• 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:
    This invention relates to a process and catalyst for producing methacrylic acid by the oxidation of methacrolein. More specifically, it relates to a process for producing methacrylic acid from methacrolein by oxidizing the same with molecular oxygen or molecular oxygen-containing gas, which is characterized by the use of a composition, as a catalyst, having a heteropolyacid structure and the general formula:
    公开号:SU797551A3
    申请号:SU772517659
    申请日:1977-09-05
    公开日:1981-01-15
    发明作者:Мацумото Мацуми；Судо Ацуси；Суги Хидеки
    申请人:Ниппон Каяку Кабусики Кайся (Фирма)；
    IPC主号:
    专利说明:

    . The invention relates to the production of catalysts for the preparation of non-corpulent acids by the oxidation of the corresponding cdedehydes, in particular the catalysts for the production of methacryolic acid by the oxidation of methacrolein. A known catalyst for the oxidation of methacrolein to methacrylic acid, containing molybdenum, palladium, platinum, mouse, and oxygen, as well as phosphorus, boron, or silicon flj. This catalyst makes it possible to obtain methacrylic acid in a yield of up to 51.5%. Closest to the invention is a catalyst for the oxidation of methacrolein to methacrylic acid, containing molybdenum, vanadium, phosphorus and oxygen, and having a heteropolyacid structure, the composition of which corresponds to the empirical formula, where a is a positive number less than L 0.1 - 12, X -. the number of oxygen atoms required to saturate the valence of all elements. The catalyst may also contain one or more elements selected from the group containing bismuth, mouse, boron, cerium, chromium, silver, iron, tungsten, nickel, niobium, lead, manganese, thallium, tellurium, tin or copper 2. To the disadvantages of the well-known catalyst should be attributed not high enough activity and selectivity, the yield of methacrylic acid is 57.6% with a selectivity of 63-66%, as well as insufficient stability of the catalyst - the activity after 30 days of operation decreases by 14%. The purpose of the invention is to increase the activity and stability of the cutter, as well as to increase the selectivity. This goal is achieved in that the catalyst for the oxidation of methacrolein to methacrylic acid, containing molybdenum, vanadium, phosphorus, oxygen, further comprises aluminum and an element selected from the group comprising copper, tin, cobalt, iron, zirconium, thorium, lead, cerium, and having the structure of a heteropoly acid, the composition of which corresponds to the empirical formula,
    de Y element selected from the group consisting of copper, tin, cobalt, iron, zirconium, thorium, lead, cerium; ten;
    a b
    0.3 3;
    0.5 10;
    c d e
    0.01-3;
    0-3;
    f
    the number of oxygen atoms required to saturate the valence of all elements.
    The catalyst contains various elements and at the same time has the structure of a heteropoly acid, as shown by d-ray diffraction, which has characteristic peaks, which are obtained at, 8.9, 9.3 ° And so on. The main component of the structure is phosphonovadomolybdic acid, the other elements of this structure serve to improve the catalytic activity and selectivity, as well as the stability of the structure, partially replacing the constituent elements of phosphomodane and molybdic acid and. including the structure of reTeponoj, sylph.
    - The catalyst is soluble in water, since it has a heteropoly-gold structure, but it also contains water-insoluble components, such as oxides of the elements included in the structure, but these components do not have a significant effect on the operation of the catalyst.
    The proposed catalyst can be obtained by methods common in the preparation of heteropolyacids, however, it is necessary to avoid forming the structure of a heteropolyacid salt, such as the ammonium salt of the heteropolyacid, in the resulting catalyst.
    The catalyst can be obtained, for example, by the following method. Heteropolyacid containing phosphorus is synthesized by methods used in the qualitative and quantitative analysis of various elements. Accordingly, the catalyst is obtained by reacting the starting materials in water or an organic solvent, and then, if necessary, extracting the reaction products with some suitable organic solvent, for example ether, followed by evaporation of the latter. If salt is obtained at this volume, it can be converted into acid in the usual way, for example, by ether extraction from an aqueous acid solution, by an ion exchange process, etc.
    The preferred method of preparation is that in which the starting material is dispersed, for example oxides or phosphates of constituents, in water; heating to dissolve and react with the addition of an arbitrary amount of hydrogen peroxide, removing insoluble components, if necessary, and then evaporating the solution with a dryness or reacting Los-L-vanadomolybenic acid with oxides, phosphate, sulphate, and the like. constituting elements.
    As starting materials containing the constituent elements, various materials are used which, when subjected to the process described above, result in the structure of the heteropolyacid and not the structure of the salt.
    The starting material for the molybdenum moiety is, for example, molybdenum trioxide, molybdic acid or its salt, heteromolybdic acid or its salt, metallic molybdenum, and the like.
    The starting material for the phosphorus component may be phosphoric acid, phosphoric acid, hypophosphoric acid or their salts, phosphorus pentoxide, and the like.
    The starting material for the vanadium component can be vanadium thioxide, vanadium oxalate, vanadium sulfate, vanadic acid and its salt, metallic vanadium, and the like.
    The starting material for the aluminum component can be the corresponding oxide, phosphate, nitrate, sulphate and aluminum molybdate, as well as metallic aluminum.
    The starting material for component Y can be the corresponding oxides, phosphates, nitrates, sulfates, carbonates, molybdates, as well as the metallic elements of Y.
    Since the proposed catcher has a high catalytic activity, the desired effects, such as improved thermal stability and increased service life, can be expected when selecting a suitable carrier. Preferred carriers are silicon carbide, α-alumina, aluminum powder, Celite (diatomaceous earth), titanium, and the like. Active carriers, reacting with heteropolyacid, are undesirable. The catalyst dissolves in water, which is an advantage, as it facilitates its application to the carrier, as well as its regeneration after a long use and loss of activity by dissolving it in water.
    The reagents in the oxidation reaction are methacrolein and molecular oxygen or molecular gas containing oxygen, and the molar ratio of oxygen to methacrolein should preferably be in the range from 0.5 to 10, and most preferably from 2 to 5. In order to calmly proceed to the reaction, it is desirable to add water vapor to the source gas, and the molar ratio of steam to methacrol. The acid should lie in the range from 1 to 20, and in the preferred embodiment from 5 to 15. Addition of water facilitates , from the surface of the catalyst and temperature control in the catalyst bed. The feed gas may also contain any inert gas, for example nitrogen, carbon dioxide, high purity hydrocarbons, and the like. Gaseous methacrolein-containing reaction products obtained by the catalytic oxidation of isobutylene or tertiary butanol can be used as a starting material.
    Reaction temperatures for practical use of the process should be in the range of about 200 ° C, and more preferably about 250 to 350 ° C. Amount of Metacroleine metamecroleine conversion, (%) Methacrolein Methacrylate yieldMetacrylic acid, (%). Methacrolein Selectivity to the Output of methacres of methacrylic Conversion of acid, (%)
    PRI me R 1. 100 g of molybdenum trioxide, 6.3 g of vanadium pentoxide, 0.36 g of alumina, 8.0 g of orthophosphoric acid are dissolved in 1000 ml of deionized water, incubated for about 24 hours at about 50 With periodic addition of an aqueous solution of hydroperoxide to obtain a clear orange-boundary solution. After removing the non-. A large amount of undissolved substance is evaporated to dryness in a hot bath. The catalyst thus obtained has the following composition: Mo, oAA.1 E, Op, and the fact that the peaks of X-ray diffraction are observed at 208, CP; 8.9; 9.3 °, etc., it can be concluded that it has a heteropoly acid structure. The catalyst is milled to 6-9 mesh and loaded into a tubular reactor made of Pyrex glass, with an internal diameter of 18 mm, immersed in a liquid bath. The source gas consisting of methacrolein, nitrogen and steam with a molar ratio of 1: 2: 18: 7, respectively, is passed through a tubular reactor at a packing speed of 1200 hours (at standard atmosphere) and subjected to oxidation reaction at 320 ° C within 30 days. . The results are presented in table 1. The feed gas supply should be in the range of about 100-5000 hours, and more preferably about 500-3000 hours (volumetric velocity under normal conditions). Since the increase in the space velocity does not have a significant effect on the results of the reaction when using the proposed catalyst, the reaction is carried out at high velocities. Since the reaction takes place at pressures both above and below atmospheric, the use of near-atmospheric pressure is most appropriate. In a preferred embodiment, the pressure should be in the range from 1 to 5 atm.
    5 The reaction can take place in any type of reactor, such as with a non-movable, moving and fluidized bed.
    The conversion of methacrolein, output
    Methacrylic acid and methacrylic acid selectivity are determined by the following crop.
    1 Example2. UOH of molybdenum trioxide, 6.3 g of vanadium pentoxide, 0.36 gOXIDE aluminum, 2.0 g of copper phosphate and 7, O g of orthophosphoric acid are used as a starting material for obtaining a dry product.
    ° 10-° 0 f ° as described in Example 1, and the reaction using the catalyst obtained is carried out under the same conditions as in Example 1. The results are shown in Table 1.
    Examples 3-9. 2.0 g phos-. for each of the examples, 1.5 g of tin phosphate, 1.2 g of cobalt phosphate, 1.4 g of ferric phosphate, 0.86 g of zirconium oxide, 1.8 are replaced for each of the examples. g of thorium oxide, 1.6 g of lead dioxide and 1.2 g of cerium oxide, respectively, receive a dry product, the composition of which is given in table 1. In the presence of the obtained catalysts, a series of continuous reactions are carried out under the conditions of Example 1. The results are presented in Table 1.
    Examples 10-13. 1.5 ppm of tin phosphate, 1.2 g of cerium oxide, 1.8 g of thorium oxide and 0.86 g of O1L1si zirconium are added to the starting materials of Example 2, respectively, and the dry products are listed in Table 2, prepared as in example 2. With used (mol) Q ,. source. (mol) acid, obtained (mol), x 100 of the original (mol of sulphate acid-X 100 methacrolein
    by preparing the obtained catalysts, continuous reactions are carried out under conditions similar to those of Example 1. The results are shown in Table 2.
    Examples 14-15. The dry products shown in Table 3 are prepared in the same manner as in Example 1 and using the resulting catalysts, continuous reactions are carried out under the same conditions as in Example 1. The results are shown in Table 3.
    Example 16. 100 g of phosphanovadomolybdic acid (O) is dissolved in 500 ml of deionized water, and 0.62 g of aluminum phosphate (A 1PO) is added to the solution and the reaction is carried out with stirring. The resulting clear orange-red solution is evaporated to dryness, resulting in a catalyst with ° -f0 o, gAlo,.
    eat this
    1 zatora conducts the catalyst
    in a bath with a temperature of 320 ° C, as in Example 1, and the following results are obtained:.
    The conversion of methacrolein,% 75,5
    Methacrylic outlet
    acid,% 55.4
    Selectivity to
    methacrylic acid,% 73,4
    Examples 17-22. Dry substances, the composition of which is given in Table 4, are obtained in the same manner as in Examples 1-9, and the continuous reactions are carried out under the same conditions as in Example 1. The results are shown in Table 4.
    Example 23. A catalyst of composition Or was prepared according to the same procedure as in Example 1, and the reaction was carried out continuously using the above catalyst under the same conditions as in Example 1. The results are shown in Table 5.
    Example 24. Preparing a catalyst of composition V A and;, P O /,
    according to the same procedure as ttrimer 2, and carried out continuous reactions using the above catalyst under the same conditions as in example 1. The results are shown in .6.
     Examples 25-32. Catalysts whose composition is presented in i
    Table 7, prepared in the same manner as in Examples 1 and 2, and used under the same conditions as in Example 1. The data obtained are presented in Table 7.
    The examples given illustrate catalysts which contain the corresponding components in widely varying ratios within the limits of the claimed ranges.
    Comparative example 1. Dried substances having a composition of Mo. V P Of is prepared in the same manner as in Example 1, but with the addition of 0.36 g of alumina, and in their presence as cat5 of LIZ ators, P15-continuous reactions are carried out. The results are shown in table.8.
    Comparative with a 0.m.e2.2. 28% aqueous ammonia solution is added to the clear orange-red solution obtained in Example 1, 0) until a pH of 5.3 is obtained. After evaporation, the dried substances are ground to 6–9 mesh and calcined in air at 380 ° C for 8 hours. The catalyst obtained has the composition (MH4) Mo, dU AC 0, and the structure of the ammonium salt of the heteropoly Q acid, which is confirmed by X-ray diffraction and 1 absorption spectrum. Such a prolonged reaction is carried out with use. this catalyst. results
    e are given in table.8.
    Comparative example 3. To determine the service life of a known catalyst is carried out
    l long experience of methacrolein oxidation continuously for 30 days under the conditions of example 6 ...
    The results in table 9 show that the known catalyst is worse for the duration of the active
    5 service than the proposed catalyst.
    The proposed catalyst has 0 increased activity and selectivity - the yield of methacrylic acid reaches 67.6% with a selectivity of up to 79.5%. The catalyst also has a fairly high stability for 30 days of work, the activity is reduced by 0.7. Table 3
    ,
     lO o / l Vf
    27
    Mo V AL P ... O10 1 Qfi 0.6
    28, .Vf
    29 .Of
    thirty
    Table 5
    Table 6
    Table 7
    Continued table. 7
    .Table 8
    Table 9
    权利要求:
    Claims (1)
    [1]
    Claim
    A catalyst for the oxidation of methacrolein to methacrylic acid; including molybdenum, vanadium, phosphorus, oxygen and having a heteropoly acid structure, characterized in that, in order to increase the selectivity and stability of the catalyst, it additionally contains aluminum, as well as an element selected from the group consisting of copper, tin, cobalt , yellow, zirconium, thorium, lead, cerium, and the composition of the catalyst corresponds to the empirical formula Mo a v t> p with A 'd Y e> where Y is an element selected from the group consisting of copper, tin, and b with d e f cobalt, iron, zirconium, thorium, lead, cerium;
    10;
    0.3-3;
    0.5-10;
    0.01-3;
    0 - 3 the number of oxygen atoms needed to saturate the valency of all elements.
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    同族专利:
    公开号 | 公开日
    FR2363372B1|1980-04-18|
    DE2739779A1|1978-03-30|
    CA1083557A|1980-08-12|
    JPS5519206B2|1980-05-24|
    FR2363372A1|1978-03-31|
    JPS5331615A|1978-03-25|
    NL171980C|1983-06-16|
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    NL7709632A|1978-03-08|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3156706A|1960-12-14|1964-11-10|Petro Tex Chem Corp|Production of dicarboxylic acid anhydrides by the catalytic oxidation of aliphatic hydrocarbons|
    GB1084143A|1964-09-30|
    US3320331A|1966-01-27|1967-05-16|Exxon Research Engineering Co|Oxidative dehydrogenation of aliphatic hydrocarbons over aluminum phosphate supported molybdenum and vanadium|
    US3644497A|1968-11-01|1972-02-22|Celanese Corp|Conversion of ethylenically unsaturated compounds using heteropoly-molybdic and heteropolytungstic acids as catalysts|
    BE789241A|1971-09-28|1973-03-26|Halcon International Inc|Catalyst for the oxidation of unsaturated aldehydes|
    GB1534348A|1975-03-27|1978-12-06|Standard Oil Co|Process for the preparation of acrylic and methacrylic acids and catalysts for use in this process|
    US3875220A|1973-10-11|1975-04-01|Standard Oil Co Ohio|Process for the preparation of methacrylic acid from methacrolein|
    US4075244A|1973-11-22|1978-02-21|Nippon Zeon Co. Ltd.|Process for preparing methacrylic acid|
    US4049574A|1974-05-28|1977-09-20|Petro-Tex Chemical Corporation|Catalyst and process for preparing maleic anhydride from C4 hydrocarbons|
    JPS555379B2|1974-12-02|1980-02-06|
    US4056487A|1975-10-02|1977-11-01|Petro-Tex Chemical Corporation|Vanadium phosphorus oxygen oxidation catalysts useful for preparing anhydrides from alkanes|EP0005769B1|1978-05-31|1982-04-21|Nippon Kayaku Kabushiki Kaisha|A process for producing methacrolein and methacrylic acid|
    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|
    DE3161102D1|1980-08-28|1983-11-10|Roehm Gmbh|Process for the oxidizing dehydrogenation of isobutyric acid to methacrylic acid|
    JPH0516308B2|1984-10-09|1993-03-04|Mitsubishi Rayon Co|
    US4757044A|1985-04-17|1988-07-12|The Standard Oil Company|Lanthanide metal salts of heteropolyanions as catalysts for alcohol conversion|
    DE4132684A1|1991-10-01|1993-04-08|Basf Ag|METHOD FOR CATALYTIC GAS PHASE OXIDATION FROM METHACROLEIN TO METHACRYLIC ACID|
    JP4564317B2|2004-09-27|2010-10-20|三菱レイヨン株式会社|Method for producing a catalyst for methacrylic acid production|
    KR100942893B1|2007-03-08|2010-02-17|주식회사 엘지화학|Catalyst preparation method for methacrylic acid production with high selectivity|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP10577676A|JPS5519206B2|1976-09-06|1976-09-06|
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