CN110461472A - 由廉价金属氧化物合成MoVTeNb催化剂 - Google Patents
由廉价金属氧化物合成MoVTeNb催化剂 Download PDFInfo
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- CN110461472A CN110461472A CN201880009489.5A CN201880009489A CN110461472A CN 110461472 A CN110461472 A CN 110461472A CN 201880009489 A CN201880009489 A CN 201880009489A CN 110461472 A CN110461472 A CN 110461472A
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- Prior art keywords
- mixed oxide
- precursor compound
- tellurium
- oxide material
- mixture
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims description 34
- 229910044991 metal oxide Inorganic materials 0.000 title description 3
- 150000004706 metal oxides Chemical class 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000010955 niobium Substances 0.000 claims abstract description 28
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 28
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 18
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 18
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011733 molybdenum Substances 0.000 claims abstract description 16
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 9
- 230000014759 maintenance of location Effects 0.000 claims abstract description 8
- 229910017488 Cu K Inorganic materials 0.000 claims abstract description 6
- 229910017541 Cu-K Inorganic materials 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 14
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 claims description 14
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- 229910004273 TeO3 Inorganic materials 0.000 claims description 3
- 230000008901 benefit Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 7
- FXADMRZICBQPQY-UHFFFAOYSA-N orthotelluric acid Chemical compound O[Te](O)(O)(O)(O)O FXADMRZICBQPQY-UHFFFAOYSA-N 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229910003069 TeO2 Inorganic materials 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910000484 niobium oxide Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 238000004438 BET method Methods 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000012154 double-distilled water Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 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
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical class O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- 230000001376 precipitating effect Effects 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- -1 tellurium Cation Chemical class 0.000 description 1
- 150000003498 tellurium compounds Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- 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
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- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
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Abstract
本发明涉及一种用于制备混合氧化物材料的方法,所述方法包括以下步骤:a)制备初始化合物的混合物,所述混合物包含含有钼、钒、铌和碲的初始化合物以及两种螯合性含氧配体,b)在100℃至300℃的温度下以水热法处理所述初始化合物的混合物,以获得产物悬浮液,c)将包含在从步骤b)产生的产物悬浮液中的固体分离出来并干燥,d)将从步骤c)获得的固体在惰性气体中活化。本发明还涉及一种用于氧化乙烷的混合氧化物材料,所述混合氧化物材料包括元素钼、钒、铌和碲,具有以下化学计量比:Mo1VaNbbTecOx,其中0.27<a<0.31;0.08<b<0.12;0.08<c<0.12,所述混合氧化物材料在使用Cu‑Kα辐射时在XRD中具有如下的衍射反射h、i、k和l,其顶点大致位于衍射角度(2·)26.2°±0.5°(h),27.0°±0.5°(i),7.8°±0.5°(k)和28.0°±0.5°(l),所述混合氧化物材料能够根据本发明所述的方法制备。
Description
本发明涉及一种用于制备包含钼、钒、碲和铌的混合氧化物材料的新型方法,所述混合氧化物材料作为用于将乙烷氧化脱氢为乙烯或将丙烷氧化为丙烯酸的催化剂,并且涉及一种用于制备所述混合氧化物材料的方法。
用于将丙烷氧化为丙烯酸或用于将乙烷氧化脱氢为乙烯的MoVNbTe混合氧化物是现有技术。超过200项专利和大量的科技公开物涉及基于MoVNbTe混合氧化物的催化剂。用周期表的其他金属来增强这种混合氧化物是已知的。在此,最高的前述的丙烯酸产率为60%而乙烯产率为约80%。
基于四种元素的用于催化剂的MoVNbTe基体系由三菱提出,用于将丙烷氨氧化成丙烯腈(1989年,EP 318295 A1)以及氧化成丙烯酸(1994年,EP 6088038 A2)。在JP H07-053414(三菱)中公开了一种催化方法,用于在低温下通过氧化氢化乙烷而制备乙烯,该方法具有高产率和高选择性。这种用于通过在提高的温度下在催化剂组合物存在下将乙烷与包含氧分子的气体进行接触以制备乙烯的方法包括:使该催化剂组合物包含混合金属氧化物,所述混合金属氧化物具有钼、钒、碲和氧作为主要成分并且显示出基本上具有以下相对峰强度的粉末X射线衍射谱:2θ(+-0.4°),相对强度:22.1°(100),28,2°(400-3),36,2°(80-3),45.1°(40-3),50°(50-3)。
MoVNbTe催化剂主要由两种斜方晶系的相组成,被称为“M1”和“M2”(T.Ushikubo,K.Oshima,A.Kayou,M.Hatano,Studies in Surface Science and Catalysis 112,(1997),473)。M1相在选择性氧化反应中展现出重要作用。
根据P.De Santo等人,Z.Kristallogr.219(2004)152,用于选择性氧化的多金属氧化物催化剂中的主要相M1和M2例如能够用以下总式描述:
M1:Mo1V0,15Te0,12Nb0,128O3,7或Mo7,8V1,2Te0,937Nb1O28,9
M2:*Mo1V0.32Te0.42Nb0.08O4.6或Mo4.31V1.36Te1.81Nb0.33O19.81
这两种主要相还能以略微不同的化学计量比存在。因此钒以及钼都在由氧原子形成的八面体的中心并且因此在所述结构中是部分可交换的,使得相同的结构(例如M1相)也可以具有更高的钒含量。在此方面的详细研究可以在P.Botella等人,Solid StateScience 7(2005)507-519中找到。特别地,M2相对于乙烷的氧化脱氢是无活性的(见J.S.Valente等人,ACS Catal.4(2014),1292-1301特别是第1293页)。即,对于乙烷的氧化脱氢而言所希望的是由尽可能纯的M1相组成的催化剂。因此尝试以干净且分离的方式制备这些晶相。
EP 529853A2公开了一种适合用于从烷烃制备腈的催化剂,其中所述催化剂具有经验式MoVbTecXxOn,其中X为Nb、Ta、W、Ti、Al、Zr、Cr、Mn、Fe、Ru、Co、Rh、Ni、Pd、Pt、Sb、Bi、B和Ce中的至少一种,b为0.01至1.0,c为0.01至1.0;x为0.01至1.0,且n为如下的数:根据这个数,金属元素的总价数得以满足并且所述催化剂在其X射线衍射图案中在以下的2θ角度下具有X射线衍射峰:衍射角为2θ(22.1°+/-0.3°,28.2°+/-0.3°,36.2°+/-0.3°,45.2°+/-0.3°,50.0°+/-0.3°)。
JP H07-232071公开了在使用烷烃作为原材料以及某种催化剂的情况下在相对较低的温度下且以高产率制备腈的方法。所述催化剂的主要组分是由钼、钒、碲、氧和X(X选自铌、钽等的组中的一种或多种元素)形成的混合金属氧化物,其中主要组分(即除了氧以外)的比率通过式I至IV表达:I)0.25<rMo<0.98,II)0.003<rV<0.50,III)0.003<rTe<0.50,IV)0≤rX<0.5,(rMo、rV、rTe和rX分别为钼、钒、碲和X的摩尔比例)并且在XRD中,这种混合氧化物的XRD带显示在不同的2θ角度9.0°±0.3°,22.1°±0.3°,27.3°±0.3°,29.2°±0.3°和35.4°±0.3°。据此可以如下地制备腈:在不存在卤化物质的情况在低温下以高产率将烷烃例如与水等在反应体系中进行转化。
用于制备纯M1相的其他卓有成效的实验是基于将M2相从相混合物中溶出。这种实验例如记载在EP 1301457 A2、EP 1558569 A1或WO 2009106474 A2中。
A.C.Sanfiz等人,Top.Catal.50(2008)19-32描述了水热法合成MoVNbTe氧化物。在这种合成中,仅仅从可溶性化合物出发。通常使用碲酸Te(OH)6作为碲的可溶性化合物。在最常见的氧化物型碲化合物TeO2中,碲具有+4氧化态。然而二氧化碲(TeO2)难溶于水。但在碲酸中,碲具有+6氧化态。即在制备碲酸时,碲必须被氧化成高价。常见的合成通过用过氧化氢氧化氧化碲来进行,这在大规模下带来了安全性问题,因为过氧化氢在自身分解时歧化为水和氧气。因此很难大量制备碲酸。
因此,在不使用碲酸的情况下,MoVNbTe混合氧化物的合成具有明显成本更低廉的潜力。
在MoVNbTe混合氧化物的合成中使用的Nb成分一般是草酸铌铵。相反,氧化铌是难溶的并且因此仅有条件地适合用作初始化合物。
Watanabe(Applied Catal.A General,194-195(2000)479-485)尤其说明了从低溶解度的前体MoO3、V2O5和TeO2进行水热法合成。水热法合成产生了用于氨氧化催化剂的前体,在煅烧之后所述催化剂与通过已知的干式方法制备的催化剂相比具有两倍高的活性。通过固体反应制备的混合氧化物显示出了更低的活性。所建议的是,通过水热法制备的催化剂的较高活性主要与较大的表面积有关。
本发明的目的在于,提供一种具有高M1相含量的包含钼、钒、碲和铌的混合氧化物材料(“MoVTeNb混合氧化物”),所述混合氧化物材料作为特别用于将乙烷氧化成乙烯的催化剂材料具有尽可能高的活性和选择性。
这个目的通过一种用于制备混合氧化物材料的方法实现,所述方法包括以下步骤:
a)制备初始化合物的混合物,所述混合物包含含有钼、钒、铌和碲的初始化合物以及两种螯合性含氧配体,
b)在100℃至300℃的温度下以水热法处理所述初始化合物的混合物,以获得产物悬浮液,
c)将包含在从步骤b)产生的产物悬浮液中的固体分离出来并干燥,
d)将从步骤c)获得的固体在惰性气体中活化。
初始化合物的混合物优选作为水性悬浮液存在并且随后被水热处理。术语“水热法”主要涉及用于在水存在下且在提高的温度和/或提高的压力下(例如在高压釜中)制备催化剂材料的反应条件。在此,压力可以在5至30bar、优选10至27bar的范围内。示例性的压力范围为11至20bar。
通过水热处理(步骤b))获得了包含MoVNbTe混合氧化物作为固体的产物悬浮液。在本发明的方法中,在步骤c)中分离出悬浮液的固体可以通过一个或多个过滤步骤(例如过滤掉母液)来进行。干燥可以在一个步骤中进行或在两个步骤中在流动或静止空气中进行。在此,第一干燥步骤优选在60℃至150℃(特别优选在80℃至120℃)下进行,而第二干燥步骤在200℃至350℃(特别优选在220℃至280℃)下进行。另外,本发明方法的步骤c)可以包含一个或多个清洗、煅烧(热处理)和/或研磨的步骤。煅烧可以在200至500℃下、优选250℃至350℃下在空气中进行。
在步骤c)中的滤液的干燥之后,将干燥的混合物例如在流动的或静止的惰性气体氛围中在大约500℃至700℃下活化至少1小时(步骤d)。尤其氮气、氦气或氩气适合用作惰性气体。优选的是,所述活化在550℃至650℃范围内进行。例如,在大约600℃下活化可以进行大约2小时。
所述初始化合物为含有钼、钒、碲和铌的水热合成反应物(前体化合物)。这些反应物分别包含元素钼、钒、碲或铌中的一种或多种。
包含钼的初始化合物可以例如为七钼酸铵或三氧化钼,包含钒的初始化合物可以例如为偏钒酸铵、硫酸氧钒或五氧化二钒,包含铌的初始化合物可以例如为草酸铌铵或草酸铌或氧化铌。根据本发明的包含碲的初始化合物优选为二氧化碲。
包含碲的初始化合物可以为其中碲处于+6或+4氧化态(就是说为碲(IV)或碲(VI)阳离子)的初始化合物。特别优选的是碲酸、二氧化碲或式Mx n+TeO3的化合物(其中n=1或2,并且x=2/n),其中M为碱金属或碱土金属,例如Na2TeO3。特别优选地,所述包含碲的初始化合物为二氧化碲,它可以任意的水合度存在。倘若将二氧化碲用作初始化合物,则适用的是,二氧化碲具有D90<100μm的粒径。特别优选地适用的是,用作初始化合物的二氧化碲的D50值低于35μm。
此外,包含铌的初始化合物(优选氧化铌)同样可以具有D90<100μm、优选D90<75μm、特别优选D90<50μm的粒径。任选地,所使用的包含铌的初始化合物(优选氧化铌)可以具有D50<50μm或<35μm的粒径。
此外,所使用的所有初始化合物可以具有D90<100μm、优选D90<75μm、特别优选D90<50μm的粒径。任选地,初始化合物可以具有D50<50μm或<35μm的粒径。
例如如此作为初始化合物所使用的金属氧化物(如二氧化碲)作为粉末存在并且具有粒径分布。粒径D90被定义为在粒径分布中所有颗粒的90%位于其下的颗粒直径限值。中位粒径,即在粒径分布中所有颗粒的一半低于该值的粒径,也被称为粒径D50。特别优选地适用的是,用作初始化合物的二氧化碲的粒径D50低于35μm。
所希望的初始化合物的粒径D90或D50可以如下方式获得:从具有较粗颗粒的粒径分布的粉末出发并且将颗粒机械地粉碎。这可以通过研磨来进行,其中可以使用所有适当的且本领域技术人员熟悉的装置,因此例如冲击磨机、行星磨机、研钵等。
本发明的制备方法的优点在于,使用不溶且价格低廉的氧化物,例如MoO3、V2O5、Nb2O5和TeO2,作为初始化合物来合成M1相。已经证明,特别是柠檬酸、二醇和草酸特别适合作为螯合性含氧配体。
这两种螯合性的含氧配体优选应在初始化合物的混合物中分别以1:0.01至1:1、优选1:0.08至1:0.4、更优选1:0.15至1:0.25的Mo/含氧配体比存在。这两种螯合性含氧配体在此可以分别具有相同的或不同的Mo/含氧配体比。
本发明的合成不仅提供关于M1相具有高相纯度的MoVTeNb混合氧化物,而且所获得的MoVTeNb混合氧化物还是对于将乙烷氧化成乙烯而言具有改进的活性的催化剂材料。本发明的M1相合成的另一个优点是通过水热法合成造成的初始物质的高转化效率。
倘若反应物的化学计量比在Mo/V/Nb/Te=1:0.22:0.1:0.1至1:0.3:0.17:0.17的范围内变动,Mo、V、Nb和Te就几乎完全转化为M1相,使得所有金属的小于100ppm保留在母液中。M1相的可能的化学计量比是由文献中充分已知的并且能够通过式Mo1VaNbbTecOx表示,其中a=0.2至0.3,b=0.1至0.2,c=0.1至0.25且x为取决于金属(Mo、V、Nb和Te)的氧化态而造成电荷平衡的数值。
另外还已经发现,在将MoO3、V2O5、Nb2O5和TeO2与柠檬酸、二醇和草酸一起使用时,突出地实现了水热法结晶。在不存在铵离子的情况下特别好地实现了结晶。因此,优选的是,在合成时不存在铵离子。
通过本发明的方法获得了一种用于氧化乙烷的混合氧化物材料,包括元素钼、钒、铌和碲,所述混合氧化物材料具有以下化学计量比:
Mo1VaNbbTecOx
其中0.27<a<0.31;0.08<b<0.12;0.08<c<0.12,所述混合氧化物材料在XRD中具有如下的衍射反射h、i、k和l,其顶点大致位于衍射角度(2·)26.2°±0.5°(h),27.0°±0.5°(i),7.8°±0.5°(k)和28.0°±0.5°(l)。
本发明的MoVTeNb混合氧化物可以用作用于将烃类氧化和/或氧化脱氢(“ODH”)的催化剂材料,尤其用于将乙烷氧化脱氢为乙烯。所述混合氧化物可以具有5至25m2/g、特别优选5至15m2/g的BET表面积。
根据本发明方法制备的MoVTeNb混合氧化物可以用作催化剂或催化剂材料。能以不同方式将其用在商业催化剂中。例如可以通过制片而被加工成催化剂片料,然后可以将其填入反应器中。
所述催化剂材料还可以与适合的粘结剂一起被加工成挤出物(片料、成型体、蜂窝体等)。可以使用本领域技术人员熟悉的且表现为适合的粘结剂作为粘结剂。优选的粘结剂尤其为伪勃姆石以及硅酸盐类粘结剂,如胶体氧化硅或氧化硅溶胶。
所述催化剂材料另外可以与其他成分一起、优选与粘结剂、特别优选与有机粘结剂(例如有机粘合剂、聚合物、树脂或蜡)一起被加工成载体涂层(Washcoat),所述载体涂层可以施加到金属或陶瓷载体上。在某些情况下可以进行额外的浸渍步骤或煅烧步骤。
在使用Cu-Kα辐射时,根据本发明方法形成的MoVTeNb混合氧化物的X射线衍射图具有如下的衍射反射h、i、k和l,其顶点位于衍射角度(2·)26.2°±0.5°(h),27.0°±0.5°(i),7.8°±0.5°(k)和28.0°±0.5°(l),其中衍射反射h、i、k和l的强度Ph、Pi、Pk、Pl可以满足以下关系,其中Rx(x=1至3)为由这些关系定义的强度比:
R1=Ph/(Ph+Pi)>0.3,优选>0.35且特别优选>0.4;和/或
R2=Pi/(Pi+Pl)>0.5,优选>0.6且特别优选>0.63;和/或
R3=Pi/(Pi+Pk)<0.8,优选<0.75且特别优选<0.7。
在混合氧化物材料的实施方式的X射线衍射图(XRD)中,衍射反射i可以具有第二大的强度和/或衍射反射h可以具有第三大的强度。
本发明的MoVNbTe混合氧化物在实施例中作为催化剂材料使用并且因此在实验说明中有时被称为催化剂。
图1:来自实施例1的MoVTeNb混合氧化物的XRD。
图2:来自实施例2的MoVTeNb混合氧化物的XRD。
图3:来自对比实施例1的MoVTeNb混合氧化物的XRD。
图4:来自实施例1的MoVTeNb混合氧化物的孔分布。
图5:来自实施例2的MoVTeNb混合氧化物的孔分布。
图6:来自对比实施例1的MoVTeNb混合氧化物的孔分布。
图7:在乙烷的ODH中,根据实施例2和对比实施例1的MoVTeNb混合氧化物的催化活性对比。
根据本发明的新方法制备的MoVTeNb混合氧化物是明显更具活性的。在标准化至1g催化剂的情况下,它实现了比根据对比实施例的按照现有技术的催化剂(图7)更高的活性。这证明了,通过本发明的方法获得了具有新特性的混合氧化物材料。然而,新的混合氧化物材料的新特性无法简单地用常规的标准方法来测定。
表征方法:
为了测定本发明催化剂的参数,使用了以下方法:
1.BET表面积
测定根据DIN 66131按照BET方法进行;BET方法的公开内容也可以在J.Am.Chem.Soc.60.309(1938)中找到。测量在Sorptomatic1990设备上在77K进行。在测量之前将样品在523K抽真空2小时。根据BET方法的等温线的线性回归在p/p0=0.01-0.3(p0=730Torr)的压力范围内进行。
2.粉末X射线衍射测量法(XRD)
在配备有Medipix PIXcel 3D检测器的PANalytical Empyrean上,在Θ-Θ几何形状中在2Θ=5-70°的角度范围内记录X射线衍射图。X射线管产生Cu-K辐射。通过在入射X射束的辐照路径中使用Ni过滤器来抑制Cu-Kβ辐射,使得在样品处仅具有15.4nm波长(E=8.04778keV)的Cu-Kα辐射被衍射。源侧的辐照路径的高度通过自动的发散狭缝(可编程发散狭缝-PDS)进行适配,使得样品在长度为12mm的整个角度区域上都被辐照。检测器侧的X射束的宽度通过固定的挡板限制在10mm。水平方向的发散通过使用0.4rad的Soller狭缝来最小化。
类似于源侧的辐照路径,检测器侧的辐照路径的高度借助于自动的抗折射狭缝(可编程抗散射狭缝-PASS)进行适配,使得在长度为12mm的整个角度区域上在样品上都检测到反射的X射线。
依据存在的量不同,样品在无定形的硅样品盘上制备或作为平板样品以制片的方式制备。
3.孔分布
在Sorptomatic仪器或TriStar 3000仪器上在77K下借助于氮气吸附测量来进行孔径分布测量。在测量之前将样品在523K下抽真空2小时。测定了吸附和脱附等温线并且将其用于根据Barrett-Joyner-Halenda方法(BJH)进行分析。
现借助于下文中的不理解为限制性的实施例来详细解说本发明。
实施例:
实施例1:
将TeO2(Alfa Aesar)悬浮在200g蒸馏水中并且在行星球磨中用1cm球(ZrO2)研磨。随后将这部分用500ml蒸馏水转移到玻璃烧杯中。将Nb2O5悬浮在200g蒸馏水中并且在相同的球磨中研磨。
随后将这部分用500ml蒸馏水转移到玻璃烧杯中。第二天早晨将其加热到80℃,向Nb2O5悬浮液中加入107.8g的二水合草酸并且搅拌约1小时。在高压釜(40L)中预先放入6L蒸馏水并且在搅拌(搅拌器速度90rpm)下加热到80℃。如果水已经达到这个温度,则向草酸中相继加入61.58g的柠檬酸、19.9g的乙二醇、615.5g的MoO3(Sigma Aldrich)、124.5g的V2O5、经研磨的TeO2和经研磨的Nb2O5。使用850ml蒸馏水来转移和清洗容器。在高压釜中全部的水量为8.25L。
然后用氮气覆盖。在40L的高压釜中在190℃下进行水热法合成48小时。在合成之后借助于真空泵通过蓝带滤纸过滤并且将滤饼用5L蒸馏水清洗。
在80℃下在干燥箱中干燥3天并且随后将产物在冲击磨机中磨碎。实现了0.8kg的固体产量。
然后在空气中在280℃下煅烧4小时(加热速率5℃/分钟,空气:1L/分钟)。
在蒸馏器中在600℃下活化2小时(加热速率5℃/分钟,N2:0.5L/分钟)。
产品具有9m2/g的BET表面积和=0.04cm3/g的孔体积。
实施例2:
在100mL的PTFE烧杯中预先放入75mL的双蒸馏水,滴加177.8mg的(单)乙二醇并且随后使5397.9mg的MoO3、1023.9mg的V2O5、599.1mg的TeO2、549.5mg的Nb205·xH2O(Nb=63.45重量%)、540.9mg的柠檬酸和338.3mg的草酸悬浮。将特氟龙烧杯封闭并转移到不锈钢高压釜罩壳中。将其压力密封地封闭并且在预热到190℃的烘箱中夹持在水平旋转的轴上。在48小时之后将高压釜壳从烘箱中取出并且立即在流动水下淬火并且随后在冰浴中冷却45分钟。
所产生的产物悬浮液通过滤纸(孔宽3μm)过滤并且固体用200mL双蒸馏水清洗。
如此获得的产物在干燥箱中在80℃下干燥16小时并且之后在手动研钵中磨碎。
固体产量为6.2g。活化在600℃下进行2小时(加热速率10℃/分钟,N2:100mL/分钟)。在图2中示出了产物的XRD衍射图,BET表面积为7.3m2/g,孔体积低于0.012cm3/g。
对比实施例1:
在高压釜(40L)中预先放入3.3L蒸馏水并且在搅拌下加热到80℃。在此期间添加725.58g的四水合七钼酸铵(来自HC Starck)并且将其溶解(AHM溶液)。在三个5L玻璃烧杯中分别将1.65L蒸馏水在磁力搅拌器的搅拌下通过控温同样加热到80℃。然后在这些玻璃烧杯中分别加入405.10g的水合硫酸氧钒(来自GfE,V含量:21.2%)、185.59g草酸铌铵(HCStarck,Nb含量:20.6%)以及94.14g碲酸并且溶解(V溶液、Nb溶液和Te溶液)。
随后借助于软管泵相继将V溶液、Te溶液且最后将Nb溶液泵送到AHM溶液中。泵送时间:V溶液:4.5分钟,190rpm(软管直径:8x5mm),Nb溶液:6分钟,130rpm(软管直径:8x5mm)。
所产生的悬浮液在80℃下继续搅拌10分钟。在沉淀时搅拌器的速度为90rpm。
随后用氮气覆盖,其方式为,在高压釜中用氮气升高压力直至约6bar并且将泄放阀打开,直至在N2压力下流过高压釜(5分钟)。在结束时通过排气阀将压力再次泄放到直至1bar的残余压力。
在40L高压釜中在175℃下通过锚式搅拌器在90rpm的搅拌速度下进行水热法合成20小时(加热时间:3小时)。
在合成之后借助于真空泵通过蓝带滤纸过滤并且将滤饼用5L蒸馏水清洗。
在80℃下在干燥箱中干燥3天并且随后在冲击磨机中磨碎,固体产量为0.8kg。
在280℃下煅烧4小时(加热速率5℃/分钟,空气:1L/分钟)。在蒸馏器中在600℃下活化2小时(加热速率5℃/分钟,N2:0.5L/分钟)。
产物的BET表面积为9m2/g,孔体积=0.055cm3/g。
实施例3:
在管式反应器中在大气压力下在330至420℃的温度范围内对来自实施例2和对比实施例的催化剂在乙烷的氧化脱氢中的催化活性进行研究。为此将25mg(实施例2)或200mg(对比实施例1)的催化剂(粒径150-212μm)用碳化硅(粒径150-212μm)以1:5的质量比稀释。在催化剂床的上方和下方填入分别250mg的相同粒径碳化硅形成的层并且通过石英棉塞将管式反应器的末端封闭。
在实验开始之前用惰性气体冲刷反应器并且随后在50sccm的氦气流下加热到330℃。在达到所希望的温度并且稳定一小时之后,切换到反应混合物。
进入气体组成为在50sccm的总体积流量下C2H6/O2/He=9.1/9.1/81.8(v/v)。
对产物气流的分析在配备有Haysep N柱和Haysep Q柱、分子筛柱5A和热导率检测器的气相色谱中进行。
在图7中展示了在上述条件下的乙烯形成速率。
Claims (13)
1.一种用于制造混合氧化物材料的方法,包括以下步骤:
a)制备初始化合物的混合物,所述混合物包含含有钼、钒、铌和碲的初始化合物以及两种螯合性含氧配体,
b)在100℃至300℃的温度下以水热法处理所述初始化合物的混合物,以获得产物悬浮液,
c)将包含在从步骤b)产生的产物悬浮液中的固体分离出来并干燥,
d)将从步骤c)获得的固体在惰性气体中活化。
2.根据权利要求1所述的方法,其特征在于,在步骤d)中的活化在450℃至700℃之间、优选550℃至650℃的温度下进行。
3.根据权利要求1或2所述的方法,其特征在于,所述初始化合物的混合物包含三氧化钼。
4.根据以上权利要求之一所述的方法,其特征在于,所述初始化合物的混合物包含五氧化二钒。
5.根据以上权利要求之一所述的方法,其特征在于,所述初始化合物的混合物包含五氧化二铌。
6.根据权利要求5所述的方法,其特征在于,所述五氧化二铌具有小于100μm的粒径D90。
7.根据以上权利要求之一所述的方法,其特征在于,所述包含碲的初始化合物为氧化碲或者式Mx n+TeO3的化合物,其中n=1或2并且x=2/n,其中M为碱金属或碱土金属。
8.根据权利要求7所述的方法,其特征在于,所述二氧化碲具有小于100μm的粒径D90。
9.根据以上权利要求之一所述的方法,其特征在于,所述螯合性含氧配体之一为乙二醇。
10.根据以上权利要求之一所述的方法,其特征在于,所述螯合性含氧配体之一为柠檬酸。
11.一种用于氧化乙烷的混合氧化物材料,所述混合氧化物材料包括元素钼、钒、铌和碲,具有以下化学计量比:
Mo1VaNbbTecOx
其中0.27<a<0.31;0.08<b<0.12;0.08<c<0.12,所述混合氧化物材料在使用Cu-Kα辐射时在XRD中具有如下的衍射反射h、i、k和l,其顶点大致位于衍射角度(2·)26.2°±0.5°(h),27.0°±0.5°(i),7.8°±0.5°(k)和28.0°±0.5°(l),所述混合氧化物材料能够根据权利要求1所述的方法制备。
12.根据权利要求10所述的催化剂用于将乙烷氧化脱氢为乙烯的用途。
13.根据权利要求11所述的催化剂用于将丙烷氧化的用途。
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EP3576875A1 (de) | 2019-12-11 |
WO2018141654A1 (de) | 2018-08-09 |
KR20190115455A (ko) | 2019-10-11 |
WO2018141654A4 (de) | 2018-10-04 |
US11014075B2 (en) | 2021-05-25 |
JP2020506800A (ja) | 2020-03-05 |
DE102017000861A1 (de) | 2018-08-02 |
JP6872027B2 (ja) | 2021-05-19 |
KR102322199B1 (ko) | 2021-11-08 |
US20200290026A1 (en) | 2020-09-17 |
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