CN111683748B - 结晶羟基氧化物过渡金属钼钨酸盐 - Google Patents
结晶羟基氧化物过渡金属钼钨酸盐 Download PDFInfo
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- CN111683748B CN111683748B CN201880087252.9A CN201880087252A CN111683748B CN 111683748 B CN111683748 B CN 111683748B CN 201880087252 A CN201880087252 A CN 201880087252A CN 111683748 B CN111683748 B CN 111683748B
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- China
- Prior art keywords
- transition metal
- varies
- crystalline transition
- metal molybdenum
- molybdenum tungstate
- 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.)
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- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 57
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000011733 molybdenum Substances 0.000 title claims abstract description 53
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 50
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 59
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 11
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 45
- 239000011230 binding agent Substances 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910017052 cobalt Chemical group 0.000 claims description 5
- 239000010941 cobalt Chemical group 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000010908 decantation Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 21
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 239000002244 precipitate Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000003917 TEM image Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000002159 nanocrystal Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000005486 sulfidation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002178 crystalline material Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical class [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- -1 naphtha Substances 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[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 PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 2
- QLTKZXWDJGMCAR-UHFFFAOYSA-N dioxido(dioxo)tungsten;nickel(2+) Chemical compound [Ni+2].[O-][W]([O-])(=O)=O QLTKZXWDJGMCAR-UHFFFAOYSA-N 0.000 description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CXVCSRUYMINUSF-UHFFFAOYSA-N tetrathiomolybdate(2-) Chemical compound [S-][Mo]([S-])(=S)=S CXVCSRUYMINUSF-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 229910013504 M-O-M Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- NSEQHAPSDIEVCD-UHFFFAOYSA-N N.[Zn+2] Chemical compound N.[Zn+2] NSEQHAPSDIEVCD-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J Tungsten(IV) chloride Inorganic materials Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 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
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 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
- ZRUWFKRETRELPY-UHFFFAOYSA-N azane;nickel(2+) Chemical compound N.[Ni+2] ZRUWFKRETRELPY-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 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
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- 239000010779 crude oil 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 description 1
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 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
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 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
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- XEBWQGVWTUSTLN-UHFFFAOYSA-M phenylmercury acetate Chemical group CC(=O)O[Hg]C1=CC=CC=C1 XEBWQGVWTUSTLN-UHFFFAOYSA-M 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- BGRYSGVIVVUJHH-UHFFFAOYSA-N prop-2-ynyl propanoate Chemical compound CCC(=O)OCC#C BGRYSGVIVVUJHH-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 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
- 238000006467 substitution reaction Methods 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
- LSWWNKUULMMMIL-UHFFFAOYSA-J zirconium(iv) bromide Chemical compound Br[Zr](Br)(Br)Br LSWWNKUULMMMIL-UHFFFAOYSA-J 0.000 description 1
Classifications
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- 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
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- 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
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- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
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- 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)
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- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
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- B01J37/20—Sulfiding
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
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Abstract
已经开发出一种独特的结晶过渡金属钼钨酸盐物质。所述物质可被硫化以生成金属硫化物，所述金属硫化物在转化方法诸如氢化处理中用作催化剂。所述氢化处理可包括加氢脱氮、加氢脱硫、加氢脱金属、加氢脱硅、加氢脱芳烃、加氢异构化、加氢处理、加氢精制和加氢裂解。
Description
技术领域
本发明涉及新型氢化处理催化剂。更具体地讲，本发明涉及一种新型结晶羟基氧化物过渡金属钼钨酸盐及其作为氢化处理催化剂的用途。氢化处理可包括加氢脱氮、加氢脱硫、加氢脱金属、加氢脱硅、加氢脱芳烃、加氢异构化、加氢处理、加氢精制和加氢裂解。
背景技术
为了满足对石油产品的日益增长的需求，存在对含硫原油的更大利用，这在与关于燃料内氮和硫浓度的环境法规更严格结合时，导致精制问题加重。在精制的加氢处理步骤期间的目的是从燃料原料移除含硫(加氢脱硫-HDS)和含氮(加氢脱氮-HDN)的化合物，并且该目的通过将有机氮和硫分别转化成氨和硫化氢实现。
自二十世纪40年代后期，已经证明使用含镍(Ni)和钼(Mo)或钨(W)的催化剂移除至多至80％的硫。参见，例如，V.N.Ipatieff、G.S.Monroe、R.E.Schaad，石油化学分会，第115次ACS会议，旧金山，1949年(V.N.Ipatieff，G.S.Monroe，R.E.Schaad，Division ofPetroleum Chemistry，115th Meeting ACS，San Francisco，1949)。数十年来，现在十分关注针对开发用于催化深度脱硫的物质，从而将硫浓度降低到ppm水平。一些近期的突破已经聚焦于开发和应用更活泼和稳定的催化剂，从而目标为生产用于超低硫燃料的进料。一些研究已经证明通过消除载体(诸如例如Al2O3)改善了HDS和HDN活性。使用无载体的本体物质提供一种提高反应器中的活性相载荷的途径，以及提供靶向这些催化剂的另选的化学。
该领域中更近期的研究聚焦于通过无载体的Ni-Mo/W“三金属”物质来实现超深度脱硫特性，例如，US 6,156,695中所报道的。由钼、钨和镍组成的广泛无定形混合金属氧化物的受控合成显著优于常规加氢处理催化剂。三金属混合金属氧化物物质的结构化学与水滑石家族物质相似，参见详述层状钼酸镍物质的合成和表征的文献作品，其报道了用钨部分地取代钼导致广泛的无定形相的产生，其在通过硫化分解时产生优异的加氢处理活性。
这些层状水滑石样物质的化学首先由H.Pezerat，对锌、钴和镍水合物钼酸盐研究的贡献，科学研究院记录，第261期，第5490页(H.Pezerat，contributionàl′étude desmolybdates hydrates de zinc，cobalt et nickel，C.R.Acad.Sci.，261，5490)报道，其中确定了具有以下理想式的一系列相：MMoO4.H2O，EHM2O-(MoO4)2.H2O和E2-x(H3O)xM2O(MoO4)2，其中E可以为NH4 +、Na+或K+，并且M可以为Zn2+、Co2+或Ni2+。
Pezerat将所观察到的不同相归类为Φc、Φx或Φy，并测定了Φx和Φy的晶体结构，然而，由于小微晶尺寸、受限的晶体学能力和物质的复杂性质的组合，提出对于物质的结构评估质量存在疑问。在二十世纪70年代中期期间，Clearfield等人试图更详细地分析Φx和Φy相，参见示例，A.Clearfield、M.J.Sims、R.Gopal，无机化学，第15期，第335页(A.Clearfield，M.J.Sims，R.Gopal，Inorg.Chem.，15，335)；A.Clearfield、R.Gopal、C.H.Saldarriaga-Molina，无机化学，第16期，第628页(A.Clearfield，R.Gopal，C.H.Saldarriaga-Molina，Inorg.Chem.，16，628)。对由水热方法获得的产物进行的单晶研究允许确认Φx结构，然而他们在尝试合成Φy时失败，而是合成了另选的相，Na-Cu(OH)(MoO4)，参见A.Clearfield、A.Moini、P.R.Rudolf，无机化学，第24期，第4606页(A.Clearfield，A.Moini，P.R.Rudolf，Inorg.Chem.，24，4606)。
Φy的结构直至1996才被Ying等人确认。他们为了追求层状钼酸锌铵研究了室温chimie douce合成技术，导致亚稳态的铝取代的红锌矿相，其通过煅烧Zn/Al层状双氢氧化物(Zn4Al2(OH)12CO3.zH2O)制备。参见示例，D.Levin、S.L.Soled、J.Y.Ying，无机化学，1996年，第35期，第4191-4197页(D.Levin，S.L.Soled，J.Y.Ying，Inorg.Chem.，1996，35，4191-4197)。使该物质与七钼酸铵的溶液在室温下反应以生产高度结晶的化合物，其结构不能通过常规的从头开始(ab-initio)方法来测定。Astier报道了，将该物质进行指标化，得到与钼酸镍铵相同的结晶学参数，参见示例M.P.Astier、G.Dji，S.Teichner，化学年鉴(巴黎)，1987年，第12期，第337页(M.P.Astier，G.Dji，S.Teichner，J.Ann.Chim.(Paris)，1987，12，337)，属于铵-胺-镍-钼氧化物的家族的物质与Pezerat的物质紧密相关。Astier未公布关于该物质家族的任何详细结构数据，从而导致Ying等人重新制备该物质以通过高分辨率粉末衍射进行分析，以便阐明其结构。Ying等人将这类物质命名为“层状过渡金属钼酸盐”或LTM。
自从US 6,156,695首次报道了无载体的Ni-Mo/W含氧前体(oxidic precursors)以来，已有几篇报道描述了当被硫化时声称具有增强的加氢处理活性的物质。US 6,534,437公开了用于制备混合金属催化剂的方法，该混合金属催化剂具有在2.53埃和1.70埃处显示反射的粉末x-射线衍射图案。US 6,534,437基于WO 9903578中存在的更多分辨反射的特征半高全宽线宽而将其本身与US 3,678,124和WO 9903578区分开，其声称US 6,534,437的发明与现有技术(prior work)WO 9903578具有“不同的微结构”。
美国专利8,722,563描述了用包含至少一种VI族金属和一种来自VIII族至X族的金属的组合物制备一系列催化剂前体。该专利中描述的比较例中的一个产生与美国专利6,534,437中所获得的粉末x-射线衍射图案相当的粉末x-射线衍射图案，并且被描述为原样合成并干燥的六边形NiWO4催化剂前体。
美国专利7,648,941公开了一系列不同的双金属物质的合成示例，并指出本发明的本体双金属催化剂具有亚稳结构，并且进一步断言本发明的优选催化剂中的亚稳六边形NiW04相的结晶2θ结构具有晶格参数 和/>并且本体催化剂具有亚稳六边形结构，该亚稳六边形结构具有单次反射在58°至65°之间的X-射线衍射图案。作为参考点，通过晶格参数为/>和/>的六边形单元可在x-射线衍射图案中生成的最大两个d-间距为/>和/>
A.Dias和V.S.T.Ciminelli，欧洲陶瓷学会杂志，2001年，第21期，第2061-2065页(A.Dias and V.S.T.Ciminelli，J.Eur.Ceramic.Soc，2001，21，2061-2065)报道了水热合成钨酸镍的热力学计算和建模。他们呈现了在各种合成温度下的一系列计算的产物图，突出显示了产生NiWO4的pH和试剂浓度。他们所有的计算都预测钨酸镍在pH 2和7.5之间形成，其中在较高pH下氢氧化镍为主要产物。作者示出了在200℃、230℃和260℃处产生的在其预测的产物区之内和之外的样品的x-射线衍射图案。在200℃处合成的NiWO4物质的x-射线衍射图案可被描述为结晶差，并且该参考文献断言重要的是注意结晶物质在200℃处获得，但具有由宽X-射线衍射峰指示的极细粒度。该参考文献断言，这可由沉淀的能垒来解释，该能垒与主要形成过程中的速率控制步骤的性质密切相关。该参考文献提出，更高的反应温度由于具有克服转化能垒的更大热能而加速结晶过程，并且因此可获得具有更高结晶度和/或粒度的物质。该参考文献表明，在200℃处获得的相基本上是结晶差的纳米钨锰铁矿(NiWO4)，并且该结论与该参考文献的计算产物图一致。
Y.Bi、H.Nie、D.Li、Z.Seng、Q.Yang和M.Li，化学通讯，2010年，第46期，第7430-7432页(Y.Bi，H.Nie，D.Li，S.Zeng，Q.Yang and M.Li，Chemical Communications，2010，46，7430-7432)讨论了制备NiWO4纳米颗粒作为有前景的加氢脱硫催化剂，从而指出典型粉末x-射线衍射图案中的所有反射都可毫无争议地索引到单斜NiWO4钨锰铁矿相。该参考文献断言，图1示出了原样制备样品的典型X-射线衍射(XRD)图案，并且所有反射都可毫无争议地索引到单斜NiWO4相(JCPDS卡72-1189)。该参考文献的结论是，仔细检查后发现，XRD图案中的反射略宽，反映了纳米级物质的特征。
发明内容
已经生产了新型结晶过渡金属钼钨酸盐物质并且任选地硫化，以产生活性氢化处理催化剂。该新型结晶过渡金属钼钨酸盐物质具有独特的x-射线粉末衍射图案，其示出在和/>处的峰。该新型结晶过渡金属钼钨酸盐物质具有下式：
M(OH)aMoxWyOz
其中“M”为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的混合物的金属；“a”从0.001至2变化；“x”从0.001至1.2、或从0.01至1、或从0.1至0.5变化；“y”从0.4至1.2、或从0.45至1、或从0.5至0.9变化；(x+y)的总和从0.4至1.4、或从0.45至1.2、或从0.5至1变化；“z”为满足M、x和y的化合价的总和的数；所述物质的特征还在于示出表A中所列的d-间距处的峰的x-射线粉末衍射图案：
表A
另一个实施方案涉及一种制备具有下式的新型结晶过渡金属钼钨酸盐物质的方法：
M(OH)aMoxWyOz
其中“M”为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的混合物的金属；“a”从0.001至2变化；“x”从0.001至1.2、或从0.01至1、或从0.1至0.5变化；“y”从0.4至1.2、或从0.45至1、或从0.5至0.9变化；(x+y)的总和从0.4至1.4、或从0.45至1.2、或从0.5至1变化；“z”为满足M、x和y的化合价的总和的数；所述物质的特征还在于示出表A中所列的d-间距处的峰的x-射线粉末衍射图案：
表A
该方法包括形成包含M、Mo和W的来源的水性反应溶液；并且添加NH4OH以产生6.5至10的pH，然后在开放或密封容器中在高温处使混合物一起反应，然后回收新型结晶过渡金属钼钨酸盐物质。
另一个实施方案涉及一种转化方法，该转化方法包括使进料在转化条件下与催化剂接触以得到至少一种产物，该催化剂包含：具有下式的新型结晶过渡金属钼钨酸盐物质：
M(OH)aMoxWyOz
其中“M”为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的混合物的金属；“a”从0.001至2变化；“x”从0.001至1.2、或从0.01至1、或从0.1至0.5变化；“y”从0.4至1.2、或从0.45至1、或从0.5至0.9变化；(x+y)的总和从0.4至1.4、或从0.45至1.2、或从0.5至1变化；“z”为满足M、x和y的化合价的总和的数；所述物质的特征还在于示出表A中所列的d-间距处的峰的x-射线粉末衍射图案：
表A
本发明的附加特征和优点将从本文所提供的本发明的说明书、附图和权利要求显而易见。
附图说明
图1示出了从实施例1的晶体计算的傅立叶变换振幅，其用于测量在图2的透射电子显微镜(TEM)图像中观察到的晶格间距。
图2是示出由实施例1制备的结晶过渡金属钼钨酸盐的单个纳米晶体的高分辨率透射电子显微镜(TEM)。
图3是通过实施例中所述的方法制备的结晶过渡金属钼钨酸盐的x-射线粉末衍射图案。
具体实施方式
本发明涉及新型结晶过渡金属钼钨酸盐组合物和制备所述组合物的方法。该物质具有名称UPM-2。该组合物具有以下经验式：
M(OH)aMoxWyOz
其中“M”为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的混合物的金属；“a”从0.001至2变化；“x”从0.001至1.2、或从0.01至1、或从0.1至0.5变化；“y”从0.4至1.2、或从0.45至1、或从0.5至0.9变化；(x+y)的总和从0.4至1.4、或从0.45至1.2、或从0.5至1变化；“z”为满足M、x和y的化合价的总和的数。
本发明的结晶组合物的特征在于具有M-O-M的扩展网络，其中M表示上文所列的金属或金属的组合。结构单元本身重复成为至少两个相邻的晶胞，但不终止键合。该组合物可具有一维网络，诸如例如直链。
该新型结晶过渡金属钼钨酸盐组合物的特征还在于独特的x-射线粉末衍射图案，其示出表A中所列的d-间距处的峰。
表A
本发明的新型结晶过渡金属钼钨酸盐组合物的特征还在于图3中所示的x-射线粉末衍射图案以及图1和图2中的图像
该新型结晶过渡金属钼钨酸盐组合物可通过反应混合物的溶剂加热结晶来制备，通常通过使反应性的钼源和钨源与合适金属“M”混合来制备。
Mo、W或M的来源包括但不限于Mo、W或M的相应卤化物、硫化物、乙酸盐、硝酸盐、碳酸盐、硫酸盐、草酸盐、硫醇、氢氧化物盐和氧化物。来源的具体示例包括但不限于硝酸锰、氯化锰、溴化锰、硫酸锰、碳酸锰、硫化锰、氢氧化锰、氧化锰、硝酸锆、氯氧化锆、溴化锆、硫酸锆、碱式碳酸锆、氢氧化锆、氧化锆、硝酸铜、氯化铜、溴化铜、硫酸铜、碳酸铜、乙酸铜、草酸铜、硫化铜、氢氧化铜、氧化铜、硝酸锌、氯化锌、溴化铁、硫酸锌、碳酸锌、乙酸锌、草酸锌、硫化锌、氢氧化锌、氧化锌以及它们的任何混合物。附加的具体来源包括氯化镍、溴化镍、硝酸镍、乙酸镍、碳酸镍、氢氧化镍、氯化钴、溴化钴、硝酸钴、乙酸钴、碳酸钴、氢氧化钴、硫化钴、氯化镍、氧化钴、溴化镍、硫化镍、氧化镍、乙酸铁、草酸铁、硝酸铁、氯化铁、溴化铁、硫酸铁、碳酸铁、草酸铁、硫化铁、氧化铁、氯化镁、氧化钛、四氯化钛、氯化钒以及它们的任何混合物。其他附加来源包括但不限于钼酸盐、钨酸盐、硫羟钼酸盐和硫羟钨酸盐，诸如三氧化钼、二钼酸铵、硫代钼酸铵、七钼酸铵、二钼酸钠、硫代钼酸钠、七钼酸钠、二钼酸钾、硫代钼酸钾、七钼酸钾、硫化钼、三氧化钨、钨酸、四氯氧化钨、六氯化钨、钨酸氢盐(hydrogentungstate)、二钨酸铵、二钨酸钠、偏钨酸铵、仲钨酸铵、二钨酸钠、二钨酸钠、偏钨酸钠、仲钨酸钠以及它们的任何混合物。
一般来讲，用于制备本发明的组合物的方法涉及形成反应混合物，其中所有组分诸如例如Ni、Mo、W、NH4OH和H2O在溶液中混合在一起。作为一个具体示例，可形成反应混合物，所述反应混合物根据氧化物的摩尔比由下式表示：
MOx：AMoOy：BWOz：C(NH3)：H2O
其中“M”选自由铁、钴、镍、钒、锰、铜、锌以及它们的混合物组成的组；“x”为满足“M”化合价的数；“A”表示“Mo”相对于“M”的比率并且可从0.1至3、或从0.75至2、或从1至1.5变化；“y”为满足“Mo”化合价的数；“B”表示“W”相对于“M”的比率并且可从0.1至3、或从0.75至2、或从1至1.5变化；“z”为满足“W”化合价的数；“C”表示“NH3”相对于“M”的比率并且可从0.5至15、或从1至10、或从3至7变化；H2O相对于“M”的比率从0.1至1000、或从1至300、或从1至100变化。
混合物的pH调节至6.5至10、或8.5至10的值。混合物的pH可通过添加碱诸如NH4OH、氢氧化季铵、胺等来控制。
一旦形成反应混合物，就使反应混合物在90℃至250℃范围内的温度处反应30分钟至约14天范围内的一段时间。在一个实施方案中，反应的温度范围为约90℃至120℃，并且在另一个实施方案中，温度在130℃至180℃的范围内。在一个实施方案中，反应时间为2小时至4小时，并且在另一个实施方案中，反应时间为4天至7天。反应在大气压下进行或在自生压力下在密封容器中进行。在一实施方案中，合成可在开放容器中进行。将新型结晶过渡金属钼钨酸盐组合物作为反应产物回收。回收可通过倾析、过滤或离心进行。该新型结晶过渡金属钼钨酸盐组合物的特征在于独特的x-射线粉末衍射图案，如上表A和图3所示。进一步的分析示于图1和图2中。
在金属氧化物的水热合成领域中，众所周知，氢氧化物缺陷出现在由该途径制备的金属氧化物中，并且作为缺陷位于内部或作为被至少部分羟基化的通常大的外表面积的结果位于外部。这些非化学计量的量的氢氧化物部分与氧化物离子一起附加地构成组合物中金属离子的总化合价。
一旦形成，该新型结晶过渡金属钼钨酸盐可掺入粘结剂，其中粘结剂的选择包括但不限于阴离子粘土和阳离子粘土，诸如水滑石、鳞镁铁矿-水镁铁石-水滑石、蒙脱土和相关的粘土、高岭土、海泡石、二氧化硅、氧化铝诸如(假)勃姆石、三水铝石、快速煅烧的三水铝石、η-氧化铝、氧化锆、氧化钛、氧化铝涂覆的氧化钛、二氧化硅-氧化铝、二氧化硅涂覆的氧化铝、氧化铝涂覆的二氧化硅、以及它们的混合物，或通常被称为颗粒粘结剂从而保持颗粒完整性的其他物质。这些粘结剂可在胶溶或不胶溶的情况下施用。可将粘结剂添加到本体结晶过渡金属钼钨酸盐组合物中，并且粘结剂的量可以为最终催化剂的1重量％至30重量％，或最终催化剂的5重量％至26重量％。粘结剂可与新型结晶过渡金属钼钨酸盐组合物化学键合，或者以与新型结晶过渡金属钼钨酸盐组合物的物理混合物存在。
在具有或不具有粘结剂的情况下，或在包含粘结剂之前或之后，结晶过渡金属钼钨酸盐的至少一部分可在应用中原位硫化或预硫化以形成金属硫化物，该金属硫化物继而用于应用中。硫化可在多种硫化条件下进行，诸如通过使结晶过渡金属钼钨酸盐与硫化剂诸如含硫的料流或进料流接触以及使用2S/H2的气体混合物来进行。结晶过渡金属钼钨酸盐的硫化在升高的温度下执行，通常在50℃至600℃、或150℃至500℃、或250℃至450℃的范围内。硫化步骤可在以下位置中进行：远离其他合成步骤的位置，远离将要使用结晶过渡金属钼钨酸盐的应用的位置，或者既远离合成位置又远离使用位置的位置。由硫化步骤所得的物质被称为金属硫化物，这些金属硫化物可用作转化方法中的催化剂。
如所讨论的，本发明的结晶过渡金属钼钨酸盐的至少一部分可被硫化，并且所得的金属硫化物在转化方法诸如烃转化方法中用作催化剂。氢化处理是一类烃转化方法，其中结晶过渡金属钼钨酸盐或由其衍生的金属硫化物可用作催化剂。具体的氢化处理方法的示例是本领域所熟知的，并且包括加氢脱氮、加氢脱硫、加氢脱金属、加氢脱硅、加氢脱芳烃、加氢异构化、加氢处理、加氢精制和加氢裂解。在一个实施方案中，转化方法包括使结晶过渡金属钼钨酸盐与硫化剂接触以生成金属硫化物，该金属硫化物在转化条件下与进料流接触以生成至少一种产物。
上文所列的氢化处理方法的操作条件通常包括2.5MPa至17.2MPa、或在5.5MPa至17.2MPa的范围内的反应压力，与在245℃至440℃的范围内、或在285℃至425℃的范围内的反应温度。进料和活性催化剂的接触时间(被称为液时空速(LHSV))应当在0.1h-1至10h-1、或2.0h-1至8.0h-1的范围内。取决于所用的原料，可采用这些范围的具体子集。例如，当加氢处理典型的柴油原料时，操作条件可包括3.5MPa至8.6MPa，315℃至410℃，0.25/h至5/h，以及84Nm3H2/m3至850Nm3H2/m3进料。其他原料可包括汽油、石脑油、煤油、瓦斯油、馏出物和重整油。
下面提供了实施例以便可更完整地描述本发明。这些实施例仅是举例说明的，并且不应解释为是对在所附权利要求书中示出的本发明的宽范围的限制。
在以下实施例中，高分辨率TEM成像是使用在300kV加速电压下操作的JEOL 3000FTEM进行的。图像记录在Gatan US1000 CCD相机上。图2中所示的TEM图像示出了来自实施例1的单个纳米晶体。图1示出了从晶体计算的傅立叶变换振幅，其用于测量在TEM图像中观察到的晶格间距。使用精确到间距的5％以内的定向金箔的(200)间距来评估这些测量对于仪器和成像条件的不确定性。
以下实施例中呈现的X-射线衍射图案使用标准x-射线粉末衍射技术获得。辐照源是高强度的x-射线管，其在45kV和35mA下操作。来自铜K-α辐照的衍射图案通过合适的基于计算机的技术获得。将粉末样品以扁平方式压成平板，并从3°至70°(2θ)连续地扫描。由表示为θ的衍射峰的位置获得晶面间距(d)，其单位为埃，其中θ是如由数字化数据所观察到的布拉格角。强度由减去背景之后的衍射峰积分面积来确定，“IO”为最强线或峰的强度，并且“I”为其他峰中的每一个的强度。如本领域技术人员将理解的，参数2θ的测定经历人为和机械误差两者，所述误差的组合可赋予每个记录的2θ值±0.4°的不确定度。这种不确定度也被转换为记录的d-间距值，其由2θ值计算。在所记录的一些x-射线图案中，d-间距的相对强度由符号vs、s、m和w指示，其分别表示非常强、强、中等和弱。根据100(I/I0)，将上述名称定义为：
w＝0.0001-15，m＝15-60：s＝60-80且vs＝80-100。
在某些情况下，合成产物的纯度可参照其x-射线粉末衍射图案来评估。因此，例如，如果样品被描述为纯的，则其仅旨在表示样品的x-射线图案不含可归因于结晶杂质的线，不表示不存在无定形物质。如本领域的技术人员将理解的，不同的不良结晶物质可在相同的位置处产生峰。如果物质由多种不良结晶物质组成，则对于每种不良结晶物质单独观察到的峰位置将在所得的汇总衍射图案中观察到。同样，在不同的单相结晶物质内在相同位置处可能具有一些峰出现，这可能仅反映物质内的相似距离，而不表示这些物质具有相同的结构。
实施例1
将偏钨酸铵水合物(53.28g，0.21摩尔的W)、七钼酸铵四水合物(31.74g，0.18摩尔的Mo)和硝酸镍六水合物(104.76g，0.36摩尔的Ni)溶解于1000ml的DI H2O中，添加浓氢氧化铵(30％)以调节pH至约7.5。将该溶液转移至2000ml不锈钢反应器中，并在3小时内以150rpm的搅拌速率加热至150℃。将反应在150℃处保持7天，之后使其冷却至室温。将该沉淀物冷却至室温，过滤，用90ml的90℃水洗涤，然后在100℃处干燥。干燥的沉淀物的单个纳米晶体示于图2的TEM图像中，并且图1示出了从晶体计算的傅里叶变换振幅，其用于测量在TEM图像中观察到的晶格间距。干燥的沉淀物的X-射线衍射图案示于图3中。
实施例2
将偏钨酸铵水合物(87.5g，0.347摩尔的W)溶解于600ml的H2O中。使用浓NH4OH将溶液的pH增加至约pH 10。通过将七钼酸铵四水合物(30.5g，0.173摩尔的Mo)和硝酸镍六水合物(125.7g，0.43摩尔的Ni)溶解于600ml的H2O中来制备第二溶液。将两种溶液混合在一起并使用NH4OH将pH调节至pH 8，然后将其转移至2000ml不锈钢反应器中，并在3小时内以300rpm的搅拌速率加热至180℃。将反应在180℃处保持24小时，之后使其冷却至室温。将该沉淀物冷却至室温，过滤，用热水(90℃)洗涤，然后在100℃处干燥。干燥的沉淀物的单个纳米晶体示于图2的TEM图像中，并且图1示出了从晶体计算的傅里叶变换振幅，其用于测量在TEM图像中观察到的晶格间距。干燥的沉淀物的X-射线衍射图案示于图3中。
实施例3
将偏钨酸铵水合物(77g，0.305摩尔的W)溶解于600ml的H2O中。使用浓NH4OH将溶液的pH增加至约pH 10。通过将三氧化钼(23.2g，0.16摩尔的Mo)和硝酸镍六水合物(125.7g，0.43摩尔的Ni)添加到600ml的H2O中来制备第二溶液。将两种溶液混合在一起并使用NH4OH将pH调节至pH 8，然后将其转移至2000ml不锈钢反应器中，并在3小时内以300rpm的搅拌速率加热至180℃。将反应在180℃处保持24小时，之后使其冷却至室温。将该沉淀物冷却至室温，通过离心(10,000rpm，15分钟)分离，并用热水(90℃)洗涤，然后在100℃处干燥。干燥的沉淀物的单个纳米晶体示于图2的TEM图像中，并且图1示出了从晶体计算的傅里叶变换振幅，其用于测量在TEM图像中观察到的晶格间距。干燥的沉淀物的X-射线衍射图案示于图3中。
实施方案
第一实施方案为一种具有下式的结晶过渡金属钼钨酸盐物质：
M(OH)aMoxWyOz
其中“M”为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的混合物的金属；“a”从0.001至2变化；“x”从0.001至1.2变化；“y”从0.4至1.2变化；(x+y)的总和从0.4至1.4变化；“z”为满足M、x和y的化合价的总和的数；所述物质的特征还在于示出表A中所列的d-间距处的峰的x-射线粉末衍射图案：
表A
另一个实施方案为第一实施方案的结晶过渡金属钼钨酸盐物质，其中所述物质以与至少一种粘结剂的混合物存在，并且其中所述混合物包含至多25重量％粘结剂。所述粘结剂可选自由二氧化硅、氧化铝和二氧化硅-氧化铝组成的组。M可以为镍或钴。M可以为镍。所述结晶过渡金属钼钨酸盐物质可被硫化。
第二实施方案为一种制备具有下式的结晶过渡金属钼钨酸盐物质的方法：
M(OH)aMoxWyOz
其中“M”为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的混合物的金属；“a”从0.001至2变化；“x”从0.001至1.2变化；“y”从0.4至1.2变化；(x+y)的总和从0.4至1.4变化；“z”为满足M、x和y的化合价的总和的数；所述物质的特征还在于示出表A中所列的d-间距处的峰的x-射线粉末衍射图案：
表A
所述方法包括：
a.形成包含H2O、M、W和Mo的反应混合物；
b.将所述反应混合物的pH调节至6.5至10的pH；
c.使所述反应混合物在自生环境中在90℃至250℃的温度处反应；以及
d.回收所述结晶过渡金属钼钨酸盐物质。
所述反应可进行30分钟至14天的一段时间。所述回收可通过过滤、离心或倾析进行。所述方法还可包括将粘结剂添加到所回收的结晶过渡金属钼钨酸盐物质中。所述粘结剂可选自由氧化铝、二氧化硅和氧化铝-二氧化硅组成的组。所回收的结晶过渡金属钼钨酸盐物质可以为硫化物。
第三实施方案为一种转化方法，所述转化方法包括使物质与硫化剂接触以将所述物质的至少一部分转化为金属硫化物，并且使所述金属硫化物在转化条件下与进料接触以得到至少一种产物，所述物质包含：具有下式的结晶过渡金属钼钨酸盐物质：
M(OH)aMoxWyOz
其中“M”为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的混合物的金属；“a”从0.001至2变化；“x”从0.001至1.2变化；“y”从0.4至1.2变化；(x+y)的总和从0.4至1.4变化；“z”为满足M、x和y的化合价的总和的数；所述物质的特征还在于示出表A中所列的d-间距处的峰的x-射线粉末衍射图案：
表A
转化方法可为氢化处理。转化方法可为加氢脱氮、加氢脱硫、加氢脱金属、加氢脱硅、加氢脱芳烃、加氢异构化、加氢处理、加氢精制或加氢裂解。所述物质可以与至少一种粘结剂的混合物存在，并且其中所述混合物包含至多25重量％的粘结剂。
Claims (18)
1.一种具有下式的结晶过渡金属钼钨酸盐物质：
M(OH)aMoxWyOz
其中“M”为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的混合物的金属；“a”从0.001至2变化；“x”从0.001至1.2变化；“y”从0.4至1.2变化；(x+y)的总和从0.4至1.4变化；“z”为满足M、x和y的化合价的总和的数；所述物质的特征还在于示出表A中所列的d-间距处的峰的x-射线粉末衍射图案：
表A
关于I/I0，上述名称定义为：w＝0.0001-15，m＝15-60，s＝60-80，vs＝80-100。
2.根据权利要求1所述的结晶过渡金属钼钨酸盐物质，其中所述物质以与至少一种粘结剂的混合物存在，并且其中所述混合物包含至多25重量％的粘结剂。
3.根据权利要求2所述的结晶过渡金属钼钨酸盐物质，其中所述粘结剂选自由二氧化硅、氧化铝和二氧化硅-氧化铝组成的组。
4.根据权利要求1所述的结晶过渡金属钼钨酸盐物质，其中M为镍或钴。
5.根据权利要求1所述的结晶过渡金属钼钨酸盐物质，其中M为镍。
6.根据权利要求1所述的结晶过渡金属钼钨酸盐物质，其中所述结晶过渡金属钼钨酸盐物质被硫化。
7.一种制备具有下式的结晶过渡金属钼钨酸盐物质的方法：
M(OH)aMoxWyOz
其中“M”为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的混合物的金属；“a”从0.001至2变化；“x”从0.001至1.2变化；“y”从0.4至1.2变化；(x+y)的总和从0.4至1.4变化；“z”为满足M、x和y的化合价的总和的数；所述物质的特征还在于示出表A中所列的d-间距处的峰的x-射线粉末衍射图案：
表A
关于I/I0，上述名称定义为：w＝0.0001-15，m＝15-60，s＝60-80，vs＝80-100所述方法包括：
a.形成包含H2O、M、W和Mo的反应混合物；
b.将所述反应混合物的pH调节至6.5至10的pH；
c.使所述反应混合物在自生环境中在90℃至250℃的温度处反应；以及
d.回收所述结晶过渡金属钼钨酸盐物质。
8.根据权利要求7所述的方法，其中所述反应进行30分钟至14天的一段时间。
9.根据权利要求7所述的方法，其中所述回收通过过滤、离心或倾析进行。
10.根据权利要求7所述的方法，还包括将粘结剂添加到所回收的结晶过渡金属钼钨酸盐物质中。
11.根据权利要求10所述的方法，其中所述粘结剂选自由氧化铝、二氧化硅和氧化铝-二氧化硅组成的组。
12.根据权利要求7所述的方法，还包括硫化所回收的结晶过渡金属钼钨酸盐物质的至少一部分以生成金属硫化物。
13.一种转化方法，所述转化方法包括使物质与硫化剂接触以将所述物质的至少一部分转化为金属硫化物，并且使所述金属硫化物在转化条件下与进料接触以得到至少一种产物，所述物质包含：具有下式的结晶过渡金属钼钨酸盐物质：
M(OH)aMoxWyOz
其中“M”为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的混合物的金属；“a”从0.001至2变化；“x”从0.001至1.2变化；“y”从0.4至1.2变化；(x+y)的总和从0.4至1.4变化；“z”为满足M、x和y的化合价的总和的数；所述物质的特征还在于示出表A中所列的d-间距处的峰的x-射线粉末衍射图案：
表A
关于I/I0，上述名称定义为：w＝0.0001-15，m＝15-60，s＝60-80，vs＝80-100。
14.根据权利要求13所述的方法，其中所述转化方法为氢化处理。
15.根据权利要求13所述的方法，其中所述转化方法选自加氢处理。
16.根据权利要求13所述的方法，其中所述转化方法选自加氢精制。
17.根据权利要求13所述的方法，其中所述转化方法选自加氢脱氮、加氢脱硫、加氢脱金属、加氢脱硅、加氢脱芳烃、加氢异构化和加氢裂解。
18.根据权利要求13-17中任一项所述的方法，其中所述物质以与至少一种粘结剂的混合物存在，并且其中所述混合物包含至多25重量％的粘结剂。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214435A (zh) * | 2007-12-26 | 2008-07-09 | 广西南宁化学制药有限责任公司 | 固定化钼酸盐催化剂的制备方法 |
| CN103492066A (zh) * | 2011-03-30 | 2014-01-01 | 艾尼股份公司 | 过渡金属的混合氧化物、由其获得的加氢处理催化剂和制备方法 |
| WO2017106125A1 (en) * | 2015-12-15 | 2017-06-22 | Uop Llc | Crystalline bis-ammonia transition metal molybdotungstate |
Family Cites Families (75)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4820677A (en) | 1984-04-02 | 1989-04-11 | Jacobson Allan J | Amorphous, iron promoted Mo and W sulfide hydroprocessing catalysts and process for their preparation |
| US4904634A (en) | 1986-12-29 | 1990-02-27 | Aluminum Company Of America | Active material useful as adsorbent comprising metal oxide/hydroxide surfaces reacted with one or more phosphorous-containing materials having selected organic radicals attached thereto |
| US5278121A (en) | 1990-10-01 | 1994-01-11 | Exxon Research & Engineering Company | Multimetallic sulfide catalyst containing noble metals for hydrodenitrogenation |
| JP3802106B2 (ja) | 1995-06-08 | 2006-07-26 | 日本ケッチェン株式会社 | 炭化水素油の水素化処理触媒とその製造方法およびその活性化方法 |
| RU2098181C1 (ru) | 1996-04-23 | 1997-12-10 | Завод по производству катализаторов Акционерного общества "Куйбышевнефтеоргсинтез" | Способ приготовления катализатора для гидроочистки нефтяных фракций |
| US6620313B1 (en) | 1997-07-15 | 2003-09-16 | Exxonmobil Research And Engineering Company | Hydroconversion process using bulk group VIII/Group VIB catalysts |
| US6635599B1 (en) | 1997-07-15 | 2003-10-21 | Exxonmobil Research & Engineering Company | Mixed metal catalyst, its preparation by co-precipitation, and its use |
| US6783663B1 (en) | 1997-07-15 | 2004-08-31 | Exxonmobil Research And Engineering Company | Hydrotreating using bulk multimetallic catalysts |
| US7288182B1 (en) | 1997-07-15 | 2007-10-30 | Exxonmobil Research And Engineering Company | Hydroprocessing using bulk Group VIII/Group VIB catalysts |
| US7232515B1 (en) | 1997-07-15 | 2007-06-19 | Exxonmobil Research And Engineering Company | Hydrofining process using bulk group VIII/Group VIB catalysts |
| US6156695A (en) | 1997-07-15 | 2000-12-05 | Exxon Research And Engineering Company | Nickel molybdotungstate hydrotreating catalysts |
| US7229548B2 (en) | 1997-07-15 | 2007-06-12 | Exxonmobil Research And Engineering Company | Process for upgrading naphtha |
| US6582590B1 (en) | 1997-07-15 | 2003-06-24 | Exxonmobil Research And Engineering Company | Multistage hydroprocessing using bulk multimetallic catalyst |
| US6863803B1 (en) | 1997-07-15 | 2005-03-08 | Exxonmobil Research And Engineering Company | Production of low sulfur/low nitrogen hydrocrackates |
| US6712955B1 (en) | 1997-07-15 | 2004-03-30 | Exxonmobil Research And Engineering Company | Slurry hydroprocessing using bulk multimetallic catalysts |
| US6162350A (en) | 1997-07-15 | 2000-12-19 | Exxon Research And Engineering Company | Hydroprocessing using bulk Group VIII/Group VIB catalysts (HEN-9901) |
| US6929738B1 (en) | 1997-07-15 | 2005-08-16 | Exxonmobil Research And Engineering Company | Two stage process for hydrodesulfurizing distillates using bulk multimetallic catalyst |
| US7513989B1 (en) | 1997-07-15 | 2009-04-07 | Exxonmobil Research And Engineering Company | Hydrocracking process using bulk group VIII/Group VIB catalysts |
| JP4174887B2 (ja) | 1998-05-21 | 2008-11-05 | 堺化学工業株式会社 | ニッケル、コバルト又は銅の炭酸塩又は水酸化物の微細な球状の粒子の製造方法 |
| US6534437B2 (en) | 1999-01-15 | 2003-03-18 | Akzo Nobel N.V. | Process for preparing a mixed metal catalyst composition |
| US6299760B1 (en) | 1999-08-12 | 2001-10-09 | Exxon Research And Engineering Company | Nickel molybodtungstate hydrotreating catalysts (law444) |
| US7557062B2 (en) | 2003-02-24 | 2009-07-07 | Shell Oil Company | Catalyst composition, its preparation and use |
| AR043242A1 (es) | 2003-02-24 | 2005-07-20 | Shell Int Research | Preparacion y uso de una composicion de catalizador |
| US7232934B2 (en) | 2003-09-19 | 2007-06-19 | Exxonmobil Chemical Patents Inc. | Hydrogenation of oxo aldehydes to oxo alcohols in the presence of a nickel-molybdenum catalyst |
| US7691257B2 (en) | 2004-04-22 | 2010-04-06 | Exxonmobil Research And Engineering Company | Process to manufacture low sulfur diesel fuels |
| US7780845B2 (en) | 2004-04-22 | 2010-08-24 | Exxonmobil Research And Engineering Company | Process to manufacture low sulfur distillates |
| US7776205B2 (en) | 2004-04-22 | 2010-08-17 | Exxonmobil Research And Engineering Company | Process to upgrade hydrocarbonaceous feedstreams |
| US7709412B2 (en) | 2004-04-22 | 2010-05-04 | Exxonmobil Research & Engineering Company | Bulk metal hydrotreating catalyst used in the production of low sulfur diesel fuels |
| AU2005235711B2 (en) | 2004-04-22 | 2008-11-13 | Albemarle Netherlands B.V. | Hydrotreating catalyst containing a group V metal |
| US7544632B2 (en) | 2004-09-22 | 2009-06-09 | Exxonmobil Research And Engineering Company | Bulk Ni-Mo-W catalysts made from precursors containing an organic agent |
| US7591942B2 (en) | 2004-09-22 | 2009-09-22 | Exxonmobil Research And Engineering Company | Bulk bi-metallic catalysts made from precursors containing an organic agent |
| US7648941B2 (en) | 2004-09-22 | 2010-01-19 | Exxonmobil Research And Engineering Company | Bulk bimetallic catalysts, method of making bulk bimetallic catalysts and hydroprocessing using bulk bimetallic catalysts |
| MXPA05009283A (es) * | 2005-08-31 | 2007-02-27 | Mexicano Inst Petrol | Procedimiento para la preparacion de una composicion catalitica para el hidroprocesamiento de fracciones del petroleo. |
| US7605107B2 (en) | 2005-09-29 | 2009-10-20 | Exxonmobil Research And Engineering Company | Method of preparing a supported hydrotreating catalyst |
| US7538066B2 (en) | 2005-09-29 | 2009-05-26 | Exxonmobil Research And Engineering Company | Method of preparing a hydrotreating catalyst on a support containing a rare earth metal |
| WO2007048598A2 (en) | 2005-10-26 | 2007-05-03 | Albemarle Netherlands Bv | A bulk catalyst comprising nickel tungsten metal oxidic particles |
| WO2007050636A2 (en) | 2005-10-26 | 2007-05-03 | Exxonmobil Research And Engineering Company | Hydroprocessing using bulk bimetallic catalysts |
| AU2006306308B2 (en) | 2005-10-26 | 2011-03-03 | Exxonmobil Research And Engineering Company | Hydroprocessing using hydrothermally-prepared bulk multimetallic catalysts |
| EP1994123B1 (en) | 2006-01-17 | 2018-10-31 | ExxonMobil Research and Engineering Company | Selective catalysts having silica supports for naphtha hydrodesulfurization |
| US7951746B2 (en) | 2006-10-11 | 2011-05-31 | Exxonmobil Research And Engineering Company | Bulk group VIII/group VIB metal catalysts and method of preparing same |
| FR2910351B1 (fr) | 2006-12-22 | 2009-02-27 | Total France Sa | Catalyseur d'hydrotraitement, son procede de preparation et son utilisation. |
| WO2009058783A1 (en) | 2007-10-31 | 2009-05-07 | Chevron U.S.A. Inc. | Hydroconversion processes employing multi-metallic catalysts and method for making thereof |
| US20090114566A1 (en) | 2007-10-31 | 2009-05-07 | Chevron U.S.A. Inc. | Method of upgrading heavy hydrocarbon streams to jet products |
| JP5325891B2 (ja) | 2007-11-09 | 2013-10-23 | エクソンモービル リサーチ アンド エンジニアリング カンパニー | バルク金属性第ｖｉｉｉ族／第ｖｉｂ族金属触媒の調製 |
| EP2237881A4 (en) | 2007-12-04 | 2013-10-02 | Exxonmobil Res & Eng Co | HYDROPROCESSING HYDROCARBONS USING A BULK CATALYST COMPOSITION |
| WO2009073785A1 (en) | 2007-12-04 | 2009-06-11 | Albemarle Netherlands, B.V. | Bulk catalyst composition comprising bulk metal oxide particles |
| EP2103347A1 (en) | 2008-03-17 | 2009-09-23 | ExxonMobil Research and Engineering Company | Hydrocarbon hydroprocessing using bulk catalyst composition |
| CN101544904B (zh) | 2008-03-28 | 2012-11-14 | 中国科学院大连化学物理研究所 | 一种复合金属氧化物催化剂及制备和应用 |
| TW200950880A (en) | 2008-04-09 | 2009-12-16 | Basf Se | Coated catalysts comprising a multimetal oxide comprising molybdenum, bismuth and iron |
| US8383543B2 (en) | 2009-04-29 | 2013-02-26 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
| US8080492B2 (en) | 2009-04-29 | 2011-12-20 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
| CN102049265B (zh) | 2009-10-27 | 2013-01-09 | 中国石油化工股份有限公司 | 一种加氢处理催化剂及其制备方法 |
| CA2781893C (en) * | 2009-12-08 | 2016-10-04 | Exxonmobil Research And Engineering Company | Hydroprocessing of high nitrogen feed using bulk catalyst |
| US8636967B2 (en) | 2010-01-21 | 2014-01-28 | Intevep, S.A. | Metal recovery from hydroconverted heavy effluent |
| US8586500B2 (en) | 2010-11-11 | 2013-11-19 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
| EA024283B1 (ru) | 2010-11-11 | 2016-09-30 | Шеврон Ю.Эс.Эй. Инк. | Мультиметаллический катализатор гидропереработки и способ его получения |
| US8658558B2 (en) | 2010-11-11 | 2014-02-25 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
| WO2012092006A2 (en) | 2010-12-30 | 2012-07-05 | Chevron U.S.A. Inc. | Hydroprocessing catalysts and methods for making thereof |
| US10507458B2 (en) | 2012-08-29 | 2019-12-17 | Indian Oil Corporation Limited | Hydrotreating catalyst and process for preparing the same |
| US9435043B2 (en) | 2014-04-14 | 2016-09-06 | California Institute Of Technology | Oxygen evolution reaction catalysis |
| US10336626B2 (en) * | 2015-04-28 | 2019-07-02 | Nichia Corporation | Nickel cobalt complex hydroxide particles and method for producing the same, positive electrode active material for non-aqueous electrolyte secondary battery and method for producing the same, and non-aqueous electrolyte secondary battery |
| US10053637B2 (en) | 2015-12-15 | 2018-08-21 | Uop Llc | Transition metal tungsten oxy-hydroxide |
| US10052614B2 (en) | 2015-12-15 | 2018-08-21 | Uop Llc | Mixed metal oxides |
| US10052616B2 (en) | 2015-12-15 | 2018-08-21 | Uop Llc | Crystalline ammonia transition metal molybdotungstate |
| US10322404B2 (en) | 2015-12-15 | 2019-06-18 | Uop Llc | Crystalline transition metal oxy-hydroxide molybdate |
| US10400181B2 (en) | 2015-12-15 | 2019-09-03 | Uop Llc | Crystalline bis-ammonia metal molybdate |
| US10399063B2 (en) * | 2015-12-15 | 2019-09-03 | Uop Llc | Mixed metal oxides |
| US10005812B2 (en) | 2015-12-15 | 2018-06-26 | Uop Llc | Transition metal molybdotungsten oxy-hydroxide |
| US10046315B2 (en) | 2015-12-15 | 2018-08-14 | Uop Llc | Crystalline transition metal molybdotungstate |
| US10232357B2 (en) | 2015-12-15 | 2019-03-19 | Uop Llc | Crystalline ammonia transition metal molybdate |
| US10399065B2 (en) | 2015-12-15 | 2019-09-03 | Uop Llc | Crystalline transition metal tungstate |
| US10233398B2 (en) | 2015-12-15 | 2019-03-19 | Uop Llc | Crystalline transition metal oxy-hydroxide molybdotungstate |
| DK3408023T3 (da) | 2016-01-29 | 2024-04-29 | Totalenergies Onetech | Homogent dispergerede multimetal oxyhydroxid katalysatorer |
| US10882030B2 (en) | 2017-08-25 | 2021-01-05 | Uop Llc | Crystalline transition metal tungstate |
| US10773245B2 (en) | 2017-08-25 | 2020-09-15 | Uop Llc | Crystalline transition metal molybdotungstate |
-
2018
- 2018-11-13 US US16/189,057 patent/US10875013B2/en active Active
- 2018-12-20 CN CN201880087252.9A patent/CN111683748B/zh active Active
- 2018-12-20 WO PCT/US2018/066633 patent/WO2019126404A1/en unknown
- 2018-12-20 EP EP18891334.7A patent/EP3727684A4/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214435A (zh) * | 2007-12-26 | 2008-07-09 | 广西南宁化学制药有限责任公司 | 固定化钼酸盐催化剂的制备方法 |
| CN103492066A (zh) * | 2011-03-30 | 2014-01-01 | 艾尼股份公司 | 过渡金属的混合氧化物、由其获得的加氢处理催化剂和制备方法 |
| WO2017106125A1 (en) * | 2015-12-15 | 2017-06-22 | Uop Llc | Crystalline bis-ammonia transition metal molybdotungstate |
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