CN1093950A - 多种金属氧化物的组合物 - Google Patents
多种金属氧化物的组合物 Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 21
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 21
- 238000002360 preparation method Methods 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000006392 deoxygenation reaction Methods 0.000 claims description 2
- 239000011872 intimate mixture Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000010949 copper Substances 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000000843 powder Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- -1 propene aldehyde Chemical class 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000004563 wettable powder Substances 0.000 description 2
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 241000545067 Venus Species 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- REROKLPNVNAPBD-UHFFFAOYSA-N azane;tetrahydrate Chemical compound N.O.O.O.O REROKLPNVNAPBD-UHFFFAOYSA-N 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
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000012050 conventional carrier Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- FSBVERYRVPGNGG-UHFFFAOYSA-N dimagnesium dioxido-bis[[oxido(oxo)silyl]oxy]silane hydrate Chemical compound O.[Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O FSBVERYRVPGNGG-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
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- 238000004898 kneading Methods 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
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 239000003973 paint Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-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
- 239000011800 void material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8878—Chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
- C01B13/185—Preparing mixtures of oxides
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- 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
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- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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Abstract
多种金属氧化物的组合物，其基本成分包括氧化
物形式的Mo、V、W、Cu、Ni元素，并成一定摩尔比
例，以及制备此种多种金属氧化物的组合物的方法，
以及其作为丙烯醛气相催化氧化成为丙烯酸的催化
剂的用途。
Description
本发明涉及多种金属氧化物的组合物，其基本成分包含：氧化物形式的Mo、V、W、Cu、Ni，其前提是：各种组成元素具有如下的摩尔比：
Mo∶V＝12∶1至2∶1，
Mo∶W＝60∶1至3∶1，
Mo∶Cu＝24∶1至2∶1，
Cu∶Ni＝5∶1至1∶3。
本发明还涉及制备该等组合物的方法及该组合物的用途。
EP-A-427508，DE-A-2909671，DE-C-3151805，DE-B-2626887披露了多种金属氧化物组合物，其中除含有其他元素的氧化物之外，以氧化物形式的Mo、V、W、Cu作为基本成分。其中披露的实施例中包括Mo∶V、Mo∶W、Mo∶Cu的摩尔比在本发明限定的范围之内的多种金属氧化物组合物。这些组合物的建议用途特别是用于气相氧化丙烯醛成为丙烯酸的催化剂。
然而，在此用途中，此等多种金属氧化物组合物不能满足对活性及生成丙烯酸选择性的要求。此外，这些组合物只是在相当长的操作时间之后才达到其形成丙烯酸的最终选择性（对于给定的转化率而言）。
EP-A-235760披露了适用于丙烯醛气相催化氧化成丙烯酸的多种金属氧化物组合物，并且其含有氧化物形式的Ni作为Mo、V、W、Cu之外的另一种基本成分。然而，此等组合物的缺点在于其中Cu和Ni元素的摩尔比为小于1∶3，这表示该等组合物也不能完全满足用作为丙烯醛气相催化氧化制取丙烯酸。
本发明目的是提供这样的多种金属氧化物组合物，它更能满足作为丙烯醛气相氧化成为丙烯酸的催化剂的用途。
本发明人发现，使用本文开端所限定的组合物可以达到上述目的。
按本发明的多种金属氧化物组合物则提供了优越性，这在于：其中Cu对Ni的元素成分摩尔比为3∶1至1∶2，特别优选是2∶1。
按本发明特别优良的组合物符合如下的实验式（Ⅰ）：
式中，X1是一种或多种碱金属;
X2是一种或多种碱土金属;
X3是Cr、Mn、Ce和/或Nb;
X4是Sb和/或Bi;
X5是Si、Al、Ti和/或Zr;
a是1-6;
b是0.2-4;
c是0.5-6;
d是0.2-6;
c∶d＝5∶1至1∶3;
e＝0至2;
f＝0至3;
g＝0至5;
h＝0至40;
i＝0至40;
n是一个数字，其决定于式Ⅰ中除氧之外各元素的价态和频率（频繁次数）。
其中，优选情况是其中化学计量系数e、f、g和h是零的情况。
本发明的组合物的一般是以本身已知的方式制备，即使适当的起始化合物进行极密切的干混合，这些化合物中含有各催化剂元素成分，其后于200-500℃焙烧该干混混合物，优选用300-400℃。其中唯一必要的特征是，所用的起始化合物或者已经是氧化物，抑或者是在加热后可以转化成氧化物的化合物，因此适用的化合物具体有卤化物、硝酸盐、甲酸盐、乙酸盐、碳酸盐、氢氧化物。适用的Mo、W、V的起始化合物还有它们的钼酸盐、钨酸盐、钒酸盐，或者由它们衍生的酸。
各起始化合物的密切混合可以以干态或湿态进行。若采取干态，方便方式是使用细粉末的起始化合物，并且在混合后进行压制（例如压成片，例如使之成为所要几何形状的催化剂），然后进行焙烧。
然而，优选采用湿法进行混合。为此，通常将各起始化合物以水溶液或悬浮液形式混合到一起，然后将含水的组合物干燥并焙烧。
干燥过程优选在该含水混合物制备之后立即进行，并采用喷雾干燥法（起始温度一般为100-150℃）。此时得到的粉末可直接去压制。但是，常常发现这样对于直接去进一步加工是粉末过于细微，因此有利方式是先加入水进行捏和。
捏和后的组合物可以进一步成形成为所要几何形状的催化剂、干燥然后焙烧（成为未载于载体的催化剂），或者是不成形先焙烧，然后磨碎成为细粉末（通常＜80μm），通常于其中加入小量水，若需要还加入常规的粘结剂，并以湿组合形式施涂到惰性载体上。上述涂布作业完成后，进一步干燥，得到即可使用的壳状催化剂。但从原则上讲，焙烧后粉末也可以粉末状催化剂使用。
在起始化合物以含水湿态混合时，Cu和Ni成分的化合物优选是水溶性铜和镍盐，例如硝酸盐或乙酸盐，以乙酸盐为特别有利。当然该乙酸盐也可以在混合时就地形成（例如，使用碳酸盐为起始化合物，加入乙酸）。
若是不用载体的催化剂，式Ⅰ中系数i最好是15-40，否则i优选为零，因为X5的氧化物在本质上只起到冲淡组合物中其他成分的效果。
若各起化合物是以水溶液形式混合，还可以浸渍到惰性多孔性载体中，干燥，然后焙烧成为载于载体的催化剂。不用载体的催化剂优选几何形状是空心圆柱，如DE-A-3113179所述。
然而，当本发明的多种金属氧化物组合物用作为丙烯醛气相氧化制取丙烯酸时，优选使用壳状催化剂。常规的载体物料例如可使用多孔或非多孔的氧化铝、二氧化硅、二氧化钍、二氧化锆、碳化硅，或硅酸盐如硅酸镁或硅酸铝。载体可以是规则或不规则形状的;规则形载体具有明显的表面粗糙度，例如珠状或空心圆柱为优选。其中以珠状特别有利。特别有利的是使用基本上非多孔、表面粗糙、由滑石制成的载体，其直径为1-6mm，优选4-5mm。活性组合物的涂布厚度可选自50-500μm范围。应指出，在制备壳状催化剂时，也可在焙烧之前进行载体上涂布作业，亦即，例如使用打湿的可湿性粉末。
在密切混合物含有该起始化合物的干组合物的焙烧其有利方式是在通入空气的回转窑中进行。
在制备壳状催化剂时被载元素的涂布通常是在适当的回转式容器中进行，例如DE-A-2909671或EP-A-293859所披露者。
起始化合物、涂布工艺和焙烧条件的优选是按EP-A-293859的已知方式，即使得到的多种金属氧化物活性组合物的比表面积为0.50-150m2/g，比孔隙体积为0.10-0.90cm3/g，孔直径分布为每种情况下至少10%的孔隙总体积是落在孔直径0.1至＜1μm范围，1.0至＜10μm范围以及10μm至＜100μm范围。上述孔隙分布为EP-A-293859中的优选，亦确定为优选条件。
按本发明的多种金属氧化物组合物特别适于作为具高活性和选择性的由丙烯醛气相氧化为丙烯酸的催化剂。所用的丙烯醛优选为丙烯由适当气相催化氧化所得者。丙烯醛的气相催化氧化通常是用管束式反应器进行非均相固定床式氧化。所用氧化剂是常规的氧，最好由惰性气体所稀释。适宜的惰性气体为N2和/或水蒸汽。反应温度和压力为本领域技术人员已知（见DE-A-4132263）。值得指出的是，按本发明的多种金属氧化物催化剂具有相关于生成丙烯酸的选择性的缩短的活化时间，这就是说，若在管束式反应器中装入按本发明的组合物，并在本领域技术人员熟知的条件下操作，由含丙烯醛的气流进行氧化并以生成丙烯酸为目的，可在较短的时间内使生成丙烯酸的选择性增加到一个最大值的平稳区。
然而，按本发明的多种金属氧化物组合物还适用于其他有机化合物的催化氧化，例如氧化烷烃、烷醇、烷醛、链烯以及其他烯醛，成为烯类不饱和醛和/或羧酸，以及相应的腈（氨氧化，例如丙烯成为丙烯腈，以及2-甲基丙烯或叔丁醇成为甲基丙烯腈）。所述有机化合物中碳原子数通常为3-6，优选3或4。
实施例
（a）制备多种金属氧化物组合物的一般步骤作为对比实例，按如下制备具Mo12V3W1.2Cu2.4Ox组成的催化活性组合物C1：
将190g乙酸铜（Ⅱ）单水合物溶解于2700g水，得溶液Ⅰ。将860g钼（Ⅶ）酸铵四水合物（ammonium heptamolybdate tetrahydrate），143g偏钒酸铵和126g钟钨酸铵七水合物按序溶解于5500g95℃水中，得溶液Ⅱ。然后于搅拌下将溶液Ⅰ一次倾入溶液Ⅱ中。以出口温度110℃将所得含水混合物喷雾干燥。然后该可湿性粉末与水混配每Kg粉末0.15Kg水。在通空气的回转窑中将该组合物以3小时的进程加热至400℃，然后于400℃焙烧5小时。将已焙烧的催化活性物料磨碎至粒度范围0.1-50μm。
按上述相似过程，制备以下组成的多种金属氧化物粉末（Ni成分使用乙酸镍（Ⅱ）四水合物）：
Mo12V3W1.2Cu1.6Ni0.8Ox （E1）
Mo12V3W1.2Cu0.8Ni1.6Ox （E2）
Mo12V3W1.2Ni2.4Ox （C2）
Mo12V3W1.2Cu2.0Ni0.4Ox （E3）
Mo12V3W1.2Cu2.4Ni0.8Ox′ （E4）
Mo12V3W1.2Cu1.6Ox″ （C3）
Mo12V3W1.2Cu0.4Ni2.0Ox （C4）
（b）制备壳状催化剂
将（a）所得的活性组合物粉末在转鼓中涂布到非多孔、表面粗糙的直径4-5mm的滑石珠粒上，涂布量为每200g滑石珠使用50g粉末，同时加入18g水。涂布层然后于110℃用空气干燥。
（c）丙烯醛气相氧化
用内径25mm的反应管（V2A，2mm壁厚）装入（b）所得壳状催化剂和惰性稀释物的混合物共1升，用盐浴加热。然后进料，每小时2300升（标准温度压力）的混合气体，组成为5%丙烯醛、7%氧、10%水蒸汽、其余为氮，均为体积百分率。
每一次的盐浴温度都是调定到使丙烯醛单程转化率约99%（摩尔）。在操作时间3星期后，所需要的盐浴温度与所用壳状催化剂的关系（作为其活性的量度，盐浴温度低表示活性高）以及所达到的选择性（基于生成的丙烯酸）示于下列的表中，表中还示出所测为该丙烯酸选择性的活化时间。
表
催化剂 丙烯醛 盐浴温度 选择性%, 活化时间,
转化率,%, ℃ 摩尔 天
摩尔
C1 99.1 275 95.0 10
E1 99.0 264 96.2 2
E2 98.9 265 95.8 3
C2 98.2 283 94.3 3
E3 99.1 267 95.7 3
E4 98.9 265 95.6 4
C3 99.0 267 95.3 8
C4 98.5 279 94.5 3
Claims (4)
1、一种多种金属氧化物的组合物，包括作为基本成分的氧化形式的Mo、V、W、Cu、Ni，其前提是在各元素成分之间存在以下的比例：
Mo∶V=12∶1至2∶1，
Mo∶W=60∶1至3∶1，
Mo∶Cu=24∶1至2∶1，
Cu∶Ni=5∶1至1∶3。
2、权利要求1的组合物，其符合下列实验式Ⅰ：
X1是一种或多种碱金属;
X2是一种或多种碱土金属;
X3是Cr、Mn、Ce和/或Nb;
X4是Sb和/或Bi;
X5是Si、Al、Ti和/或Zr;
a是1-6;
b是0.2-4;
c是0.5-6;
d是0.2-6;
c∶d＝5∶1至1∶3;
e＝0至2;
f＝0至3;
g＝0至5;
h＝0至40;
i＝0至40;
n是一个数字，其决定于式Ⅰ中除氧之外各元素的价态和频率。
3、权利要求1的多种金属氧化物的组合物的用途，用作为丙烯醛气催化氧化成为丙烯酸的催化剂。
4、权利要求1的多种金属氧化物的组合物的制备方法，该方法包括：制备含有所述多种金属元素氧化物成分的起始化合物的干的密切混合物，然后将此干混合物于200-500℃焙烧。
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| DEP4302991.4 | 1993-02-03 | ||
| DE4302991A DE4302991A1 (de) | 1993-02-03 | 1993-02-03 | Multimetalloxidmassen |
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| US5102486A (en) * | 1991-01-09 | 1992-04-07 | Minnesota Mining And Manufacturing Company | Loop applying assembly |
| DE4132263A1 (de) * | 1991-09-27 | 1993-04-01 | Basf Ag | Verfahren zur katalytischen gasphasenoxidation von acrolein zu acrylsaeure |
-
1993
- 1993-02-03 DE DE4302991A patent/DE4302991A1/de not_active Withdrawn
-
1994
- 1994-01-25 EP EP94101021A patent/EP0609750B1/de not_active Expired - Lifetime
- 1994-01-25 ES ES94101021T patent/ES2092840T3/es not_active Expired - Lifetime
- 1994-01-25 DE DE59400838T patent/DE59400838D1/de not_active Expired - Lifetime
- 1994-01-28 US US08/187,494 patent/US5446004A/en not_active Expired - Fee Related
- 1994-01-31 JP JP6009490A patent/JPH06279030A/ja active Pending
- 1994-02-01 CA CA002114681A patent/CA2114681A1/en not_active Abandoned
- 1994-02-01 CZ CZ991212A patent/CZ285881B6/cs not_active IP Right Cessation
- 1994-02-01 CZ CZ94213A patent/CZ285760B6/cs not_active IP Right Cessation
- 1994-02-03 CN CN94101759A patent/CN1050779C/zh not_active Expired - Fee Related
-
1995
- 1995-02-24 US US08/394,280 patent/US5493052A/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100382889C (zh) * | 2003-02-27 | 2008-04-23 | 株式会社日本触媒 | 复合氧化物催化剂以及使用该催化剂的丙烯酸制备方法 |
| CN102451702A (zh) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | 丙烯醛氧化制丙烯酸催化剂及其制备方法 |
| CN102451702B (zh) * | 2010-10-21 | 2014-05-28 | 中国石油化工股份有限公司 | 丙烯醛氧化制丙烯酸催化剂及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0609750B1 (de) | 1996-10-16 |
| CZ285881B6 (cs) | 1999-11-17 |
| EP0609750A1 (de) | 1994-08-10 |
| CZ285760B6 (cs) | 1999-11-17 |
| DE59400838D1 (de) | 1996-11-21 |
| US5493052A (en) | 1996-02-20 |
| ES2092840T3 (es) | 1996-12-01 |
| CN1050779C (zh) | 2000-03-29 |
| CA2114681A1 (en) | 1994-08-04 |
| DE4302991A1 (de) | 1994-08-04 |
| JPH06279030A (ja) | 1994-10-04 |
| CZ21394A3 (en) | 1994-08-17 |
| CZ121299A3 (cs) | 1999-08-11 |
| US5446004A (en) | 1995-08-29 |
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