CN1223903A - 用于丙烯腈和氰化氢制备的改进的催化剂 - Google Patents
用于丙烯腈和氰化氢制备的改进的催化剂 Download PDFInfo
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- CN1223903A CN1223903A CN98117923A CN98117923A CN1223903A CN 1223903 A CN1223903 A CN 1223903A CN 98117923 A CN98117923 A CN 98117923A CN 98117923 A CN98117923 A CN 98117923A CN 1223903 A CN1223903 A CN 1223903A
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- molybdenum
- acrylonitrile
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- 239000003054 catalyst Substances 0.000 title claims abstract description 12
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title description 24
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title description 18
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011575 calcium Substances 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 4
- 229910052745 lead Inorganic materials 0.000 claims abstract description 4
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 4
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000011777 magnesium Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 238000005915 ammonolysis reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- DTDQFVRSJWCWNK-UHFFFAOYSA-N [Fe].[Bi].[Mo] Chemical compound [Fe].[Bi].[Mo] DTDQFVRSJWCWNK-UHFFFAOYSA-N 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
- 230000008901 benefit Effects 0.000 description 2
- 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 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 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
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BYUANIDVEAKBHT-UHFFFAOYSA-N [Mo].[Bi] Chemical compound [Mo].[Bi] BYUANIDVEAKBHT-UHFFFAOYSA-N 0.000 description 1
- UNDKFRGFXJGGAL-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Ca+] Chemical compound [N+](=O)([O-])[O-].[Ca+] UNDKFRGFXJGGAL-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid 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
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [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
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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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
- B01J23/8876—Arsenic, antimony or bismuth
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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- B01J37/08—Heat treatment
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- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/02—Preparation, separation or purification of hydrogen cyanide
- C01C3/0208—Preparation in gaseous phase
- C01C3/0212—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process
- C01C3/0216—Preparation in gaseous phase from hydrocarbons and ammonia in the presence of oxygen, e.g. the Andrussow-process characterised by the catalyst used
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Abstract
一种含有铁,铋,钼和钙的催化氧化物的配合物的催化剂组合物,其特征具有下列的经验式:AaBbCcDdFeeBifMo12Ox其中A=一个或多个Li,Na,K,Rb和Cs或其混合物;B=一个或多个Mg,Mn,Ni,Co,Ag,Pb,Re,Cd和Zn或其混合物;C=一个或多个Ce,Cr,Al,Sb,P,Ge,La,Sn,V,和W或其混合物;D=一个或多个Ca,Sr,Ba,或其混合物;和a=0.01—1.0;b和e=1.0—10;c,d和f=0.1—5.0和X是由其它元素存在所要求的化合价确定的数。
Description
本发明涉及一种用于在不饱和烃的氨氧化反应中的改进的催化剂，上述的不饱和烃经氨氧化反应成为相应的不饱和腈，其中，在副产物达到意外高的产率时不会降低不饱和腈的收率。特别是。本发明涉及一种用于丙烯和/或异丁烯的氨氧化反应，分别成为丙烯腈和甲基丙烯腈的改进的催化剂，其中，伴随氰化氢副产物产品的增加而不会降低腈的收率。
有许多专利涉及使用铋-钼-铁流化床催化剂生产丙烯腈，特别是，GB1436475；U.S.4,766,232；4,377,534；4,040,978；4,168,246；5,223,469；和4,863,891；每个都涉及铋-钼-铁催化剂，可以用Ⅱ族元素促进生产丙烯腈。另外，U.S.4,190,608公开了类似的促进的铋-钼-铁催化剂用于链烯的氧化。最近公开的U.S.5,093,299所涉及的铋-钼催化剂显示丙烯腈的高收率。如在上述专利中公开的含有铁，铋，钼的氧化物和促进的适宜的元素的催化剂，长期以来，被用于在氨和氧存在，升高温度下丙烯腈转化以制备丙烯腈。在伴随着丙烯腈作为主产品的同时，保持氰化氢作为主要的副产品。
在丙烯或异丁烯的氨氧化反应分别成为它门的相应的不饱和腈，丙烯腈和甲基丙烯腈中，研究者们长期的奋斗目标为，就是能够得到最多的丙烯腈或甲基丙烯腈产品。然而，近年来，必需要考虑这些氨化反应的主要副产物所带来的重要的日益增大的经济利益。事实上，在某种操作中，对于氰化氢副产物最大产率是最希望有的，特别是如果这种氰化氢产率的提高的实现不会引起通常的所伴随的丙烯腈的生产水平降低。
可以改变在丙烯腈反应器中的生产条件，以提高氰化氢的产率。然而，改变操作条件以提高氰化氢产率总是引起丙烯腈生产收率的降低，在经济上说来是不能被接受的。通常，对于每提高1％氰化氢产品，将会降低2％的丙烯腈。
本发明的目的在于解决这个问题。
本发明的第一个目的就是为了得到一种新的氨氧化反应催化剂，这种催化剂可在制备丙烯腈中提高所生产的氰化氢副产物的产率，同时在基本相同的条件下，保持丙烯腈生产水平。
本发明的另一个目的就是为了得到一种新的氨氧化反应催化剂，在类似的的操作条件下，能够提高氰化氢的收率而不会使丙烯腈的生产在经济上带来不能接受的损失。
本发明的其它目的和优点将在下面的描述中和通过本发明的实践中得以体现，本发明的目的和优点，也可通过并结合所附的权利要求看到并得以实现。
为了实现上述的本发明的目的并根据本发明的目的，下面具体的并详细的描述本发明的催化剂，其特征具有下述的经验式：
AaBbDdFeeBifMo12Ox
其中 A=一个或多个Li,Na,K,Rb和Cs或其混合物；
B=一个或多个Mg,Mn,Ni,Co,Ag,Pb,Re,Cd和Zn或其混合物；
C=一个或多个Ce,Cr,Al,Sb,P,Ge,La,Sn,V，和W或其混合物；
D=一个或多个Ca,Sr,Ba，或其混合物；
和a=0.01-1.0；b和e=1.0-10；c,d和f=0.1-5.0和X是由其它元素存在所要求的化合价确定的数；
在一本发明的优选的实施例中，A选自一个或多个锂，钠，钾和铯，特别优选铯和钾；
在另一优选的实施例中，B选自镁，锰，镍和钴或其混合物组成的基团；
在还有一个优选实施例中，C选自包括铈，铬，锑，磷，锗，钨及其混合物，特别优选铈，铬，磷和锗的基团；
在本发明的又一优选的实施例中，D选自Ca,Sr，和其混合物，特别优选Ca组成的基团；
在本发明的另一优选的实施例中，a可从0.05-0.9，特别优选0.1-0.7；
在本发明的又一个优选的实施例中，b和e可从2-9，特别优选2-8；在本发明的还有的另一个优选的实施例中，c,d和f可从0.1-4，特别是0.1-3；
使用本发明的催化剂可有载体或没有载体；优选在二氧化硅，氧化铝或氧化锆或其混合物上，特别优选在二氧化硅上载有催化剂；
本发明的催化剂可通过本领域的专业人员熟知的诸多的催化剂制备方法中的任意一个来制备。例如通过共一沉淀多个成分来制备。然后，干燥共一沉淀物质并研磨成适当大小。根据传统技术，共一沉淀物质可制成浆状的并被喷雾干燥；催化剂可被挤塑成片状的或按照公知技术在油中形成球状。催化剂成分可与浆液状的载体混合，接着干燥或可在硅或其它的载体中浸渍它们；对于制备催化剂的特定的过程可参见U.S.5,093,299；4,863,891和4,766,232，在此引作参考；
通常，催化剂的A成分可作为一种氧化物或作为一种盐(在焙烧中得到氧化物)加入催化剂中；优选容易得到及容易溶解的盐类如硝酸盐用作将A元素结合进催化剂中的工具。
铋作为氧化物或作为一种盐可加入催化剂中，上述盐可在焙烧中得到氧化物。优选容易分散的并在热处理中形成坚固的氧化物的水溶性盐。对于加入的铋，特别优选硝酸铋，因为它们可在硝酸的溶液中溶解。
对于加入催化剂的铁成分可是在焙烧中生成氧化物的铁的任意成分。含有的其它成分，水溶性盐是优选的，因为它们可均匀的分散到催化剂中。最优选硝酸铁。
钴，镍和镁可加入到使用硝酸盐的催化剂中，然而，作为不溶性的在热处理中可生成氧化物的碳酸盐或氢氧化物可加入到催化剂中。
加入到催化剂的钼成分可来源于任意钼氧化物，例如二氧化物，三氧化物，五氧化物，七氧化物。然而，优选使用可水解的或可分解的钼盐作为钼的来源；最优选开始的物料是七钼酸铵。
作为碱金属盐或碱土金属盐或铵盐的磷可加入到催化剂中，但优选作为磷酸加入到催化剂中。钙作为本发明的催化剂中的基本成分可以经由预先形成的钙钼酸盐或通过浸渍或通过其它公知的方法加入(通常，作为钙一硝酸盐与其它硝酸盐一起加入)。
本发明涉及一种氨氧化催化剂，其特征有下列的经验式：
AaBbCcDdFeeBifMo12Ox
其中 A=一个或多个Li,Na,K,Rb和Cs或其混合物；
B=一个或多个Mg,Mn,Ni,Co,Ag,Pb,Re,Cd和Zn或其混合物；
C=一个或多个Ce,Cr,Al,Sb,P,Ge,La,Sn,V，和W或其混合物；
D=一个或多个Ca,Sr,Ba，或其混合物；
和a=0.01-1.0；b和e=1.0-10；c,d和f=0.1-5.0和X是由其它元素存在所要求的化合价确定的数；
通过混合七钼酸铵水溶液和含有该化合物的硅溶胶制备催化剂，优选加入其它元素的硝酸盐。然后干燥、脱氮、焙烧固体物质。优选在110-350℃，更优选在110-250℃，最优选在110-180℃喷雾干燥催化剂。脱氮的温度从100-450℃，优选150-425℃。焙烧的温度在300-700℃，优选350-650℃。
下列实例仅是对本发明用途的说明。
表1
| 实例 | 催化剂成分 | 转化率(Conv) | AN | HCN |
| Ⅰ在HCN收率和AN收率上操作条件的影响 | ||||
| 1对比例 | Cs0.1K0.1Ni7.6Mg3.1Fe4Bi0.5Ce0.5Cr0.5Mo15.6Ox | 98.0 | 75.5 | 8.1 |
| 2对比例 | 提高压力从9.5-18磅/平方英寸 | 96.9 | 69.1 | 9.0 |
| 3对比例 | 提高NH3/C3 =从1.2-1.3 | 95.3 | 67.7 | 9.3 |
| Ⅱ对比例 | ||||
| 4 | Cs0.1K0.1Ni6.2Mg2.5Fe2Bi0.5W2.3Mo10Ox | 94.0 | 67.1 | 8.1 |
| 5 | K0.1Ni2.5Co4.5Fe3Bi1P0.5Mo12Ox | 97.3 | 71.3 | 7.9 |
| 6 | Cs0.1K0.1Ni6.2Mg2.5Fe2Bi0.5Ce0.5P1Mo10.8Ox | 95.7 | 64.4 | 7.7 |
| Ⅲ发明例 | ||||
| 7 | Cs0.1K0.1Ni6.2Mg2.5Fe2Bi0.5Ce0.5Ca0.5Mo12.8Ox | 97.7 | 73.4 | 8.2 |
| 8 | Cs0.1K0.1Ni6.2Mg2.5Fe2Bi0.5Ce0.5Ca0.5Mo13.4Ox | 98.4 | 72.3 | 8.8 |
| 9 | Cs0.1K0.1Ni6.2Mg2.5Fe2Bi0.5Ce0.5Ca1.25Mo13.6Ox | 98.2 | 70.9 | 9.4 |
| 10 | Cs0.1K0.1Ni6.2Mg2.5Fe2Bi0.5Ce0.5Ca1.5Mo13.85Ox | 98.0 | 74.2 | 8.6 |
| 11 | Cs0.1K0.1Ni6.2Mg2.5Fe4Bi0.5Ce0.5Ca0.75Mo15.55Ox | 98.2 | 74.9 | 8.3 |
| 12 | 提高NH3/C3 =到1.25和空气/C3 =到10.1 | 98.2 | 74.5 | 9.2 |
1-6的比较例和实例7-12是在基本相同的条件下试验的，其条件为是在40cc流体床反应器中，输入量为0.1-0.12wwh，使用含有1C3 =/1.2NH3/9.8-10空气的混合物的原料，430-460℃,15磅/平方英寸(表压)。
上述结合特定的实施例描述了本发明，显然，根据上述的描述，本领域的专业人员可以对其进行改变，改进和变化，然而包括这些改变，改进和变化都属于所附的权利要求的精神和范围之中。
Claims (18)
1．一种含有铁，铋，钼和钙的催化氧化物的配合物的催化剂组合物，其特征具有下列的经验式：
AaBbCcDdFeeBifMo12Ox
其中A=一个或多个Li,Na,K,Rb和Cs或其混合物；
B=一个或多个Mg,Mn,Ni,Co,Ag,Pb,Re,Cd和Zn或其混合物；
C=一个或多个Ce,Cr,Al,Sb,P,Ge,La,Sn,V，和W或其混合物；
D=一个或多个Ca,Sr,Ba，或其混合物；
和a=0.01-1.0；b和e=1.0-10；c,d和f=0.1-5.0和X是由其它元素存在所要求的化合价确定的数；
2．权利要求1的催化剂，在惰性载体上载有上述的催化剂，所述载体选自二氧化硅，氧化铝，氧化锆和其混合物组成的基团。
3．权利要求1的催化剂，其中A选自铯，钾和其混合物组成的基团。
4．权利要求3的催化剂，其中A是铯和钾的混合物。
5．权利要求1的催化剂，其中B是一或多个Mg,Mn,Ni,Co和其混合物。
6．权利要求5的催化剂，其中B是一或多个Mg,Ni,Co和其混合物。
7．权利要求1的催化剂，其中C是一或多个Ce,Cr,Sb,P,Ge,W和其混合物。
8．权利要求7的催化剂，其中C是一或多个Ce,Cr,,P,Ge，和其混合物。
9．权利要求1的催化剂，其中D是一或多个Ca,Sr和其混合物。
10．权利要求1的催化剂，其中D选用作Ca。
11．权利要求1的催化剂，其中a=0.05-0.9。
12．权利要求11的催化剂，其中a=0.1-0.7。
13．权利要求1的催化剂，其中b和e=2-9。
14．权利要求13的催化剂，其中b和e=2-8。
15．权利要求1的催化剂，其中c,d和f=0.1-4。
16．权利要求15的催化剂，其中c,d和f=0.1-3。
17．权利要求9的催化剂，其中d=0.1-4。
18．权利要求17的催化剂，其中d=0.1-3。
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| US08/923,878 US5840648A (en) | 1997-09-02 | 1997-09-02 | Catalyst for the manufacture of acrylonitrile and hydrogen cyanide |
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-
1997
- 1997-09-02 US US08/923,878 patent/US5840648A/en not_active Expired - Lifetime
-
1998
- 1998-08-12 SG SG1998002982A patent/SG65779A1/en unknown
- 1998-08-13 ZA ZA987256A patent/ZA987256B/xx unknown
- 1998-08-17 EP EP03075784A patent/EP1321188A1/en not_active Withdrawn
- 1998-08-17 EP EP98306542A patent/EP0900592A1/en not_active Ceased
- 1998-08-28 TR TR1998/01695A patent/TR199801695A3/tr unknown
- 1998-08-28 BR BR9806573-4A patent/BR9806573A/pt not_active Application Discontinuation
- 1998-08-31 RO RO98-01345A patent/RO115333B1/ro unknown
- 1998-08-31 KR KR1019980035514A patent/KR100538965B1/ko not_active IP Right Cessation
- 1998-09-01 CN CN98117923A patent/CN1131725C/zh not_active Expired - Lifetime
- 1998-09-01 MY MYPI98003990A patent/MY121722A/en unknown
- 1998-09-01 RU RU98117081/04A patent/RU2217232C2/ru not_active IP Right Cessation
- 1998-09-01 BG BG102741A patent/BG64461B1/bg unknown
- 1998-09-02 JP JP24879898A patent/JP4169398B2/ja not_active Expired - Fee Related
- 1998-11-10 TW TW087114484A patent/TW470666B/zh not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| TR199801695A2 (xx) | 1999-05-21 |
| BR9806573A (pt) | 2000-05-09 |
| TR199801695A3 (tr) | 1999-05-21 |
| JPH11169715A (ja) | 1999-06-29 |
| KR100538965B1 (ko) | 2006-02-28 |
| KR19990029382A (ko) | 1999-04-26 |
| CN1131725C (zh) | 2003-12-24 |
| BG64461B1 (bg) | 2005-03-31 |
| US5840648A (en) | 1998-11-24 |
| MY121722A (en) | 2006-02-28 |
| JP2008110345A (ja) | 2008-05-15 |
| RU2217232C2 (ru) | 2003-11-27 |
| BG102741A (en) | 1999-04-30 |
| SG65779A1 (en) | 1999-06-22 |
| ZA987256B (en) | 1999-02-15 |
| EP1321188A1 (en) | 2003-06-25 |
| TW470666B (en) | 2002-01-01 |
| JP4169398B2 (ja) | 2008-10-22 |
| RO115333B1 (ro) | 2000-01-28 |
| EP0900592A1 (en) | 1999-03-10 |
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