CN113825564A - 用于加氢处理烃油的催化剂和使用该催化剂加氢处理烃油的方法 - Google Patents
用于加氢处理烃油的催化剂和使用该催化剂加氢处理烃油的方法 Download PDFInfo
- Publication number
- CN113825564A CN113825564A CN202080036129.1A CN202080036129A CN113825564A CN 113825564 A CN113825564 A CN 113825564A CN 202080036129 A CN202080036129 A CN 202080036129A CN 113825564 A CN113825564 A CN 113825564A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- group
- periodic table
- mass
- metal
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 27
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 27
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 27
- 239000003921 oil Substances 0.000 claims abstract description 53
- 230000000737 periodic effect Effects 0.000 claims abstract description 50
- 239000011148 porous material Substances 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 238000001179 sorption measurement Methods 0.000 claims abstract description 11
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 239000000470 constituent Substances 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000011574 phosphorus Substances 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract description 8
- 230000023556 desulfurization Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 description 24
- 239000002131 composite material Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000005470 impregnation Methods 0.000 description 11
- -1 etc.) Chemical compound 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 8
- 239000010941 cobalt Substances 0.000 description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 239000003350 kerosene Substances 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000006259 organic additive Substances 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 229910021476 group 6 element Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 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 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 239000013076 target substance Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 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 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- QOPUBSBYMCLLKW-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]-4-hydroxybutanoic acid Chemical compound OCCC(C(O)=O)N(CC(O)=O)CCN(CC(O)=O)CC(O)=O QOPUBSBYMCLLKW-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 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 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 229960002303 citric acid monohydrate Drugs 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- 229940015975 1,2-hexanediol Drugs 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- WYMDDFRYORANCC-UHFFFAOYSA-N 2-[[3-[bis(carboxymethyl)amino]-2-hydroxypropyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)CN(CC(O)=O)CC(O)=O WYMDDFRYORANCC-UHFFFAOYSA-N 0.000 description 1
- HHBZZTKMMLDNDN-UHFFFAOYSA-N 2-butan-2-yloxybutane Chemical compound CCC(C)OC(C)CC HHBZZTKMMLDNDN-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- 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
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910018864 CoMoO4 Inorganic materials 0.000 description 1
- 229920002558 Curdlan Polymers 0.000 description 1
- 239000001879 Curdlan Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229920002527 Glycogen Polymers 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 description 1
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 description 1
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 235000009697 arginine Nutrition 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 description 1
- OYSYRRRAJPTBHI-UHFFFAOYSA-N chromium molybdenum tungsten Chemical compound [Cr][W][Mo] OYSYRRRAJPTBHI-UHFFFAOYSA-N 0.000 description 1
- QNHZQZQTTIYAQM-UHFFFAOYSA-N chromium tungsten Chemical compound [Cr][W] QNHZQZQTTIYAQM-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940078035 curdlan Drugs 0.000 description 1
- 235000019316 curdlan Nutrition 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 229940096919 glycogen Drugs 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 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
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229960000292 pectin Drugs 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
- B01J2523/31—Aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/40—Constitutive chemical elements of heterogeneous catalysts of Group IV (IVA or IVB) of the Periodic Table
- B01J2523/41—Silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/40—Constitutive chemical elements of heterogeneous catalysts of Group IV (IVA or IVB) of the Periodic Table
- B01J2523/47—Titanium
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
-
- 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
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/308—Gravity, density, e.g. API
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- Nanotechnology (AREA)
Abstract
提供一种具有等于或优于现有技术的加氢处理(加氢、脱硫和脱氮)性能的催化剂作为烃油的加氢处理催化剂,以及一种使用所述催化剂的烃油加氢处理方法。[解决问题的方法]一种用于烃油的加氢处理催化剂,其包含至少一种选自周期表第6族的金属、至少一种选自周期表第8族至第10族的金属以及任选地另外的磷和/或硼作为负载在基于氧化铝的无机多孔载体上的催化活性组分,其中所述无机多孔载体包含相对于氧化物的质量小于1质量%的量的二氧化硅作为其构成组分和小于13质量%的量的周期表第4族的金属作为氧化物;其中所述周期表第4族的金属高度分散在所述无机多孔载体中,其分散程度通过以下来显示:通过拉曼光谱在100至200cm‑1的波数范围内基本上没有观察到峰以及通过X射线衍射分析基本上没有观察到晶体;其中所述加氢处理催化剂具有100至300m2/g的比表面积、0.2至0.5ml/g的孔体积、6至10nm的平均孔径和4.5cm3/ml或更大的NO吸附量作为催化特性;并且其中通过X射线衍射分析基本上没有观察到衍生自周期表第6族的金属氧化物盐的晶体。
Description
技术领域
本发明涉及用于去除烃油中所含的杂质(诸如硫和氮)的加氢催化剂及其使用方法。
背景技术
鉴于近年来全球改善空气质量的趋势,需要对作为主要燃料的馏分油执行加氢精制(诸如脱硫、脱氮等)的加氢催化剂进行进一步的性能改善。用于烃油的常用加氢处理催化剂是无机耐热载体(诸如氧化铝或二氧化硅),其上负载有钼和加氢活性金属组分(诸如钴或镍)。
然而,近年来,催化剂不仅仅需要脱硫性能的改善,还需要催化剂性能的稳定性和有助于加氢处理单元操作效率的经济性。作为对这种需求的一种回答,已经提出了使用复合氧化物作为载体的催化剂技术。
专利文献1公开了一种用于石油烃油的加氢脱硫催化剂,其包含载体,所述载体含有除氧化铝之外的4质量%至8质量%的量的二氧化硅、二氧化钛、氧化锆、氧化硼等,其上负载有镍和/或钴和钼。然而,除氧化铝之外的组分的含量较少,并且在催化活性方面不太可能展现出作为复合氧化物载体的效果。
专利文献2涉及一种用于烃油的加氢脱硫催化剂,其包含二氧化硅-二氧化钛-氧化铝复合氧化物载体,所述载体负载通过X射线衍射分析确定的周期表第VIA族或第VIII族的金属组分。然而,由于源自钛的晶体保留在用过的载体中,存在影响催化活性的复合氧化物组分的分散性的问题。
专利文献3公开了一种用于烃油的加氢处理催化剂,相对于无机氧化物载体上的100质量份的催化剂,所述加氢处理催化剂含有钼和/或钨、钴和/或镍以及衍生自有机酸的碳。然而,由于没有提及无机氧化物组分在载体中的高分散性能,催化性能没有得到充分改善。
引文列表
专利文献
[专利文献1:]JP-A-2005-254141
[专利文献2:]JP-A-2011-72928
[专利文献3:]JP-A-2016-203074
发明内容
本发明待解决的问题
本发明的目的是提供一种具有等于或优于现有技术的加氢处理(加氢、脱硫和脱氮)性能和活性稳定性的催化剂作为烃油的加氢处理催化剂,以及一种使用所述催化剂的烃油加氢处理方法。
解决问题的方法
本发明人鉴于现有技术的上述问题进行了大量潜心研究,特别集中于作为催化剂载体的复合氧化物组分的可分配性的改善、活性金属组分的负载方法和孔结构的优化。结果,我们发现,通过将加氢活性组分负载在含有特定量的二氧化硅、高度分散在无机多孔载体中的周期表第4族金属的无机多孔载体上而获得的催化剂对于烃油的加氢处理是高度有效的,从而完成本发明。
换言之,本发明是一种用于烃油的加氢处理催化剂,其包含作为其构成组分的至少一种选自周期表第6族的金属、至少一种选自周期表第8族至第10族的金属以及任选地另外的磷和/或硼作为负载在基于氧化铝的无机多孔载体上的催化活性组分,其中所述无机多孔载体包含相对于氧化物的质量小于1质量%的量的二氧化硅和小于13质量%的量的周期表第4族的金属作为氧化物;其中所述周期表第4族的金属高度分散在所述无机多孔载体中,其分散程度通过以下来显示:通过拉曼光谱在100至200cm-1的波数范围内基本上没有观察到峰以及通过X射线衍射分析基本上没有观察到晶体;其中所述加氢处理催化剂具有100至300m2/g的比表面积、0.2至0.5ml/g的孔体积、6至10nm的平均孔径和4.5cmVml或更大的NO吸附量作为催化特性;并且其中通过X射线衍射分析基本上没有观察到衍生自周期表第6族的金属氧化物盐的晶体。
另外,在本发明的加氢处理催化剂中,按催化剂氧化物计,选自周期表第6族的金属的负载量是15质量%至30质量%,选自周期表第8族至第10族的金属的负载量是0.5质量%至5质量%。
并且,本发明的用于烃油的加氢处理催化剂包含按催化剂氧化物计0.5质量%至5质量%的磷和/或硼。
此外,本发明的烃油加氢处理方法包括在300至450℃的反应温度、1至20MPa的氢分压、0.1至10h1的液时空速和50至1,200Nm3/kl的氢/油比的条件下使本发明的加氢催化剂与烃油接触。
发明效果
使用本发明的加氢处理催化剂不仅可以有效地去除杂质(诸如硫和氮)并显示出长期稳定的活性,而且可以有效和经济地操作加氢处理单元。
用于实施本发明的模式
(1)载体
我们将在下面详细描述本发明。
用于本发明催化剂的载体是以氧化铝作为基材的、含有特定量的二氧化硅和周期表第4族的金属的氧化物的复合氧化物。
作为二氧化硅起始材料,可以使用各种类型的硅化合物,诸如碱金属硅酸盐、烷氧基硅烷、四氯化硅、正硅酸盐、有机硅、硅溶胶、硅胶等。此外,作为氧化铝起始材料,可以使用氢氧化铝(三羟铝石(bayerite)、三水铝石(gibbsite)、水铝石(diaspore)、勃姆石(boehmite)、假勃姆石(pseudoboehmite)等)、氯化铝、硝酸铝、硫酸铝、烷醇铝、碱金属铝酸盐和其他无机盐、有机盐或氧化铝溶胶。
另一方面,用于周期表第4族的金属的氧化物的起始材料包括氧化物、氯氧化物、氯化物、氢氧化物、氢化物、硝酸盐、碳酸盐、含氧硫酸盐、硫酸盐和有机酸盐。钛、锆和铪可用作周期表第4族的元素。然而,优选使用钛和锆,并且从活性和经济性能的观点来看,钛是特别优选的。
通过煅烧通过共沉淀法或捏合法制备的含有二氧化硅-周期表第4族的金属的水合物来获得含有特定量的二氧化硅和周期表第4族的金属的复合氧化物载体。
水合物可以通过多种方法中的任一种来制备,诸如二氧化硅和氧化铝起始材料与第4族金属化合物的共沉淀;氧化铝水合物、硅化合物和第4族金属化合物的捏合;氧化铝-第4族金属水合物和硅化合物的混合;或硅化合物-第4族金属的混合以及氧化铝水合物的捏合。然而,从改善复合氧化物组分的分散性的角度来看,共沉淀是特别优选的。
按复合氧化物载体计,二氧化硅组分优选小于1质量%、优选为0.01质量%至0.99质量%、更优选为0.02质量%至0.95质量%。另一方面,周期表第4族的金属的氧化物小于13质量%、优选为7质量%至12.9质量%、更优选为8.1质量%至12质量%。
将含有二氧化硅-周期表第4族金属氧化物的水合物与盐酸、硫酸、硝酸、有机酸(甲酸、乙酸、丙酸、草酸、丙二酸、苹果酸、酒石酸、柠檬酸、葡糖酸等)、氨或氢氧化钠的水溶液一起添加,以控制孔结构或根据需要改善组分的分散性和水合物的可成形性,并且通过添加各种类型的基于纤维素的模塑助剂进行捏合,以模塑成所需形状(粒料、球体、挤出体等)。模塑制品通常在空气中在450℃至750℃(不是大气温度,而是模塑制品的温度)、优选地490℃至720℃、更优选地500℃至700℃的温度下煅烧0.1小时至5小时、优选地0.5小时至3小时,以产生复合氧化物载体。
复合氧化物载体优选具有通过紫外光谱法测量的源自周期表第4族金属的吸收峰的在350nm或更小、优选在348nm或更小的吸收边缘波长(在库贝卡-芒克(Kubelka-Munk)转换后的光谱强度值(K-M值)为0.3或更高的最大波长)和在323nm或更小、优选在320nm或更小的最大波长,其中K-M值为1.5或更小。
具有吸收边缘波长在所述范围之外的长而平缓的K-M曲线的复合氧化物载体具有周期表第4族的金属氧化物的不充分分散。因此,负载活性组分后的催化活性将不会改善。
通过使用附着有用于漫反射方法的UV-2200系列的积分球附着装置(ISR-2200(产品名称))的紫外-可见分光光度计(由Shimadzu Corporation制造:UV-2450(产品名称))来执行复合氧化物载体的紫外光谱分析。此外,使用白色硫酸钡板进行背景测量。表1示出了测量条件。
[表1]
表1.紫外光谱分析条件
使用库贝卡-芒克函数对测量数据进行库贝卡-芒克转换(K-M转换),并且计算光谱强度值(K-M值)为0.3或更高的最大波长(吸收边缘波长)和K-M值为1.5或更低的最大波长。
将加氢活性组分添加到通过上述步骤获得的载体中,并且在干燥之后,根据需要提供进一步的加热处理以负载加氢活性组分。
添加方法没有特别限制,并且例如,可以应用各种工业方法,诸如浸渍、涂覆或喷涂,但从可管理性和添加效率的观点来看优选的是浸渍法。吸附、平衡吸附、孔隙填充法、初湿含浸法、蒸干和喷雾的浸渍法均可应用于本申请的发明。然而,从可加工性的观点来看,优选的是孔隙填充法。
对加氢活性组分的添加顺序没有特别限制并且其可以连续或同时顺序。在浸渍法的情况下,可以使用其中各组分溶解于各种极性有机溶剂、水、水-有机溶剂的混合物中的溶液,但最优选的溶剂是水。
(2)负载的组分
在待负载到载体上的加氢活性组分中,周期表的第6族元素是选自铬、钼和钨中的至少一种。这些元素中的任一种可以单独使用,但从经济性和活性的观点来看,优选的是钼和钨,特别是钼。其也可以组合使用,这取决于原料的反应性和反应器的操作条件。组合的实例包括铬-钼、铬-钨、钼-钨和铬-钼-钨。
按氧化物催化剂的质量计,作为周期表第6族元素的氧化物的总量,负载量为15质量%至30质量%、优选为17质量%至28质量%、更优选为18质量%至25质量%。当所述量小于15质量%时,催化活性较低,并且即使当所述量超过30质量%时,活性也没有增加。
周期表第6族元素的原材料包括铬酸盐、钼酸盐、钨酸盐、三氧化物、卤化物、杂多酸、杂多酸盐等。
作为加氢活性组分的周期表第8族至第10族元素包括铁、钴和镍。
这些元素中的任一种可以单独使用,但从经济性和活性的观点来看,优选的是钴和镍。其也可以组合使用,这取决于原料的反应性和反应器的操作条件。组合的实例包括铁-钴、铁-镍、钴-镍和铁-钴-镍。
按氧化物催化剂的质量计,作为周期表第8族至第10族元素的氧化物的总量,负载量为0.5质量%至5质量%、优选为1质量%至4.8质量%、更优选为2质量%至4.5质量%。当所述量小于0.5质量%时,催化活性较低,并且即使当所述量超过5质量%时,活性也没有增加。
用于负载的铁、钴和镍的化合物包括氧化物、氢氧化物、卤化物、硫酸盐、硝酸盐、碳酸盐、有机酸盐等。当制备加氢活性组分的浸渍溶液时,可以单独制备周期表的第6族元素或周期表的第8族至第10族元素,或者可以将其混合为均匀溶液。
为了调节溶液的pH并增加溶液稳定性和催化剂加氢活性,必要时可将氨水、过氧化氢水、硝酸、硫酸、盐酸、磷酸、硼酸、氢氟酸等添加到加氢活性组分的浸渍溶液中。
磷酸和硼酸也可以作为催化剂组分添加,并且在这种情况下,按氧化物催化剂的质量计,作为氧化物,添加范围为0.5质量%至5质量%、优选为0.8质量%至4.5质量%、更优选为1质量%至4质量%。此外,除了添加到加氢活性组分的浸渍溶液中之外,可以在制备二氧化硅-氧化铝-周期表第4族金属氧化物载体的过程中添加全部或部分磷酸和硼酸。
此外,为了改善浸渍溶液的稳定性和负载后加氢活性组分的分散性,可以在加氢活性组分的浸渍溶液中添加如下所示的水溶性有机添加剂。
有机添加剂选自多元醇及其醚、多元醇或醚的酯、糖类、羧酸及其盐、氨基酸及其盐、各种螯合剂等。
多元醇及其醚的实例包括诸如以下的多元醇:乙二醇、二乙二醇、三乙二醇、丙二醇、异丙二醇、二丙二醇、三丙二醇、丁二醇(1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇)、戊二醇(例如,1,5-戊二醇,包括其他异构体)、3-甲基-1,5-戊二醇、新戊二醇、己二醇(例如,1,2-己二醇和1,6-己二醇,包括其他异构体)、己二醇、聚乙烯醇、聚乙二醇(平均分子量:200-600)、聚丙二醇(仅水溶性的)、甘油、三羟甲基乙烷、三羟甲基丙烷、己三醇(例如,1,2,6-己三醇,包括其他异构体)、赤藓糖醇和季戊四醇,以及其醚(水溶性的单醚、二醚和三醚,其选自甲基醚、乙基醚、丙基醚、异丙基醚、丁基醚、异丁基醚、仲丁基醚和叔丁基醚)。
多元醇或醚的酯的实例包括上述多元醇或醚的酯(与甲酸、乙酸等的单酯、二酯和三酯,其是水溶性的)。
糖类的实例包括诸如以下的糖类:葡萄糖、果糖、异构化糖、半乳糖、麦芽糖、乳糖、蔗糖、海藻糖、淀粉、糊精、果胶、糖原、凝胶多糖等。
羧酸及其盐的实例包括诸如以下的羧酸:甲酸、乙酸、丙酸、草酸、丙二酸、琥珀酸、马来酸、富马酸、酒石酸、柠檬酸(酸酐、一水合物)、苹果酸、葡糖酸和戊二酸,及其盐。
氨基酸及其盐的实例包括诸如以下的氨基酸:天冬氨酸、丙氨酸、精氨酸、甘氨酸和谷氨酸,及其盐。
不同螯合剂的实例包括诸如以下的各种螯合剂:乙二胺(EDA)、二亚乙基三胺(DETA)、三亚乙基四胺(TETA)、四亚乙基五胺(TEPA)、五亚乙基六胺(PEHA)、乙二胺四乙酸(EDTA)、羟乙基乙二胺四乙酸(HEDTA)、二亚乙基三胺五乙酸(DTPA)、三乙基四胺六乙酸(TTHA)、羟乙基亚氨基二乙酸(HIDA)、1,3-丙烷二氨基四乙酸(PDTA)、1,3-二氨基-2-羟基丙烷四乙酸(PDTA-OH)、反式-1,2-环己烷二氨基四乙酸(CyDTA)、二醇醚二氨基四乙酸(GEDTA)、次氮基三乙酸(NTA)、二羟乙基甘氨酸(DHEG)和(S,S)-乙二胺-N,N'-二琥珀酸(EDDS)。
上述有机添加剂可以单独使用或以适当的组合使用。
待添加的有机添加剂的量是周期表的第6族元素和周期表的第8族至第10族元素的总摩尔数的0.01倍至3倍、优选为0.03倍至2.8倍、最优选为0.05倍至2.5倍。催化剂性能在小于0.03倍摩尔量下没有得到改善。在大于3倍摩尔量下未获得活性的进一步增加。
在将含有加氢活性组分的浸渍液添加到复合氧化物载体中之后,可以通过将混合物例如在空气中在30至250℃的物质温度下干燥0.1小时至3小时和通过任选在450至630℃、优选地在500至600℃下煅烧0.5小时至3小时来获得成品催化剂。
(3)成品催化剂的性质
为了使成品催化剂展现出令人满意的催化剂性能,其优选具有以下物理性质和孔结构。
具体地,平均孔径为6nm至10nm、优选为6.5nm至9.5nm、更优选为7nm至9nm。如果平均孔径小于6nm,那么烃油向孔中的扩散不足,并且如果直径超过10nm,那么比表面积降低,从而降低催化剂性能。
此外,优选的总孔体积为0.2ml/g至0.5ml/g。更优选的范围是0.25ml/g至0.45ml/g。小于0.2ml/g的总孔体积不足以使烃油扩散到孔中,并且如果所述体积超过0.5ml/g,那么装载到反应器中的催化剂的绝对重量太轻而不能展现出足够的催化性能。
作为显示催化剂孔的均匀性的指标,期望催化剂的孔结构使得其直径保持在平均孔径+1nm与-1nm之间的范围内的孔的体积占总孔体积的50%至90%。优选的范围是60%至85%。如果其小于50%,那么将存在增加比例的不参与反应的微孔,以及具有低表面积的大孔,而如果其大于90%,那么这将抑制在具有相对大的分子尺寸的烃油的孔中的扩散,从而潜在地降低催化活性。
本发明催化剂的孔径分布是以平均孔径及其附近为中心的单峰分布。
比表面积优选为100至300m2/g、更优选为150至290m2/g,并且甚至更优选为180至250m2/g。如果其小于100m2/g,那么催化剂性能将不足,而如果其大于300m2/g,那么平均孔径将太小,从而可能引起反应期间孔的堵塞。
同时,分别地,孔结构(孔体积、平均孔径、孔径分布等)的值通过水银压入法(接触角140度,表面张力480dyn/cm)来获得,并且比表面积的值通过BET法来获得。为了测量成品催化剂的孔结构和比表面积并且为了测量加氢活性组分的负载量,将成品催化剂在空气中在450℃下处理1小时,以在测量之前去除含于其中的水分和有机材料,并且将这里获得的分析和测量值用作氧化物催化剂质量的值。此外,使用荧光X射线分析仪测量加氢活性组分和载体构成组分。
作为成品催化剂的化学性质,硫化处理后的NO吸附量优选为4.5cmVml或更多。如果其小于4.5cmVml,那么催化剂活性位点的数量太小而不能实现所需的催化性能。
此外,成品催化剂需要在100至200cm2、特别是120至160cm-1的波数范围内通过激光拉曼光谱仪(laser Raman spectrometer)基本上没有观察到的峰。当在所述范围内出现峰时,这意味着作为复合氧化物载体的组分的周期表第4族金属聚集而没有高度分散,即没有均匀分散。结果,认为催化剂活性和活性稳定性通过促进负载的加氢活性组分的聚集而降低。
另一方面,同样重要的是,基本上没有观察到源自周期表第4族金属氧化物(约2θ=25至30°)和周期表第6族金属氧化物(约2θ=25至35°)的晶体的衍射峰。可分别例举作为周期表第4族的金属氧化物的Ti02、Zr02、Hf02和作为周期表第6族的金属氧化物盐的FeMo04、CoMoO4、N1M0O4、FeW04、C0WO4、NiW04等。这些衍射峰的存在指示载体构成组分和负载的加氢活性组分的聚集,这导致催化剂活性和活性稳定性的降低。
另外,上文所谓“基本上未观察到”是指即使在来自目标物质的峰出现在目标物质所出现的测量范围中的情况下,在峰前后峰半宽的20倍的范围内确定基线上的最大值和最小值,并且目标物质的峰值不超过差值的半值的值的三倍。
根据下述程序测量催化剂的NO吸附量。
将用200目至330目过筛的催化剂样品在450℃下预处理1小时,称取其约0.1g,装入样品管中,并且使2.7%H2S/30%H2/Ar气体在50℃下循环30分钟,在35分钟内升温至400℃后,在400℃下硫化处理2小时。然后,将混合的气体流冷却至50℃以改变为He流,并且通过脉冲法(TCD检测器)使用15%NO/He气体测量催化剂的NO吸附量。通过将测得的每单位重量催化剂的NO吸附量(cmVg)乘以催化剂的压实堆积密度(g/ml)以获得每单位催化剂体积的NO吸附量(cmVml)来获得NO吸附量。
在表2所示的条件下,相对于插入载玻片之间的压碎的催化剂样品(约0.1g),通过在室温下使用由Thermo Fisher Scientific Co.,Ltd.制造的激光拉曼光谱装置(DXR系列(商品名称))来执行催化剂的拉曼光谱分析。
[表2]
表2.拉曼光谱分析条件
激光波长 | 532nm |
激光强度 | 10mW |
测量范围 | 1,800至100cm<sup>-1</sup> |
物镜放大率 | 10倍 |
狭缝尺寸 | 50μm针孔 |
曝光时间 | 1秒 |
曝光次数 | 1,000倍 |
在表3所示的条件下,使用由PANalytical制造的粉末X射线衍射仪(X'PERT PRO(商品名称))执行催化剂的X射线衍射分析,以检查是否存在衍生自周期表第4族的氧化物和周期表第6族的金属氧化物盐的衍射峰。
[表3]
表3.XRD分析条件
起始角 | 3° |
终止角 | 80° |
步长 | 0.0167° |
步骤时间 | 50.165秒 |
扫描速度 | 0.0422°/秒 |
成品催化剂通常在预硫化之后使用,并且预硫化可以在反应器内部或外部进行。
所采用的预硫化方法可以是在氢气氛下使用加热状态的含硫的煤油或瓦斯油馏分用液相硫化,或使用添加到这种油中的合适量的硫化试剂(诸如二硫化碳、丁硫醇、二甲基二硫化物(DMDS)或二叔壬基多硫化物(TNPS)),或使用硫化氢或二硫化碳作为加热的氢流中的硫化试剂的气相硫化方法。
(4)烃油
用于通过本发明的催化剂进行加氢处理的烃油是基于ASTM D-86具有不高于560℃、优选不高于540℃的90%沸点温度和100℃或更高、优选150℃或更高的初沸点的蒸馏油。
具体实例主要包括基于石油的石脑油、直馏煤油、直馏瓦斯油、重瓦斯油、真空瓦斯油和重真空瓦斯油,但也包括自加氢裂化器、热裂化器或流化催化裂化器获得的煤油和瓦斯油馏分(轻循环油或焦化瓦斯油)和自重油直接脱硫器获得的煤油和瓦斯油馏分,以及自煤或自动物和植物生物质获得的煤油和瓦斯油对应馏分和包含上述馏分的任何共混油。
同时,期望待处理的原料中的金属(诸如钒和镍)的含量为5质量ppm或更少、优选为1质量ppm或更少,并且碳渣含量为1质量%或更少、优选为0.9质量%或更少。诸如常压渣油(long residue)、减压渣油(short residue)、溶剂脱沥青油、煤液化油、页岩油或焦油砂油的重油也可以与待加氢处理的馏分油混合,以满足金属含量和碳渣含量。
(5)加氢处理方法
本发明的加氢处理催化剂可用于各种加氢处理反应,其中使烃油在氢气存在下,在诸如固定床、移动床等的反应器中进行加氢、加氢脱硫、加氢脱氮、加氢脱氧、加氢裂化、加氢异构化等。
本发明的加氢处理催化剂的更优选用途是基于石油的蒸馏油的脱硫或脱氮,尤其是将煤油或瓦斯油馏分中的硫含量降低至不大于80重量ppm、更优选不大于10重量ppm。
对于在加氢处理装置中使用,反应条件将取决于原料的类型,但通常是氢分压为1至20MPa并优选为3至18MPa,氢/油比为50至1,200Nm3/kl并优选为100至1,000Nm3/kl,液时空速为0.1至10h-1并优选为0.5至8h-1,并且反应温为300℃至450℃并优选为320℃至430℃。
实施例
通过以下实施例进一步说明本发明。然而,以下实施例根本不限制本发明。
制备催化剂
(实施例1)
添加硫酸铝溶液(以Al203计8.1质量%)、铝酸钠溶液(以Al203计21.6质量%)和硫酸氧钛溶液(以TiO2计13.6质量%)以及水玻璃并混合以制备二氧化硅-二氧化钛-氧化铝水合物凝胶(二氧化硅/二氧化钛/氧化铝质量比:0.2/9.8/90.0)。从溶液中分离水合物后,使用温水冲洗并去除杂质,通过添加有机酸胶溶,使用捏合机热捏合以将水含量调节至67%,挤出并模塑,并且在空气中在600℃下煅烧1.5小时以获得二氧化硅-二氧化钛-氧化铝载体。
用含有三氧化钼、碱性碳酸钴、磷酸和柠檬酸一水合物(相对于钼和钴的物质的量为0.1倍摩尔量)的水溶液浸渍载体,以便使载体含有按氧化物催化剂的质量计24质量%的三氧化钼、4质量%的氧化钴和2质量%的氧化磷。在120℃下干燥两小时后,使载体在空气中进行热空气干燥处理,并且在500℃的物质温度下干燥1.5小时后,获得催化剂A。表4显示了催化剂A的物理性质和化学组成。
(实施例2)
通过与实施例1相同的方法来制备催化剂B,不同之处在于分别以相对于钼和钴的总摩尔数的0.1倍摩尔量和0.2倍摩尔量使用待添加到实施例1中的浸渍溶液中的有机添加剂柠檬酸一水合物和聚乙二醇(平均分子量:200)。表4显示了催化剂B的物理性质和化学组成。
(实施例3)
通过与实施例1相同的方法来制备催化剂C,不同之处在于在实施例1中改变硫酸氧钛的添加量以制备二氧化硅-二氧化钛-氧化铝水合物凝胶(二氧化硅/二氧化钛/氧化铝质量比:0.2/8.2/91.6)。表4显示了催化剂C的物理性质和化学组成。
(实施例4)
通过与实施例1相同的方法来制备催化剂D,不同之处在于在实施例1中改变硫酸氧钛的添加量以制备二氧化硅-二氧化钛-氧化铝水合物凝胶(二氧化硅/二氧化钛/氧化铝质量比:0.2/12.7/87.1)。表4示出了催化剂D的物理性质和化学组成。
(实施例5)
通过与实施例1相同的方法来制备催化剂E,不同之处在于使用没有添加有机添加剂的浸渍溶液。表4显示了催化剂E的物理性质和化学组成。
(实施例6)
通过与实施例1相同的方法来制备催化剂F,不同之处在于基于氧化物催化剂的质量,将碱性碳酸钴变为碱性碳酸镍作为氧化物镍。表4示出了催化剂F的物理性质和化学组成。
(比较实施例1)
通过与实施例1相同的方法来制备催化剂G,不同之处在于在制备二氧化硅-二氧化钛-氧化铝载体时的焙烧温为800℃。表5示出了催化剂G的物理性质和化学组成。
(比较实施例2)
通过与实施例1相同的方法来制备催化剂H,不同之处在于在实施例1中活性组分浸渍之后的煅烧温为650℃。表5示出了催化剂H的物理性质和化学组成。
(比较实施例3)
通过与实施例1相同的方法来制备催化剂I,不同之处在于改变硫酸氧钛的添加量以形成二氧化硅-二氧化钛-氧化铝水合物凝胶(二氧化硅/二氧化钛/氧化铝质量比:0.2/14/85.8)。表5示出了催化剂I的物理性质和化学组成。
(比较实施例4)
通过与实施例1相同的方法来制备催化剂I,不同之处在于改变硫酸氧钛的添加量以形成二氧化硅-二氧化钛-氧化铝水合物凝胶(二氧化硅/二氧化钛/氧化铝质量比:0.2/3/96.8)。表5示出了催化剂J的物理性质和化学组成。
(比较实施例5)
通过与实施例1相同的方法来制备催化剂K,不同之处在于在实施例1中不使用硫酸氧钛来形成二氧化硅-氧化铝水合物凝胶(二氧化硅/氧化铝质量比:0.2/99.8)。表6示出了催化剂K的物理性质和化学组成。
[表4]
表4.制备的催化剂1的性质
1)UV分析中K.-M值为0.3或以上时的最大波长(吸收端波长)
2)UV分析中K-M值为1.5或更小时的最大波长。
3)具有平均孔径±1.0nm的孔体积与总孔体积的比率
4)存在或不存在衍生自周期表第4族金属化合物的峰
5)存在或不存在衍生自周期表第6族金属化合物的峰
6)通过拉曼分析在100至200cm-1的波数处存在或不存在峰
[表5]
表5.制备的催化剂2的性质
1)UV分析中K.-M值为0.3或以上时的最大波长(吸收端波长)
2)UV分析中K-M值为1.5或更小时的最大波长。
3)具有平均孔径±1.0nm的孔体积与总孔体积的比率
4)存在或不存在衍生自周期表第4族金属化合物的峰
5)存在或不存在衍生自周期表第6族金属化合物的峰
6)通过拉曼分析在100至200cm-1的波数处存在或不存在峰
加氢活性测试
馏出物加氢处理测试
将实施例1至6和比较实施例1至5的催化剂中的每一种装入固定床微流反应器后,用向直馏柴油中添加二甲基二硫化物获得的硫化油进行预硫化(对应于2.5质量%的总硫含量),然后转换为表6中所列的原料,并且在表7中所列的条件下从360℃的反应温度开始每100小时升温2℃来进行加氢处理测试,以计算在操作开始后100小时和600小时基于比较实施例5的催化剂的相对脱硫活性。
相对脱硫活性是基于式(1)和(2)通过荧光X射线法测量测试中获得的各产物油的硫含量而获得的相对活性。测试结果示于表8和9中。
[表6]
表6.原料性质
[表7]
表7.活性测试条件1
式1
式2
加氢脱硫反应:k=LHSV/(n-1)x{1/Y(n_1)-1/x(n_1)} 式(2)
(其中n=1.2th)
在式中,LHSV是液时空速,k是反应速率常数,n是反应级数,X是原料中的硫质量比,Y是产物油中的硫质量比。
[表8]
表8.性能测试结果1
[表9]
表9.性能测试结果2
馏出物的加氢处理测试结果(表8和9)显示,与使用基于常规二氧化硅-氧化铝的载体的催化剂和比较实施例的催化剂相比,使用本发明的含有二氧化硅-周期表第4族金属氧化物的复合载体的加氢处理催化剂在相对活性和活性稳定性方面展现出140或更高的优异的加氢脱硫活性。
此外,由于本发明的催化剂具有高加氢脱硫活性,因此其可应用于其他加氢处理反应(加氢、加氢脱氮、加氢脱芳构化、通过加氢去除碳渣等)。
由此,可以理解,本发明的催化剂具有长的催化剂寿命,并且可以有助于提高脱硫单元操作的经济效率。
Claims (4)
1.一种用于烃油的加氢处理催化剂,其包含至少一种选自周期表第6族的金属、至少一种选自周期表第8族至第10族的金属以及任选地另外的磷和/或硼作为负载在基于氧化铝的无机多孔载体上的催化活性组分,
其中所述无机多孔载体包含相对于氧化物的质量小于1质量%的量的二氧化硅作为其构成组分和小于13质量%的量的周期表第4族的金属作为氧化物;其中所述周期表第4族的金属高度分散在所述无机多孔载体中,其分散程度通过以下来显示:通过拉曼光谱在100至200cm-1的波数范围内基本上没有观察到峰以及通过X射线衍射分析基本上没有观察到晶体;
其中所述加氢处理催化剂具有100至300m2/g的比表面积、0.2至0.5ml/g的孔体积、6至10nm的平均孔径和4.5cmVml或更大的NO吸附量作为催化特性;并且其中通过X射线衍射分析基本上没有观察到衍生自周期表第6族的金属氧化物盐的晶体。
2.根据权利要求1所述的加氢处理催化剂,其中按催化剂氧化物计,所述选自周期表第6族的金属的负载量是15质量%至30质量%,并且所述选自周期表第8族至第10族的金属的负载量是0.5质量%至5质量%。
3.根据权利要求1或2所述的加氢处理催化剂,其包含按催化剂氧化物计0.5质量%至5质量%的磷和/或硼。
4.一种烃油加氢处理方法,其中,在300至450℃的反应温度、1至20MPa的氢分压、0.1至10h1的液时空速和50至1,200Nm3/kl的氢/油比的条件下,使权利要求1至3中任一项中所公开的加氢催化剂与烃油接触)。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019091779A JP6630458B1 (ja) | 2019-05-15 | 2019-05-15 | 炭化水素油の水素化処理触媒及び当該触媒を用いる炭化水素油の水素化処理方法 |
JP2019-091779 | 2019-05-15 | ||
PCT/JP2020/018149 WO2020230630A1 (en) | 2019-05-15 | 2020-04-28 | A catalyst for hydrotreating hydrocarbon oil and a method of hydrotreating hydrocarbon oil using the catalyst |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113825564A true CN113825564A (zh) | 2021-12-21 |
Family
ID=69146716
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202080036129.1A Pending CN113825564A (zh) | 2019-05-15 | 2020-04-28 | 用于加氢处理烃油的催化剂和使用该催化剂加氢处理烃油的方法 |
Country Status (10)
Country | Link |
---|---|
US (1) | US20220203342A1 (zh) |
EP (1) | EP3969172A4 (zh) |
JP (1) | JP6630458B1 (zh) |
KR (1) | KR20220009402A (zh) |
CN (1) | CN113825564A (zh) |
AU (1) | AU2020273798A1 (zh) |
BR (1) | BR112021021884A2 (zh) |
CA (1) | CA3138845A1 (zh) |
SG (1) | SG11202111348XA (zh) |
WO (1) | WO2020230630A1 (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113075148B (zh) * | 2021-03-22 | 2023-06-16 | 久泰能源(准格尔)有限公司 | 一种mto工艺中催化剂表面碳含量的测定方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10118495A (ja) * | 1996-10-22 | 1998-05-12 | Catalysts & Chem Ind Co Ltd | チタニア−アルミナ担体とその製造方法並びにそれを使用した水素化処理触媒 |
US20150209766A1 (en) * | 2012-08-29 | 2015-07-30 | Indian Oil Corporation Ltd. | Hydrotreating catalyst and process for preparing the same |
CN105579135A (zh) * | 2013-10-11 | 2016-05-11 | 克斯莫石油株式会社 | 重质烃油的加氢处理催化剂、重质烃油的加氢处理催化剂的制造方法以及重质烃油的加氢处理方法 |
CN105754640A (zh) * | 2014-12-17 | 2016-07-13 | 中国石油化工股份有限公司 | 一种重油加氢处理方法 |
JP2016203074A (ja) * | 2015-04-20 | 2016-12-08 | 日揮触媒化成株式会社 | 炭化水素油の水素化処理触媒、その製造方法、および水素化処理方法 |
JP2018167196A (ja) * | 2017-03-30 | 2018-11-01 | Jxtgエネルギー株式会社 | 炭化水素油の水素化脱硫触媒及び水素化脱硫触媒の製造方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5013658B2 (ja) | 2004-03-11 | 2012-08-29 | Jx日鉱日石エネルギー株式会社 | 石油系炭化水素油の水素化脱硫触媒および水素化脱硫方法 |
JP5517541B2 (ja) | 2009-09-30 | 2014-06-11 | Jx日鉱日石エネルギー株式会社 | 炭化水素油の水素化脱硫触媒およびその製造方法 |
US9469580B2 (en) * | 2010-12-17 | 2016-10-18 | Exxonmobil Chemical Patents Inc. | Dehydrogenation process |
US8802587B2 (en) * | 2010-12-30 | 2014-08-12 | Chevron U.S.A. Inc. | Hydroprocessing catalysts and methods for making thereof |
JP5815321B2 (ja) * | 2011-07-29 | 2015-11-17 | コスモ石油株式会社 | 炭化水素油の水素化処理触媒、炭化水素油の水素化処理触媒の製造方法及び炭化水素油の水素化処理方法 |
JP6681259B2 (ja) * | 2016-04-25 | 2020-04-15 | 日揮触媒化成株式会社 | 炭化水素油の水素化処理触媒、その製造方法、および水素化処理方法 |
JP2018144016A (ja) * | 2017-03-09 | 2018-09-20 | 千代田化工建設株式会社 | 脱水素触媒及びその製造方法並びにそれを用いた脱水素処理方法 |
-
2019
- 2019-05-15 JP JP2019091779A patent/JP6630458B1/ja active Active
-
2020
- 2020-04-28 US US17/609,952 patent/US20220203342A1/en not_active Abandoned
- 2020-04-28 SG SG11202111348XA patent/SG11202111348XA/en unknown
- 2020-04-28 EP EP20805477.5A patent/EP3969172A4/en not_active Withdrawn
- 2020-04-28 KR KR1020217039429A patent/KR20220009402A/ko not_active Application Discontinuation
- 2020-04-28 WO PCT/JP2020/018149 patent/WO2020230630A1/en unknown
- 2020-04-28 CA CA3138845A patent/CA3138845A1/en active Pending
- 2020-04-28 AU AU2020273798A patent/AU2020273798A1/en active Pending
- 2020-04-28 BR BR112021021884A patent/BR112021021884A2/pt unknown
- 2020-04-28 CN CN202080036129.1A patent/CN113825564A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10118495A (ja) * | 1996-10-22 | 1998-05-12 | Catalysts & Chem Ind Co Ltd | チタニア−アルミナ担体とその製造方法並びにそれを使用した水素化処理触媒 |
US20150209766A1 (en) * | 2012-08-29 | 2015-07-30 | Indian Oil Corporation Ltd. | Hydrotreating catalyst and process for preparing the same |
CN105579135A (zh) * | 2013-10-11 | 2016-05-11 | 克斯莫石油株式会社 | 重质烃油的加氢处理催化剂、重质烃油的加氢处理催化剂的制造方法以及重质烃油的加氢处理方法 |
CN105754640A (zh) * | 2014-12-17 | 2016-07-13 | 中国石油化工股份有限公司 | 一种重油加氢处理方法 |
JP2016203074A (ja) * | 2015-04-20 | 2016-12-08 | 日揮触媒化成株式会社 | 炭化水素油の水素化処理触媒、その製造方法、および水素化処理方法 |
JP2018167196A (ja) * | 2017-03-30 | 2018-11-01 | Jxtgエネルギー株式会社 | 炭化水素油の水素化脱硫触媒及び水素化脱硫触媒の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JP2020185534A (ja) | 2020-11-19 |
JP6630458B1 (ja) | 2020-01-15 |
WO2020230630A1 (en) | 2020-11-19 |
US20220203342A1 (en) | 2022-06-30 |
AU2020273798A1 (en) | 2021-12-23 |
SG11202111348XA (en) | 2021-11-29 |
EP3969172A1 (en) | 2022-03-23 |
BR112021021884A2 (pt) | 2021-12-28 |
CA3138845A1 (en) | 2020-11-19 |
KR20220009402A (ko) | 2022-01-24 |
EP3969172A4 (en) | 2023-01-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10507458B2 (en) | Hydrotreating catalyst and process for preparing the same | |
JP6378902B2 (ja) | 水素化処理触媒、当該触媒の製造方法、並びに当該触媒を用いる炭化水素油の水素化処理方法 | |
JP5635752B2 (ja) | 水素化処理触媒の製造方法、並びに当該触媒を用いる炭化水素油の水素化処理方法 | |
CN107530695B (zh) | 基于γ-酮基戊酸的催化剂及其在加氢处理和/或加氢裂化方法中的用途 | |
JP6706629B2 (ja) | γ−バレロラクトンおよび/またはその加水分解生成物をベースとする触媒および水素化処理および/または水素化分解の方法におけるその使用 | |
US7538066B2 (en) | Method of preparing a hydrotreating catalyst on a support containing a rare earth metal | |
RU2715424C2 (ru) | Катализатор гидроочистки, содержащий металлоорганические сульфиды на легированных носителях | |
US20040182749A1 (en) | Catalyst composition preparation and use | |
CA2289692A1 (en) | Catalyst for hydrogenation treatment and method for hydrogenation treatment of hydrocarbon oil | |
CN113825564A (zh) | 用于加氢处理烃油的催化剂和使用该催化剂加氢处理烃油的方法 | |
EP2723494B1 (en) | Method of making a hydroprocessing catalyst | |
JP4245226B2 (ja) | 水素化処理用触媒およびこれを使用する炭化水素油の水素化処理方法 | |
JP6454708B2 (ja) | 触媒の調製方法、触媒および水素化転化および/または水素化処理の方法におけるその使用 | |
KR20190040206A (ko) | 극성 첨가제-함유 수소화처리 촉매, 그의 제조방법 및 용도 | |
CA3204573A1 (en) | High activity hydrotreating catalysts and processes using same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20211221 |
|
WD01 | Invention patent application deemed withdrawn after publication |