CN1288445A - 多金属氧化物材料 - Google Patents
多金属氧化物材料 Download PDFInfo
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- CN1288445A CN1288445A CN99802281A CN99802281A CN1288445A CN 1288445 A CN1288445 A CN 1288445A CN 99802281 A CN99802281 A CN 99802281A CN 99802281 A CN99802281 A CN 99802281A CN 1288445 A CN1288445 A CN 1288445A
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- oxide materials
- polymetal oxide
- propane
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- 239000000463 material Substances 0.000 title claims abstract description 41
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000001294 propane Substances 0.000 claims abstract description 23
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000011149 active material Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 238000006392 deoxygenation reaction Methods 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 22
- 239000003054 catalyst Substances 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000007789 gas Substances 0.000 description 30
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 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
- 238000007600 charging Methods 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000001404 mediated effect Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000012254 powdered material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- -1 preferred Co Substances 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
- 238000005507 spraying Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000010425 asbestos Substances 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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- B01J23/882—Molybdenum and cobalt
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/006—Compounds containing, besides molybdenum, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
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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
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/24—Chromium, molybdenum or tungsten
- C07C2523/28—Molybdenum
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明涉及一种有特定元素组成和物理特征的多金属氧化物材料,它们适合用作丙烷氧化催化脱氢生产丙烯的催化剂。
Description
本发明涉及式Ⅰ的多金属氧化物材料
M1 aMo1-bM2 bOx (Ⅰ)，式中，M1为Co、Ni、Mg、Zn、Mn和/或Cu、优选Co、Ni和/或Mg、特别优
选Co和/或Ni，M2为W、V、Te、Nb、P、Cr、Fe、Sb、Ce、Sn和/或La、优选Sn、W、
P、Sb和/或Cr、特别优选W、Sn和/或Sb，a为0.5-1.5、优选0.7-1.2、特别优选0.9-1.0，b为0-0.5、优选＞0-0.5、特别优选0.01-0.3和x为一个数值，它由式(Ⅰ)中除氧以外的元素的化合价和出现率决定，其条件是多金属氧化物材料(Ⅰ)的平均孔径为≤0.04微米和≥0.01微米，以及多金属氧化物材料(Ⅰ)的比表面积为≥20米2/克。
本发明还涉及使用多金属氧化物材料(Ⅰ)作为催化剂，使丙烷气相催化氧化脱氢生产丙烯的方法。
化学计量式(Ⅰ)的多金属氧化物材料是已知的。例如，这样的多金属氧化物材料在以下文献中描述：催化作用，3(1996),265-275；催化作用通讯，35(1995),57-64；今日催化作用，24(1995),327-333；工业与工程化学研究35(1996),14-18；US-A 4255284；第3届世界氧化催化作用大会，R.K.Grasselli等(编辑)1997,E1sevier Science B.V.,357-364；催化杂志167(1997),560-569；催化作用通讯10(1991),181-192；US-A 5086032；US-A4255284；US-A 5086032；催化杂志170(1997),346-356以及在先申请DE-A 19751046，它们适用于作为丙烷气相催化氧化脱氢、以生产丙烯的适合催化剂。但是，现有技术的上述多金属氧化物材料的缺点是，在一定的含丙烷和分子氧的反应原料气体混合物的负荷下，在一定的反应条件下，用所述的多金属氧化物材料可得到的丙烯或丙烯、丙烯醛和丙烯酸(都是所需的产物)的时空产率是不能令人满意的。
本发明的一个目的是提供新型的多金属氧化物材料，当它们用作丙烷催化氧化脱氢、以生产丙烯或丙烯、丙烯醛和丙烯酸的催化剂时，在一定的负荷下和在一定的反应条件下可得到更高的时空产率。
我们已发现，这一目的可通过开始规定的多金属氧化物材料(Ⅰ)来达到。
根据本发明，多金属氧化物材料(Ⅰ)优选为式(Ⅱ)的那些多金属氧化物材料
[Co,Ni和/或Mg]aMo1-b[Sn,W,P,Sb和/或Cr]bOx (Ⅱ)，式中，a为0.5-1.5、优选0.7-1.2、特别优选0.9-1.0；b为0-0.5、优选＞0-0.5、特别优选0.01-0.3，和x为一个数值，它由式(Ⅱ)中除氧以外的元素的化合价和出现率决定。
根据本发明，多金属氧化物材料(Ⅰ)中特别优选式(Ⅲ)的那些多金属氧化物材料
[Co和/或Ni]aMo1-b[W,Sn和/或Sb]bOx (Ⅲ)，a、b和x有上述含义。
式(Ⅰ)、(Ⅱ)和(Ⅲ)中其他优选的多金属氧化物材料为那些平均孔径为≥0.02微米和≤0.035微米的多金属氧化物材料。根据本发明，那些平均孔径为≥0.025微米和≤0.030微米的多金属氧化物材料(Ⅰ)、(Ⅱ)和(Ⅲ)也是适用的。
如果上述多金属氧化物材料有上述的平均孔径与≥25米2/克或≥30米2/克的比表面积相结合也是有利的。通常，新型的多金属氧化物材料的比表面积为≤50米2/克。
在本申请书中，比表面积0为压汞法测定的比表面积(测量范围：1微米至3纳米孔径)。在本申请书中，平均孔径规定为用上述压汞法测定的总孔体积与比表面积0之比的4倍。
原则上，适合于本发明的活性多金属氧化物材料(Ⅰ)可按简单的方式用以下的步骤来制备：由元素成分的适合来源产生一个水溶液；将所述的溶液喷雾干燥(出口温度宜为100-150℃)；然后在一旋转容器中焙烧。通常，焙烧温度为450-1000℃、优选450-700℃，常常为450-600℃或550-570℃。焙烧可在惰性气体下或在氧化气氛例如空气或惰性气体和氧的混合物下进行，或在还原气氛例如惰性气体、氧和NH3、CO和/或H2的混合物下进行。这一焙烧可以简单的方式、将相应的气体混合物流过旋转的容器来实现。适合的旋转容器例如为旋转炉或旋转的圆底石英烧瓶。
活性多金属氧化物(Ⅰ)中元素成分的适合来源是那些已为氧化物的化合物和/或那些至少在氧存在下通过加热可转化成氧化物的化合物。除了氧化物外，特别适合的这类原料化合物是卤化物、硝酸盐、甲酸盐、草酸盐、柠檬酸盐、醋酸盐、碳酸盐、胺络合物、铵盐和/或氢氧化物(例如NH4OH、(NH4)2CO3、NH4NO3、NH4CHO2、CH3COOH、NH4CH3CO2和/或草酸铵，它们最后在随后的焙烧过程中分解和/或可分解成完全以气体形式放出的化合物，它们还可结合在水溶液中)。为了促进在水介质中的溶解，如果需要，所述的介质可被酸化，与碱混合和/或加热升温。
特别适合的Mo、V、W和Nb的原料化合物为它们的含氧化合物(钼酸盐、钒酸盐、钨酸盐和铌酸盐)或由这些化合物得到的酸(钼酸铵、钒酸铵、钨酸铵)。
对于丙烷的气相催化氧化脱氢生产丙烯来说，新型的多金属氧化物材料(Ⅰ)可以粉末形式使用，或成型成特定的催化剂几何形状，在最后的焙烧以前或以后进行成型是可能的。例如，可用以下方法由粉末状的活性材料或其未焙烧的前体材料制备未负载的催化剂：压紧以得到所需的催化剂几何形状(例如用造粒或挤条的方法)，如果需要，可加入助剂例如石墨或硬脂酸作为润滑剂和/或模塑助剂以及增强材料，例如玻璃、石棉、碳化硅或钛酸钾的微纤维。未负载的催化剂的适合几何形状例如为实心圆柱体或空心圆柱体，其外径和长度为2-10毫米。在空心圆柱体的情况下，壁厚宜为1-3毫米。当然，未负载的催化剂也可为球形，球直径为2-10毫米是可能的。
当然，粉状活性材料或它的未焙烧的粉状前体材料的成型也可通过涂覆到预成型的惰性催化剂载体上来进行。对于涂覆催化剂的制备，通常在适合的旋转容器中进行载体的涂层，例如在DE-A 2909671或EP-A 293859中公开的。为了涂覆载体，宜将要涂覆的粉末材料润温和在涂覆后再干燥，例如用热空气干燥。涂覆到载体上的粉末材料的涂层厚度宜为50-500微米、优选150-250微米。
常规的多孔或非多孔氧化铝、氧化硅、二氧化钍、二氧化锆、碳化硅或硅酸盐例如硅酸镁或硅酸铝可用作载体材料。载体可有规则的或不规则的形状，那些有规则形状和很粗糙表面的载体例如球体或空心圆柱体是优选的。
基本上非多孔的球形冻石载体的使用是适宜的，它们有粗糙的表面，其直径为1-8毫米、优选4-5毫米。
在实践中，新的方法宜在管束反应器中进行，例如在EP-A 700893和EP-A 700714中公开的。本发明使用的固定床催化剂存在在金属管(通常由不锈钢制成)中，而加热介质(通常为盐熔体)从金属管周围通过，也就是说在最简单的形式中，每一反应管装有至少一多金属氧化物(Ⅰ)作为活性材料的催化剂床层。
反应原料气体混合物宜由≥50％(体积)丙烷、≥15％(体积)O2和0-35％(体积)惰性气体组成。有利的是，反应原料气体混合物含有≤30、优选≤20、特别优选≤10％(体积)或≤5％(体积)的惰性气体。当然，反应原料气体混合物也可能不含惰性气体。
在这里，将惰性气体理解为在反应原料气体混合物通过本发明使用的固定床催化剂的过程中其转化率为≤5％(摩尔)的那些气体。适合的惰性气体的例子为H2O、CO2、CO、N2和/或稀有气体。
此外，反应原料气体混合物宜含有≥60或≥70或≥80％(体积)丙烷。通常，本发明使用的反应原料气体混合物的丙烷含量为≤85、常常≤83或≤82或≤81或≤80％(体积)。在新的方法中，反应原料气体混合物中分子氧的含量可一直到35％(体积)。有利的是，它至少为20％(体积)或至少为25％(体积)。
本发明的反应原料气体混合物优选含有≥65％(体积)和≤85％(体积)丙烷以及≥15％(体积)和≤35％(体积)分子氧。
根据本发明，如果反应原料气体混合物中丙烷与分子氧的摩尔比为≤5∶1、优选≤4.7∶1、更优选≤4.5∶1、特别优选≤4∶1。通常，上述比例为≥1∶1或≥2∶1。
反应压力通常为≥0.5巴。通常，反应压力不超过100巴，即为≥0.5至100巴。反应压力常常宜为＞1至50或＞1至20巴。优选的是，反应压力为≥1.25或≥1.5或≥1.75或≥2巴。上限常常不超过10或20巴。
当然，反应压力也可为1巴(上述有关适用于新方法的反应压力是普适的)。此外，优选这样来选择负荷，以致反应气体混合物在催化剂床层上的停留时间为0.5-20、优选1-10、特别优选1-4、常常为3秒。
如果新方法连续进行，可将反应产物混合物中所含的未转化丙烷分离出来，再循环回新的催化氧化脱氢。
此外，新方法可继之有另外的多相催化的氧化段，如已知在多相催化下使丙烷气相氧化生成丙烯醛和/或丙烯酸以及在在先申请DE-A19751046中公开的。
实施例
实施例1
a)多金属氧化物材料Ⅰ的制备
在45℃下，将877.2克七钼酸铵(Ammoniumheptamolybat)(81.5％(重量)MoO3)溶于3.6公斤水中，然后将2227.2克硝酸钴水溶液(按溶液计，12.5％(重量)Co)加到生成的溶液中。将生成的红色透明溶液在Niro公司的喷雾干燥器中喷雾干燥，进口温度为330-340℃，出口温度为110℃(A/S Niro Atomizer，可移动的小型设备)。
将450克喷雾干燥的粉末与75毫升水一起捏合40分钟(Werner &Pfleiderer公司的1升∑型叶片捏合机)，然后在循环干燥器中110℃下干燥16小时。然后将干燥过的固体在旋转的圆底石英烧瓶中焙烧如下，空气流过石英烧瓶，石英烧瓶以15转/分的速率旋转，其内体积为2升，恒定的空气流量为250升/小时(平炉加热)：
首先，以180℃/小时的加热速率从室温(25℃)加热到225℃。此后，将225℃的温度保持0.5小时，然后以60℃/小时的加热速率将焙烧温度从225℃升至300℃。将这一温度保持3小时。此后，以125℃/小时的加热速率将焙烧温度从300℃升至550℃。然后将这一温度保持6小时。
将如此制得的多金属氧化物粉碎，筛分出最大粒度为0.6-1.2毫米的颗粒筛分，用作催化活性的多金属氧化物材料(Ⅰ)，其化学计量式为Mo1Co0.95Ox。
活性材料的平均孔径为0.027微米，比表面积为33.1米2/克。
b)丙烷的氧化催化脱氢
长度1.4米的反应管(V2A不锈钢；壁厚2.5厘米；内径8.5毫米；电加热)在催化剂支架上(7厘米长)从底部到顶部装料，首先装入23厘米长的石英屑(数均最大粒度为1-2毫米)，然后装入75厘米长的多金属氧化物材料Ⅰ，再装入35厘米长的石英屑(数均最大粒度为1-2毫米)。
将如上装料的反应管在其全长上加热到395℃，然后从顶部向下进料56标准升/小时含有80％(体积)丙烷和20％(体积)氧的反应原料气体混合物。反应管进口处的压力为1.6巴(绝对)。沿反应管的压力降为0.22巴。
一次通过，得到有以下特征的产物气体混合物：
丙烷转化率： 12.4％(摩尔)
生成丙烯的选择性： 69％(摩尔)
生成丙烯醛的选择性： 2％(摩尔)
生成丙烯酸的选择性： 4％(摩尔)
丙烯的时空产率： 3.8摩尔/升催化剂·小时
目的产物的时空产率： 4.1摩尔/升催化剂·小时
对比例
a)多金属氧化物材料Ⅰ的制备
在80℃下，将292.4克七钼酸铵(81.5％(重量)MoO3)溶于1.2公斤水中，然后将742.4克硝酸钴水溶液(按溶液计，12.5％(重量)Co)加到生成的溶液中。将生成的溶液在水浴上、在100℃下蒸发，同时搅拌，一直到生成糊状材料。将糊状材料与30毫升水一起捏合40分钟(Werner & Pfleiderer公司的1升∑型叶片捏合机)。将生成的材料在干燥炉中、在110℃下干燥16小时，然后在马弗炉中焙烧如下，空气通过马弗炉，马弗炉的内容积为60升，空气流速为500升/小时：首先以120℃/小时的加热速率从25℃加热到300℃。
此后，将300℃的温度保持3小时，然后以125℃/小时的加热速率将焙烧温度从300℃升至550℃。然后将这一温度保持6小时。将如此制得的多金属氧化物粉碎，筛分出最大粒度为0.6-1.2毫米的颗粒筛分，用作为催化活性的多金属氧化物材料Ⅰ，其化学计量式为Mo1Co0.95Ox。活性材料的平均孔径为0.048微米，比表面积为28.4米2。
b)丙烷的氧化催化脱氢
丙烷的氧化催化脱氢按实施例1进行，但所用的活性材料为对比例a)的活性材料。
一次通过，得到有以下特征的产物气体混合物：
丙烷转化率： 8.8％(摩尔)
生成丙烯的选择性： 76％(摩尔)
生成丙烯醛的选择性： 2％(摩尔)
生成丙烯酸的选择性： 2％(摩尔)
丙烯的时空产率： 2.9摩尔/升催化剂·小时
目的产物的时空产率： 3.1摩尔/升催化剂·小时
实施例2
在45℃下，将877.2克七钼酸铵(81.5％(重量)MoO3)溶于3.6公斤水中，然后将2227.2克硝酸钴水溶液(按溶液计，12.5％(重量)Co)加到生成的溶液中。将生成的红色透明溶液在实施例1,a)中的喷雾干燥器中喷雾干燥。象实施例1,a)中那样，将450克喷雾干燥的粉末与水一起捏合，然后干燥和焙烧。与实施例1,a)不同，在焙烧中，焙烧温度最后以133℃/小时的加热速率从300℃升至565℃，然后将这一焙烧温度保持6小时。
将如此制得的多金属氧化物粉碎，筛分出最大粒度为0.6-1.2毫米的颗粒筛分，用作为催化活性的多金属氧化物材料Ⅰ，其化学计量式为Mo1Co0.95Ox。
活性材料的平均孔径为0.024微米，比表面积为29.2米2/克。
b)丙烷的氧化催化脱氢
象实施例1那样，将实施例2的活性材料装入反应管。将装入活性材料的反应管整个长度加热到400℃，然后用112升/小时含有80％(体积)丙烷和20％(体积)氧的反应原料气体混合物进料。反应器进口处的压力为2.7巴(绝对)。沿反应管的压力降为0.5巴。
一次通过，得到有以下特征的产物气体混合物：
丙烷转化率： 9.4％(摩尔)
生成丙烯的选择性： 77％(摩尔)
生成丙烯醛的选择性： 2％(摩尔)
生成丙烯酸的选择性： 3％(摩尔)
丙烯的时空产率： 6.3摩尔/升催化剂·小时
目的产物的时空产率： 6.8摩尔/升催化剂·小时。
Claims (2)
1．一种式Ⅰ的多金属氧化物材料
M1 aMo1-bM2 bOx (Ⅰ)，式中，M1为Co、Ni、Mg、Zn、Mn和/或Cu，M2为W、V、Te、Nb、P、Cr、Fe、Sb、Ce、Sn和/或La，a为0.5-1.5，b为0-0.5，和x为一个数值，它由式(Ⅰ)中除氧以外的元素的化合价和出现率决定，其条件是多金属氧化物材料(Ⅰ)的平均孔径为≤0.04微米和≥0.01微米，以及多金属氧化物材料(Ⅰ)的比表面积为≥20米2/克。
2．一种使丙烷氧化催化脱氢生产丙烯的方法，其特征在于，使用了这样的催化剂，其活性材料为按权利要求1所要求的多金属氧化物材料。
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| DE19807269A DE19807269A1 (de) | 1998-02-20 | 1998-02-20 | Multimetalloxidmassen |
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| DE19838312A DE19838312A1 (de) | 1998-08-24 | 1998-08-24 | Multimetalloxidmassen |
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|---|---|---|---|---|
| US6534437B2 (en) | 1999-01-15 | 2003-03-18 | Akzo Nobel N.V. | Process for preparing a mixed metal catalyst composition |
| US6355854B1 (en) | 1999-02-22 | 2002-03-12 | Symyx Technologies, Inc. | Processes for oxidative dehydrogenation |
| US6436871B1 (en) | 1999-02-22 | 2002-08-20 | Symyx Technologies, Inc. | Catalysts for oxidative dehydrogenation |
| CA2363035C (en) | 1999-02-22 | 2007-09-04 | Symyx Technologies, Inc. | Compositions comprising nickel and their use as catalyst in oxidative dehydrogenation of alkanes |
| US6677497B2 (en) | 2001-03-22 | 2004-01-13 | Symyx Technologies, Inc. | Ni catalysts and methods for alkane dehydrogenation |
| ZA200209470B (en) * | 2001-12-04 | 2003-06-03 | Rohm & Haas | Improved processes for the preparation of olefins, unsaturated carboxylic acids and unsaturated nitriles from alkanes. |
| JP2010260793A (ja) * | 2007-08-30 | 2010-11-18 | Nippon Shokubai Co Ltd | アルカンの酸化脱水素用触媒、当該触媒の製造方法、並びに当該触媒を用いた不飽和炭化水素化合物および／または含酸素炭化水素化合物の製造方法、または不飽和酸の製造方法。 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE755313A (fr) * | 1969-08-27 | 1971-02-26 | Exxon Research Engineering Co | Procede de synthese epitaxiale |
-
1999
- 1999-02-11 AU AU27249/99A patent/AU2724999A/en not_active Abandoned
- 1999-02-11 EP EP99907537A patent/EP1060129B1/de not_active Expired - Lifetime
- 1999-02-11 DE DE59900495T patent/DE59900495D1/de not_active Expired - Lifetime
- 1999-02-11 CN CN99802281A patent/CN1288445A/zh active Pending
- 1999-02-11 WO PCT/EP1999/000890 patent/WO1999042404A1/de active IP Right Grant
- 1999-02-11 BR BR9907937-2A patent/BR9907937A/pt not_active Application Discontinuation
- 1999-02-11 JP JP2000532362A patent/JP2002503628A/ja not_active Withdrawn
- 1999-02-20 MY MYPI99000605A patent/MY133084A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE59900495D1 (en) | 2002-01-17 |
| JP2002503628A (ja) | 2002-02-05 |
| BR9907937A (pt) | 2000-11-14 |
| AU2724999A (en) | 1999-09-06 |
| EP1060129B1 (de) | 2001-12-05 |
| MY133084A (en) | 2007-10-31 |
| WO1999042404A1 (de) | 1999-08-26 |
| EP1060129A1 (de) | 2000-12-20 |
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