinery is required to be started at the fastest speed, and the starting process is required to be simple and fast. Before the hydrogenation device is started, the hydrogenation catalyst not only needs to be subjected to conventional preparation steps of dipping, drying, roasting and the like, but also needs to be subjected to vulcanization treatment to convert oxidation state metal into vulcanization state metal, so that the hydrogenation catalyst has higher hydrogenation performance. The vulcanization process of the hydrogenation catalyst has the characteristics of high vulcanization temperature, high hydrogen sulfide concentration, extremely toxic vulcanizing agent, more complicated vulcanization process and the like. At present, most of hydrogenation catalyst is vulcanized in a reactor, one set of hydrogenation device is usually required to be vulcanized once every three years, and special equipment required in the vulcanization process is in an idle state in most of the running time of the device, so that the investment of the device is additionally increased. The hydrogenation catalyst is firstly vulcanized outside the device, so that the requirements of a refinery on reducing the start-up risk and saving the start-up time can be met. Meanwhile, for a catalyst production plant, a catalyst needs to be screened, packaged, transported to a vulcanizing device after being prepared into an oxidation state by a production device, then unpacked and filled for vulcanization, and if the oxidation state preparation process and the vulcanization state preparation process of the catalyst can be combined to be completed on one device, the production cost can be reduced, the total preparation time of the catalyst can be saved, the start-up time of an oil refinery can be saved, and good economic benefits can be created for the catalyst production plant and the oil refinery. The technical difficulty is how to complete the catalyst sulfiding process on the oxidation state catalyst preparation unit.
Many reports have been made at home and abroad about the passivation of a vulcanizing agent of a hydrogenation catalyst.
CN201010204326.8 discloses an ex-situ sulfurization method of a catalyst, which comprises the steps of loading an oxidation state hydrogenation solid catalyst into a sulfurization reactor, purging with inert gas and introducing sulfuration gas for prevulcanization, introducing oxygen-containing passivation gas after cooling, discharging the passivated catalyst from the sulfurization reactor, bagging, sealing, transporting and storing, loading into a hydrogenation reactor, purging with inert gas, introducing sulfuration gas for activation after heating, and activating the vulcanized passivated catalyst. CN200880129246.1 discloses a method of incorporating sulfur in the pores of solid particles of a catalyst or sorbent. CN1107701C discloses a sulfurization method of a hydrotreating catalyst, which comprises sulfurizing the hydrotreating catalyst by a method of first dry sulfurization and then wet sulfurization.
Disclosure of Invention
The invention aims to provide a preparation method of a vulcanized hydrogenation catalyst, the catalyst prepared by the method and application of the catalyst in hydrogenation reaction. In order to implement the present invention, the following detailed description of the invention is provided.
The invention provides a preparation method of a vulcanized hydrogenation catalyst, which comprises the following steps of sequentially treating an oxidized catalyst:
(1) carrying out first heat treatment on the oxidation state catalyst in the presence of an inert gas atmosphere, a vulcanizing agent and immersion oil, wherein the treatment temperature is T1, and the treatment pressure is P1;
(2) carrying out secondary heat treatment on the catalyst obtained in the step (1) in the atmosphere of first reducing gas, wherein the treatment temperature is T2, and the treatment pressure is P2;
(3) carrying out third heat treatment on the catalyst obtained in the step (2) in a second reducing gas atmosphere, wherein the treatment temperature is T3, and the treatment pressure is P3;
(4) passivating the catalyst obtained in the step (3) in a passivation gas atmosphere;
wherein, T3> T2> T1.
The invention also provides a sulfurized hydrogenation catalyst prepared by the method and the sulfurized hydrogenation catalystThe application of the hydrogenation catalyst comprises the steps of filling the catalyst into a hydrogenation reactor, and then directly introducing raw oil for reaction; the reaction conditions include: the reaction temperature is 200-420 ℃, the pressure is 0.1-30 MPa, and the liquid hourly space velocity is 0.3-10 hours-1The volume ratio of the hydrogen to the oil is 50-5000; the reaction conditions are preferably: the reaction temperature is 220-400 ℃, the pressure is 1-15 MPa, and the liquid hourly space velocity is 0.3-6 hours-1The hydrogen-oil ratio is 50 to 1000.
Compared with the prior art, the preparation method of the sulfurized hydrogenation catalyst provided by the invention is simpler and more effective, the sulfurized hydrogenation catalyst obtained by the preparation method provided by the invention has better performance, and when the sulfurized hydrogenation catalyst provided by the invention is applied, the start-up time of a hydrogenation device can be greatly shortened, and the start-up risk is reduced.
Detailed Description
For a better understanding of the present invention, the technical solutions claimed in the present invention will be explained and illustrated in detail below. It is first noted that the endpoints of the ranges and any values disclosed in this specification are not limited to the precise range or value, and that such ranges or values are 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 preparation method of the sulfurized hydrogenation catalyst mainly comprises three heat treatments and one passivation process. Wherein, the starting material is usually an oxidation state hydrogenation catalyst. The source of the oxidation state hydrogenation catalyst is not limited, and the oxidation state hydrogenation catalyst can be a commercial reagent or an oxidation state hydrogenation catalyst prepared according to the prior art. Typically, the oxidation state hydrogenation catalyst comprises a support, at least one metal component selected from group VIII and at least one metal component selected from group VIB, and with or without organic compounds. Wherein the carrier is porous heat-resistant inorganic oxide commonly used as catalyst carrier, preferably alumina, wherein the alumina can be selected from gamma, or gamma, or a combination thereof,One or more of eta, theta, delta and alpha, and is preferably gamma-alumina. The alumina has the specific surface and pore volume of the conventional alumina, and the specific surface of preferential alumina is 150-350 m2Per gram, preferably 180-320 m2The pore volume of alumina is preferably 0.4 to 1.1 ml/g, more preferably 0.5 to 0.9 ml/g. Either commercially available or prepared by any of the methods known in the art. For example, it may be prepared by molding and calcining a mixture of one or more selected from alumina trihydrate, alumina monohydrate and amorphous aluminum hydroxide. The alumina is formed by conventional methods such as tabletting, rolling ball and extruding. In the case of molding by a conventional method, it is permissible to introduce an auxiliary agent into the aforementioned material to be molded (for example, a mixture of one or more of alumina trihydrate, alumina monohydrate and amorphous aluminum hydroxide) in order to ensure smooth molding, and for example, when extruding, an appropriate amount of an extrusion aid and water may be introduced into the aforementioned material to be molded, followed by extrusion molding. The type and amount of the extrusion aid can be conventional in the art, for example, the common extrusion aid can be one or more selected from sesbania powder, methyl cellulose, starch, polyvinyl alcohol and polyethylene glycol. When the carrier is formed alumina, the carrier can contain one or more auxiliary components selected from silica, titanium oxide, magnesium oxide, zirconia, thorium oxide and beryllium oxide, and the mass fraction of the auxiliary components is less than 10 wt% and preferably 0.3-5 wt% based on the carrier. Further, when the carrier is formed alumina and contains or does not contain one or more auxiliary components selected from silica, titanium oxide, magnesium oxide, zirconium oxide, thorium oxide and beryllium oxide, the carrier can also contain clay and/or molecular sieve, and the mass fraction of the clay and/or molecular sieve is less than 35 wt%, preferably 1-20 wt% based on the carrier. The active metal component in the catalyst is of conventional choice and may generally be selected from group VIII and group VIB metal components, for example, the group VIII metal component is selected from cobalt and/or nickel and the group VIB metal component is selected from molybdenum and/or tungsten. In the preparation process, the raw materials are mixed,the group VIII metal compound is selected from one or more soluble compounds of these metals, for example, one or more nitrates, acetates, carbonates, chlorides, and soluble complexes of these metals. The group VIB metal compound is selected from one or more soluble compounds of the metals, and can be one or more of molybdate, paramolybdate, tungstate, metatungstate and ethyl metatungstate. According to the preparation method of the sulfurized hydrogenation catalyst provided by the invention, the content of each component in the oxidized catalyst serving as a starting material is not particularly limited, and can be adjusted according to specific purposes. For example, the components are used in such amounts that the support content in the oxidation state catalyst is from 40 to 95% by weight, the active metal content, calculated as oxides, is from 5 to 40% by weight and the organic content is from 0 to 20% by weight.
According to the invention, the main purpose of step (1) is that the oxidation state catalyst adsorbs the carbon source of sulphides and carbon deposits and undergoes a preliminary sulphiding under heating conditions to form metal oxysulphides. In the research process, the inventor of the invention finds that sulfide can generate better adsorption with catalyst metal without generating hydrogen sulfide by putting the sulfide into the catalyst at one time to be mixed with the catalyst and thermally treated, and simultaneously puts immersion oil, so that the catalyst is properly deposited with carbon under the inert gas thermal treatment condition in the step (1) to protect the active phase of the catalyst. The carbon source and the vulcanizing medium are introduced simultaneously, so that the subsequent carbon deposition can play a good role in protecting a target active phase, the catalyst is prevented from being directly contacted with the inferior raw oil to be quickly inactivated in the application process, and the effect of initial activation and stability is achieved. The catalyst adsorbs sulfide, metal oxide is converted into metal oxysulfide, the valence state of metal is mostly unchanged, and the adsorption reaction of sulfide is mainly used, for example, molybdenum exists in the oxidation state catalyst in the form of molybdenum trioxide, and after the step (1), molybdenum trioxide and sulfide are subjected to adsorption reaction to generate molybdenum oxysulfide. The sulfide may be a sulfiding agent that reacts with hydrogen to produce hydrogen sulfide, e.g., mercaptans, sulfides, disulfides, thiophenes, elemental sulfur, and the like. The oxidation state catalyst can be a roasting oxidation state catalyst, and can also be a complex oxidation state catalyst containing organic matters, wherein the organic matters can be commonly used organic matters for preparing the complex catalyst, the organic matters are selected from organic carboxylic acids or ammonium salts thereof, and the organic carboxylic acids are selected from one or more of trans-1, 2-cyclohexanediamine tetraacetic acid, ethylenediamine tetraacetic acid, aminotriacetic acid, citric acid, oxalic acid, acetic acid, formic acid, glyoxylic acid, glycolic acid, tartaric acid and malic acid. In the specific implementation process, the oxidation state hydrogenation catalyst, the vulcanizing agent and the immersion oil can be placed in a reactor together, the oxidation state hydrogenation catalyst, the vulcanizing agent and the immersion oil are fully and uniformly mixed in a stirring or rotating mode, and then the first heat treatment is carried out after the atmosphere is adjusted to be inert gas.
According to the invention, the impregnating oil is an oil which can be coked during the vulcanization process. The oil product can be petroleum-based distillate oil, and can also be bio-based distillate oil, such as diesel oil, wax oil, residual oil, vegetable oil, animal oil, etc., preferably bio-based distillate oil, and more preferably vegetable oil. The oil product is preferably catalytic gasoline, coking gasoline, catalytic diesel oil, coking diesel oil, oil slurry, residual oil, vegetable oil, animal oil and other oil products rich in olefin and/or aromatic hydrocarbon, wherein the olefin and/or aromatic hydrocarbon are deposited under the conditions of high temperature and low hydrogen partial pressure in the vulcanization process. In order to better ensure the introduction of the carbon deposition precursors, the impregnating oil preferably contains unsaturated hydrocarbons, wherein the unsaturated hydrocarbons can be olefins, dienes, alkynes, aromatic hydrocarbons and the like, further preferably the content of the unsaturated hydrocarbons in the impregnating oil is not less than 10 wt%, or more preferably 20-50 wt%, and more preferably a mixture of oils containing different types of carbon deposition precursors.
According to the present invention, the vulcanizing agent may be any sulfur-containing compound, and may be hydrogen sulfide, or may be a substance that can be converted into hydrogen sulfide at a high temperature, such as sulfur, thiol, thioether, disulfide, polysulfide, thiophene, substituted thiophene, and the like.
According to the method provided by the invention, the heat treatment temperature in the first-stage heat treatment reactor can be 20-400 ℃, the pressure is 0-10.0MPa, preferably the temperature is 100-350 ℃, the pressure is 0-5.0 MPa, further preferably the temperature is 150-300 ℃, and the pressure is 0-2 MPa.
The inert gas in the present invention includes both inert gases in the conventional sense such as helium, nitrogen, neon, argon, etc., and gases that do not participate in the reaction in the step, such as the inert gas in step (1) may be one or more of methane, ethane, propane, butane, carbon dioxide, preferably nitrogen. Hydrogen is not needed in the step (1), so that no hydrogen sulfide is released in the step (1) process, and corrosion of equipment is slowed down.
According to the present invention, the main purpose of step (2) is to reduce the metal oxysulfide, i.e. to reduce the metal oxysulfide in a high valence state to a metal sulfide in a low valence state, such as molybdenum oxysulfide and hydrogen to form molybdenum disulfide and water, wherein the molybdenum disulfide is a highly active hydrogenation active center. According to the invention, the first reducing gas in the step (2) is preferably hydrogen or a mixed gas of hydrogen and inert gas and/or hydrogen sulfide; further preferably, hydrogen is slowly introduced during the heat treatment in step (2) at a rate such that the exhaust gas is substantially free of hydrogen sulfide. Therefore, the metal oxysulfide can be gradually reduced into water, almost no hydrogen sulfide is generated in the reduction process, and all sulfur in the sulfide and metal are subjected to a vulcanization reaction, so that the utilization rate of sulfur can be improved, the emission can be reduced, and the corrosion of equipment can be slowed down.
According to the present invention, the heat treatment temperature in step (2) is higher than the heat treatment temperature in step (1), preferably, the heat treatment temperature in step (2) is 20 to 450 ℃, the pressure is 0 to 10.0MPa, more preferably, the temperature is 100 to 400 ℃, the pressure is 0 to 5.0MPa, and even more preferably, the temperature is 150 to 350 ℃, and the pressure is 0 to 2 MPa.
According to the invention, the purpose of step (3) is to remove part of the organic carbides on the surface of the metal sulfide by hydrogenation in a reducing atmosphere, the organic carbides react with hydrogen to generate micromolecular gaseous hydrocarbons, so that the organic carbides are removed from the surface of the metal sulfide, part of the metal sulfide is exposed, high hydrogenation activity and stability are shown, and an active phase containing a small amount of carbon deposition can be directly contacted with an inferior raw material in the application process. According to the invention, the second reducing gas atmosphere in the step (3) is preferably hydrogen gas or a mixed gas of hydrogen gas and inert gas; it should be noted that the second reducing gas atmosphere in step (3) does not contain hydrogen sulfide, and the surface of the catalyst is reduced in the absence of hydrogen sulfide, so as to ensure that the final effluent gas does not contain sulfide, and only discharge hydrogen, water and a small amount of organic matters, thereby reducing pollution and equipment corrosion.
In order to further ensure that the heat treatment of step (3) is carried out in the complete absence of hydrogen sulfide, it is preferable to include between step (2) and step (3) a purging step with an inert gas and/or hydrogen, said purging being such that the second reducing gas atmosphere is substantially free of hydrogen sulfide. By this operation, it is further ensured that the exhaust gas discharged after the heat treatment of step (3) contains substantially no hydrogen sulfide.
According to the invention, the heat treatment temperature in the step (3) is higher than the heat treatment temperature in the step (2), preferably, the heat treatment temperature in the step (3) is 20-500 ℃, the pressure is 0-10.0MPa, more preferably, the temperature is 100-450 ℃, the pressure is 0-5.0 MPa, and more preferably, the temperature is 150-400 ℃, and the pressure is 0-2 MPa.
In the specific implementation process, the heat treatment temperature and pressure in the above steps can be selected more specifically, for example, T1 is 100-300 ℃, preferably 150-250 ℃, P1 is 0-4.0MPa, preferably 0.2-2.0 MPa; t2 is 200-400 ℃, preferably 250-350 ℃, and P2 is 0.5-6.0MPa, preferably 1.0-3.0 MPa; t3 is 280-480 ℃, preferably 300-400 ℃, and P3 is 1-10.0MPa, preferably 1.5-5.0 MPa. Further preferably, the pressure of the three heat treatments is increased in sequence, i.e. P3> P2> P1.
The pressure described in the present invention is generally a gauge pressure unless otherwise specified.
The passivation treatment in the step (4) is to selectively oxidize the metal sulfide exposed on the surface of the catalyst in a sulfidation state to oxidize the metal sulfide into metal oxysulfide to form a layer of protective film, thereby preventing oxygen from oxidizing the metal oxysulfide in the catalystThe metal sulfide is deeply oxidized and used for protecting a sulfide catalyst and preventing the hydrogenation activity from being reduced due to long-term exposure to the air environment. The passivation process of the catalyst is to passivate the catalyst at a certain temperature by using oxygen-containing compounds, the oxidizing substances are preferably oxygen which is easy to obtain, other oxygen-containing compounds such as water and ethanol can be used, and oil products with heavy fractions can be used for wrapping the surface of the catalyst to isolate air, so that the catalyst can complete the processes of unloading, packaging, transporting and the like. The passivation according to the invention is preferably carried out using oxygen and the inert gas is preferably nitrogen. According to the invention, the passivation treatment in step (4) is conventionally selected, for example, conditions of the passivation treatment include: the oxidation temperature in the reactor is 20-100 ℃, the pressure is normal pressure-2.0 MPa, and the time is 1-10 hours; preferably, the oxidation temperature is 30-80 ℃, and the pressure is normal pressure-1.8 MPa; more preferably, the oxidation temperature is 40-60 ℃, the pressure is normal pressure-1.5 MPa, and the space velocity of the volume of the passivation gas is 100--1(ii) a The passivation gas atmosphere contains inert gas and oxygen-containing substances, the inert gas is one or more of helium, nitrogen, neon, argon, methane, ethane, propane, butane and carbon dioxide, and the oxygen-containing substances are one or more of oxygen, water and ethanol; the content of oxygen-containing substances in the passivation gas is 0.1-21% by volume, and the content of nitrogen is 79-99.9% by volume; preferably, the content of oxygen-containing substances is 0.3-15 vol%, and the content of inert gases is 85-99.7 vol%; more preferably, the content of the oxygen-containing substance is 0.5 to 10 vol%, and the content of the inert gas is 90 to 99.5 vol%.
In order to provide higher activity to the final sulfided hydrogenation catalyst, the present invention may also control the heat treatment of the steps (1) - (3) such that the final sulfided catalyst has a sulfidation degree of at least 30%, more preferably 40-95%, and even more preferably 50-90%. In the invention, the vulcanization degree of the VIII group active metal A in the hydrogenation catalyst is defined as the percentage of the element A in the active phase A-B-S in the total amount of the element A, and the vulcanization degree of the VIB group active metal B in the hydrogenation catalyst is defined as B4+Percentage of the total amount of element B, active phases A-B-S and B4+In an amount ofCalculating according to the analysis result of X-ray photoelectron spectroscopy, and making specific reference to Qiolimei article (X-ray photoelectron spectroscopy method for researching chemical state of active element in hydrodesulfurization catalyst [ J)]And petroleum science and newspaper: petroleum processing, 2011, 27 (4): 638-642). For example, for cobalt molybdenum catalysts, the degree of molybdenum sulfidation is defined as Mo4+The degree of cobalt sulfidation is defined as the percentage of the element Co in the Co-Mo-S to the total Co.
On the other hand, the inventors of the present invention found through further studies that the carbon content in the final catalyst, particularly the ratio of the carbon content at the decomposition temperature of 350 to 450 ℃ to the total carbon content has a significant influence on the initial activity stability of the catalyst. Therefore, in order to improve the initial activity stability of the catalyst, the impregnating oil is used in the step (1) so that the ratio of carbon to metal content in terms of elements in the finally obtained sulfurized hydrogenation catalyst is 0.01 to 1, preferably 0.03 to 0.5, and more preferably 0.05 to 0.3. The treatment of the steps (1) to (4) enables the carbon content in the finally obtained vulcanized catalyst to be 1.5 to 30 weight percent, and preferably 2.0 to 20 weight percent; the proportion of the carbon content of the carbon having a decomposition temperature of 350 to 450 ℃ in the carbon to the total carbon content is not less than 50 wt%, preferably not less than 60 wt%, and more preferably 65 to 95 wt%.
In addition, the inventor of the present invention also finds that the catalyst prepared by the method of the present invention has better antioxidant stability besides the above mentioned better initial activity and initial activity stability.
The total carbon content mentioned in the invention refers to the carbon which can be converted into carbon dioxide to be separated from the catalyst when the catalyst is heated to 800 ℃ in the air atmosphere, and the carbon with the decomposition temperature of 350-450 ℃ refers to the carbon which can be converted into carbon dioxide to be separated from the catalyst when the catalyst is heated in the air atmosphere and at the temperature of 350-450 ℃. The specific test and calculation methods are described in the following description and examples.
The sulfurized hydrogenation catalyst can be hydrofining, hydrocracking, hydrotreating catalyst and the like, so that the sulfurized hydrogenation catalyst can be prepared by the method provided by the invention. For other applications, catalysts or other materials requiring the sulfidation of oxidized form metals to sulfided form metals may also be used with the methods provided herein.
The invention also provides the catalyst prepared by the method and the application of the catalyst in hydrogenation reaction, in particular to the application in hydrofining reaction which mainly aims at hydrodesulfurization reaction. In the present invention, the hydrogenation reaction conditions are not particularly limited, and preferable reaction conditions include: the reaction temperature is 200-420 ℃, the pressure is 0.1-30 MPa, and the liquid hourly space velocity is 0.3-10 hours-1The volume ratio of the hydrogen to the oil is 50-5000; the reaction conditions are further preferably: the reaction temperature is 220-400 ℃, the pressure is 1-15 MPa, and the liquid hourly space velocity is 0.3-6 hours-1The hydrogen-oil ratio is 50 to 1000.
The present invention is described in detail below with reference to specific examples, but the present invention is not limited thereto.
Unless otherwise specified, the oxidation state hydrogenation catalysts used in the following examples and comparative examples were prepared by the following steps: preparing NiMo/Al by using industrial alumina carrier (long-distance catalyst factory, 1.3mm external diameter, 2-4mm long strip)2O3The catalyst is specifically as follows: weighing 20.98 g of molybdenum trioxide, 5.87 g of phosphoric acid and 9.15 g of basic nickel carbonate to prepare an aqueous solution, impregnating 100 g of alumina carrier, introducing air for drying after impregnation is finished, drying at 160 ℃, and roasting at 420 ℃ for 4h after drying is finished to obtain the oxidation state hydrogenation catalyst C0.
The loading of the catalysts used in the following examples and comparative examples was carried out by the following procedure, unless otherwise specified: 20ml of catalyst and 16-18 meshes of porcelain balls are mixed and put into a constant temperature area of a hydrogenation test device reactor of a small reactor for hydrogenation reaction. The hydrogenation reaction uses straight-run diesel containing 20 percent of catalytic diesel, the sulfur content of the raw oil is 0.98 percent, the reaction temperature is 340 ℃, the reaction pressure is 6.4MPa, and the volume space velocity is 1.5h-1Hydrogen to oil volume ratio 300.
In the invention, the proportion of carbon with carbon content and decomposition temperature of 350-450 ℃ to the total carbon content adopts a NETZSCH STA409 instrumentAnalyzing by a analyzer, heating the sample to 800 ℃ in the air atmosphere, wherein the heating rate is 10 ℃/min, monitoring by a mass spectrometer at the gas outlet of the analyzer, and obtaining CO in the sample decomposition tail gas2Concentration versus temperature curve. To CO2Performing peak-splitting fitting on the curve, and corresponding to CO with the decomposition temperature of 350-450 DEG C2Peak area divided by total CO2The peak area is the proportion of carbon with the decomposition temperature of 350-450 ℃ in the total carbon.
The unsaturated hydrocarbon in the immersion oil is determined by a mass spectrometry method, and the determination method refers to a method of SH0606-2019 to determine the saturated hydrocarbon mass percentage, wherein the unsaturated hydrocarbon mass percentage is 100% -the saturated hydrocarbon mass percentage.
Example 1
Weighing 1000 g of catalyst C0, adding the catalyst C0 into a rotary kiln reactor, then adding 79 g of elemental sulfur and 100 g of coker gasoline, wherein the content of unsaturated hydrocarbon of the coker gasoline is 49 wt%, removing air, then introducing nitrogen, controlling the pressure in the reactor to be 1.0MPa, heating to 200 ℃ for first heat treatment, and keeping the temperature for 6 hours; slowly introducing hydrogen, controlling the pressure of the reactor to be 1.5MPa, raising the temperature to 290 ℃, and keeping the temperature for 4 hours to perform secondary heat treatment; introducing hydrogen for the first time until the pressure is 2.0MPa, raising the temperature to 340 ℃, and keeping the temperature for 3 hours for carrying out third heat treatment; and reducing the temperature of the reactor after tail gas is discharged, controlling the volume concentration of oxygen in the reactor to be 3 percent, the volume concentration of nitrogen in the reactor to be 97 percent, controlling the reaction temperature to be 30-70 ℃, keeping the temperature for 4 hours and carrying out passivation treatment under the pressure of 1.0 MPa. The resulting catalyst was named C1.
Example 2
Weighing 1000 g of catalyst C0, pouring into a rotary kiln reactor for one time, pouring 117 g of dimethyl disulfide and 195 g of catalytic diesel oil, wherein the content of unsaturated hydrocarbon in the catalytic diesel oil is 45%, removing air, filling nitrogen, controlling the pressure in the reactor to be 0.8MPa, heating to 160 ℃, performing first heat treatment, and keeping the temperature for 8 hours; slowly introducing hydrogen, controlling the pressure of the reactor to be 2.0MPa, raising the temperature to 260 ℃, and keeping the temperature for 8 hours to carry out secondary heat treatment; introducing hydrogen for the first time until the pressure is 2.5MPa, raising the temperature to 360 ℃, and keeping the temperature for 2 hours for carrying out third heat treatment; and reducing the temperature of the reactor after tail gas is discharged, controlling the volume concentration of oxygen in the reactor to be 5 percent and the volume concentration of nitrogen to be 95 percent, controlling the reaction temperature to be 30-70 ℃, keeping the temperature for 2 hours and carrying out passivation treatment under the pressure of 0.8 MPa. The resulting catalyst was named C2.
Example 3
Weighing 1000 g of catalyst C0, pouring into a rotary kiln reactor once, pouring 80 g of elemental sulfur and 180 g of corn oil, wherein the content of unsaturated hydrocarbon in the corn oil is 50%, removing air, filling nitrogen, controlling the pressure in the reactor to be 1.5MPa, heating to 250 ℃, carrying out first heat treatment, and keeping the temperature for 3 hours; slowly introducing hydrogen, controlling the pressure of the reactor to be 2.0MPa, raising the temperature to 300 ℃, and keeping the temperature for 4 hours to perform secondary heat treatment; introducing hydrogen for the first time until the pressure is 3.0MPa, raising the temperature to 360 ℃, and keeping the temperature for 2 hours for carrying out third heat treatment; and reducing the temperature of the reactor after tail gas is discharged, controlling the volume concentration of oxygen to be 1 percent and the volume concentration of nitrogen to be 99 percent in the reactor, keeping the reaction temperature at 30-70 ℃ for 8 hours, and carrying out passivation treatment under the pressure of 1.0 MPa. The resulting catalyst was named C3.
Example 4
Weighing 1000 g of catalyst C0, pouring the catalyst C0 into a rotary kiln reactor for one time, removing air in the reactor, introducing nitrogen, adding 79 g of hydrogen sulfide and 195 g of catalytic diesel oil, controlling the content of unsaturated hydrocarbon in the catalytic diesel oil to be 45 percent, controlling the pressure in the reactor to be 0.8MPa, heating to 230 ℃ for the first heat treatment, and keeping the temperature for 8 hours; slowly introducing hydrogen, controlling the pressure of the reactor to be 2.0MPa, raising the temperature to 320 ℃, and keeping the temperature for 8 hours to perform secondary heat treatment; introducing hydrogen for the first time until the pressure is 2.5MPa, raising the temperature to 400 ℃, and keeping the temperature for 2 hours for carrying out third heat treatment; and reducing the temperature of the reactor after tail gas is discharged, controlling the volume concentration of oxygen to be 1 percent and the volume concentration of nitrogen to be 99 percent in the reactor, keeping the reaction temperature at 30-70 ℃ for 2 hours, and carrying out passivation treatment under the pressure of 0.8 MPa. The resulting catalyst was named C4.
Comparative example 1
Mixing 20mL of catalyst C0 and 16-18 meshes of porcelain balls, loading the mixture into a reactor constant-temperature area of a hydrogenation test device of a small reactor, and vulcanizing the catalyst by using an in-reactor vulcanization method, wherein the vulcanization pressure is 6.4MPa, and the volume space velocity is 2.0h-1Hydrogen-oil volume ratio of 300, sulfurization temperature of 320 ℃ and sulfurization time of 8hThe catalyst was named D1 by sulfiding kerosene having a DMDS concentration of 2%, and the activity of the catalyst was evaluated directly after sulfiding.
Comparative example 2
Mixing 20mL of catalyst C0 and 16-18 meshes of porcelain balls, loading the mixture into a constant-temperature area of a reactor of a hydrogenation test device of a small reactor, vulcanizing the catalyst by using an in-reactor vulcanization method, wherein the vulcanization pressure is 0.3MPa, the volume ratio of a gas agent is 400, the vulcanization temperature is 320 ℃, the vulcanization time is 8H, and H is used2And (3) vulcanizing the sulfur gas with the S concentration of 3%, and directly evaluating the activity of the catalyst after the catalyst is named as D2.
Comparative example 3
Weighing 1000 g of catalyst C0, pouring into a rotary kiln reactor once, pouring 79 g of elemental sulfur and 100 g of coker gasoline, wherein the content of unsaturated hydrocarbon in the coker gasoline is 49%, removing air, then filling nitrogen, controlling the pressure in the reactor to be 1.0MPa, heating to 200 ℃ for first heat treatment, and keeping the temperature for 6 hours; slowly introducing hydrogen, controlling the pressure of the reactor to be 1.5MPa, raising the temperature to 290 ℃, and keeping the temperature for 4 hours to perform secondary heat treatment; and reducing the temperature of the reactor after tail gas is discharged, controlling the volume concentration of oxygen in the reactor to be 3 percent, the volume concentration of nitrogen in the reactor to be 97 percent, controlling the reaction temperature to be 30-70 ℃, keeping the temperature for 4 hours and carrying out passivation treatment under the pressure of 1.0 MPa. The resulting catalyst was named D3.
Comparative example 4
Weighing 1000 g of catalyst C0, pouring into a rotary kiln reactor for one time, pouring 117 g of dimethyl disulfide and 195 g of catalytic diesel oil, wherein the content of unsaturated hydrocarbon in the catalytic diesel oil is 45%, removing air, filling nitrogen, controlling the pressure in the reactor to be 0.8MPa, heating to 160 ℃, performing first heat treatment, and keeping the temperature for 8 hours; slowly introducing hydrogen, controlling the pressure of the reactor to be 2.0MPa, raising the temperature to 260 ℃, and keeping the temperature for 8 hours to carry out secondary heat treatment; and reducing the temperature of the reactor after tail gas is discharged, controlling the volume concentration of oxygen in the reactor to be 5 percent and the volume concentration of nitrogen to be 95 percent, controlling the reaction temperature to be 30-70 ℃, keeping the temperature for 4 hours and carrying out passivation treatment under the pressure of 1.0 MPa. The resulting catalyst was named D4.
Comparative example 5
Weighing 1000 g of catalyst C0, pouring into a rotary kiln reactor for one time, pouring 117 g of dimethyl disulfide and 195 g of catalytic diesel oil, wherein the content of unsaturated hydrocarbon in the catalytic diesel oil is 45%, removing air, filling nitrogen, controlling the pressure in the reactor to be 0.8MPa, heating to 350 ℃, performing first heat treatment, and keeping the temperature for 8 hours; slowly introducing hydrogen, controlling the pressure of the reactor to be 2.0MPa, reducing the temperature to 290 ℃, and keeping the temperature for 8 hours to perform secondary heat treatment; introducing hydrogen for the first time until the pressure is 2.5MPa, reducing the temperature to 230 ℃, and keeping the temperature for 8 hours for carrying out third heat treatment; and reducing the temperature of the reactor after tail gas is discharged, controlling the volume concentration of oxygen in the reactor to be 5 percent and the volume concentration of nitrogen to be 95 percent, controlling the reaction temperature to be 30-70 ℃, keeping the temperature for 2 hours and carrying out passivation treatment under the pressure of 0.8 MPa. The resulting catalyst was named D5.
Comparative example 6
Weighing 1000 g of catalyst C0, pouring into a rotary kiln reactor once, pouring 117 g of dimethyl disulfide, removing air, introducing nitrogen, controlling the pressure in the reactor to be 0.8MPa, heating to 160 ℃ for first heat treatment, and keeping the temperature for 8 hours; slowly introducing hydrogen, controlling the pressure of the reactor to be 2.0MPa, raising the temperature to 260 ℃, and keeping the temperature for 8 hours to carry out secondary heat treatment; introducing hydrogen for the first time until the pressure is 2.5MPa, raising the temperature to 360 ℃, and keeping the temperature for 2 hours for carrying out third heat treatment; and reducing the temperature of the reactor after tail gas is discharged, controlling the volume concentration of oxygen in the reactor to be 5 percent and the volume concentration of nitrogen to be 95 percent, controlling the reaction temperature to be 30-70 ℃, keeping the temperature for 2 hours and carrying out passivation treatment under the pressure of 0.8 MPa. The resulting catalyst was named D6.
TABLE 1 catalyst sulfidity and hydrodesulfurization catalytic Properties
The results in table 1 show that, compared with the prior art, the hydrogenation catalyst obtained by the method provided by the invention has better hydrodesulfurization activity, the proportion of carbon with the decomposition temperature of 350-450 ℃ in the catalyst to total carbon is higher, and the content of hydrogen sulfide in tail gas is 0, so that the environmental protection requirement is met.
Claims (13)
1. A preparation method of a vulcanized hydrogenation catalyst comprises the following steps of sequentially carrying out treatment on an oxidized catalyst:
(1) carrying out first heat treatment on the oxidation state catalyst in the presence of an inert gas atmosphere, a vulcanizing agent and immersion oil, wherein the treatment temperature is T1, and the treatment pressure is P1;
(2) carrying out secondary heat treatment on the catalyst obtained in the step (1) in the atmosphere of first reducing gas, wherein the treatment temperature is T2, and the treatment pressure is P2;
(3) carrying out third heat treatment on the catalyst obtained in the step (2) in a second reducing gas atmosphere, wherein the treatment temperature is T3, and the treatment pressure is P3;
(4) passivating the catalyst obtained in the step (3) in a passivation gas atmosphere;
wherein, T3> T2> T1.
2. The process according to claim 1, wherein the oxidation state catalyst comprises a support and an active metal supported on the support, the active metal being at least one metal component selected from group VIII and at least one metal component selected from group VIB; the VIII group metal component is selected from cobalt and/or nickel, the VIB group metal component is selected from molybdenum and/or tungsten, and the carrier is a heat-resistant inorganic oxide, preferably alumina, and more preferably gamma-alumina; optionally, the oxidation state catalyst contains an organic substance; based on the total amount of the oxidation state catalyst, the content of the carrier is 40-95 wt%, the content of active metal calculated by oxide is 5-40 wt%, and the content of organic matter is 0-20 wt%.
3. The method according to claim 1, wherein the vulcanizing agent is one or more selected from elemental sulfur, hydrogen sulfide, carbon disulfide, mercaptans, sulfides, polysulfides, thiophene sulfides.
4. The method according to claim 1, wherein the unsaturated hydrocarbon oil is a hydrocarbon oil containing at least one kind of unsaturated compounds of aromatic hydrocarbons, olefins, dienes, and alkynes, and the unsaturated hydrocarbon oil is at least one of natural vegetable oil, animal oil, and mineral oil.
5. The method of claim 1, wherein the impregnating oil is petroleum distillate oil and/or bio-based distillate oil, the petroleum distillate oil is one or more of gasoline, diesel oil and residual oil, or is oil obtained by any one of the treatment processes including catalytic cracking, coking, coal liquefaction and coal dry distillation, and the bio-based distillate oil is vegetable oil and/or animal oil; preferably, the content of unsaturated hydrocarbon in the impregnating oil is not less than 10 wt%, preferably 20-50 wt%, and the amount of the impregnating oil is such that the ratio of carbon to metal content in terms of element in the finally obtained sulfurized hydrogenation catalyst is 0.01-1, preferably 0.03-0.5, and more preferably 0.05-0.3.
6. The method as claimed in claim 1, wherein the first reducing gas in step (2) is hydrogen gas or a mixed gas of hydrogen gas and inert gas and/or hydrogen sulfide; and (3) the second reducing gas atmosphere is hydrogen or a mixed gas of hydrogen and inert gas.
7. The method according to claim 6, further comprising a step of purging with an inert gas and/or hydrogen between step (2) and step (3), wherein the purging is such that the second reducing gas atmosphere is substantially free of hydrogen sulfide.
8. The method of claim 1, wherein the conditions of the passivation process in step (4) comprise: the temperature is between room temperature and 100 ℃, the pressure is between normal pressure and 10 MPa, the time is between 1 and 10 hours, and the space velocity of the volume of the passivation gas is between 100 and 3000 hours-1(ii) a The passivation gas atmosphere contains inert gas and oxygen-containing substances, the inert gas is one or more of helium, nitrogen, neon, argon, methane, ethane, propane, butane and carbon dioxide, and the oxygen-containing substances are one or more of oxygen, water and ethanol; the content of oxygen-containing substances in the passivation gas is 0.1-10 vol%, and the content of inert gasIs 90 to 99.9 vol%.
9. The process according to claim 1, wherein T1 is 100-; t2 is 200-400 ℃, preferably 250-350 ℃, P2 is 0-6.0MPa, preferably 1.0-3.0 MPa; t3 is 280-480 ℃, preferably 300-400 ℃, and P3 is 0-10.0MPa, preferably 1.5-5.0 MPa.
10. The process according to claim 1, wherein the heat treatment of steps (1) to (3) is such that the final sulfided catalyst has a sulfidation degree of at least 30%, preferably 40-95%, more preferably 50-90%.
11. The process according to claim 1, wherein the treatments of steps (1) to (4) result in a carbon content in the final sulfided catalyst of from 1.5% to 30% by weight, preferably from 2.0% to 20% by weight; the proportion of the carbon content of the carbon with the decomposition temperature of 350-450 ℃ in the total carbon content is not less than 50 wt%, preferably not less than 60 wt%, and more preferably 65-95 wt%.
12. A sulfided hydrogenation catalyst prepared by the process of any of claims 1-11.
13. The use of the sulfided hydrogenation catalyst of claim 12, comprising loading the catalyst into a hydrogenation reactor and then directly introducing the feedstock oil into the reactor to react; the reaction conditions include: the reaction temperature is 200-420 ℃, the pressure is 0.1-30 MPa, and the liquid hourly space velocity is 0.3-10 hours-1The volume ratio of the hydrogen to the oil is 50-5000; the reaction conditions are preferably: the reaction temperature is 220-400 ℃, the pressure is 1-15 MPa, and the liquid hourly space velocity is 0.3-6 hours-1The hydrogen-oil ratio is 50 to 1000.
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| CN111068794A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | External presulfurization method of hydrogenation catalyst |
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| CN111068794A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | External presulfurization method of hydrogenation catalyst |
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