CN108367277B - 结晶双氨过渡金属钼钨酸盐 - Google Patents
结晶双氨过渡金属钼钨酸盐 Download PDFInfo
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- CN108367277B CN108367277B CN201680073308.6A CN201680073308A CN108367277B CN 108367277 B CN108367277 B CN 108367277B CN 201680073308 A CN201680073308 A CN 201680073308A CN 108367277 B CN108367277 B CN 108367277B
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- transition metal
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- bisammonia
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 51
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 70
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 36
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 21
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 229910052721 tungsten Inorganic materials 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000011541 reaction mixture Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- 239000011701 zinc Substances 0.000 description 11
- 239000010949 copper Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002178 crystalline material Substances 0.000 description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 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 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910015667 MoO4 Inorganic materials 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 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
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000000694 effects Effects 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
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- -1 transition metal molybdate Chemical class 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
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 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
- NSEQHAPSDIEVCD-UHFFFAOYSA-N N.[Zn+2] Chemical compound N.[Zn+2] NSEQHAPSDIEVCD-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000367 ab initio method Methods 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
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 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
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 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
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 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
- 238000012790 confirmation Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method 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
- 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 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
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008246 gaseous mixture 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 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
- 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
- 150000002739 metals Chemical class 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-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
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001935 peptisation Methods 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
- 238000010992 reflux Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910001845 yogo sapphire 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
Images
Classifications
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- 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
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
-
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Abstract
本发明开发了独特的结晶双氨过渡金属钼钨酸盐材料。此材料可以用作加氢操作催化剂。加氢操作可以包括：加氢脱氮，加氢脱硫，加氢脱金属化，加氢脱芳构化，加氢脱硅，加氢异构化，加氢处理，加氢精制，以及加氢裂解。
Description
在先国家申请的优先权
本申请要求2015年12月15日递交的美国申请No.62/267,865的优先权，将其内容全部引入本文以供参考。
发明领域
本发明涉及新的加氢操作催化剂。更具体而言，本发明涉及独特的结晶双氨过渡金属钼钨酸盐及其作为加氢操作催化剂的用途。加氢操作可以包括加氢脱氮，加氢脱硫，加氢脱金属化，加氢脱硅，加氢脱芳构化，加氢异构化，加氢处理，加氢精制和加氢裂解。
背景技术
为了满足日益增长的对石油产品的需求，希望更多地利用含硫石油，当与在燃料中的氮和硫浓度相关的环境法规更严格时，含硫石油引起精制问题加重。在精制工艺的加氢处理期间的目的是从燃料原料去除含硫(加氢脱硫–HDS)和含氮(加氢脱氮–HDN)的化合物，此目的是通过将有机氮和硫分别转化成氨和硫化氢实现的。
从1940年开始，已经证明使用含镍(Ni)和钼(Mo)或钨(W)的催化剂能除去至多80％的硫。参见例如V.N.Ipatieff,G.S.Monroe,R.E.Schaad,Division of PetroleumChemistry,115th Meeting ACS,San Francisco,1949。数十年来，现在十分关注开发能催化深度脱硫的材料，从而将硫浓度降低到ppm水平。一些近期的突破致力于开发和使用更活泼和稳定的催化剂以生产用于超低硫燃料的原料。一些研究已经证明通过消除载体例如Al2O3改进了HDS和HDN活性。使用无载体的本体材料提供一种提高在反应器中的活性相载荷的途径，并提供另一种关于这些催化剂的化学机理。
在此领域中，较近期的研究致力于通过无载体的Ni-Mo/W“三金属”材料实现超深脱硫性能，例如参见US 6,156,695。含有钼、钨和镍的广泛无定形混合金属氧化物的受控合成明显优于常规的加氢处理催化剂。三金属混合金属氧化物材料的结构化学与水滑石类材料相似，参见详细描述层状钼酸镍材料的合成和表征的文献，其中报道了用钨部分地代替钼能获得广泛的无定形相，其在通过硫化分解时获得优异的加氢处理活性。
这些层状的类似水滑石的材料的化学性质首先由H.Pezerat,contributionàl‘étude des molybdates hydrates de zinc,cobalt et nickel,C.R.Acad.Sci.,261,5490报道，其中确认了具有理想式MMoO4.H2O、EHM2O-(MoO4)2.H2O和E2-x(H3O)xM2O(MoO4)2的一系列相，其中E可以是NH4 +、Na+或K+，并且M可以是Zn2+、Co2+或Ni2+。
Pezerat将所观察到的不同相归类为Φc、Φy或Φy，并检测Φx和Φy的晶体结构；但是由于小微晶尺寸、受限的结晶学能力和材料的复杂性质的组合，对于这些材料的结构评估质量存在疑问。在70年代中期，Clearfield等人试图更详细地分析Φx和Φy相，参见例如A.Clearfield,M.J.Sims,R.Gopal,Inorg.Chem.,15,335；A.Clearfield,R.Gopal,C.H.Saldarriaga-Molina,Inorg.Chem.,16,628。对于从水热方法得到的产物进行的单晶研究允许确认Φx结构；但是他们没有成功合成Φy，而是合成了另一个相Na-Cu(OH)(MoO4)，参见A.Clearfield,A.Moini,P.R.Rudolf,Inorg.Chem.,24,4606。
Φy的结构未得到确认，直到1996年Ying等人的研究。他们研究了室温ChimieDouce合成技术以得到层状钼酸锌铵，得到亚稳态的铝取代的红锌矿相，这通过煅烧Zn/Al层状双氢氧化物(Zn4Al2(OH)12CO3.zH2O)制得。参见例如D.Levin,S.L.Soled,J.Y.Ying,Inorg.Chem.,1996,35,4191-4197。此材料与七钼酸铵的溶液在室温下反应以制备高度结晶的化合物，其结构不能通过常规的从头开始(ab-initio)方法测定。Astier将此材料进行指标化，得到与钼酸镍铵相同的结晶学参数，参见例如M.P.Astier,G.Dji,S.Teichner,J.Ann.Chim.(Paris),1987,12,337，属于铵-胺-镍-钼氧化物类的材料与Pezerat的材料紧密相关。Astier没有公开此类材料的任何详细结构数据，所以Ying等人重新制备此材料并通过高分辨率粉末衍射进行分析，从而明确其结构。Ying等人将此类材料命名为“层状过渡金属钼酸盐”或LTM。
发明概述
本发明制备了独特的结晶双氨过渡金属钼钨酸盐材料，并任选地进行硫化，从而得到活性加氢操作催化剂。结晶双氨过渡金属钼钨酸盐材料具有独特的x-射线粉末衍射图案，其中在7.33、5.06和
处显示强峰。结晶双氨过渡金属钼钨酸盐材料具有下式：
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内，或是0.6-1.3，或是0.8-1.2；‘y’在0.01-0.25的范围内，或是0.1-0.2；(x+y)的总和必须≤1.501或≤1.2；‘z’是满足M、Mo和W的价键总和的数值；所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
另一个实施方案涉及制备具有下式的结晶双氨过渡金属钼钨酸盐材料的方法，
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内，或是0.6-1.3，或是0.8-1.2；‘y’在0.01-0.25的范围内，或是0.1-0.2；(x+y)的总和必须≤1.501或≤1.2；‘z’是满足M、Mo和W的价键总和的数值；所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
此方法包括：形成含有NH4OH、H2O以及M、W和Mo的源物质的反应混合物；将反应混合物的pH调节到8.5-10的pH；并回收结晶双氨金属钼酸盐材料。
再一个实施方案涉及一种转化方法，包括使进料与催化剂在转化条件下接触以得到至少一种产物，所述催化剂包含：具有下式的结晶双氨过渡金属钼钨酸盐材料：
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内，或是0.6-1.3，或是0.8-1.2；‘y’在0.01-0.25的范围内，或是0.1-0.2；(x+y)的总和必须≤1.501或≤1.2；‘z’是满足M、Mo和W的价键总和的数值；所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
本发明的其它特征和优点将从本发明的下文描述、附图和权利要求显现出来。
附图简述：
图1是如实施例1-3中所述通过沸腾结晶制备的结晶双氨过渡金属钼钨酸盐的x-射线粉末衍射图案。
本发明的详细描述
本发明涉及结晶双氨过渡金属钼钨酸盐组合物，制备此组合物的方法，以及使用此组合物作为催化剂的转化方法。此组合物被指定为UPM-6。此组合物具有经验式：
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内，或是0.6-1.3，或是0.8-1.2；‘y’在0.01-0.25的范围内，或是0.1-0.2；(x+y)的总和必须≤1.501或≤1.2；‘z’是满足M、Mo和W的价键总和的数值。
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表示上述金属，或上述金属的组合。结构单元本身重复成为至少两个相邻的单元，且没有键接的终止。此组合物可以具有一维网络，例如直链。
结晶双氨过渡金属钼钨酸盐组合物进一步的特征在于具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
本发明的结晶双氨过渡金属钼钨酸盐具有如图1所示的x-射线粉末衍射图案。
结晶双氨过渡金属钼钨酸盐是通过反应混合物的溶剂加热结晶制备的，所述反应混合物通常是通过将反应性的钼源和钨源和合适金属‘M’的源物质和溶剂以及氨源混合制得的。可用于本发明中的钼源的具体例子包括、但不限于三氧化钼，二钼酸铵，硫代钼酸铵，以及七钼酸铵。可用于本发明中的钨源的具体例子包括、但不限于三氧化钨、二钨酸铵、硫代钨酸铵和偏钨酸铵。其它金属“M”的源物质包括、但不限于相应的卤化物、乙酸盐，硝酸盐、碳酸盐、硫醇和氢氧化物盐。具体例子包括：氯化镍，氯化钴，溴化镍，溴化钴，氯化镁，氯化锌，硝酸镍，硝酸钴，硝酸铁，硝酸锰，硝酸锌，乙酸镍，乙酸钴，乙酸铁，碳酸镍，碳酸钴，氢氧化锌，氢氧化镍和氢氧化钴。
氨源可以包括、但不限于：氢氧化铵，碳酸铵，碳酸氢铵，氯化铵，氟化铵，或其混合物。
通常，用于制备本发明组合物的工艺涉及形成反应混合物，其中所有组分例如Ni、Mo、W、NH4OH和H2O在溶液中一起混合。例如，反应混合物可以按照由下式表示的氧化物摩尔比率形成：
AMOx：BMoOy：CWOz：D(NH3)：H2O
其中‘M’是选自铁、钴、镍、锰、铜、锌及其混合物；‘A’表示‘M’的摩尔比率，并且可以在0.1-3的范围内，或是0.75-2，或是1-1.5；‘x’是满足M价键的数值；‘B’表示‘Mo’的摩尔比率，并且可以在0.1-3的范围内，或是0.75-2，或1-1.5；‘y’是满足Mo价键的数值；‘C’表示‘W’的摩尔比率，并且可以在0.01-2的范围内，或是0.05-1，或0.2-0.75；‘z’是满足W价键的数值；‘D’表示NH3的摩尔比率，并且可以在0.5-15的范围内，或是1-10，或是3-7；H2O的摩尔比率是在0.1-1000的范围内，或是1-300，或是1-100。
必要的是将反应混合物的pH调节到8.5-10的pH。混合物的pH可以通过加入碱来控制，例如NH4OH、季铵氢氧化物、胺等。
一旦形成反应混合物，反应混合物在60-250℃的温度下反应30分钟至约14天的时间。在一个实施方案中，反应温度的范围是70-180℃；在另一个实施方案中的温度范围是80-140℃。在一个实施方案中，反应时间是1-48小时；在另一个实施方案中，反应时间是2-12小时。此反应是在大气压下或在密封容器中在自生压力下进行。在一个实施方案中，合成可以在开放容器中在回流条件下进行。结晶双氨过渡金属钼钨酸盐的特征在于其独特的x-射线粉末衍射图案，如上表A和图1中所示。
在形成后，可以向结晶双氨过渡金属钼钨酸盐组合物中引入粘合剂，其中选择的粘合剂包括但不限于：阴离子性和阳离子性粘土，例如水滑石，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，氧化铝例如(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，氧化铝涂布的氧化钛，二氧化硅-氧化铝，二氧化硅涂布的氧化铝，氧化铝涂布的二氧化硅，以及它们的混合物，或通常称为颗粒粘合剂的用于保持颗粒完整性的其它材料。这些粘合剂可以在胶溶或不胶溶的情况下施用。可以将粘合剂加入本体结晶双氨过渡金属钼钨酸盐组合物中，并且粘合剂的量可以是最终催化剂的1-30重量％，或是最终催化剂的5-26重量％。粘合剂可以与结晶双氨过渡金属钼钨酸盐化学连接，或者作为与结晶双氨过渡金属钼钨酸盐的物理混合物存在。
含有或不含粘合剂的结晶双氨过渡金属钼钨酸盐可以然后在各种硫化条件下进行硫化或预硫化，这些包括通过结晶双氨过渡金属钼钨酸盐与含硫进料接触以及使用H2S/H2的气态混合物。结晶双氨过渡金属钼钨酸盐的硫化是在升高的温度下进行，通常是50-600℃，或150-500℃，或250-450℃。
本发明的无载体的结晶双氨过渡金属钼钨酸盐材料可以在各种烃转化方法中用作催化剂或催化剂载体。加氢操作方法是一种烃转化方法，其中结晶双氨过渡金属钼钨酸盐材料用作催化剂。加氢操作方法的具体例子是本领域公知的，包括加氢处理或加氢精制，氢化，加氢脱芳构化，加氢脱金属化，加氢脱硅，加氢裂解，加氢脱氮，和加氢脱硫。
上述加氢操作方法的操作条件通常包括反应压力为2.5-17.2MPa或5.5-17.2MPa，反应温度为245-440℃或285-425℃。进料与活性催化剂接触的时间由液体小时空速(LHSV)表示，应当在0.1h-1至10h-1的范围内，或是2.0h-1至8.0h-1。可以根据所用的进料使用这些范围的具体子范围。例如当对典型的柴油进料进行加氢处理时，操作条件可以包括3.5-8.6MPa、315-410℃、0.25-5/h，以及84-850Nm3H2/m3进料。其它进料可以包括汽油、石脑油、煤油、瓦斯油、馏出物和重整油。
下文提供实施例以更完全地描述本发明。这些实施例仅仅用于说明目的，不应理解为限制本发明权利要求的宽范围。
在以下实施例中所示的图案是使用标准x-射线粉末衍射技术得到的。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辐照的衍射图案是通过合适的基于计算机的技术得到的。将粉末样品以扁平方式压成平板，并连续地从3°至70°(2θ)扫描。从由θ表示的衍射峰位置得到晶面间距(d)，其单位为埃，其中θ是从数字化数据观察得到的布拉格角。强度是从减去背景之后的衍射峰积分面积测定的，其中“IO”是最强线或峰的强度，“I”是每个其它峰的强度。如本领域技术人员理解的那样，参数2θ的检测存在人为和机械误差，这些误差的组合导致每个2θ报告数值的不确定度为±0.4°。这种不确定度也可以解读成d-间距的报告数值，此报告数值是从2θ数值计算的。在报告的一些x-射线图案中，d-间距的相对强度是由符号vs、s、m和w表示的，它们分别表示非常强、强、中等和弱。按照100(I/I0)计，上述符号定义为：
w＝0-15，m＝15-60，s＝60-80，和vs＝80-100。
在一些情况下，合成产物的纯度可以参照其x-射线粉末衍射图案来评价。因此，例如如果样品被描述为是纯的，则这仅仅表示样品的x-射线图案不含归属于结晶杂质的线，并不表示不存在无定形物质。本领域技术人员将能理解不同的不良结晶材料可以在相同的位置产生峰。如果材料是由多种不良结晶材料组成的，则对于每种不良结晶材料观察到的峰位置将在所得的汇总衍射图案中观察到。同样，可以在不同的单相结晶材料中在相同位置具有一些峰，这可以简单地表示在这些材料内的相似距离，并不表示这些材料具有相同的结构。
实施例1
在陶瓷盘中，将15.21g碳酸镍(0.15摩尔Ni)、13.24g七钼酸铵(0.075摩尔Mo)和18.20g偏钨酸铵(0.075摩尔W)加入25ml的浓缩氢氧化铵溶液中。在定期混合的情况下将此溶液于150℃干燥18小时。经干燥的残余物通过上述x-射线衍射进行分析，X-射线粉末衍射图案如图1所示。
实施例2
溶液A：在3L烧瓶中，将35.61g碳酸镍(0.3摩尔Ni)和28.79g三氧化钼(0.2摩尔Mo)加入300ml水中以形成浆液。溶液B：在500ml烧瓶中，将13.05g偏钨酸铵(0.05摩尔W)加入90ml的浓缩NH4OH溶液中。将溶液B加入溶液A中，然后于100℃回流。在加热期间，沉淀物溶解以在形成石灰绿色沉淀物之前得到清澈的深蓝色溶液。在2小时后，观察到绿色沉淀物悬浮在蓝色的pH 9溶液中。此沉淀物被冷却到室温，过滤，用90ml的90℃水洗涤，然后于100℃干燥。经干燥的沉淀物的x-射线衍射图案符合如图1所示的X-射线粉末衍射图案。
实施例3
溶液A：在3L烧瓶中，将35.61g碳酸镍(0.3摩尔Ni)和28.79g三氧化钼(0.2摩尔Mo)加入300ml水中以形成浆液。溶液B：在500ml烧瓶中，将26.1g偏钨酸铵(0.1摩尔W)加入90ml的浓缩NH4OH溶液中。将溶液B加入溶液A中，然后于100℃回流。在加热期间，沉淀物溶解以在形成石灰绿色沉淀物之前得到清澈的深蓝色溶液。在3小时后，观察到绿色沉淀物悬浮在蓝色的pH 9溶液中。此沉淀物被冷却到室温，过滤，用90ml的90℃水洗涤，然后于100℃干燥。经干燥的沉淀物的x-射线衍射图案符合如图1所示的X-射线粉末衍射图案。
本发明的实施方案：
实施方案1是具有下式的结晶双氨过渡金属钼钨酸盐材料：
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内，或是0.6-1.3，或是0.8-1.2；‘y’在0.01-0.25的范围内，或是0.1-0.2；(x+y)的总和必须≤1.501或≤1.2；‘z’是满足M、Mo和W的价键总和的数值，所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
实施方案1的结晶双氨过渡金属钼钨酸盐材料可以作为与至少一种粘合剂的混合物存在，并且其中此混合物含有至多25重量％的粘合剂。
实施方案1的结晶双氨过渡金属钼钨酸盐材料可以作为与至少一种粘合剂的混合物存在，并且其中此混合物含有至多25重量％的粘合剂，其中粘合剂是选自二氧化硅、氧化铝和二氧化硅-氧化铝。
实施方案1的结晶双氨过渡金属钼钨酸盐材料，其中M是镍或钴。
实施方案1的结晶双氨过渡金属钼钨酸盐材料，其中M是镍。
实施方案1的结晶双氨过渡金属钼钨酸盐材料，其中此材料是被硫化的。
实施方案2是制备具有下式的结晶双氨过渡金属钼钨酸盐材料的方法，
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内，或是0.6-1.3，或是0.8-1.2；‘y’在0.01-0.25的范围内，或是0.1-0.2；(x+y)的总和必须≤1.501或≤1.2；‘z’是满足M、Mo和W的价键总和的数值，所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
此方法包括：形成含有M、Mo和W的源物质的反应混合物；将反应混合物的pH调节到8.5-10的pH；将反应混合物加热到85-100℃，直到所得的pH是8.5-9.5；然后回收结晶双氨过渡金属钼钨酸盐材料。
实施方案2的方法，其中所述回收可以通过过滤或离心进行。
实施方案2的方法，其中还包括将粘合剂加入所回收的结晶双氨过渡金属钼钨酸盐材料中。
实施方案2的方法，其中还包括将粘合剂加入所回收的结晶双氨过渡金属钼钨酸盐材料中，其中粘合剂可以选自氧化铝、二氧化硅和氧化铝-二氧化硅。
实施方案2的方法，其中还包括使所回收的结晶双氨过渡金属钼钨酸盐材料进行硫化。
实施方案3是一种转化方法，此方法包括使进料与催化剂在转化条件下接触以得到至少一种产物，所述催化剂包含：具有下式的结晶双氨过渡金属钼钨酸盐材料：
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内，或是0.6-1.3，或是0.8-1.2；‘y’在0.01-0.25的范围内，或是0.1-0.2；(x+y)的总和必须≤1.501或≤1.2；‘z’是满足M、Mo和W的价键总和的数值，所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
实施方案3的方法，其中转化方法是加氢操作。
实施方案3的方法，其中转化方法是选自加氢脱氮，加氢脱硫，加氢脱金属化，加氢脱芳构化，加氢异构化，加氢脱硅，加氢处理，加氢精制，以及加氢裂解。
实施方案3的方法，其中结晶双氨过渡金属钼钨酸盐材料作为与至少一种粘合剂的混合物存在，和其中此混合物含有至多25重量％的粘合剂。
实施方案3的方法，其中结晶双氨过渡金属钼钨酸盐材料是被硫化的。
Claims (11)
1.具有下式的结晶双氨过渡金属钼钨酸盐材料：
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内；‘y’在0.01-0.25的范围内；(x+y)的总和必须≤1.501；‘z’是满足M、Mo和W的价键总和的数值，所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
2.权利要求1的结晶双氨过渡金属钼钨酸盐材料，其中结晶双氨过渡金属钼钨酸盐材料是作为与选自二氧化硅、氧化铝和二氧化硅-氧化铝的至少一种粘合剂的混合物存在，并且其中此混合物含有至多25重量％的粘合剂。
3.权利要求1的结晶双氨过渡金属钼钨酸盐材料，其中结晶双氨过渡金属钼钨酸盐材料是被硫化的。
4.一种制备具有下式的结晶双氨过渡金属钼钨酸盐材料的方法，
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内；‘y’在0.01-0.25的范围内；(x+y)的总和必须≤1.501；‘z’是满足M、Mo和W的价键总和的数值，所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
此方法包括：
(a)形成含有M、W和Mo的源物质的反应混合物；
(b)将反应混合物的pH调节到8.5-10的pH，其中混合物的pH通过加入碱来控制，碱选自NH4OH、季铵氢氧化物和胺；
(c)将反应混合物加热到85-100℃，直到所得的pH是8.5-9.5；和
(d)回收结晶双氨过渡金属钼钨酸盐材料。
5.权利要求4的方法，还包括将选自氧化铝、二氧化硅和氧化铝-二氧化硅的粘合剂加入所回收的结晶双氨过渡金属钼钨酸盐材料中。
6.权利要求4的方法，还包括使所回收的结晶双氨过渡金属钼钨酸盐材料进行硫化。
7.一种转化方法，包括使进料与催化剂在转化条件下接触以得到至少一种产物，所述催化剂包含：具有下式的结晶双氨过渡金属钼钨酸盐材料：
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内；‘y’在0.01-0.25的范围内；(x+y)的总和必须≤1.501；‘z’是满足M、Mo和W的价键总和的数值，所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
8.权利要求7的方法，其中转化方法是加氢操作方法，和其中加氢操作方法是选自加氢脱金属化，加氢脱芳构化，加氢异构化，加氢脱硅，加氢精制，以及加氢裂解。
9.权利要求8的方法，其中加氢精制选自加氢脱氮和加氢脱硫。
10.权利要求7的方法，其中结晶双氨过渡金属钼钨酸盐材料是作为与至少一种粘合剂的混合物存在，并且其中此混合物含有至多25重量％的粘合剂。
11.权利要求7的方法，其中结晶双氨过渡金属钼钨酸盐材料是被硫化的。
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| US10773245B2 (en) | 2017-08-25 | 2020-09-15 | Uop Llc | Crystalline transition metal molybdotungstate |
| US10882030B2 (en) | 2017-08-25 | 2021-01-05 | Uop Llc | Crystalline transition metal tungstate |
| US11007515B2 (en) | 2017-12-20 | 2021-05-18 | Uop Llc | Highly active trimetallic materials using short-chain alkyl quaternary ammonium compounds |
| US10843176B2 (en) * | 2017-12-20 | 2020-11-24 | Uop Llc | Highly active quaternary metallic materials using short-chain alkyl quaternary ammonium compounds |
| US11117811B2 (en) | 2017-12-20 | 2021-09-14 | Uop Llc | Highly active quaternary metallic materials using short-chain alkyl quaternary ammonium compounds |
| US10995013B2 (en) | 2017-12-20 | 2021-05-04 | Uop Llc | Mixed transition metal tungstate |
| US11034591B2 (en) | 2017-12-20 | 2021-06-15 | Uop Llc | Highly active quaternary metallic materials using short-chain alkyl quaternary ammonium compounds |
| US10875013B2 (en) * | 2017-12-20 | 2020-12-29 | Uop Llc | Crystalline oxy-hydroxide transition metal molybdotungstate |
| US11078088B2 (en) | 2017-12-20 | 2021-08-03 | Uop Llc | Highly active multimetallic materials using short-chain alkyl quaternary ammonium compounds |
| US10822247B2 (en) | 2017-12-20 | 2020-11-03 | Uop Llc | Highly active trimetallic materials using short-chain alkyl quaternary ammonium compounds |
| US10682632B2 (en) * | 2018-06-26 | 2020-06-16 | Uop Llc | Transition metal tungstate material |
| US10688479B2 (en) | 2018-06-26 | 2020-06-23 | Uop Llc | Crystalline transition metal tungstate |
| US10737248B2 (en) | 2018-06-26 | 2020-08-11 | Uop Llc | Crystalline transition metal tungstate |
| US10737249B2 (en) | 2018-06-26 | 2020-08-11 | Uop Llc | Crystalline transition metal molybdotungstate |
| US11033883B2 (en) | 2018-06-26 | 2021-06-15 | Uop Llc | Transition metal molybdotungstate material |
| US10981151B2 (en) * | 2018-06-29 | 2021-04-20 | Uop Llc | Poorly crystalline transition metal molybdotungstate |
| US10737246B2 (en) | 2018-06-29 | 2020-08-11 | Uop Llc | Poorly crystalline transition metal tungstate |
| US10933407B2 (en) | 2018-12-13 | 2021-03-02 | Uop Llc | Ammonia-free synthesis for Al or Si based multimetallic materials |
| US11213803B2 (en) | 2018-12-13 | 2022-01-04 | Uop Llc | Ammonia-free synthesis for Al or Si based multimetallic materials |
| US11426711B2 (en) | 2019-05-22 | 2022-08-30 | Uop Llc | Method of making highly active metal oxide and metal sulfide materials |
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| US10449523B2 (en) | 2019-10-22 |
| US20180169633A1 (en) | 2018-06-21 |
| EP3389856A4 (en) | 2020-11-11 |
| EP3389856A1 (en) | 2018-10-24 |
| NZ742219A (en) | 2019-10-25 |
| KR102115689B1 (ko) | 2020-05-26 |
| RU2699797C1 (ru) | 2019-09-11 |
| SA518391640B1 (ar) | 2021-12-09 |
| WO2017106125A1 (en) | 2017-06-22 |
| JP2019505465A (ja) | 2019-02-28 |
| KR20180091073A (ko) | 2018-08-14 |
| CN108367277A (zh) | 2018-08-03 |
| CA3004603A1 (en) | 2017-06-22 |
| CA3004603C (en) | 2020-12-08 |
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