CN1450934A - 改进的制造丙烯腈的催化剂 - Google Patents
改进的制造丙烯腈的催化剂 Download PDFInfo
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- CN1450934A CN1450934A CN01814136A CN01814136A CN1450934A CN 1450934 A CN1450934 A CN 1450934A CN 01814136 A CN01814136 A CN 01814136A CN 01814136 A CN01814136 A CN 01814136A CN 1450934 A CN1450934 A CN 1450934A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims abstract description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011777 magnesium Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 16
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 14
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 150000001336 alkenes Chemical class 0.000 claims abstract description 11
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 10
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 10
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 8
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 6
- 229910052738 indium Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011591 potassium Substances 0.000 claims abstract description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims abstract description 4
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- 229910021529 ammonia Inorganic materials 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 235000013495 cobalt Nutrition 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
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- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 3
- 238000005915 ammonolysis reaction Methods 0.000 description 3
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- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DTDQFVRSJWCWNK-UHFFFAOYSA-N [Fe].[Bi].[Mo] Chemical compound [Fe].[Bi].[Mo] DTDQFVRSJWCWNK-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- -1 nitrate Chemical class 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 238000004821 distillation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- NWJZFGOFYNPABH-UHFFFAOYSA-N prop-1-ene;prop-2-enenitrile Chemical group CC=C.C=CC#N NWJZFGOFYNPABH-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
-
- 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
- B01J23/8876—Arsenic, antimony or bismuth
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
催化剂组合物，包括铁、铋、钼、钴、铈、锑的催化氧化物的复合物，镍或镁中至少一种，锂、钠、钾、铷或铊中至少一种，由下述经验式表征：AaBbCcFedBieCofCegSbhMomOx，其中A为Cr、P、Sn、Te、B、Ge、Zn、In、Mn、Ca、W或其混合物中至少一种，B为Li、Na、K、Rb、Cs、Tl或其混合物中至少一种，C为Ni、Mg或其混合物中至少一种，a为0～4.0，b为0.01～1.5，c为1.0～10.0，d为0.1～5.0，e为0.1～2.0，f为0.1～10.0，g为0.1～2.0，h为0.1～2.0，m为12.0～18.0，x值由存在的其它元素的化合价需要而定。该催化剂用于烯烃氨氧化工艺中，烯烃选自丙烯、异丁烯或其混合物，分别生成丙烯腈、甲基丙烯腈或其混合物。
Description
发明背景
技术领域
本发明涉及改进的用于不饱和烃氨氧化生成相应的不饱和腈的催化剂。具体来说，本发明涉及改进的丙烯和/或异丁烯分别氨氧化生成丙烯腈和/或甲基丙烯腈的方法和催化剂。更具体地说，本发明涉及一种新型的、改进的氨氧化催化剂，它包括铁、铋、钼、钴、铈、锑的催化氧化物的复合物，镍或镁中至少一种，和锂、钠、钾、铷或铊中至少一种。
背景技术
有许多专利涉及用铋-钼-铁流化床催化剂生产丙烯腈。具体来说，英国专利GB1436475；美国专利US4,766,232；4,377,534；4,040,978；4,168,246；5,223,469和4,863,891都涉及铋-钼-铁催化剂，其中催化剂可用第II族元素促进来生产丙烯腈。除此，US4,190,608公开了类似的促进的铋-钼-铁催化剂用于烯烃氧化。US5,093,299和5,212,137涉及具有高丙烯腈产率促进的铋-钼催化剂。
正如前述专利所描述，以合适元素促进的含铁、铋、钼氧化物的催化剂早就用于丙烯在高温、氨和氧(通常为空气)存在下转化生成丙烯腈。
本发明之目的是新型催化剂，它包括独特的助催化剂组合物，在丙烯、异丁烯或其混合物催化氨氧化分别生成丙烯腈、甲基丙烯腈或其混合物的过程中具有更好的性能。
发明概述
本发明涉及改进的丙烯和/或异丁烯分别氨氧化生成丙烯腈和/或甲基丙烯腈的催化剂和方法。本发明是一种新型催化剂，以下述经验公式表征：
AaBbCcFedBieCofCegSbhMomOx
其中，A为Cr、P、Sn、Te、B、Ge、Zn、In、Mn、Ca、W或其混合物中至少一种
B为Li、Na、K、Rb、Cs、Tl或其混合物中至少一种
C为Ni、Mg或其混合物中至少一种
a为0～4.0
b为0.01～1.5
c为1.0～10.0
d为0.1～5.0
e为0.1～2.0
f为0.1～10.0
g为0.1～2.0
h为0.1～2.0
m为12.0～18.0
以及x值根据存在的其它元素的化合价需要而定。
本发明也涉及选自丙烯、异丁烯或其混合物的烯烃分别转化为丙烯腈、甲基丙烯腈或其混合物的方法，其中在气相下使所述烯烃在高温、高压下与含气体的分子氧和氨在混合金属氧化物催化剂存在下反应，其中的催化剂具有上述的经验公式。发明详述
本发明涉及一种氨氧化催化剂，它包括铁、铋、钼、钴、铈、锑的催化氧化物的复合物，镍或镁中至少一种，和锂、钠、钾、铷或铊中至少一种，以下述经验公式表征：
AaBbCcFedBieCofCegSbhMomOx
其中，A为Cr、P、Sn、Te、B、Ge、Zn、In、Mn、Ca、W或其混合物中至少一种
B为Li、Na、K、Rb、Cs、Tl或其混合物中至少一种
C为Ni、Mg或其混合物中至少一种
a为0～4.0
b为0.01～1.5
c为1.0～10.0
d为0.1～5.0
e为0.1～2.0
f为0.1～10.0
g为0.1～2.0
h为0.1～2.0
m为12.0～18.0
以及x值根据存在的其它元素的化合价需要而定。
“A”组分为上述催化剂中可选元素。若“A”存在，则它优选选自Cr、P、Ge、Ca或其混合物。在本发明的优选具体实施方案中，“B”选自Li、Na、K、Cs或其混合物中的一种或多种，特别优选为Li、Cs、K或其混合物。在本发明的优选具体实施方案中，“C”为Ni和Mg的混合物即催化剂既含Ni又含Mg。
在本发明的其它优选具体实施方案中，“a”独立为约0.1～4.0，特别优选为约0.1～3.0；“b”独立为约0.05～1.2，特别优选为约0.1～1.0；“c”独立为约2.0～9.0，特别优选为约2.0～8.0；“d”独立为约0.5～5.0，特别优选为约1.0～4.0；“e”独立为约0.1～1.5，特别优选为约0.1～1.0；“f”独立为约1.0～7.0，特别优选为约1.0～1.5；“g”独立为约0.3～1.5，特别优选为约0.3～1.2；“h”独立为约0.3～1.5，特别优选为约0.3～1.2；以及“m”独立为约13.0～16.0。
本发明的催化剂既可负载也可不负载，优选地，催化剂负载于氧化硅、氧化铝、(氧化)锆、氧化钛或其混合物上，特别优选作为催化剂载体的是氧化硅。使用的催化剂载体量可变化。典型地，载体约占催化剂总重量的30％～70％，更优选约为催化剂总重量的50％。
本发明催化剂组合物例子包括：
K0.2Ni3.0Mg2.0Fe2.0Bi0.5Co3.5Ce1.0Sb0.5Mo13.6Ox+50wt％SiO2
K0.2Ni4.5Mg1.5Fe2.0Bi0.5Ca0.2Co1.7Ce0.5Sb0.5Mo13.6Ox+50wt％SiO2
Cs0.1K0.1Mg2.0Fe2.0Bi0.5Co6.2Ce0.5Sb0.3Mo13.6Ox+50wt％SiO2
Cs0.15Ni3.0Mg2.5Fe1.5Bi0.3Co3.0Ce0.5Sb0.5W0.2Mo13.0Ox+50wt％SiO2
Cs0.15Ni2.5Mg2.5Fe1.5Bi0.3Li1.0.2Co2.8Ce1.0Sb0.5Mo13.0Ox+50wt％SiO2
CS0.1K0.1Ni5.0Mg2.5Fe1.5Bi0.3P0.2Co1.0Ce0.5Sb0.5Mo13.0Ox+50wt％SiO2
Cs0.1K0.1Ni4.0Mg2.0Fe2.0Bi0.5Co2.2Ce0.3Cr0.2Sb0.3Mo13.6Ox+50wt％SiO2
本发明中催化剂可用本领域普通技术人员已知的众多催化剂制备方法中任何一种制备。例如，催化剂可通过共沉淀多种组分制备。共沉淀物质经干燥后研磨为适当大小。作为选择，按传统技术共沉淀物质可被淤浆化，喷雾干燥。催化剂可用本领域熟知的方法挤成片状或在油中形成珠状。作为选择，催化剂组分和载体可以淤浆形式混合，然后干燥或者浸渍在氧化硅或其它载体上。关于催化剂制备的具体过程，可参见US5,093,299；4,863,891和4,766,232，它们已转让给本发明的受让人，在此引入作为参考。
催化剂的组分“A”(即Cr、P、Sn、Te、B、Ge、Zn、In、Mn、Ca、W或其混合物中至少一种)可从任何适当的来源得到。例如，钴、镍、镁可用硝酸盐引入催化剂。另外，镁还可用不溶性碳酸盐或经加热处理生成氧化物的氢氧化物引入催化剂。磷可用碱金属盐或碱土金属盐或铵盐引入催化剂，但优选作为磷酸引入。钙可通过先形成钼酸钙加入或用浸渍法或用其它本领域已知的方法加入。
典型地，催化剂的组分“B”(即Li、Na、K、Rb、Cs、Tl或其混合物中至少一种)可以氧化物或经焙烧生成氧化物的盐引入催化剂。优选易得和易溶的盐如硝酸盐，按在催化剂中引入A元素的方法使用。
铋用氧化物或经焙烧生成氧化物的盐引入催化剂。优选为易分散但经加热形成稳定氧化物的水溶性盐。引入铋的更优选的来源是已在硝酸溶液中溶解的硝酸铋。
为将铁组分引入催化剂，可用任何经焙烧生成氧化物的铁化合物。和其它元素一样，水溶性盐为优选，因它们容易均一地分散在催化剂中。更优选为硝酸铁。
催化剂的钼组分可从钼氧化物如二氧化物、三氧化物、五氧化物或七氧化物引入催化剂。但是，优选可水解或分解的钼盐作为钼的来源。最优选的原料为七钼酸铵。
制备催化剂时将七钼酸铵的水溶液与硅胶混合，在其中加入含化合物的淤浆，优选为其它元素的硝酸盐。然后固体物质经干燥、脱硝酸盐和焙烧。优选地，催化剂在温度110℃～350℃下喷雾干燥，优选为110℃～250℃，最优选为110℃～180℃。脱氮的温度为100℃～500℃，优选为250℃～450℃。最后，焙烧在300℃～700℃温度下进行，优选为350℃～650℃。
本发明催化剂在选自丙烯、异丁烯或其混合物的烯烃分别转化为丙烯腈、甲基丙烯腈或其混合物的氨氧化方法中应用，其中在气相下使所述烯烃在高温、高压下与含气体的分子氧和氨在催化剂存在下反应。
优选地，氨氧化反应在流化床反应器中进行，但预期其它类型的反应器如移动管线反应器也可使用。对丙烯腈的制造，流化床反应器在现有技术中众所周知。例如US3,230,246公开的反应器设计是合适的，在此引入作为参考。
氨氧化反应发生的条件也在现有技术中众所周知，如US5,093,299；4,863,891；4,767,878和4,503,001中清楚的描述，在此引入作为参考。典型地，进行氨氧化操作时，在高温、氨和氧存在下，将丙烯或异丁烯与流化床催化剂接触生成丙烯腈或甲基丙烯腈。任何来源的氧均可用。但出于经济原因，优选使用空气。典型的氧与原料中烯烃的摩尔比应为0.5∶1～4∶1，优选为1∶1～3∶1。反应中氨与原料中烯烃的摩尔比为0.5∶1～5∶1。氨-烯烃比的确没有上限，但出于经济原因，一般没有理由大于5∶1。用本发明的催化剂生产丙烯腈，优选的原料比为：氨与丙烯比为0.9∶1～1.3∶1，空气与烯烃比为8.0∶1～12.0∶1。
反应在约260℃～600℃温度下进行，优选为310℃～500℃，特别优选为350℃～480℃。接触时间虽然不关键，一般为0.1～50秒，优选为1～15秒。
反应产品的回收和精制可用本领域普通技术人员已知的任何方法。一种这样的方法包括用冷水或合适的溶剂从反应器中洗涤流出气体以移走反应产品，然后用蒸馏精制反应产品。
本发明催化剂的主要用途是丙烯氨氧化为丙烯腈。但是，本催化剂也可用于丙烯氧化为丙烯酸。该工艺典型为两步法，其中丙烯在第一步中在催化剂存在下主要转化为丙烯醛，丙烯醛在第二步中在催化剂存在下主要转化为丙烯酸。本催化剂对一步或两步都适用。
具体实施方案
为了阐明本发明，仅为说明需要举出下面各例。实施例：公式为K0.2Ni3.0Mg2.0Fe2.0Bi0.5Co3.5Ce1.0Sb0.5Mo13.6Ox+50wt％SiO2的催化剂按下述步骤制备：196.49g七钼酸铵溶解于400mL水中。在其中先加入含40wt％SiO2的硅胶625g，再加入5.96g Sb2O3。最后，加入熔融金属硝酸盐的混合物作为50％的溶液，包括：66.12gFe(NO3)3·9H2O，71.39g Ni(NO3)2·6H2O，83.36g Co(NO3)2·6H2O，41.96gMg(NO3)2·6H2O，19.85g Bi(NO3)3·5H2O，1.66g KNO3和89.73gCe(NH4)2(NO3)6·6H2O。形成的浆液经搅拌，然后喷雾干燥，得到479g催化剂。催化剂在290℃加热处理3小时，然后425℃处理3小时，最后600℃处理3小时，得到成品催化剂。
对比例A到G：用上述制备方法，同样制备几个其它催化剂，其中制备中不用钴、铈或锑中一个或多个元素。这些催化剂组合物列于表1中。
为了鉴别本发明要求的钴、铈和锑促进的催化剂与不含三者中一种或多种的类似催化剂的性能，所有催化剂均在相似的反应条件下进行评价。含1C3 ＝/1.2NH3/9.5空气的混合物原料在约430℃、10psig和0.09wwh下进入通过在直径为1"反应器中的下列催化剂。收集和测定丙烯腈的产量。
表1
| 实施例 | 催化剂组合物(所有组合物均加50wt％SiO2) | 总C3 ＝转化率 | 生成AN的转化率 |
| 实施例 | K0.2Ni3.0Mg2.0Fe2.0Bi0.5Co3.5Ce1.0Sb0.5Mo13.6Ox | 98.0％ | 79.8％ |
| 对比例A | K0.2Ni3.0Mg2.0Fe2.0Bi0.5 - Ce1.0Sb0.5Mo13.6Ox | 71.7％ | 56.9％ |
| 对比例B | K0.2Ni3.0Mg2.0Fe2.0Bi0.5Co3.5 - Sb0.5Mo13.6Ox | 80.4％ | 64.1％ |
| 对比例C | K0.2Ni3.0Mg2.0Fe2.0Bi0.5Co3.5Ce1.0 - Mo13.6Ox | 97.1％ | 76.2％ |
| 对比例D | K0.2Ni3.0Mg2.0Fe2.0Bi0.5Co3.5 - - Mo13.6Ox | 85.7％ | 67.3％ |
| 对比例E | K0.2Ni3.0Mg2.0Fe2.0Bi0.5 - - Sb0.5Mo13.6Ox | 79.6％ | 64.2％ |
| 对比例F | K0.2Ni3.0Mg2.0Fe2.0Bi0.5 - Ce1.0 - Mo13.6Ox | 85.1％ | 66.8％ |
| 对比例G | K0.2Ni3.0Mg2.0Fe2.0Bi0.5 - - - Mo13.6Ox | 79.7％ | 60.4％ |
注：
1.“总C3 ＝转化率”为单程丙烯转化为所有产物的摩尔百分数。
2.“生成AN的转化率”为单程丙烯转化为丙烯腈的摩尔百分数。
本发明的催化剂组合物独特之处在于它含有三种助催化元素钴、铈和锑，之前在单一的氨氧化催化剂配方中没有结合使用过。如表1说明，对丙烯氨氧化为丙烯腈，本发明催化剂比现有技术中不含、含一种或含两种上述三种元素的催化剂具有更好的性能。更具体来说，在高温下及在氨和空气存在下，丙烯在含钴、铈和锑的催化剂上氨氧化反应时，该催化剂表现出更高的总转化率和生成丙烯腈的转化率。
虽然本发明结合上述的具体实施方案进行了描述，但对本领域的普通技术人员来说，根据上面的描述，本发明有许多变化、修饰和改变是显而易见的。因此，意欲包括所附权利要求的精神和宽范围内的所有这些变化、修饰和改变。
Claims (8)
1.催化剂组合物包括铁、铋、钼、钴、铈、锑的催化氧化物的复合物，镍或镁中至少一种，和锂、钠、钾、铷或铊中至少一种，具有下述经验公式：
AaBbCcFedBieCofCegSbhMomOx
其中，A为Cr、P、Sn、Te、B、Ge、Zn、In、Mn、Ca、W或其混合物中至少一种
B为Li、Na、K、Rb、Cs、Tl或其混合物中至少一种，
C为Ni、Mg或其混合物中至少一种，
a为0～4.0，
b为0.01～1.5，
c为1.0～10.0，
d为0.1～5.0，
e为0.1～2.0，
f为0.1～10.0，
g为0.1～2.0，
h为0.1～2.0，
m为12.0～18.0，
以及x值根据存在的其它元素的化合价需要而定。
2.如权利要求1所述催化剂，负载于选自氧化硅、氧化铝、氧化锆、氧化钛和其混合物的惰性载体上。
3.如权利要求1所述催化剂，其中B选自Na、Li、K、Cs或其混合物。
4.如权利要求1所述催化剂，其中C为Ni和Mg的混合物。
5.一种将选自丙烯、异丁烯或其混合物的烯烃分别转化为丙烯腈、甲基丙烯腈或其混合物的方法，它通过在气相中所述烯烃在高温、高压下与含气体的分子氧和氨在氧化物催化剂存在下反应来进行，其中催化剂具有下述经验公式：
AaBbCcFedBieCofCegSbhMomOx
其中，A为Cr、P、Sn、Te、B、Ge、Zn、In、Mn、Ca、W或其混合物中至少一种
B为Li、Na、K、Rb、Cs、Tl或其混合物中至少一种
C为Ni、Mg或其混合物中至少一种
a为0～4.0
b为0.01～1.5
c为1.0～10.0
d为0.1～5.0
e为0.1～2.0
f为0.1～10.0
g为0.1～2.0
h为0.1～2.0
m为12.0～18.0
以及x值根据存在的其它元素的化合价需要而定。
6.如权利要求5所述方法，其中催化剂负载于选自氧化硅、氧化铝、氧化锆、氧化钛和其混合物的惰性载体上。
7.如权利要求5所述方法，其中B选自Na、Li、K、Cs或其混合物。
8.如权利要求5所述方法，其中C为Ni和Mg的混合物。
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2001
- 2001-08-02 WO PCT/US2001/024253 patent/WO2002013963A2/en active IP Right Grant
- 2001-08-02 RU RU2003107043/04A patent/RU2266784C2/ru active
- 2001-08-02 JP JP2002519095A patent/JP4937487B2/ja not_active Expired - Lifetime
- 2001-08-02 AU AU2001278136A patent/AU2001278136A1/en not_active Abandoned
- 2001-08-02 EP EP01956103A patent/EP1309402B1/en not_active Expired - Lifetime
- 2001-08-02 MX MXPA03001409A patent/MXPA03001409A/es active IP Right Grant
- 2001-08-02 BR BRPI0113310-1A patent/BR0113310B1/pt not_active IP Right Cessation
- 2001-08-02 DE DE60128811T patent/DE60128811T2/de not_active Expired - Lifetime
- 2001-08-02 ES ES01956103T patent/ES2287146T3/es not_active Expired - Lifetime
- 2001-08-02 AT AT01956103T patent/ATE363944T1/de not_active IP Right Cessation
- 2001-08-02 CA CA002417987A patent/CA2417987C/en not_active Expired - Fee Related
- 2001-08-02 KR KR1020037002308A patent/KR100786051B1/ko active IP Right Grant
- 2001-08-02 CN CNB018141366A patent/CN1255215C/zh not_active Expired - Lifetime
- 2001-08-16 TW TW090120073A patent/TWI284058B/zh not_active IP Right Cessation
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2002
- 2002-08-06 US US10/213,755 patent/US6965046B2/en not_active Expired - Lifetime
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2003
- 2003-02-05 BG BG107525A patent/BG66322A/en unknown
- 2003-02-05 BG BG107525D patent/BG107525A/bg unknown
- 2003-02-05 ZA ZA200301006A patent/ZA200301006B/xx unknown
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103894203A (zh) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | 烯烃氨氧化反应高负荷催化剂 |
| CN103894203B (zh) * | 2012-12-27 | 2017-02-08 | 中国石油化工股份有限公司 | 烯烃氨氧化反应高负荷催化剂 |
| CN107282094A (zh) * | 2016-04-13 | 2017-10-24 | 中国石油化工股份有限公司 | 氨氧化法丙烯腈催化剂 |
| CN106000461A (zh) * | 2016-05-27 | 2016-10-12 | 张玲 | 一种甲基丙烯腈催化剂的制备方法 |
| CN114669306A (zh) * | 2022-03-27 | 2022-06-28 | 上海师范大学 | (甲基)丙烯醛氨氧化法制(甲基)丙烯腈的催化剂及其制备方法和应用 |
| CN114669306B (zh) * | 2022-03-27 | 2023-11-28 | 上海师范大学 | (甲基)丙烯醛氨氧化法制(甲基)丙烯腈的催化剂及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| BG107525A (bg) | 2003-12-31 |
| US20020198398A1 (en) | 2002-12-26 |
| MXPA03001409A (es) | 2004-05-04 |
| JP4937487B2 (ja) | 2012-05-23 |
| WO2002013963A2 (en) | 2002-02-21 |
| ZA200301006B (en) | 2004-02-13 |
| KR100786051B1 (ko) | 2007-12-17 |
| BG66322B1 (bg) | 2013-05-31 |
| DE60128811D1 (de) | 2007-07-19 |
| KR20030027036A (ko) | 2003-04-03 |
| CA2417987C (en) | 2007-10-23 |
| RU2266784C2 (ru) | 2005-12-27 |
| CA2417987A1 (en) | 2002-02-21 |
| EP1309402A2 (en) | 2003-05-14 |
| EP1309402B1 (en) | 2007-06-06 |
| DE60128811T2 (de) | 2008-02-21 |
| JP2004505766A (ja) | 2004-02-26 |
| WO2002013963A3 (en) | 2002-05-02 |
| US6458742B1 (en) | 2002-10-01 |
| BR0113310B1 (pt) | 2012-01-24 |
| CN1255215C (zh) | 2006-05-10 |
| TWI284058B (en) | 2007-07-21 |
| BG66322A (en) | 2013-05-31 |
| ATE363944T1 (de) | 2007-06-15 |
| AU2001278136A1 (en) | 2002-02-25 |
| ES2287146T3 (es) | 2007-12-16 |
| US6965046B2 (en) | 2005-11-15 |
| BR0113310A (pt) | 2003-06-24 |
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