CN116917038A - 多金属本体加氢加工催化剂 - Google Patents
多金属本体加氢加工催化剂 Download PDFInfo
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- CN116917038A CN116917038A CN202180094726.4A CN202180094726A CN116917038A CN 116917038 A CN116917038 A CN 116917038A CN 202180094726 A CN202180094726 A CN 202180094726A CN 116917038 A CN116917038 A CN 116917038A
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- Prior art keywords
- bulk catalyst
- acid
- precursor
- catalyst precursor
- containing precursor
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- GRWPYGBKJYICOO-UHFFFAOYSA-N 2-methylpropan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] GRWPYGBKJYICOO-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MYGIQXSVMRAVKX-UHFFFAOYSA-I O.C(C(=O)[O-])(=O)[O-].[Nb+5].[NH4+].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-] Chemical compound O.C(C(=O)[O-])(=O)[O-].[Nb+5].[NH4+].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-] MYGIQXSVMRAVKX-UHFFFAOYSA-I 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910004353 Ti-Cu Inorganic materials 0.000 description 1
- 241001399594 Venator Species 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- IFMWVBVPVXRZHE-UHFFFAOYSA-M chlorotitanium(3+);propan-2-olate Chemical compound [Cl-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-] IFMWVBVPVXRZHE-UHFFFAOYSA-M 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000009 copper(II) carbonate Inorganic materials 0.000 description 1
- 229910000153 copper(II) phosphate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 description 1
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 235000019854 cupric carbonate Nutrition 0.000 description 1
- 239000011646 cupric carbonate Substances 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000011737 fluorine Chemical group 0.000 description 1
- 229910052731 fluorine Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- IYFXESRMJKRSNZ-UHFFFAOYSA-L hydrogen carbonate;nickel(2+) Chemical compound [Ni+2].OC([O-])=O.OC([O-])=O IYFXESRMJKRSNZ-UHFFFAOYSA-L 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011630 iodine Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229960001855 mannitol Drugs 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
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate 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
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 1
- CGAFRZVAXRQUEI-UHFFFAOYSA-N niobium(5+);propan-1-olate Chemical compound [Nb+5].CCC[O-].CCC[O-].CCC[O-].CCC[O-].CCC[O-] CGAFRZVAXRQUEI-UHFFFAOYSA-N 0.000 description 1
- LZRGWUCHXWALGY-UHFFFAOYSA-N niobium(5+);propan-2-olate Chemical compound [Nb+5].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] LZRGWUCHXWALGY-UHFFFAOYSA-N 0.000 description 1
- DSYRJFDOOSKABR-UHFFFAOYSA-I niobium(v) bromide Chemical compound [Br-].[Br-].[Br-].[Br-].[Br-].[Nb+5] DSYRJFDOOSKABR-UHFFFAOYSA-I 0.000 description 1
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol 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
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229960002920 sorbitol Drugs 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 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
- 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
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also 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
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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Abstract
提供了多金属本体催化剂及用于合成该多金属本体催化剂的方法。所述多金属本体催化剂含有镍、钼、钨、铌和任选地,钛和/或铜。所述催化剂可用于烃原料的加氢加工,特别是加氢脱硫和加氢脱氮。
Description
相关申请的交叉引用
本申请要求于2021年2月16日提交的美国临时申请号63/149,736的优先权权益,其公开内容以引用方式并入本文。
技术领域
本公开涉及用于烃原料加氢加工(hydroprocessing)的多金属本体催化剂,以及用于制备此类催化剂的工艺。
背景技术
烃原料的加氢加工通常包括其中烃原料与氢在催化剂存在下和在加氢加工条件下,通常在高温和高压下反应的所有工艺。加氢加工包括诸如加氢脱硫、加氢脱氮、加氢脱氧、加氢脱金属、加氢脱芳构化、氢化、氢解、加氢处理(hydrotreating)、加氢异构化和加氢裂化的工艺。
加氢加工催化剂通常包含位于耐火载体(诸如氧化铝)上的一种或多种硫化的第6族金属与一种或多种作为促进剂的第8至10族非贵金属。特别适用于加氢脱硫以及加氢脱氮的加氢加工催化剂通常包含用金属诸如钴、镍、铁或它们的组合促进的硫化钼或硫化钨。
除了负载催化剂之外,使用本体催化剂(也称为“非负载”催化剂)的加氢加工也是已知的。尽管本体加氢加工催化剂组合物相对于常规负载加氢加工催化剂具有相对高的催化活性,但是在本领域中仍然需要开发具有进一步改善的加氢加工活性的新型本体催化剂组合物。
发明内容
在第一方面,提供了一种本体催化剂前体,其包含:(a)基于金属氧化物计1wt.%至60wt.%的Ni;(b)基于金属氧化物计1wt.%至40wt.%的Mo;(c)基于金属氧化物计5wt.%至80wt.%的W;(d)基于金属氧化物计0.01wt.%至20wt.%的Nb;(e)基于金属氧化物计0wt.%至45wt.%的Ti;和(f)基于金属氧化物计0wt.%至10wt.%的Cu。
在第二方面,提供了一种硫化的本体催化剂,其特征在于其是已经硫化的本文所述的本体催化剂前体。
在第三方面,提供了一种用于制备本文所述的本体催化剂前体的方法,该方法包括:(a)将以下组合在反应混合物中:(i)含Ni前体;(ii)含Mo前体;(iii)含W前体;(iv)含Nb前体;(v)任选地,含Ti前体和/或含Cu前体;(vi)任选地,基于有机化合物的组分;和(vii)质子液体;以及(b)使该混合物在足以引起该本体催化剂前体沉淀的条件下反应;其中制备本体催化剂前体的步骤在不超过200℃的温度下进行。
在第四方面,提供了一种用于制备本文所述的本体催化剂前体的方法,该方法包括:(a)将以下组合在反应混合物中:(i)含Ni前体;(ii)含Mo前体;(iii)含W前体;(i)含Nb前体;(v)任选地,含Cu前体;(vi)任选地,基于有机化合物的组分;和(vii)质子液体;以及(b)使该混合物在足以导致中间体本体催化剂前体沉淀的条件下反应;以及(c)将该中间体本体催化剂前体与含Ti前体复合,以形成本体催化剂前体;其中制备该本体催化剂前体的步骤在不超过200℃的温度下进行。
在第五方面,提供了一种用于加氢加工烃原料的工艺,该工艺包括在本体催化剂存在下在加氢加工条件下使烃原料与氢气接触以得到至少一种产物,其中本体催化剂衍生自或可衍生自催化剂前体,该催化剂前体包含:(a)基于金属氧化物计1wt.%至60wt.%的Ni;(b)基于金属氧化物计1wt.%至40wt.%的Mo;(c)基于金属氧化物计5wt.%至80wt.%的W;(d)基于金属氧化物计0.01wt.%至20wt.%的Nb;和(e)基于金属氧化物计0wt.%至45wt.%的Ti;以及(f)基于金属氧化物计0wt.%至10wt.%的Cu。
具体实施方式
定义
当描述混合的金属催化剂组合物时,术语“本体(bulk)”可与“未负载”互换使用,意指催化剂组合物不属于常规催化剂形式,该常规催化剂形式具有预形成的成形催化剂载体,该催化剂载体然后通过浸渍或沉积催化剂而装载有金属。
术语“大气压力”在本文中用于描述其中不使用外部压力调节装置的地球空气压力。通常,除非在极端地球海拔高度下实践,否则“大气压力”为约1个大气压(可替代地,约14.7psi或约101kPa)。
除非另外指明,否则术语“重量百分比”和“wt.%”可互换使用,表示基于组合物的总重量的给定组分的重量百分比。即,除非另有说明,所有wt.%值都是基于组合物的总重量。应当理解,所公开的组合物或制剂中所有组分的wt.%值的总和等于100。
本体催化剂和本体催化剂前体
提供了包含Ni、Mo、W、Nb和任选的Ti和/或Cu的氧化物的多金属本体催化剂前体组合物。在用于加氢加工之前,催化剂前体可被硫化,这将金属转化成金属硫化物。在硫化之后,组合物对应于/被定义为用于所附权利要求的目的的“催化剂”。
本体催化剂和/或相应的本体催化剂前体包含镍(Ni)、钼(Mo)、钨(W)、铌(Nb)以及任选的钛(Ti)和/或铜(Cu)金属。本体催化剂和/或相应的本体催化剂前体可含有基于金属氧化物计1wt.%至60wt.%,诸如5wt.%至40wt.%或20wt.%至60wt.%的Ni;基于金属氧化物计1wt.%至40wt.%,诸如1wt.%至25wt.%或3wt.%至20wt.%的Mo;基于金属氧化物计5wt.%至80wt.%,诸如10wt.%至35wt.%或20wt.%至75wt.%的W;基于金属氧化物计0.01wt.%至20wt.%,诸如0.1wt.%至20wt.%或1wt.%至20wt.%的Nb;基于金属氧化物计0wt.%至45wt.%,诸如2wt.%至45wt.%、5wt.%至40wt.%、10wt.%至35wt.%或20wt.%至30wt.%的Ti;以及基于金属氧化物计0wt.%至10wt.%,诸如0.01wt.%至10wt.%、0.1wt.%至10wt.%或1wt.%至10wt.%的Cu。因此,本文公开的本体催化剂具有命名Ni-Mo-W-Nb、Ni-Mo-W-Nb-Ti、Ni-Mo-W-Nb-Cu或Ni-Mo-W-Nb-Ti-Cu,其中每种金属以上文指定的量存在。
本体催化剂和/或相应的本体催化剂前体中金属的摩尔比原则上可在很宽的范围内变化。本体催化剂和/或相应的本体催化剂前体中Nb/(Ni+Mo+W+Ti+Cu)的摩尔比可在10:1至1:10或3:1至1:3的范围内。本体催化剂和/或相应的本体催化剂前体中Ni/W的摩尔比可在10:1至1:10的范围内。本体催化剂和/或相应的催化剂前体中W/Mo的摩尔比可在100:1至1:100的范围内。
本体催化剂前体是氢氧化物并且可被表征为具有以下化学式:
Av[Ni1-a-bNbaCub(OH)x(L)p y]z[MomW1-mO4][Ti(OH)nO2-n/2]w
其中:(i)A是碱金属阳离子、稀土金属阳离子、铵阳离子、有机铵阳离子、鏻阳离子或它们的组合;(ii)L是基于有机化合物的组分;并且(iii)0<a<1;0≤b<1;a+b<1;0<y≤2/p;0≤x<2;0≤v<2;0<z;0<m<1;0<n<4;0<w/(z+1)<10。
在通过硫化形成本体催化剂之前,本体催化剂前体可包含至少55wt.%(至少60wt.%、至少70wt.%、至少80wt.%或至少90wt.%)的Ni、Mo、W和Nb的氧化物。在任何方面,本体催化剂和/或相应的本体催化剂前体可含有40wt.%或更少的粘合剂材料。可添加粘合剂材料以改善催化剂的物理和/或热特性。
本体催化剂和/或相应的本体催化剂前体还可以包含基于有机化合物的组分,该基于有机化合物的组分可基于或衍生自用于制备本体催化剂和/或相应的本体催化剂前体的至少一种有机络合剂。当存在基于有机化合物的组分时,组合物中的镍与基于有机化合物的组合物的摩尔比可在3:1至20:1的范围内。
本体催化剂和/或相应的本体催化剂前体可具有至少20m2/g、至少50m2/g、至少75m2/g、至少100m2/g的BET比表面积。在任何方面,自负载催化剂和/或相应的自负载催化剂前体可具有250m2/g或更小、200m2/g或更小、175m2/g或更小、150m2/g或更小,或125m2/g或更小的BET表面积。BET比表面积的以上下限中的每一个下限均明确地与以上上限中的每一个上限结合考虑。术语“BET比表面积”是指如根据S.Brunauer、P.H.Emmett和E.Teller(J.Am.Chem.Soc.1938,60,309-331)的方法由氮吸附数据确定的比表面积。
本体催化剂和/或相应的本体催化剂前体可具有至少0.02cm3/g、至少0.03cm3/g、至少0.04cm3/g、至少0.05cm3/g、至少0.06cm3/g、至少0.08cm3/g、至少0.09cm3/g、至少0.10cm3/g、至少0.11cm3/g、至少0.12cm3/g、至少0.13cm3/g、至少0.14cm3/g、至少0.15cm3/g的孔体积。在任何方面,自负载催化剂和/或相应的自负载催化剂前体可具有0.80cm3/g或更小、0.70cm3/g或更小、60cm3/g或更小、50cm3/g或更小、0.45cm3/g或更小、0.40cm3/g或更小、0.35cm3/g或更小、0.30cm3/g或更小的孔体积。孔体积的以上下限中的每一个下限均明确地与以上上限中的每一个上限结合考虑。孔体积是根据E.P.Barrett、L.G.Joyner和P.P.Halenda(J.Am.Chem.Soc.1951,73,373-380)所述的程序由氮吸附数据确定的。
本体催化剂和/或相应的本体催化剂前体可具有至少1.00g/cm3(例如,至少1.10g/cm3、至少1.20g/cm3、至少1.30g/cm3、至少1.40g/cm3、至少1.50g/cm3或至少1.60g/cm3)的颗粒密度。在任何方面,自负载催化剂和/或相应的自负载催化剂前体可具有3.00g/cm3或更小(例如,2.90g/cm3或更小、2.80g/cm3或更小、2.70g/cm3或更小、2.60g/cm3或更小、2.50g/cm3或更小,或2.40g/cm3或更小、2.30g/cm3或更小,或2.20g/cm3或更小)的颗粒密度。颗粒密度的以上下限中的每一个下限均明确地与以上上限中的每一个上限结合考虑。通过应用公式D=M/V获得颗粒密度(D),其中M是催化剂样品的重量,并且V是催化剂样品的体积。该体积是通过在28mm Hg真空下将样品浸入到汞中测量体积位移来确定的。
本体催化剂和/或相应的本体催化剂前体可通过粉末X射线衍射被表征为具有低强度的宽衍射峰的结晶性差的材料。如本文所用,宽衍射峰意指半峰全宽(full width athalf maximum,FWHM)大于1°(2θ标度)的峰。
本体催化剂和催化剂前体的制备
本发明的本体催化剂前体是氢氧化物,并且通过其中在硫化形成本体催化剂之前的步骤在不超过200℃的温度下进行并且其中催化剂前体在硫化形成体催化剂之前保持为氢氧化物的方法制备。
在一个方面,制备本体催化剂前体的第一步骤是沉淀或共胶凝步骤,其涉及使反应混合物中呈溶液形式的镍和铌前体化合物与呈溶液形式的钼和钨前体化合物反应,以获得沉淀物或共凝胶。在金属前体沉淀或形成共凝胶的温度和pH下进行沉淀或共胶凝。
当存在钛时,可通过原位或异位途径引入钛。在原位途径中,可将含钛前体化合物添加到反应混合物中,以在Ni-Mo-W-Nb氧化物或Ni-Mo-W-Nb-Cu氧化物的共沉淀或共胶凝期间使钛沉淀。在异位途径中,可将一种或多种钛前体化合物与Ni-Mo-W-Nb氧化物或Ni-Mo-W-Nb-Cu氧化物的沉淀物或共凝胶复合。
在任何方面,钛的原位添加可包括:(a)将以下组合在反应混合物中:(i)含Ni前体;(ii)含Mo前体;(iii)含W前体;(iv)含Nb前体;(v)含Ti前体;(vi)任选地,含Cu前体;(vii)任选地,基于有机化合物的组分;和(viii)质子液体;以及(b)使该混合物在足以导致该本体催化剂前体沉淀的条件下反应。该反应混合物可通过以下方法获得:(1)制备第一混合物,其包含含Ni前体、含Nb前体、任选的含Cu前体、质子液体和任选的基于有机化合物的组分;(2)制备第二混合物,其包含含Mo前体、含W前体和质子液体;(3)将含Ti前体添加到第一混合物、第二混合物或它们的组合中;(4)将第一混合物和第二混合物均加热至60℃至150℃的温度;(5)将第一混合物和第二混合物组合在一起。在反应步骤之后,如果需要,可例如通过过滤或喷雾干燥将获得的本体催化剂前体与液体分离。
在任何方面,钛的异位添加可包括:(a)将以下组合在反应混合物中:(i)含Ni前体;(ii)含Mo前体;(iii)含W前体;(i)含Nb前体;(v)任选地,含Cu前体;(vi)任选地,基于有机化合物的组分;和(vii)质子液体;以及(b)使该混合物在足以导致中间体本体催化剂前体沉淀的条件下反应;以及(c)将该中间体本体催化剂前体与含Ti前体复合,以形成本体催化剂前体。该反应混合物可通过以下方法获得:(1)制备第一混合物,其包含含Ni前体、含Nb前体、任选的含Cu前体、质子液体和任选的基于有机化合物的组分;(2)制备第二混合物,其包含含Mo前体、含W前体和质子液体;(3)将第一混合物和第二混合物均加热至60℃至150℃的温度;以及(4)将第一混合物和第二混合物组合在一起。在反应步骤之后,如果需要,可例如通过过滤或喷雾干燥将获得的中间体本体催化剂与液体分离。
形成催化剂前体的温度可在60℃至150℃的范围内。如果温度低于质子液体的沸点,诸如在水的情况下为100℃,则该工艺通常在大气压力下进行。该反应也可以在其中反应温度高于质子液体的沸点温度的水热条件下进行。通常,此类条件产生高于大气压力的压力,并且然后该反应优选地在高压釜中,优选地在自生压力下(即在不施加附加的压力的情况下)进行。高压釜是设计用于将液体加热至其沸点温度以上的能够承受压力的装置。在任何方面,本体催化剂前体形成工艺在(a)大气压力下50℃至100℃范围内或(b)自生压力下高于100℃的一个或多个温度下进行。
在大气和水热反应条件下的反应时间都要被选择得足够长以基本上完成反应。该反应时间可以非常短(例如,对于高反应性反应物,短于1小时)。显然,具有低反应性的原材料可能需要更长的反应时间,也许长达24小时。在一些情况下,反应时间可以与温度成反比地变化。
通常,反应混合物在反应步骤期间被保持在其天然pH下。该pH可被维持在0至12(例如,3至9,或5至8)的范围内。可改变该pH以提高或降低沉淀或共胶凝的速率,这取决于产物的所需特征。
可将金属前体以溶液、悬浮液或它们的组合的形式添加到反应混合物中。如果如此添加可溶性盐,则它们将溶解在反应混合物中,并随后被沉淀或共胶凝。
含Mo前体化合物的代表性实例包括(二和三)氧化钼、钼酸、碱金属钼酸盐(例如钼酸钠、钼酸钾)、钼酸铵(例如钼酸铵、二钼酸铵、七钼酸铵)和杂多钼酸盐(例如硅钼酸、磷钼酸)。
含W前体化合物的代表性实例包括(二和三)氧化钨、钨酸、碱金属钨酸盐(例如钨酸钠、钨酸钾、偏钨酸钠、多钨酸钠)、钨酸铵(例如钨酸铵、偏钨酸铵、仲钨酸铵)和杂多钨酸盐(例如硅钨酸、磷钨酸)。
含Ni前体化合物的代表性实例包括乙酸镍、乙酰丙酮镍、溴化镍、碳酸镍、羟基碳酸镍、碳酸氢镍、氯化镍、硝酸镍和硫酸镍。
含Nb前体化合物的代表性实例包括草酸铌、草酸铌铵、氯化铌、溴化铌、乙醇铌、正丙醇铌和异丙醇铌。
含Cu前体化合物的代表性实例包括乙酸铜(II)、乙酰丙酮铜(II)、氢氧化铜(II)、氯化铜(II)、溴化铜(II)、碳酸铜(II)、硝酸铜(II)、磷酸铜(II)和硫酸铜(ii)。
适用于制备本文所述类型的本体催化剂的任何含钛化合物可用作含Ti前体化合物。含Ti前体可包含含四价钛(Ti4+)化合物、含三价钛(Ti3+)化合物或它们的组合。
代表性的含钛前体化合物包括TiO2纳米颗粒、胶体TiO2、热解TiO2、氢氧化钛、有机钛化合物、卤化钛和水溶性钛盐。
二氧化钛纳米颗粒可以是任何类型的二氧化钛。二氧化钛可具有高含量的锐钛矿和/或金红石。例如,二氧化钛可包含至少50重量%、55重量%、60重量%、65重量%、70重量%、75重量%、80重量%、85重量%、90重量%、95重量%、98重量%或甚至至少99重量%的锐钛矿和/或金红石。在一些实施方案中,二氧化钛基本上由锐钛矿和/或金红石组成。二氧化钛颗粒优选地具有小于100nm(例如,3nm至50nm)的中值粒度(D50)。氧化钛纳米颗粒可作为通过分散在分散剂中制备的溶胶、作为含水或含溶剂的糊剂或作为粉末引入到组合物中。用于制备溶胶的分散剂的实例包括水、醇(例如,甲醇、乙醇、异丙醇、正丁醇、异丁醇)和酮(例如,甲基乙基酮、甲基异丁基酮)。
代表性的有机钛化合物包括通用结构Ti(OR)4的钛醇盐,其中每个R独立地为C1-C4烷基和钛酰基化合物。代表性的钛醇盐包括四甲醇钛、四乙醇钛、四正丙醇钛、四异丙醇钛、四正丁醇钛和四叔丁醇钛。代表性的钛酰基化合物包括乙酰丙酮钛、乙酰丙酮氧钛(titani um oxyacetylacetonate)和乙酸钛。其他代表性的有机钛化合物包括由通式Ti(OR’)2(acac)2表示的那些,其中每个R'独立地为C1-C4烷基且“acac”为乙酰丙酮根(acetylacetonate)。
由式TiX4或TiX3表示的卤化钛可用作钛前体,其中X为氯、溴、碘或氟或它们的混合物。在一个方面,卤化钛是四氯化钛、四溴化钛或它们的组合。
本公开还考虑了使用有机钛卤化物诸如三异丙醇氯化钛[Ti(O-i-Pr)3Cl]等作为含Ti前体化合物。
代表性的水溶性钛盐包括硝酸钛和硫酸钛。
基于有机化合物的组分可以是适于在溶液中形成金属-配体络合物的有机化合物。基于有机化合物的组分可选自有机酸或其盐、糖、糖醇或它们的组合。
代表性的有机酸包括乙醛酸、丙酮酸、乳酸、丙二酸、草酰乙酸、苹果酸、富马酸、马来酸、酒石酸、葡糖酸、柠檬酸、草氨酸、丝氨酸、天冬氨酸、谷氨酸、亚氨基二乙酸、乙二胺四乙酸等。
代表性的糖包括果糖、葡萄糖、半乳糖、甘露糖、蔗糖、乳糖、麦芽糖等,以及它们的衍生物。
代表性的糖醇包括赤藓糖醇、木糖醇、甘露糖醇、山梨糖醇等,以及它们的衍生物。
质子液体可以是不干扰金属化合物反应的任何质子液体。实例包括水、羧酸和醇(例如甲醇、乙醇、乙二醇)。质子液体可以是单独的水或水与醇的混合物。
附加加工
本体催化剂前体在用于加氢加工工艺之前可经受以下工艺步骤中的一个或多个工艺步骤:(i)与选自粘合剂材料、常规加氢加工催化剂、裂化化合物或它们的混合物的组的材料复合;(ii)喷雾干燥、(闪蒸)干燥、研磨、捏合、浆料混合、干混或湿混,或它们的组合;(iii)成形;(iv)干燥和/或热处理;以及(v)硫化。将这些工艺步骤列为(i)至(v)只是为了方便;并不是说这些工艺被限制为以这种顺序执行。下面将更详细地解释这些工艺步骤。
附加工艺步骤(i)-与此外的材料复合
如果需要,可在上文所述的本体催化剂前体的制备期间或本体催化剂前体的制备之后添加选自粘合剂材料、常规加氢加工催化剂、裂化化合物或它们的混合物的组的附加材料。优选地,该材料在本体催化剂前体制备之后并且在喷雾干燥或任何替代技术之前添加,或者,如果不应用喷雾干燥或替代技术,则该材料在成形之前添加。任选地,如上文所述制备的本体金属前体可在与该材料复合之前经受固液分离。在固液分离之后,任选地,可包括洗涤步骤。进一步地,可以在任选的固液分离和干燥步骤之后并且在与该材料复合之前对本体催化剂颗粒进行热处理。
在所有上文所述的工艺的替代方案中,短语“将本体催化剂前体与材料复合”意指将材料添加到本体金属颗粒中,反之亦然,并将所得组合物混合。混合优选地在液体存在下进行(“湿混”)。这改善了最终本体催化剂组合物的机械强度。
在催化剂前体的制备期间将本体催化剂前体与附加的材料复合和/或掺入该材料可获得机械强度特别高的本体催化剂,特别是如果本体金属颗粒的中值粒度在至少0.5μm(例如,至少1μm、至少约2μm)但不大于5000μm(例如,不大于1000μm、不大于500μm、不大于150μm)的范围内。催化剂前体的中值粒度可在1μm至150μm(例如,2μm至150μm)的范围内。
本体金属颗粒与材料的复合导致本体金属颗粒嵌入在此材料中,反之亦然。通常,本体金属颗粒的形貌在所得本体催化剂组合物中基本上得到维持。
待施用的粘合剂材料可以是在加氢加工催化剂中常规用作粘合剂的任何材料。实例为二氧化硅、二氧化硅-氧化铝(例如常规二氧化硅-氧化铝、二氧化硅包覆的氧化铝和氧化铝包覆的二氧化硅)、氧化铝(例如勃姆石、假勃姆石或三水铝石)、二氧化钛、二氧化钛包覆的氧化铝、氧化锆、水滑石或它们的混合物。优选的粘合剂是二氧化硅、二氧化硅-氧化铝、氧化铝、二氧化钛、二氧化钛包覆的氧化铝、氧化锆、膨润土或它们的混合物。这些粘合剂可以原样施用或在胶溶后施用。
如果氧化铝用作粘合剂,则氧化铝的表面积可在50至600m2/g(例如,100至450m2/g)的范围内,如通过BET方法所测量。氧化铝的孔体积可在0.1至1.5cm3/g的范围内,如通过氮吸附所测量。
通常,待添加的粘合剂材料具有比本体金属颗粒低的催化活性或根本没有催化活性。总组合物的0wt.%至40wt.%的粘合剂量可以是合适的,这取决于设想的催化应用。然而,为了利用本公开的本体金属颗粒的所得高活性,待添加的粘合剂量通常在总组合物的0.1wt.%至30wt.%(例如,1wt.%至20wt.%、3wt.%至20wt.%或4至12wt.%)的范围内。
附加工艺步骤(ii)-喷雾干燥、(闪蒸)干燥、研磨、捏合、浆料混合、干混或湿混
任选地包含以上(此外的)材料中的任何材料的本体催化剂前体可经受喷雾干燥、(闪蒸)干燥、研磨、捏合、浆料混合、干混或湿混,或它们的组合,其中优选湿混和捏合或浆料混合和喷雾干燥的组合。
这些技术可在添加以上(此外的)材料中的任何材料(如果有的话)之前或之后、在固液分离之后、在热处理之前或之后以及在再润湿之后应用。
优选地,催化剂前体既与以上材料中的任何材料复合又经受以上技术中的任何技术。据信,通过应用上文所述的喷雾干燥、(闪蒸)干燥、研磨、捏合、浆料混合、干混或湿混或它们的组合的技术中的任一种,催化剂前体颗粒与以上材料中的任何材料之间的混合程度得到改善。这适用于在应用上文所述的方法中的任何方法之前以及之后添加材料的情况。然而,通常优选地在步骤(ii)之前添加材料。如果在步骤(ii)之后添加材料,则可在任何此外的工艺步骤(诸如成形)之前通过任何常规技术充分混合所得组合物。喷雾干燥的优点是当应用此技术时不会产生废水流。
喷雾干燥可在100℃至200℃(例如120℃至180℃)的出口温度下进行。
干混意指将呈干燥状态的催化剂前体颗粒与呈干燥状态的以上材料中的任何材料混合。湿混通常包括将包含催化剂前体颗粒的湿滤饼与任选的作为粉末或湿滤饼的以上材料中的任何材料混合,以形成它们的均匀糊剂。
附加工艺步骤(iii)-成形
如果需要,任选地包含以上(此外的)材料中的任何材料的本体催化剂前体可任选地在已经应用步骤(ii)之后被成形。成形包括挤出、造粒、成珠(beading)和/或喷雾干燥。应注意,如果本体催化剂组合物要应用于浆料型反应器、流化床、移动床或膨胀床中,则通常应用喷雾干燥或成珠。对于固定床或沸腾床(ebullating bed)应用,通常将本体催化剂组合物挤出、造粒和/或成珠。在后一种情况下,在成形步骤之前或期间的任何阶段,可添加常规用于促进成形的任何添加剂。这些添加剂可包括硬脂酸铝、表面活性剂、石墨、淀粉、甲基纤维素、膨润土、聚乙二醇、聚环氧乙烷或它们的混合物。进一步地,当氧化铝用作粘合剂时,可能需要在成形步骤之前添加酸诸如硝酸,以使氧化铝胶溶并提高挤出物的机械强度。
如果成形包括挤出、成珠和/或喷雾干燥,则优选地成形步骤在诸如水的液体的存在下进行。对于挤出和/或成珠,成形混合物中液体的量(用烧失量(loss-on-ignition)表示)可在20%至80%的范围内。
附加工艺步骤(iv)-干燥和/或热处理
在任选的干燥步骤(优选地高于100℃)之后,如果需要,可对所得的成形本体催化剂组合物进行热处理。然而,热处理对于本公开的工艺不是必需的。根据本公开的“热处理”是指在100℃至200℃的温度下在惰性气体诸如氮气中或在含氧气体诸如空气或纯氧中进行的持续从0.5小时至48小时不等的时间的处理。热处理可在水蒸汽的存在下进行。
在所有以上工艺步骤中,必须控制液体的量。如果在使本体催化剂组合物经受喷雾干燥之前液体的量过低,则必须添加附加的液体。相反,如果在挤出本体催化剂组合物之前液体的量太高,则必须使用固-液分离技术诸如过滤、倾析或蒸发来减少液体的量,并且如果必要,可将所得材料干燥并随后再润湿至一定程度。对于所有以上工艺步骤,适当地控制液体的量在本领域技术人员的能力范围内。
附加工艺步骤(v)-硫化
四金属本体催化剂通常以其硫化形式使用。催化剂硫化可以以有效制备呈硫化物形式的催化剂的任何方式(包括常规硫化方法)进行。硫化可通过使催化剂前体直接在其制备之后或在附加的工艺步骤(i)-(iv)中的任一个工艺步骤之后与含硫化合物诸如元素硫、硫化氢、二甲基二硫化物或者有机或无机多硫化物接触来进行。硫化步骤可在液相和气相中进行。
硫化通常可以原位和/或异位进行。优选地,硫化是原位进行的(即,硫化在本体催化剂前体组合物被装载到加氢加工单元中之后在加氢加工反应器中进行)。
在加氢加工中的用途
本公开的本体催化剂前体特别可用于加氢加工烃原料。加氢加工包括诸如加氢脱硫、加氢脱氮、加氢脱金属、加氢脱芳构化、氢化、氢解、加氢处理、加氢异构化和加氢裂化的工艺。
可根据本公开对广泛范围的石油和化学烃原料进行加氢加工。烃原料包括从原油(crude petroleum oil)、从焦油砂、从煤液化、从页岩油和从烃合成获得或衍生的那些,诸如还原原油、加氢裂化油、提余油(raffinate)、经加氢处理的油、常压和减压瓦斯油、焦化瓦斯油、常压和减压渣油、脱沥青油、脱蜡油、疏松蜡、费托蜡(Fischer-Tropsch wax)、生物可再生原料以及它们的混合物。合适的原料范围为从相对轻质的馏出物馏分到重质原料,诸如瓦斯油、润滑油和渣油。轻质馏出物原料的实例包括石脑油(典型的沸程为约25℃至约210℃)、柴油(典型的沸程为约150℃至约400℃)、煤油或喷气燃料(典型的沸程为约150℃至约250℃)等。重质原料的实例包括真空(或重质)瓦斯油(典型的沸程为约315℃至约610℃)、提余油、润滑油、循环油、蜡油等。优选的烃原料具有约150℃至约650℃(例如,约150℃至约450℃)的沸程。
加氢加工条件可包括200℃至450℃,或315℃至425℃的温度;250psig至5000psig(1.7MPa至34.6MPa),或300psig至3000psig(2.1MPa至20.7MPa)的压力;0.1至10h-1,或0.5至5h-1的液时空速(LHSV);以及100SCF/B至15,000SCF/B(17.8m3/m3至2672m3/m3),或500SCF/B至10,000SCF/B(89m3/m3至1781m3/m3)的氢气速率。
根据本公开的加氢加工可在一个或多个反应区中使用任何合适的反应器系统诸如一个或多个固定床、移动床或流化床反应器来实施。固定床反应器可包括一个或多个容器、在每个容器中的单个或多个催化剂床,以及在一个或多个容器中的加氢加工催化剂的各种组合。
实施例
以下说明性实施例旨在为非限制性的。
实施例1(比较)
本体催化剂前体的合成
[Ni(2.5)-Mo(1)-W(1)]
溶液A的制备:将45g七钼酸铵和72g偏钨酸铵添加到4L烧瓶中的2000g去离子水中。用氨水将pH调节至9.8。然后将溶液加热至80℃。
溶液B的制备:在单独的500mL烧杯中,将184.5g硝酸镍和10.1g马来酸溶解到100g去离子水中。在15分钟内将溶液B添加到溶液A中。在添加期间监测pH。一添加溶液B就形成绿色沉淀。添加后最终pH为6.0至7.0。将浆料在80℃下老化4小时。老化后,通过过滤回收产物,将产物用去离子水洗涤,并在烘箱中在130℃下干燥。
实施例2(比较)
本体催化剂前体的合成
[Ni(7.5)-Mo(1)-W(3)]
溶液A的制备:将10.4g七钼酸铵和44.8g偏钨酸铵添加到4L烧瓶中的2000g去离子水中。用氨水将pH调节至9.8。然后将溶液加热至80℃。
溶液B的制备:在单独的500mL烧杯中,将128.3g硝酸镍和5.8g马来酸溶解到100g去离子水中。
在15分钟内将溶液B添加到溶液A中。在添加期间监测pH。一添加溶液B就形成绿色沉淀。添加后最终pH为6.0至7.0。将浆料在80℃下老化4小时。老化后,通过过滤回收产物,将产物用去离子水洗涤,并在烘箱中在130℃下干燥。
实施例3(比较)
本体催化剂前体的合成
[Ni(3.8)-Mo(1)-W(1.1)]
溶液A的制备:将17.6g七钼酸铵和27.8g偏钨酸铵添加到4L烧瓶中的2000g去离子水中。用氨水将pH调节至9.8。然后将溶液加热至80℃。
溶液B的制备:在单独的500mL烧杯中,将110.3g硝酸镍和5.8g马来酸溶解到100g去离子水中。
在15分钟内将溶液B添加到溶液A中。在添加期间监测pH。一添加溶液B就形成绿色沉淀。添加后最终pH为6.0至7.0。将浆料在80℃下老化4小时。老化后,通过过滤回收产物,将产物用去离子水洗涤,并在烘箱中在130℃下干燥。
实施例4
本体催化剂前体的合成
[Ni-Mo-W-Nb]
溶液A的制备:将35g七钼酸铵和151g偏钨酸铵添加到4L烧瓶中的2500g去离子水中。用氨水将pH调节至9.8。然后将溶液加热至80℃。
溶液B的制备:在单独的1L烧杯中,将389g硝酸镍、60g草酸铌铵和20g马来酸溶解到800g去离子水中。
在30分钟内将溶液B添加到溶液A中。在添加期间监测pH。一添加溶液B就形成绿色沉淀。添加后最终pH为6.0至7.0。将浆料在80℃下老化4小时。老化后,通过过滤回收产物,将产物用去离子水洗涤,并在烘箱中在130℃下干燥。
实施例5
本体催化剂前体的合成
[Ni-Mo-W-Nb-Ti]
异位(Ex-Situ)添加Ti
溶液A的制备:将35g七钼酸铵和151g偏钨酸铵添加到4L烧瓶中的2500g去离子水中。用氨水将pH调节至9.8。然后将溶液加热至80℃。
溶液B的制备:在单独的1L烧杯中,将389g硝酸镍、60g草酸铌铵和20g马来酸溶解到800g去离子水中。
在30分钟内将溶液B添加到溶液A中。在添加期间监测pH。一添加溶液B就形成绿色沉淀。添加后最终pH为6.0至7.0。将浆料在80℃下老化4小时。老化后,通过过滤回收产物。将滤饼和87g TiO2(Venator Hombikat 8602)混合成均相并在80℃下搅拌2小时。通过过滤回收混合物,将混合物用去离子水洗涤并在烘箱中在130℃下干燥。
实施例6
本体催化剂前体的合成
[Ni(6.5)-Mo(1)-W(3)-Nb(1)]
溶液A的制备:将18g七钼酸铵和79g偏钨酸铵添加到4L烧瓶中的1875g去离子水中。用氨水将pH调节至9.8。然后将溶液加热至80℃。
溶液B的制备:在单独的500mL烧杯中,将175g硝酸镍、32g草酸铌铵和9g马来酸溶解到100g去离子水中。
在15分钟内将溶液B添加到溶液A中。在添加期间监测pH。一添加溶液B就形成绿色沉淀。添加后最终pH为6.0至7.0。将浆料在80℃下老化4小时。老化后,通过过滤回收产物,将产物用去离子水洗涤,并在烘箱中在130℃下干燥。
实施例7
本体催化剂前体的合成
[Ni(7)-Mo(1)-W(3)-Nb(0.5)]
溶液A的制备:将18g七钼酸铵和79g偏钨酸铵添加到4L烧瓶中的1875g去离子水中。用氨水将pH调节至9.8。然后将溶液加热至80℃。
溶液B的制备:在单独的500mL烧杯中,将188g硝酸镍、16g草酸铌铵和10g马来酸溶解到100g去离子水中。
在15分钟内将溶液B添加到溶液A中。在添加期间监测pH。一添加溶液B就形成绿色沉淀。添加后最终pH为6.0至7.0。将浆料在80℃下老化4小时。老化后,通过过滤回收产物,将产物用去离子水洗涤,并在烘箱中在130℃下干燥。
实施例8
本体催化剂前体的合成
[Ni(6)-Mo(1)-W(3)-Nb(1.5)]
溶液A的制备:将18g七钼酸铵和66g偏钨酸铵添加到4L烧瓶中的1875g去离子水中。用氨水将pH调节至9.8。然后将溶液加热至80℃。
溶液B的制备:在单独的500mL烧杯中,将175g硝酸镍、47g草酸铌铵水合物和9g马来酸溶解到100g去离子水中。
在15分钟内将溶液B添加到溶液A中。在添加期间监测pH。一添加溶液B就形成绿色沉淀。添加后最终pH为6.0至7.0。将浆料在80℃下老化4小时。老化后,通过过滤回收产物,将产物用去离子水洗涤,并在烘箱中在130℃下干燥。
实施例9
本体催化剂前体的合成
[Ni(6.2)-Mo(1)-W(3)-Nb(1)-Cu(0.3)]
溶液A的制备:将18g七钼酸铵和79g偏钨酸铵添加到4L烧瓶中的1875g去离子水中。用氨水将pH调节至9.8。然后将溶液加热至80℃。
溶液B的制备:在单独的500mL烧杯中,将166g硝酸镍、32g草酸铌铵、8g硝酸铜(II)和9g马来酸溶解到100g去离子水中。
在15分钟内将溶液B添加到溶液A中。在添加期间监测pH。一添加溶液B就形成绿色沉淀。添加后最终pH为6.0至7.0。将浆料在80℃下老化4小时。老化后,通过过滤回收产物,将产物用去离子水洗涤,并在烘箱中在130℃下干燥。
实施例10
挤出物的生产
在催化评价之前,将催化剂前体成形为挤出物。将经干燥的催化剂前体研磨成细粉(<100目)并与适量的粘合剂和水混合,以制备可挤出的混合物,随后在Carver压机上挤出。
实施例11
本体催化剂前体表征
测量实施例1至7和9的本体催化剂前体的颗粒密度(D),BET表面积(SA)和孔体积(PV)。结果示于下表1中,并且表明添加铌可降低颗粒密度。
表1催化剂前体特性
实施例12
催化剂评价-柴油/四氢化萘共混物进料的氢解
平行测试单元(hte GmbH)被用于使用70体积%直馏柴油/30体积%四氢化萘共混物进料对实施例2至3和6中制备的催化剂进行开环活性筛选。反应器装载有三层催化剂:60体积%的Ni-Mo加氢处理催化剂、30体积%的测试催化剂和10体积%的Ni-Mo加氢处理催化剂。所有这些催化剂均在四氢化萘测试之前被预硫化。将催化剂在450℉/800psi下硫化24小时,然后以25℉/h升温至650℉并在65℉/800psi下保持10小时。
直馏柴油/四氢化萘共混物进料的特性汇总于表2中。
表2
进料特性
API比重 | 28.33 |
硫[wt.%] | 0.8386 |
氮[ppm] | 66 |
GC蒸馏[wt.%,℉] | |
IBP | 252 |
5 | 313 |
10 | 369 |
30 | 483 |
50 | 500 |
70 | 518 |
90 | 633 |
95 | 688 |
FBP | 754 |
500℉- | 49.1 |
在700℉的温度、2300psi的氢气压力、1h-1的LHSV和3500SCF/B的氢气速率下进行催化测试。表3中比较了这三种催化剂的活性。基于配备有火焰离子化检测器的在线气相色谱(GC)定量开环反应的产率。结果表明,与实施例2至3的催化剂相比,实施例6的催化剂具有显著更高的开环活性并导致更高的API比重。结果表明此类改善可能是由于铌的添加。
表3
催化测试
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Claims (26)
1.一种本体催化剂前体,其包含:
(a)基于金属氧化物计1wt.%至60wt.%的Ni;
(b)基于金属氧化物计1wt.%至40wt.%的Mo;
(c)基于金属氧化物计5wt.%至80wt.%的W;
(d)基于金属氧化物计0.01wt.%至20wt.%的Nb;
(e)基于金属氧化物计0wt.%至45wt.%的Ti;以及
(f)基于金属氧化物计0wt.%至10wt.%的Cu。
2.如权利要求1所述的本体催化剂前体,其还包含基于有机化合物的组分。
3.如权利要求2所述的本体催化剂前体,其中所述基于有机化合物的组分选自有机酸或其盐、糖、糖醇或它们的组合的组。
4.如权利要求2所述的本体催化剂前体,其中所述基于有机化合物的组分选自乙醛酸、丙酮酸、乳酸、丙二酸、草酰乙酸、苹果酸、富马酸、马来酸、酒石酸、葡糖酸、柠檬酸、草氨酸、丝氨酸、天冬氨酸、谷氨酸、亚氨基二乙酸、乙二胺四乙酸、果糖、葡萄糖、半乳糖、甘露糖、蔗糖、乳糖、麦芽糖、赤藓糖醇、木糖醇、甘露糖醇、山梨糖醇或它们的组合的组。
5.如权利要求2所述的本体催化剂前体,其中Ni与所述基于有机化合物的组分的摩尔比在3:1至20:1的范围内。
6.如权利要求1所述的本体催化剂前体,其中Nb/(Ni+Mo+W+Ti+Cu)的摩尔比在10:1至1:10的范围内。
7.如权利要求1所述的本体催化剂前体,其中Ni/W的摩尔比在10:1至1:10的范围内。
8.如权利要求1所述的本体催化剂前体,其中W/Mo的摩尔比在100:1至1:100的范围内。
9.如权利要求1所述的本体催化剂前体,其中所述本体催化剂前体具有下式:
Av[Ni1-a-bNbaCub(OH)x(L)p y]z[MomW1-mO4][Ti(OH)nO2-n/2]w
其中:
(i)A是碱金属阳离子、稀土金属阳离子、铵阳离子、有机铵阳离子、鏻阳离子或它们的组合;
(ii)L是基于有机化合物的组分;并且
(iii)0<a<1;0≤b<1;a+b<1;0≤y≤2/p;0≤x<2;0≤v<2;0<z;0<m<1;0<n<4;0<w/(z+1)<10。
10.如权利要求1所述的本体催化剂前体,其还包含1wt.%至15wt.%的粘合剂。
11.如权利要求1所述的本体催化剂前体,其具有以下特性中的一种或多种:50m2/g至250m2/g的BET比表面积;0.02cm3/g至0.80cm3/g的孔体积;和1.00cm3/g至3.00cm3/g的颗粒密度。
12.一种硫化的本体催化剂,其特征在于其是已经硫化的根据权利要求1所述的本体催化剂前体。
13.一种制备权利要求1所述的本体催化剂前体的方法,所述方法包括:
(a)将以下组合在反应混合物中:
(i)含Ni前体;
(ii)含Mo前体;
(iii)含W前体;
(iv)含Nb前体;
(v)任选地,含Ti前体和/或含Cu前体;
(vi)任选地,基于有机化合物的组分;和
(vii)质子液体;以及
(b)使所述混合物在足以引起所述本体催化剂前体沉淀的条件下反应;
其中制备所述本体催化剂前体的步骤在不超过200℃的温度下进行。
14.如权利要求13所述的方法,其中所述反应混合物通过以下方法制备:
制备第一混合物,所述第一混合物包含含Ni前体、含Nb前体、任选的含Cu前体、质子液体和任选的基于有机化合物的组分;
制备第二混合物,所述第二混合物包含含Mo前体、含W前体和质子液体;
任选地,向所述第一混合物、所述第二混合物或它们的组合中添加含Ti前体;
将所述第一混合物和所述第二混合物均加热至60℃至150℃的温度;
将所述第一混合物和所述第二混合物组合在一起。
15.如权利要求14所述的方法,其中所述含Ti前体选自TiO2纳米颗粒、胶体TiO2、热解TiO2、氢氧化钛、有机钛化合物、卤化钛、有机钛卤化物、水溶性钛盐或它们的组合。
16.一种制备权利要求1所述的本体催化剂前体的方法,所述方法包括:
(a)将以下组合在反应混合物中:
(i)含Ni前体;
(ii)含Mo前体;
(iii)含W前体;
(iv)含Nb前体;
(v)任选地,含Cu前体;
(vi)任选地,基于有机化合物的组分;和
(vii)质子液体;以及
(b)使所述混合物在足以导致中间体本体催化剂前体沉淀的条件下反应;以及
(c)将所述中间体本体催化剂前体与含Ti前体复合,以形成所述本体催化剂前体;
其中制备所述本体催化剂前体的步骤在不超过200℃的温度下进行。
17.如权利要求16所述的方法,其中所述反应混合物通过以下方法制备:
制备第一混合物,所述第一混合物包含含Ni前体、含Nb前体、任选的含Cu前体、质子液体和任选的基于有机化合物的组分;
制备第二混合物,所述第二混合物包含含Mo前体、含W前体和质子液体;
将所述第一混合物和所述第二混合物均加热至60℃至150℃的温度;以及
将所述第一混合物和所述第二混合物组合在一起。
18.如权利要求16所述的方法,其中所述含Ti前体选自TiO2纳米颗粒、热解TiO2或它们的组合。
19.如权利要求16所述的方法,其中所述中间体本体催化剂前体是Ni-Mo-W-Nb或Ni-Mo-W-Nb-Cu本体催化剂前体。
20.如权利要求13或权利要求16所述的方法,其中所述反应在(a)大气压力下60℃至100℃范围内或(b)自生压力下高于100℃的一个或多个温度下进行。
21.如权利要求13或权利要求16所述的方法,其中所述基于有机化合物的组分选自有机酸或其盐、糖、糖醇或它们的组合。
22.如权利要求21所述的方法,其中所述基于有机化合物的组分选自乙醛酸、丙酮酸、乳酸、丙二酸、草酰乙酸、苹果酸、富马酸、马来酸、酒石酸、葡糖酸、柠檬酸、草氨酸、丝氨酸、天冬氨酸、谷氨酸、亚氨基二乙酸、乙二胺四乙酸、果糖、葡萄糖、半乳糖、甘露糖、蔗糖、乳糖、麦芽糖、赤藓糖醇、木糖醇、甘露糖醇、山梨糖醇或它们的组合。
23.如权利要求13或权利要求16所述的方法,其还包括以下步骤中的一个或多个:
将0wt.%至40wt.%的所述本体催化剂前体与选自粘合剂材料、常规加氢加工催化剂、裂化化合物或它们的混合物的组的材料复合;
喷雾干燥、(闪蒸)干燥、研磨、捏合、浆料混合、干混或湿混,或它们的组合;
成形,
在不超过200℃的温度下干燥和/或热处理;或
硫化。
24.一种用于加氢加工烃原料的工艺,所述工艺包括使所述烃原料与氢气在本体催化剂存在下在加氢加工条件下接触,以得到至少一种产物,其中所述本体催化剂衍生自或可衍生自本体催化剂前体,所述本体催化剂前体包含:
(a)基于金属氧化物计1wt.%至60wt.%的Ni;
(b)基于金属氧化物计1wt.%至40wt.%的Mo;
(c)基于金属氧化物计5wt.%至80wt.%的W;
(d)基于金属氧化物计0.01wt.%至20wt.%的Nb;
(e)基于金属氧化物计0wt.%至45wt.%的Ti;以及
(f)基于金属氧化物计0wt.%至10wt.%的Cu。
25.如权利要求24所述的工艺,其中所述加氢加工选自由加氢脱硫、加氢脱氮、加氢脱氧、加氢脱金属、加氢脱芳构化、氢化、氢解、加氢处理、加氢异构化和加氢裂化组成的组。
26.如权利要求24所述的工艺,其中所述加氢加工条件包括200℃至450℃的温度;250psig至5000psig(1.7MPa至34.6MPa)的压力;0.1h-1至10h-1的液时空速;以及100SCF/B至15,000SCF/B(17.8m3/m3至2672m3/m3)的氢气速率。
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