CN108367940A - 结晶过渡金属羟基氧化物钼酸盐 - Google Patents
结晶过渡金属羟基氧化物钼酸盐 Download PDFInfo
- Publication number
- CN108367940A CN108367940A CN201680073365.4A CN201680073365A CN108367940A CN 108367940 A CN108367940 A CN 108367940A CN 201680073365 A CN201680073365 A CN 201680073365A CN 108367940 A CN108367940 A CN 108367940A
- Authority
- CN
- China
- Prior art keywords
- acid salt
- molybdic acid
- transitional metal
- range
- metal oxyhydroxides
- 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.)
- Granted
Links
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 title claims abstract description 44
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title description 7
- 239000000463 material Substances 0.000 claims abstract description 66
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical class O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 17
- 230000001070 adhesive effect Effects 0.000 claims description 17
- 239000011541 reaction mixture Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000005864 Sulphur Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 230000009466 transformation Effects 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 3
- 238000006477 desulfuration reaction Methods 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 230000023556 desulfurization Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 15
- 238000002425 crystallisation Methods 0.000 abstract description 10
- 230000008025 crystallization Effects 0.000 abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011733 molybdenum Substances 0.000 abstract description 7
- -1 ammonia transition metal Chemical class 0.000 abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 abstract description 4
- 238000004517 catalytic hydrocracking Methods 0.000 abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 239000002131 composite material Substances 0.000 description 12
- 239000010949 copper Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910013703 M(OH)x Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 239000002178 crystalline material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 229910015667 MoO4 Inorganic materials 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
- 238000001035 drying Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 238000005406 washing 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 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
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000013078 crystal Substances 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
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 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
- 150000002739 metals Chemical class 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004073 vulcanization Methods 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910013504 M-O-M Inorganic materials 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004176 ammonification Methods 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 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
- 239000011230 binding agent Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product 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 class 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
- 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 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
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 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
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 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
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 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
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 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
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-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
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
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
- 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
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
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Abstract
本发明开发了加氢操作催化剂。此催化剂是独特的结晶过渡金属羟基氧化物钼酸盐材料。使用的结晶氨过渡金属二钼钨酸盐材料的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.62/267,862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过渡金属羟基氧化物钼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过渡金属羟基氧化物钼酸盐材料，并任选地进行硫化，从而得到活性加氢操作催化剂。结晶过渡金属羟基氧化物钼酸盐材料具有独特的x-射线粉末衍射图案，其中在9.65、7.3和处显示强的布拉格峰。结晶过渡金属羟基氧化物钼酸盐材料具有下式：
(NH4)aM(OH)xMoyOz
其中‘a’在0.1-2.0的范围内；‘M’是选自Mg、Mn、Fe、Co、Ni、Cu及其混合物的金属；‘x’在0.1-2的范围内；‘y’在0.5-1.5的范围内；z是满足(2-n)+3(x+y)的价键的数值；所述材料的进一步特征在于具有x-射线衍射图案，其中显示表A所列出的结晶峰：
表A
另一个实施方案涉及制备具有下式的结晶过渡金属羟基氧化物钼酸盐材料的方法，
(NH4)aM(OH)xMoyOz
其中‘a’在0.1-2.0的范围内；‘M’是选自Mg、Mn、Fe、Co、Ni、Cu及其混合物的金属；‘x’在0.1-2的范围内；‘y’在0.5-1.5的范围内；z是满足(2-n)+3(x+y)的价键的数值；所述材料的进一步特征在于具有独特的x-射线衍射图案，其中显示表A所列出的结晶峰：
表A
此方法包括：形成含有NH4OH、H2O以及M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；进行反应，然后回收结晶过渡金属羟基氧化物钼酸盐材料。
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：具有下式的结晶过渡金属羟基氧化物钼酸盐材料：
(NH4)aM(OH)xMoyOz
其中‘a’在0.1-2.0的范围内；‘M’是选自Mg、Mn、Fe、Co、Ni、Cu及其混合物的金属；‘x’在0.1-2的范围内；‘y’在0.5-1.5的范围内；z是满足(2-n)+3(x+y)的价键的数值；所述材料的进一步特征在于具有独特的x-射线衍射图案，其中显示表A所列出的结晶峰：
表A
本发明的其它特征和优点将从本发明的下文描述、图1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金属羟基氧化物钼酸盐的x-射线衍射图案。
本发明的详细描述
本发明涉及结晶过渡金属羟基氧化物钼酸盐组合物，以及制备此组合物的方法。此材料被指定为UPM-8。此组合物具有经验式：
(NH4)aM(OH)xMoyOz
其中‘a’在0.1-2.0的范围内；‘M’是选自Mg、Mn、Fe、Co、Ni、Cu及其混合物的金属；‘x’在0.1-2的范围内；‘y’在0.5-1.5的范围内；z是满足(2-n)+3(x+y)的价键的数值。
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。
结晶过渡金属羟基氧化物钼酸盐组合物进一步的特征在于具有独特的x-射线衍射图案，其中显示表A所列出的结晶峰：
表A
本发明的结晶过渡金属羟基氧化物钼酸盐组合物进一步由图1所示的x-射线衍射图案表征。
结晶过渡金属羟基氧化物钼酸盐组合物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与合适金属‘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。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，硝酸镍，硝酸钴，硝酸铁，硝酸锰，乙酸镍，乙酸钴，乙酸铁，碳酸镍，碳酸钴，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溶剂加热工艺涉及形成反应混合物，其中所有组分例如Ni、Mo、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：cNH4OH：dH2O
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，并且在0.1-3的范围内；‘x’满足M的价键；‘b’表示Mo的摩尔比率，并且在0.1-3的范围内；‘y’满足Mo的价键；‘c’是NH4OH的摩尔比率，并且在0.1-5的范围内；‘d’是H2O的摩尔比率，并且在10-1000的范围内。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70-230℃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115-125℃；在另一个实施方案中的温度范围是180-200℃。在一个实施方案中，反应时间是4-6小时；在另一个实施方案中，反应时间是4-7天。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。作为反应产物回收结晶过渡金属羟基氧化物钼酸盐组合物。结晶过渡金属羟基氧化物钼酸盐组合物的特征在于其独特的x-射线衍射图案，如上表A和图1中所示。
在形成后，可以向结晶过渡金属羟基氧化物钼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：二氧化硅，氧化铝，二氧化硅-氧化铝，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。可以将粘合剂加入本体结晶过渡金属羟基氧化物钼酸盐组合物中，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％。粘合剂可以与结晶过渡金属羟基氧化物钼酸盐组合物化学连接，或者作为与结晶过渡金属羟基氧化物钼酸盐组合物的物理混合物存在。
含有或不含粘合剂的结晶过渡金属羟基氧化物钼酸盐组合物可以然后在各种硫化条件下进行硫化或预硫化，这些包括通过结晶过渡金属羟基氧化物钼酸盐组合物与含硫进料接触以及使用H2S/H2的气态混合物。结晶过渡金属羟基氧化物钼酸盐组合物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过渡金属羟基氧化物钼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，其中结晶过渡金属羟基氧化物钼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操作时，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布拉格反射。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布拉格反射，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2L烧瓶中，将116.4g硝酸镍六水合物(0.4摩尔Ni)和70.58g七钼酸铵(0.4摩尔Mo)溶解在720ml水中。向此溶液加入浓缩的NH4OH(30ml)直到pH达到约9。此时，将溶液转移到2L不锈钢高压釜中，在2小时内加热到150℃，并于150℃保持7天，然后将高压釜冷却到室温，过滤，用90ml的90℃水洗涤，然后于100℃干燥。此相的X-射线衍射图符合图1所示的图谱。
实施例2
在2L烧瓶中，将58.2g硝酸镍六水合物(0.2摩尔Ni)和35.29g七钼酸铵(0.2摩尔Mo)溶解在360ml水中。向此溶液加入浓缩的NH4OH(25ml)直到pH达到约9。此时，将溶液转移到2L不锈钢高压釜中，在2小时内加热到200℃，并于200℃保持3小时，然后将高压釜冷却到室温，过滤，用90ml的90℃水洗涤，然后于100℃干燥。此相的X-射线衍射图符合图1所示的图谱。
实施例3
在2L烧瓶中，将58.2g硝酸钴六水合物(0.2摩尔Ni)和35.29g七钼酸铵(0.2摩尔Mo)溶解在360ml水中。向此溶液加入浓缩的NH4OH溶液(25ml)直到pH达到约9。此时，将溶液转移到2L不锈钢高压釜中，在2小时内加热到200℃，并于200℃保持5天，然后将高压釜冷却到室温，过滤，用90ml的90℃水洗涤，然后于100℃干燥。此相的X-射线粉末衍射图符合图1所示的图谱。
具体实施方案：
下面将描述本发明的具体实施方案，但是应当理解的是以下描述用于说明目的，并不限制在上文和所附权利要求中所述的范围。
第一个实施方案是具有式(NH4)aM(OH)xMoyOz的结晶过渡金属羟基氧化物钼酸盐材料，其中‘a’在0.1-2.0的范围内；‘M’是选自Mg、Mn、Fe、Co、Ni、Cu及其混合物的金属；‘x’在0.1-2的范围内；‘y’在0.5-1.5的范围内；z是满足(2-n)+3(x+y)的价键的数值；所述材料的进一步特征在于具有x-射线衍射图案，其中显示表A所列出的结晶峰：
表A
本发明的一个实施方案是从本段中第一个实施方案至本段中所有在先实施方案中的一个、任一个或全部方案，其中结晶过渡金属羟基氧化物钼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。本发明的一个实施方案是从本段中第一个实施方案至本段中所有在先实施方案中的一个、任一个或全部方案，其中粘合剂是选自二氧化硅、氧化铝和二氧化硅-氧化铝。本发明的一个实施方案是从本段中第一个实施方案至本段中所有在先实施方案中的一个、任一个或全部方案，其中M是镍或钴。本发明的一个实施方案是从本段中第一个实施方案至本段中所有在先实施方案中的一个、任一个或全部方案，其中M是镍。本发明的一个实施方案是从本段中第一个实施方案至本段中所有在先实施方案中的一个、任一个或全部方案，其中结晶过渡金属羟基氧化物钼酸盐材料是被硫化的。
第二个实施方案是制备具有式(NH4)aM(OH)xMoyOz的结晶过渡金属羟基氧化物钼酸盐材料的方法，其中‘a’在0.1-2.0的范围内；‘M’是选自Mg、Mn、Fe、Co、Ni、Cu及其混合物的金属；‘x’在0.1-2的范围内；‘y’在0.5-1.5的范围内；z是满足(2-n)+3(x+y)的价键的数值；所述材料的进一步特征在于具有x-射线衍射图案，其中显示表A所列出的结晶峰：
表A
此方法包括：形成含有NH4OH、H2O以及M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；反应混合物进行反应；并回收结晶过渡金属羟基氧化物钼酸盐材料。本发明的一个实施方案是从本段中第二个实施方案至本段中所有在先实施方案中的一个、任一个或全部方案，其中反应在70-200℃下进行30分钟至14天的时间。本发明的一个实施方案是从本段中第二个实施方案至本段中所有在先实施方案中的一个、任一个或全部方案，其中所述回收通过过滤或离心进行。本发明的一个实施方案是从本段中第二个实施方案至本段中所有在先实施方案中的一个、任一个或全部方案，其中还包括将粘合剂加入所回收的结晶过渡金属羟基氧化物钼酸盐材料中。本发明的一个实施方案是从本段中第二个实施方案至本段中所有在先实施方案中的一个、任一个或全部方案，其中粘合剂是选自氧化铝、二氧化硅和氧化铝-二氧化硅。本发明的一个实施方案是从本段中第二个实施方案至本段中所有在先实施方案中的一个、任一个或全部方案，其中还包括使所回收的结晶过渡金属羟基氧化物钼酸盐材料进行硫化。
第三个实施方案是一种转化方法，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式(NH4)aM(OH)xMoyOz的结晶过渡金属羟基氧化物钼酸盐材料，其中‘a’在0.1-2.0的范围内；‘M’是选自Mg、Mn、Fe、Co、Ni、Cu及其混合物的金属；‘x’在0.1-2的范围内；‘y’在0.5-1.5的范围内；z是满足(2-n)+3(x+y)的价键的数值；所述材料的进一步特征在于具有独特的x-射线衍射图案，其中显示表A所列出的结晶峰：
表A
本发明的一个实施方案是从本段中第三个实施方案至本段中所有在先实施方案中的一个、任一个或全部方案，其中转化方法是加氢操作。本发明的一个实施方案是从本段中第三个实施方案至本段中所有在先实施方案中的一个、任一个或全部方案，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，加氢处理，加氢精制，以及加氢裂解。本发明的一个实施方案是从本段中第三个实施方案至本段中所有在先实施方案中的一个、任一个或全部方案，其中结晶过渡金属羟基氧化物钼酸盐材料是作为与至少一种粘合剂的混合物存在，其中此混合物含有至多25重量％的粘合剂。本发明的一个实施方案是从本段中第三个实施方案至本段中所有在先实施方案中的一个、任一个或全部方案，其中结晶过渡金属羟基氧化物钼酸盐材料是被硫化的。
无需累述，认为通过上文的描述，本领域技术人员能够完全实施本发明并容易确认本发明的基本特征，能够在不偏离本发明主旨和范围的情况下对本发明进行各种改变和改进，并且使本发明适用于各种用途和条件。所以，应当理解的是，先前优选的具体实施方案仅仅用于说明目的，并不以任何方式限制本发明的其余公开内容，而且涵盖在所附权利要求范围内的各种改变和等同方案。
在上文中，除非另有说明，所有温度的单位是摄氏度，并且所有份数和百分比是按重量计的。
Claims (10)
1.具有下式的结晶过渡金属羟基氧化物钼酸盐材料：
(NH4)aM(OH)bMoxOy
其中‘a’在0.1-10的范围内；‘M’是选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘b’在0.1-2的范围内；‘x’在0.5-1.5的范围内；‘y’是满足a、M、b和x的价键总和的数值；所述材料具有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的结晶过渡金属羟基氧化物钼酸盐材料，其中结晶过渡金属羟基氧化物钼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的结晶过渡金属羟基氧化物钼酸盐材料，其中结晶过渡金属羟基氧化物钼酸盐材料是被硫化的。
4.一种制备具有下式的结晶过渡金属羟基氧化物钼酸盐材料的方法，
(NH4)aM(OH)bMoxOy
其中‘a’在0.1-10的范围内；‘M’是选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘b’在0.1-2的范围内；‘x’在0.5-1.5的范围内；‘y’是满足a、M、b和x的价键总和的数值；所述材料的进一步特征在于具有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NH3、H2O以及M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；
(c)反应混合物在100-220℃下在自生环境中反应；和
(d)回收结晶过渡金属羟基氧化物钼酸盐材料。
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过渡金属羟基氧化物钼酸盐材料中。
6.权利要求4的方法，还包括使所回收的结晶过渡金属羟基氧化物钼酸盐材料进行硫化。
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：具有下式的结晶过渡金属羟基氧化物钼酸盐材料：
(NH4)aM(OH)bMoxOy
其中‘a’在0.1-10的范围内；‘M’是选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘b’在0.1-2的范围内；‘x’在0.5-1.5的范围内；‘y’是满足a、M、b和x的价键总和的数值；所述材料具有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，和其中转化方法是选自加氢脱氮，加氢脱硫，加氢脱金属化，加氢脱硅，加氢脱芳构化，加氢异构化，加氢处理，加氢精制，以及加氢裂解。
9.权利要求7的方法，其中结晶过渡金属羟基氧化物钼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。
10.权利要求7的方法，其中结晶过渡金属羟基氧化物钼酸盐材料是被硫化的。
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| US10995013B2 (en) | 2017-12-20 | 2021-05-04 | Uop Llc | Mixed transition metal tungstate |
| US10843176B2 (en) | 2017-12-20 | 2020-11-24 | Uop Llc | Highly active quaternary metallic materials using short-chain alkyl quaternary ammonium compounds |
| 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 |
| US10875013B2 (en) | 2017-12-20 | 2020-12-29 | Uop Llc | Crystalline oxy-hydroxide transition metal molybdotungstate |
| US11117811B2 (en) | 2017-12-20 | 2021-09-14 | Uop Llc | Highly active quaternary metallic materials using short-chain alkyl quaternary ammonium compounds |
| US11034591B2 (en) | 2017-12-20 | 2021-06-15 | Uop Llc | Highly active quaternary metallic materials using short-chain alkyl quaternary ammonium compounds |
| US10688479B2 (en) | 2018-06-26 | 2020-06-23 | Uop Llc | Crystalline transition metal tungstate |
| US10682632B2 (en) | 2018-06-26 | 2020-06-16 | Uop Llc | Transition metal tungstate material |
| 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 |
| US10737246B2 (en) * | 2018-06-29 | 2020-08-11 | Uop Llc | Poorly crystalline transition metal tungstate |
| US10981151B2 (en) | 2018-06-29 | 2021-04-20 | Uop Llc | Poorly crystalline transition metal molybdotungstate |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100279854A1 (en) * | 2009-04-29 | 2010-11-04 | Kuperman Alexander E | Hydroconversion Multi-Metallic Catalyst and Method for Making Thereof |
Family Cites Families (72)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3678124A (en) * | 1968-10-24 | 1972-07-18 | Gennady Arkadievich Stepanov | Process for the production of mono- and diolefin hydrocarbons |
| 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 |
| US5010049A (en) * | 1989-03-24 | 1991-04-23 | The Regents Of The University Of Michigan | Modified molybdenum sulfide hydrodesulfurization/hydrodenitrogenation catalysts |
| 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 |
| US6929738B1 (en) | 1997-07-15 | 2005-08-16 | Exxonmobil Research And Engineering Company | Two stage process for hydrodesulfurizing distillates using bulk multimetallic catalyst |
| 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 |
| 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) |
| 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 |
| US7513989B1 (en) | 1997-07-15 | 2009-04-07 | Exxonmobil Research And Engineering Company | Hydrocracking process using bulk group VIII/Group VIB catalysts |
| US6783663B1 (en) | 1997-07-15 | 2004-08-31 | Exxonmobil Research And Engineering Company | Hydrotreating using bulk multimetallic catalysts |
| US6863803B1 (en) | 1997-07-15 | 2005-03-08 | Exxonmobil Research And Engineering Company | Production of low sulfur/low nitrogen hydrocrackates |
| US6582590B1 (en) | 1997-07-15 | 2003-06-24 | Exxonmobil Research And Engineering Company | Multistage hydroprocessing using bulk multimetallic catalyst |
| 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 |
| 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) |
| AR043243A1 (es) | 2003-02-24 | 2005-07-20 | Shell Int Research | Composicion de catalizador ,su preparacion y uso |
| 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 |
| US7780845B2 (en) | 2004-04-22 | 2010-08-24 | Exxonmobil Research And Engineering Company | Process to manufacture low sulfur distillates |
| US7691257B2 (en) | 2004-04-22 | 2010-04-06 | Exxonmobil Research And Engineering Company | Process to manufacture low sulfur diesel fuels |
| US7776205B2 (en) | 2004-04-22 | 2010-08-17 | Exxonmobil Research And Engineering Company | Process to upgrade hydrocarbonaceous feedstreams |
| US7608558B2 (en) | 2004-04-22 | 2009-10-27 | Sonja Eijsbouts | Hydrotreating catalyst containing a group V metal |
| 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 |
| 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. |
| 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 |
| US7605107B2 (en) | 2005-09-29 | 2009-10-20 | Exxonmobil Research And Engineering Company | Method of preparing a supported hydrotreating catalyst |
| AU2006308082B2 (en) | 2005-10-26 | 2011-07-07 | Albemarle Netherlands Bv | A bulk catalyst comprising nickel tungsten metal oxidic particles |
| US8062508B2 (en) | 2005-10-26 | 2011-11-22 | Exxonmobil Research And Engineering Company | Hydroprocessing using bulk bimetallic catalysts |
| WO2007048600A2 (en) * | 2005-10-26 | 2007-05-03 | Albemarle Netherlands Bv | A bulk catalyst comprising metal oxidic particles of group vi and viii and a process for the manufacture therof |
| DK1951425T3 (da) | 2005-10-26 | 2019-11-25 | Exxonmobil Res & Eng Co | Hydrogenbehandling ved anvendelse af hydrotermisk fremstillede bulk-multimetalkatalysatorer |
| US8216958B2 (en) | 2006-01-17 | 2012-07-10 | 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 |
| JP5325892B2 (ja) | 2007-12-04 | 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 | バルク触媒組成物を用いる炭化水素の水素処理 |
| CN101909746B (zh) | 2007-12-04 | 2013-08-14 | 雅宝荷兰有限责任公司 | 包含本体金属氧化物粒子的本体催化剂组合物 |
| 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 |
| US8080492B2 (en) | 2009-04-29 | 2011-12-20 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
| US8383543B2 (en) | 2009-04-29 | 2013-02-26 | 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 |
| US8636967B2 (en) | 2010-01-21 | 2014-01-28 | Intevep, S.A. | Metal recovery from hydroconverted heavy effluent |
| JP5797766B2 (ja) | 2010-11-11 | 2015-10-21 | シェブロン ユー．エス．エー． インコーポレイテッド | 水素化変換多金属触媒及びその作製方法 |
| US8586500B2 (en) | 2010-11-11 | 2013-11-19 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
| US8658558B2 (en) | 2010-11-11 | 2014-02-25 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
| HRP20240945T1 (hr) | 2010-12-30 | 2024-10-25 | Chevron U.S.A. Inc. | Katalizatori za hidropreradu i postupci njihove priprave |
| RU2473387C1 (ru) * | 2011-10-06 | 2013-01-27 | Учреждение Российской академии наук Институт проблем переработки углеводородов Сибирского отделения РАН (ИППУ СО РАН) | Способ получения массивного катализатора гидропереработки тяжелых нефтяных фракций |
| EP2890495A2 (en) | 2012-08-29 | 2015-07-08 | Indian Oil Corporation Ltd | Hydrotreating catalyst and process for preparing the same |
| US9435043B2 (en) | 2014-04-14 | 2016-09-06 | California Institute Of Technology | Oxygen evolution reaction catalysis |
| US10399065B2 (en) | 2015-12-15 | 2019-09-03 | Uop Llc | Crystalline transition metal tungstate |
| US10052616B2 (en) | 2015-12-15 | 2018-08-21 | Uop Llc | Crystalline ammonia transition metal molybdotungstate |
| US10046315B2 (en) | 2015-12-15 | 2018-08-14 | Uop Llc | Crystalline transition metal molybdotungstate |
| US10052614B2 (en) | 2015-12-15 | 2018-08-21 | Uop Llc | Mixed metal oxides |
| US10232357B2 (en) | 2015-12-15 | 2019-03-19 | Uop Llc | Crystalline ammonia transition metal molybdate |
| US10005812B2 (en) | 2015-12-15 | 2018-06-26 | Uop Llc | Transition metal molybdotungsten oxy-hydroxide |
| US10053637B2 (en) | 2015-12-15 | 2018-08-21 | Uop Llc | Transition metal tungsten oxy-hydroxide |
| US10399063B2 (en) | 2015-12-15 | 2019-09-03 | Uop Llc | Mixed metal oxides |
| FI3408023T3 (fi) | 2016-01-29 | 2024-04-26 | Totalenergies Onetech | Homogeenisesti dispergoituneita monimetallisia oksihydroksidikatalyyttejä |
-
2016
- 2016-12-06 US US15/370,781 patent/US10322404B2/en active Active
- 2016-12-13 WO PCT/US2016/066250 patent/WO2017106117A1/en active Application Filing
- 2016-12-13 CA CA3004611A patent/CA3004611C/en active Active
- 2016-12-13 JP JP2018531217A patent/JP6571285B2/ja active Active
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- 2016-12-13 NZ NZ742218A patent/NZ742218A/en unknown
- 2016-12-13 EP EP16876455.3A patent/EP3390281A4/en active Pending
- 2016-12-13 CN CN201680073365.4A patent/CN108367940B/zh active Active
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-
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100279854A1 (en) * | 2009-04-29 | 2010-11-04 | Kuperman Alexander E | Hydroconversion Multi-Metallic Catalyst and Method for Making Thereof |
Non-Patent Citations (3)
| Title |
|---|
| CHANGLONG YIN ET AL.: ""A novel porous ammonium nickel molybdate as the catalyst precursor towards deep hydrodesulfurization of gas oil"", 《FUEL》 * |
| DORON LEVIN ET AL.: ""Crystal Structure of an Ammonium Nickel Molybdate Prepared by Chemical Precipitation"", 《INORG. CHEM.》 * |
| DORON LEVIN ET AL.: ""Novel transition metal molybdates for catalytic oxidative dehydrogenation"", 《ENGINEERING（CHEMICAL）》 * |
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