CN112218715B - 过渡金属钨酸盐材料 - Google Patents
过渡金属钨酸盐材料 Download PDFInfo
- Publication number
- CN112218715B CN112218715B CN201980037159.1A CN201980037159A CN112218715B CN 112218715 B CN112218715 B CN 112218715B CN 201980037159 A CN201980037159 A CN 201980037159A CN 112218715 B CN112218715 B CN 112218715B
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- China
- Prior art keywords
- transition metal
- varies
- metal tungstate
- mixture
- binder
- 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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- 239000000463 material Substances 0.000 title claims abstract description 72
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 53
- -1 Transition metal tungstate Chemical class 0.000 title claims description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 19
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 49
- 239000000203 mixture Substances 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 27
- 239000011230 binding agent Substances 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 239000011541 reaction mixture 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 11
- 125000002091 cationic group Chemical group 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 238000005486 sulfidation Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000011426 transformation method Methods 0.000 claims 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical group 0.000 abstract description 6
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012018 catalyst precursor Substances 0.000 abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011572 manganese Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical class [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 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 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 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
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-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
- 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 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
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000004679 hydroxides Chemical class 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
- 238000011065 in-situ storage 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
- 150000002739 metals Chemical class 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 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
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 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
- 239000011787 zinc oxide Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 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
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 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 1
- 238000004458 analytical method Methods 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
- ZRUWFKRETRELPY-UHFFFAOYSA-N azane;nickel(2+) Chemical compound N.[Ni+2] ZRUWFKRETRELPY-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 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
- 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
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-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
- 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
- 239000013078 crystal Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000013481 data capture Methods 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
- 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
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- 230000029087 digestion Effects 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
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation 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
- 150000004820 halides Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 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
- 229910021645 metal ion Inorganic materials 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 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
- 230000009466 transformation Effects 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
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
Classifications
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- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/38—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, or compounds thereof
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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
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- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G45/72—Controlling or regulating
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G47/06—Sulfides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
已经开发了氢化处理催化剂或催化剂前体。该催化剂为过渡金属钨酸盐材料或从其衍生的金属硫化物。使用结晶氨过渡金属钨酸盐材料的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
本发明涉及一种新催化剂诸如氢化处理催化剂。更具体地讲,本发明涉及一种过渡金属钨酸盐材料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,以便明确其结构。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处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和至7.5之间形成,其中在较高pH处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,反映了纳米级材料的性能特征。
发明内容
已经生产了过渡金属钨酸盐材料并且任选地硫化,以产生活性催化剂或催化剂前体用于氢化处理催化剂。过渡金属钨酸盐材料具有显示 和/>处的峰的X-射线粉末衍射图案。过渡金属钨酸盐材料具有下式:
AmM(OH)n(W)yOz
其中‘A’选自NH3、H2O或它们的组合;m从0.001至50、或从1至25、或从2至12变化;‘n’从0.001至10变化;‘M’为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的组合的金属;‘y’从0.5至2、或从0.75至1.5、或从0.9至1.25变化;‘z’为满足所述材料中存在的阳离子物类的化合价总和的数;所述材料还由显示表A中所列d-间距处的峰的x-射线粉末衍射图案来表征:
表A
另一个实施方案涉及一种制备具有下式的过渡金属钨酸盐材料的方法:
AmM(OH)n(W)yOz
其中‘A’选自NH3、H2O或它们的组合;m从0.001至50、或从1至25、或从2至12变化;‘n’从0.001至10变化;‘M’为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的组合的金属;‘y’从0.5至2、或从0.75至1.5、或从0.9至1.25变化;‘z’为满足所述材料中存在的阳离子物类的化合价总和的数;所述材料还由显示表A中所列d-间距处的峰的x-射线粉末衍射图案来表征:
表A
所述方法包括:形成包含NH3、H2O或它们的组合、M源和W源的反应混合物;以及使该混合物在升高的温度在开口或密封的容器中反应,然后回收过渡金属钨酸盐材料。该方法还可包括将所回收的过渡金属钨酸盐材料在100℃至350℃的温度处干燥30分钟至48小时。
另一个实施方案涉及一种转化方法,该转化方法包括:使硫化剂与材料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接触以生成至少一种产物,所述物质包含:具有下式的过渡金属钨酸盐材料:
AmM(OH)n(W)yOz
其中‘A’选自NH、H2O或它们的组合;m从0.001至50、或从1至25、或从2至12变化;‘n’从0.001至10变化;‘M’为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的组合的金属;‘y’从0.5至2、或从0.75至1.5、或从0.9至1.25变化;‘z’为满足所述材料中存在的阳离子物类的化合价总和的数;所述材料还由显示表A中所列d-间距处的峰的x-射线粉末衍射图案来表征:
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
附图是通过实施例中所述的方法制备的过渡金属钨酸盐材料的x-射线粉末衍射图案。
具体实施方式
本发明涉及过渡金属钨酸盐组合物和用于制备该组合物的方法。该材料具有名称UPM-24。该组合物具有以下经验式:
AmM(OH)n(W)yOz
其中‘A’选自NH3、H2O或它们的组合;m从0.001至50、或从1至25、或从2至12变化;‘n’从0.001至10变化;‘M’为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的组合的金属;‘y’从0.5至2、或从0.75至1.5、或从0.9至1.25变化;‘z’为满足所述材料中存在的阳离子物类的化合价总和的数。
本发明的过渡金属钨酸盐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。
过渡金属钨酸盐组合物还由显示表A中所列d-间距处的峰的x-射线粉末衍射图案来表征。
表A
本发明的过渡金属钨酸盐组合物的特征还在于附图中所示的x-射线粉末衍射图案。
该过渡金属钨酸盐组合物可通过反应混合物的溶剂加热结晶来制备,通常通过使反应性钨源与合适金属‘M’混合来制备。
M源和W源包括但不限于M或W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。M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、氯化钒以及它们的任何混合物。附加的来源包括但不限于钨酸盐和硫钨酸盐,诸如三氧化钨、钨酸、四氯氧化钨、六氯化钨、氢钨酸盐、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,其中组分诸如例如Ni、W、NH4OH和H2O混合在一起。作为具体示例,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:AWOz:B(NH3):H2O
其中‘M’选自由以下项组成的组:铁、钴、镍、锰、钒、铜、锌以及它们的组合;‘x’为满足‘M’化合价的数;‘A’表示‘W’相对于‘M’的比率,并且从0.4至2、或从0.4至1.5、或从0.5至1.25变化;‘z’为满足‘W’化合价的数;‘B’表示‘NH3’的摩尔比并且可从0.1至100、或从1至50、或从2.5至25变化;H2O的摩尔比从1至5000、或从10至300、或从20至100变化。
使包含NH3、H2O或它们的组合以及M源和W源的反应混合物在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90℃至120℃,并且在另一个实施方案中,温度在200℃至250℃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,合成可在开口容器中进行。将过渡金属钨酸盐组合物作为反应产物回收。任选地,回收的过渡金属钨酸盐材料可在100℃至350℃的温度处干燥30分钟至48小时。回收可通过蒸发溶剂、滗析、过滤或离心进行。过渡金属钨酸盐组合物的特征在于如上表A和附图所示的x-射线粉末衍射图案。
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地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。
在一个实施方案中,可在反应混合物反应之前形成中间体。通过去除NH3、H2O中的至少一些或它们的组合以生成中间体而形成中间体,中间体可为沉淀或者反应混合物的至少一部分,或者沉淀和反应混合物的一部分两者。然后,使中间体作为反应混合物在25℃至500℃的温度处反应30分钟至14天的一段时间以生成过渡金属钨酸盐材料。
一旦形成,该过渡金属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、三水铝矿、快速煅烧的三水铝矿、η-氧化铝、氧化锆、二氧化钛、氧化铝涂覆的二氧化钛、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钨酸盐组合物中,并且粘结剂的量可在最终催化剂的1重量%至30重量%,或最终催化剂的5重量%至26重量%的范围内。粘结剂可与过渡金属钨酸盐组合物化学键合,或者以与过渡金属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,过渡金属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,所述金属硫化物继而作为催化剂用于应用中。硫化可在多种硫化条件下进行,诸如通过过渡金属钨酸盐与硫化剂诸如含硫流或进料流的接触,或者通过与H2S/H2的气体混合物的接触,或上述二者来进行。过渡金属钨酸盐的硫化可在升高的温度执行,该升高的温度通常在50℃至600℃、或150℃至500℃、或250℃至450℃的范围内。由硫化步骤获得的物质,分解产物被称为金属硫化物,其可用作转化方法中的催化剂。如上所述,金属硫化物可存在于与至少一种粘结剂的混合物中。硫化步骤可在以下位置中进行:远离其他合成步骤,远离转化过程的位置,或远离合成的位置和远离转化过程的位置两者。
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,过渡金属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,所述金属硫化物继而作为催化剂用于应用中。硫化可在多种硫化条件下进行,诸如通过过渡金属钨酸盐与硫化剂诸如含硫流或进料流的接触,或者通过使用H2S/H2的气体混合物,或上述二者来进行。过渡金属钨酸盐的硫化可在升高的温度执行,该升高的温度通常在50℃至600℃、或150℃至500℃、或250℃至450℃的范围内。由硫化步骤获得的物质,分解产物被称为金属硫化物,其可用作转化方法中的催化剂。如上所述,金属硫化物的至少一部分可存在于与至少一种粘结剂的混合物中。硫化步骤可在以下位置中进行:远离其他合成步骤,远离转化过程的位置,或远离合成的位置和远离转化过程的位置两者。
如所讨论的,本发明的过渡金属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,其中过渡金属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,转化方法包括使过渡金属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。进料与活性催化剂接触的时间(其被称为液时空速(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,当氢化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84Nm3 H2/m3至850Nm3 H2/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。
上述用于方法中的管线、导管、单元、设备、容器、周围环境、区域或类似物中的任一者均可配备有一个或多个监测部件,包括传感器、测量设备、数据捕获设备或数据传输设备。信号、工艺或状态测量以及来自监测部件的数据可用于监测工艺设备中、周围和与其有关的条件。由监测部件生成或记录的信号、测量和/或数据可通过一个或多个网络或连接收集、处理和/或传输,所述网络或连接可以是私有或公共的,通用的或专用的,直接的或间接的,有线的或无线的,加密的或未加密的,和/或它们的组合;本说明书并非旨在在这方面进行限制。
由监测部件生成或记录的信号、测量和/或数据可被传输到一个或多个计算设备或系统。计算设备或系统可包括至少一个处理器以及存储计算机可读指令的存储器,该计算机可读指令当由至少一个处理器执行时,使一个或多个计算设备执行可包括一个或多个步骤的工艺。例如,可配置一个或多个计算设备以从一个或多个监测部件接收与至少一件与该工艺相关联的设备相关的数据。一个或多个计算设备或系统可被配置为分析该数据。根据数据分析,一个或多个计算设备或系统可被配置为确定对本文所述的一个或多个工艺的一个或多个参数的一种或多种推荐调整。一个或多个计算设备或系统可被配置为传输加密或未加密的数据,其包括对本文所述的一个或多个工艺的一个或多个参数的一种或多种推荐调整。
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。
以下实施例中呈现的图案使用标准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=0.01-15,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中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
将六水合硝酸镍(29.1g,0.1摩尔的Ni)、偏钨酸铵水合物(25.3g,0.1摩尔的W)和脲(7.5g,0.125摩尔)在DI H2O(5g)中充分混合,并且在65℃在密封PTFE瓶中热处理24小时。然后将所得混合物转移至陶瓷坩埚并在100℃热处理另外16小时。通过X-射线粉末衍射分析所得的产物,并且将X-射线粉末衍射图案示于附图中。
实施例2
在于100℃在PTFE衬里的不锈钢消化容器中热处理12小时之前,将六水合硝酸钴(11.64g,0.04摩尔的Co)、六水合硝酸镍(11.63g,0.04摩尔的Ni)、水合偏钨酸铵(17.71g,0.07摩尔的W)和碳酸铵(30.76g,0.64摩尔的NH3)在DI H2O(2.5g)中充分混合。过滤所得浆液,并将产物在250℃干燥24小时。通过X-射线粉末衍射分析所得的产物,并且将X-射线粉末衍射图案示于附图中。
实施例3
将六水合硝酸镍(26.1g,0.09摩尔的Ni)、氧化锌(1.63g,0.02摩尔的Zn)、水合偏钨酸铵(17.71g,0.07摩尔的W)和碳酸铵(8.3g,0.17摩尔的NH3)在PTFE瓶中混合在一起。将混合物在70℃加热48小时,之后将所得绿色浆液转移到陶瓷皿中并在150℃干燥48小时。通过X-射线粉末衍射分析所得的产物,并且将X-射线粉末衍射图案示于附图中。
实施例4
将六水合硝酸镍(29.75g,0.1摩尔的Ni)和偏钨酸铵水合物(17.71g,0.07摩尔的W)以及脲(10g,0.167摩尔)和DI H2O(5g,0.278摩尔)在密封的PTFE瓶中混合在一起。将混合物在65℃伴随间歇混合进行热处理30小时,然后转移到陶瓷皿中并在200℃热处理。通过X-射线粉末衍射分析所得的产物,并且将X-射线粉末衍射图案示于附图中。
实施方案
虽然结合具体的实施方案描述了以下内容,但应当理解,该描述旨在说明而不是限制前述描述和所附权利要求书的范围。
本发明的第一实施方案为具有下式的过渡金属钨酸盐材料:
AmM(OH)n(W)yOz
其中‘A’为NH3、H2O或它们的组合;m从0.001至50变化;‘n’从0.001至10变化;‘M’为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的组合的金属;‘y’从0.5至2变化;‘z’为满足所述材料中存在的阳离子物类的化合价总和的数;所述材料还由显示表A中所列d-间距处的峰的x-射线粉末衍射图案来表征:
表A
本发明的一个实施方案为本段的先前实施方案至本段的第一实施方案中的一个、任一个或所有实施方案,其中所述过渡金属钨酸盐材料存在于与至少一种粘结剂的混合物中,并且其中所述混合物包含至多25重量%的粘结剂。本发明的一个实施方案为本段的先前实施方案至本段的第一实施方案中的一个、任一个或所有实施方案,其中所述粘结剂选自由以下项组成的组:二氧化硅、氧化铝和硅铝土。本发明的一个实施方案为本段的先前实施方案至本段的第一实施方案中的一个、任一个或所有实施方案,其中M是镍或钴。本发明的一个实施方案为本段的先前实施方案至本段的第一实施方案中的一个、任一个或所有实施方案,其中M是镍。
本发明的第二实施方案为制备具有下式的过渡金属钨酸盐材料的方法:
AmM(OH)n(W)yOz
其中‘A’为NH3、H2O或它们的组合;m从0.001至50变化;‘n’从0.001至10变化;‘M’为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的组合的金属;‘y’从0.5至2变化;‘z’为满足所述材料中存在的阳离子物类的化合价总和的数;所述材料还由显示表A中所列d-间距处的峰的x-射线粉末衍射图案来表征:
表A
所述方法包括:形成包含NH3、H2O或它们的组合、以及M源和W源的反应混合物;使所述反应混合物在自生环境中在50℃至250℃的温度处反应;以及回收所述过渡金属钨酸盐材料。本发明的一个实施方案为本段的先前实施方案至本段的第二实施方案中的一个、任一个或所有实施方案,还包括在使所述混合物在自生环境中在50℃至250℃的温度处反应之前,去除所述NH3、H2O或它们的组合中的至少一些以形成中间体。本发明的一个实施方案为本段的先前实施方案至本段的第二实施方案中的一个、任一个或所有实施方案,其中所述反应在50℃至250℃的温度处进行30分钟至14天的一段时间。本发明的一个实施方案为本段的先前实施方案至本段的第二实施方案中的一个、任一个或所有实施方案,其中所述回收是通过过滤或离心。本发明的一个实施方案为本段的先前实施方案至本段的第二实施方案中的一个、任一个或所有实施方案,还包括将所回收的结晶过渡金属钨酸盐材料在100℃至350℃的温度处干燥30分钟至48小时。本发明的一个实施方案为本段的先前实施方案至本段的第二实施方案中的一个、任一个或所有实施方案,还包括将粘结剂添加到所述回收的过渡金属钨酸盐材料中。本发明的一个实施方案为本段的先前实施方案至本段的第二实施方案中的一个、任一个或所有实施方案,其中所述粘结剂选自由以下项组成的组:氧化铝、二氧化硅和氧化铝-二氧化硅。本发明的一个实施方案为本段的先前实施方案至本段的第二实施方案中的一个、任一个或所有实施方案,还包括通过硫化来分解所述回收的过渡金属钨酸盐材料以形成金属硫化物。
本发明的第三实施方案为一种转化方法,所述转化方法包括:使材料与硫化剂接触以将所述材料的至少一部分转化为金属硫化物,以及使所述金属硫化物在转化条件下与进料接触以生成至少一种产物,其中所述材料包含具有下式的过渡金属钨酸盐材料:
AmM(OH)n(W)yOz
其中‘A’为NH3、H2O或它们的组合;m从0.001至50变化;‘n’从0.001至10变化;‘M’为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的组合的金属;‘y’从0.5至2变化;‘z’为满足所述材料中存在的阳离子物类的化合价总和的数;所述材料还由显示表A中所列d-间距处的峰的x-射线粉末衍射图案来表征:
表A
本发明的一个实施方案为本段的先前实施方案至本段的第三实施方案中的一个、任一个或所有实施方案,其中所述转化方法是氢化处理。本发明的一个实施方案为本段的先前实施方案至本段的第三实施方案中的一个、任一个或所有实施方案,其中所述转化方法选自由以下项组成的组: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。本发明的一个实施方案为本段的先前实施方案至本段的第三实施方案中的一个、任一个或所有实施方案,其中所述过渡金属钨酸盐材料、或所述金属硫化物的至少一部分、或上述两者存在于与至少一种粘结剂的混合物中,并且其中所述混合物包含至多25重量%的粘结剂。本发明的一个实施方案为本段的先前实施方案至本段的第三实施方案中的一个、任一个或所有实施方案,还包括以下项中的至少一项:感测所述方法的至少一个参数并由所述感测生成信号或数据;或者生成并且发送信号;或者生成并传输数据。
尽管没有进一步的详细说明,但据信,本领域的技术人员通过使用前面的描述可最大程度利用本发明并且可容易地确定本发明的基本特征而不脱离本发明的实质和范围以作出本发明的各种变化和修改,并且使其适合各种使用和状况。因此,前述优选的具体的实施方案应理解为仅例示性的,而不以无论任何方式限制本公开的其余部分,并且旨在涵盖包括在所附权利要求书的范围内的各种修改和等效布置。
在前述内容中,所有温度均以摄氏度示出,并且所有份数和百分比均按重量计,除非另外指明。
Claims (12)
1.一种具有下式的过渡金属钨酸盐材料:
AmM(OH)n(W)yOz
其中‘A’为NH3、H2O或它们的组合;m从0.001至50变化;‘n’从0.001至10变化;‘M’为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的组合的金属;‘y’从0.5至2变化;‘z’为满足所述材料中存在的阳离子物类的化合价总和的数;所述材料还由显示表A中所列d-间距处的峰的x-射线粉末衍射图案来表征:
表A
其中w=0.01-15,m=15-60,s=60-80以及vs=80-100。
2.根据权利要求1所述的过渡金属钨酸盐材料,其中所述过渡金属钨酸盐材料存在于与至少一种粘结剂的混合物中,所述至少一种粘结剂选自二氧化硅、氧化铝和硅铝土,并且其中所述混合物包含至多25重量%的粘结剂。
3.一种制备具有下式的过渡金属钨酸盐材料的方法:
AmM(OH)n(W)yOz
其中‘A’为NH3、H2O或它们的组合;m从0.001至50变化;‘n’从0.001至10变化;‘M’为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的组合的金属;‘y’从0.5至2变化;‘z’为满足所述材料中存在的阳离子物类的化合价总和的数;所述材料还由显示表A中所列d-间距处的峰的x-射线粉末衍射图案来表征:
表A
其中w=0.01-15,m=15-60,s=60-80以及vs=80-100,
所述方法包括:
a.形成包含NH3、H2O或它们的组合、以及M源和W源的反应混合物;
b.使所述反应混合物在自生环境中在50℃至250℃的温度处反应;以及
c.回收所述过渡金属钨酸盐材料。
4.根据权利要求3所述的方法,还包括在使所述混合物在自生环境中在50℃至250℃的温度处反应之前,去除所述NH3、H2O或它们的组合中的至少一些以形成中间体。
5.根据权利要求3所述的方法,其中所述反应在50℃至250℃的温度处进行30分钟至14天的一段时间。
6.根据权利要求3所述的方法,还包括将所回收的过渡金属钨酸盐材料在100℃至350℃的温度处干燥30分钟至48小时。
7.根据权利要求3所述的方法,还包括通过硫化来分解所述回收的过渡金属钨酸盐材料以形成金属硫化物。
8.一种转化方法,包括:使材料与硫化剂接触以将所述材料的至少一部分转化为金属硫化物,以及使所述金属硫化物在转化条件下与进料接触以生成至少一种产物,其中所述材料包含具有下式的过渡金属钨酸盐材料:
AmM(OH)n(W)yOz
其中‘A’为NH3、H2O或它们的组合;m从0.001至50变化;‘n’从0.001至10变化;‘M’为选自Mn、Fe、Co、Ni、V、Cu、Zn以及它们的组合的金属;‘y’从0.5至2变化;‘z’为满足所述材料中存在的阳离子物类的化合价总和的数;所述材料还由显示表A中所列d-间距处的峰的x-射线粉末衍射图案来表征:
表A
其中w=0.01-15,m=15-60,s=60-80以及vs=80-100。
9.根据权利要求8所述的方法,其中所述转化方法为加氢处理。
10.根据权利要求8所述的方法,其中所述转化方法选自由以下项组成的组:加氢脱氮、加氢脱硫、加氢脱金属、加氢脱硅、加氢脱芳烃和加氢异构化。
11.根据权利要求8所述的方法,其中所述转化方法选自由以下项组成的组:加氢精制和加氢裂解。
12.根据权利要求8所述的方法,其中所述过渡金属钨酸盐材料、或所述金属硫化物的至少一部分、或上述两者存在于与至少一种粘结剂的混合物中,并且其中所述混合物包含至多25重量%的粘结剂。
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