• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A catalyst having a heteropoly-acid structure and the general formula: MoaVbPcCudXeOf wherein Mo, V, P, Cu and O represent respectively molybdenum, vanadium, phosphorus, copper and oxygen, X represents one or more elements selected from the group consisting of tin, thorium, germanium, nickel, iron, cobalt, magnesium, zinc, titanium, lead, rhenium, zirconium and chromium and a, b, c, d, e and f represent the atomic ratio of the elements where, a is 10 b is a number of 3 or less than 3 excluding 0, c is a number of 0.5 to 3, d is a number of 3 or less than 3 excluding 0, e is a number of 3 or less than 3 excluding 0, f is a number determined depending on the valency and atomic ratio of other elements. There is also provided a process for producing methacrylic acid by oxidizing methacrolein with molecular oxygen or molecular oxygen-containing gas in the presence of the catalyst defined above.
    公开号:SU873868A3
    申请号:SU782679052
    申请日:1978-10-30
    公开日:1981-10-15
    发明作者:Мацумото Мацуми；Суги Хидеки；Судо Ацуси
    申请人:Ниппон Каяку Кабусики Кайся (Фирма)；
    IPC主号:
    专利说明:

    where X is an element selected from the group containing opa, thorium, germanium, nickel, iron, cobalt, magnesium, zinc, titanium, lead, rhenium, zirconium, chromium, antimony} SOUTH ... 0.5-2.0; 0.5-3, Of. 61 0.01-1, of, O1-O, 5; X is the number of oxygen atoms, which is determined depending on the valence and atomic fraction of the remaining, 1 elements. The catalyst has increased activity and stability - up to 95% conversion with selectivity up to 81.2%. The catalyst does not lose its initial activity during the working day, it has a heteropoly acid structure, so it can be obtained by the methods used to obtain ordinary heteropoly acids. The catalyst is produced by inter; the action of starting materials containing elements that make up the structure of the catalyst in water or in an organic solvent, by transferring the reaction product, if it is the ammonium salt, into the corresponding acid, extracting the reaction product if necessary, and evaporating the solution to dryness. The conversion of the ammonium salt to the corresponding acid can be carried out by conventional methods, for example, by extraction from an acidic aqueous solution, by an ion exchange method, etc. Extraction of the reaction product can be carried out using an organic solvent, for example, ester. Among the most preferred methods of obtaining are such as dispersing or dissolving the starting material, such as oxides or phosphates of the elements constituting the catalyst structure, in water, their interaction when heated, and hydrogen peroxide can be added, separation in the case of the need for insoluble components and evaporation of the solution to dryness; or the interaction of phosphorus vanadium molybdic acid with oxides, phosphates, sulfates and other similar cores of the remaining elements forming the catalyst structure. The catalyst may be supported on a carrier. Preferred carriers are silicon carbide, aL-alumina, aluminum powder, kieselguhr, titanium dioxide, etc. Unsuitable in-. active carriers that react with a heteropolyacid. Example: 100 g of molybdenum trioxide, 6.3 g of vanadium pentoxide, 3.0 g of copper phosphate, 2.1 g of tin oxide and 6.4 g of phosphoric acid are dispersed or dissolved in 1000 ml of deionized water. The resulting mixture is heated to boiling and refluxed for 6 hours with stirring under reflux until a clear orange-red solution is obtained. After separating a small amount of the undissolved residue, the solution is evaporated to dryness in a hot bath. The resulting dry product (catalyst) has the following composition:, the structure of the heteropoly acid is confirmed by diffraction peaks at 2 & 8.00, 8.9 °, etc. during x-ray diffraction. The catalyst is crushed to a particle size of 24-28 mesch and loaded into a tubular reactor made of Pyrex glass with an internal diameter of 18 mm, after which the reactor is immersed in a fluidized bed. The reaction gas, consisting of methacrolein, oxygen, nitrogen and water vapor in a molar ratio of 1: 4: 16: 10, is passed through a tubular reactor with a volumetric rate of 1600 (calculated as normal), it undergoes oxidation at 320 ° C. Provots process t 120 days. The results are shown in Table. 1o After 120 days. X-ray structural analysis of the catalyst was carried out, which confirmed the absence of molybdenum trioxide in it and a change in the structure. Examples 2-14. 2.1 g of tin oxide in the mixture in accordance with Example 1 are replaced in each of the examples, respectively, 3.7 g of thorium oxide, 1.4 g of germanium oxide, 1.0 g of nickel oxide, 1.1 g of iron oxide, 1, 1 g, 0.56 g of magnesium oxide, 1.1 g of zinc oxide, 1.1 g of titanium oxide, 3.2 g of lead oxide j3.4 g of rhenium seven-oxide, 1.7 g of zirconium oxide, 1.4 g of chromium trioxide and 2.0 g of antimony trioxide, resulting in a dry product of the composition shown in table. 1. On the basis of the diffraction peaks at 29 8.00 8.90 9.3®, etc., observed during X-ray diffraction, it was confirmed that the dry products thus obtained had a heteropoly acid structure. Conducted a series of continuous process with the use of these catalysts under the same conditions as in example 1. The results are shown in tab. 1. An X-ray structural analysis of the catalysts is carried out through the DA day after the start of the process, confirming the absence of a change in their structure. Examples 15-18, Dry products, the composition of which is given in table. 2, are obtained as in Example 1. It is confirmed by X-ray structural analysis that they have a heteropolyquide structure. Continuous processes using these catalysts are carried out under the same conditions as in Example 1. The results are shown in Table. 2. After 30 days After the start of the process, X-ray structural analysis of the catalysts was carried out, which confirmed the absence of a change in their structure. Examples 19-24. Dry products, the composition of which is given in table. 3, is also obtained as in Example 1. It was confirmed by X-ray structural analysis that they have a hetero-polyacid structure. Continuous processes using these catalysts are carried out under the same conditions as in Example 1. The results are shown in Table. After the start of the process, an X-ray structural analysis of the catalysts was obtained, which confirmed the absence of a change in their structure. S 8 Comparative example. Dry products of Cuo, Of composition are obtained in the same manner as in Example 1, but without the addition of 2.1 g of tin oxide. A continuous process using this catalyst is carried out under the same conditions. The results are shown in Table. 4. C ravn and te ss and Example 2, the ammonia solution is added to the clear orange-red solution prepared in accordance with Example 1 (pH 1.0) until the pH is adjusted to 5.3. . After evaporation of the solution to dryness, dry products are crushed to a particle size of 24-48 mesh and calcined in an atmosphere of air at 8 h. The resulting catalyst has the following composition: {MN) 5Mo, Sio3 5 oF, 0 The formation of the ammonium salt of the heteropolyacid is confirmed by X-ray analysis and IR absorption spectra. The continuous process is carried out under the same conditions as in the examples using the catalyst obtained. The results are shown in table 4. Examples 25-ZO. Catalysts, having shown in Table. 5, the formulation is prepared and the reactions are carried out as described in Example 1, using respectively these catalysts. The results are shown in Table. five
    about to n q jf
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    (About in
    g-tCD SO about with
    YU .
    Oh h
    t-v
    o50 03 O)
    about oh 00
    4 cm CO CO CO CO CO
    about
    About with
    with
    “1 tt w i;
    0
    "
    H 1787 Fo rmula of the Kata / gas inventer to produce methachric acid by oxidation of methacrolein, including molybdenum, vanadium, phosphorus to oxygen, and having a heteropoly acid structure, characterized in that, in order to increase the activity and stability of the catalyst, it also contains copper and selected from the group containing tin, thorium, germanium, nickel, iron, cobalt, magnesium, zinc, titanium, pigs, rhenium, pyrone, chrome, antimony, and the composition of the catalyst corresponds to the empirical formula where X is an element selected from the groups Containing tin, thorium, germa38 May 10, 5818 SRI, nickel, iron, kobilt, magnesium, zinc, titanium, lead, rhenium, zirconium, chromium, antimony; and S 1O: b; g 0.5-2.0; C g 0.5-3.0; E "0.01-1.0; b O, O1-0.5; is the number of oxygen atoms, depending on the valence and atomic fraction of the remaining elements. Sources of information taken into account in the examination 1. US Patent No. 3703548, cl. 260-530 N, pub. .1972. 2. US patent No. 3875220, cl. 260-530 N, Cl. C 07 C 57 / O4, published. 1975 (prototype).
    权利要求:
    Claims (1)
    [1]
    Claim
    A catalyst for the production of methacrylic acid by oxidation of methacrolein, including molybdenum, vanadium, phosphorus and oxygen, and having a heteropoly acid structure, characterized in that, in order to increase the activity and stability of the catalyst, it additionally contains copper and an element selected from the group containing tin, thorium , germanium, nickel, iron, cobalt, magnesium, zinc, titanium, lead, rhenium, zirconium, chromium, antimony, and the composition of the catalyst corresponds to the empirical formula gae X - an element selected from the group consisting of tin, thorium, germ -
    I. 8 ni, nickel, iron, cobalt, magnesium, zinc, titanium, lead, rhenium, zirconium, chromium, antimony;
    a g 10:
    5 b s * 0.5-2.0 /
    C ~ 0.5-3.0;
    <3 * = 0.01-1.0;
    e = 0.01-0.5;
    £ is the number of oxygen atoms, which is determined depending on the valency and atomic fraction of the remaining elements.
    类似技术:
    公开号 | 公开日 | 专利标题
    SU873868A3|1981-10-15|Catalyst for producing metacrylic acid
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    同族专利:
    公开号 | 公开日
    DE2847288A1|1979-05-03|
    GB2010693B|1982-04-07|
    NL7810588A|1979-05-02|
    GB2010693A|1979-07-04|
    JPS5924140B2|1984-06-07|
    CA1098507A|1981-03-31|
    US4273676A|1981-06-16|
    DE2847288C2|1987-03-12|
    JPS5466619A|1979-05-29|
    US4745217A|1988-05-17|
    FR2407022A1|1979-05-25|
    IT7829107D0|1978-10-25|
    IT1099821B|1985-09-28|
    FR2407022B1|1983-07-18|
    ES474674A1|1979-03-16|
    BE871659A|1979-04-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3380931A|1960-01-12|1968-04-30|Shell Oil Co|Oxidation catalysts|
    NL289375A|1962-03-19|
    US3485877A|1966-10-21|1969-12-23|Eastman Kodak Co|Process for converting ethylenically unsaturated hydrocarbons to carbonylic compounds|
    US3437690A|1967-11-21|1969-04-08|Eastman Kodak Co|Vapor phase process for preparing unsaturated aliphatic aldehydes and monocarboxylic acids|
    US3644497A|1968-11-01|1972-02-22|Celanese Corp|Conversion of ethylenically unsaturated compounds using heteropoly-molybdic and heteropolytungstic acids as catalysts|
    US4001316A|1973-06-15|1977-01-04|Nippon Kayaku Kabushiki Kaisha|Method for manufacture of methacrylic acid|
    CH569926A5|1973-06-15|1975-11-28|Bartolomeis Spa Forni Ed Impia|
    US3875220A|1973-10-11|1975-04-01|Standard Oil Co Ohio|Process for the preparation of methacrylic acid from methacrolein|
    DE2460541C3|1973-12-29|1979-10-18|Nippon Shokubai Kagaku Kogyo Co. Ltd., Osaka |Oxide catalyst containing phosphorus, molybdenum and vanadium and optionally copper, cobalt, zirconium, bismuth, antimony and / or arsenic and its use for the production of methacrylic acid|
    GB1430337A|1974-05-24|1976-03-31|Nippon Kayaku Kk|Process for the manufacture of methacrylic acid and oxidationcatalyst therefor|
    JPS5827255B2|1974-05-31|1983-06-08|Mitsubishi Rayon Co|
    US4000088A|1974-06-03|1976-12-28|Nippon Kayaku Co., Ltd.|Oxidation catalyst for the manufacture of methacrylic acid|
    US4192951A|1975-08-11|1980-03-11|Celanese Corporation|Hydrocarbon oxidation process|
    JPS5946934B2|1976-02-09|1984-11-15|Toyo Soda Mfg Co Ltd|
    US4101448A|1976-05-14|1978-07-18|The Standard Oil Company|Catalyst compositions especially useful for preparation of unsaturated acids|
    JPS57299B2|1977-02-22|1982-01-06|JPS6214535B2|1978-06-21|1987-04-02|Nippon Kayaku Kk|
    DD148728A5|1978-12-13|1981-06-10|Nippon Kayaku Kk|PROCESS FOR PREPARING A CATALYST HETEROPOLYSAEURESTRUCTURE|
    JPS55124734A|1979-03-22|1980-09-26|Nippon Kayaku Co Ltd|Preparation of methacrylic acid|
    US4419270A|1980-06-26|1983-12-06|Nippon Shokubai Kagaku Kogyo Co. Ltd.|Oxidation catalyst|
    DE3030243A1|1980-08-09|1982-03-18|Basf Ag, 6700 Ludwigshafen|OXIDATION CATALYST, IN PARTICULAR FOR THE PRODUCTION OF METHACRYLIC ACID BY GAS PHASE OXIDATION OF METHACROLEIN|
    US4522934A|1981-04-27|1985-06-11|Atlantic Richfield Company|Vanadotungstomolybdophosphoric acid oxidation catalyst|
    JPH0213652B2|1981-12-01|1990-04-04|Sumitomo Chemical Co|
    DE3626256A1|1986-08-02|1988-02-11|Roehm Gmbh|HETEROPOLYMOLYBDAT MIXTURES AND THEIR USE AS CATALYSTS|
    US4917820A|1986-08-26|1990-04-17|Nippon Kayaku Kabushiki Kaisha|Ethylene removal agent, postharvest preservation agent and deodorant|
    JPH0753686B2|1986-10-27|1995-06-07|三菱レイヨン株式会社|Method for producing methacrylic acid|
    JP3101821B2|1990-02-15|2000-10-23|三菱レイヨン株式会社|Preparation of catalyst for methacrylic acid production|
    JPH047037A|1990-04-23|1992-01-10|Mitsubishi Rayon Co Ltd|Preparation of catalyst for manufacturing methacrylic acid|
    DE4022212A1|1990-07-12|1992-01-16|Basf Ag|MEASURE THE GENERAL FORMULA MO1 2 P AVV B X 1 C X 2 D X 3 E S B F R E G S H O N |
    FR2680702B1|1991-09-03|1994-11-04|Atochem|NOVEL CATALYST SYSTEM AND ITS APPLICATION TO THE OXIDE OF HYDROGENATION OF SATURATED CARBOXYLIC ACIDS AND THE OXIDATION OF ALDEHYDES TO ACIDS.|
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    JP3884967B2|2002-02-07|2007-02-21|住友化学株式会社|Method for producing methacrylic acid|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP52129685A|JPS5924140B2|1977-10-31|1977-10-31|
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