• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 引用文献
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  • 优先权
    • 专利摘要:
    A process for producing methacrylic acid by vapor phase oxidation of methacrolein with molecular oxygen or molecular oxygen-containing gas in the presence of isobutylene and/or tertiary butanol and in the presence of a catalyst having a heteropolyacid structure represented by the following general formula: MoaVbPcXdOe wherein Mo, V, P, and O represent molybdenum, vanadium, phosphorus, and oxygen respectively, X represents the coexistence of copper and aresenic and the a, b, c, d and e represent the atomic ratio of the elements where: a is 10, b is a number of 6 or less excluding 0, c is a number of 0.5 to 6, d is a number of 3 or less excluding 0, and e is a number determined depending on the valance and atomic ratio of the other elements.
    公开号:SU1246889A3
    申请号:SU802896304
    申请日:1980-03-21
    公开日:1986-07-23
    发明作者:Мацумото Муцуми；Вада Коуити
    申请人:Ниппон Каяку Кабусики Кайся (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to an improved process for producing methacrylic acid by vapor-phase oxidation of methacrolein.
    Methacrylic acid is an xoAtbiM compound for the production of valuable polymeric materials.
    The aim of the invention is to increase the stability of the process.
    Example 1. Too g of ibdenium trioxide, 6.3 g of vanadium pentoxide, g of copper oxide and 8.0 g of orthophosphoric acid are dispersed or dissolved in 1000 ml of deionized water. The resulting mixture is boiled and refluxed with stirring for 6 hours to obtain a clear orange-red solution. After removing a small amount of insoluble compounds, it is scrubbed to dryness in a hot bath. The dried product (catalyst) thus obtained has a composition of V P Cu 0. By observing the diffraction peaks of 15 X-CX X-rays at, 0; 8.9; 9.3 °, etc. identified as a heteropoly acid. The catalyst is crushed to a size of 24-48 mesh. (0.7-0.3 mm) and 10 ml of it are placed in a cylindrical reactor made of plastic glass with an internal diameter of 18 mm. The reactor is placed in a fluidized bed bath and a gaseous mixture containing l / h: methacrolein (MAL) 0.475 is introduced into it; isobutylene (IB) 0.025; oxygen IjS nitrogen 8.0; water vapor 5.0 (molar ratio methacrolein: isobutylene: oxygen: nitrogen: water vapor 0.475:: 0.025: 1.5: 8.0: 3.0), and the reaction is carried out.
    Examples 2-15. 1.1 g of 1 oxide of example 1 are alternately replaced by the following substances, g: tin oxide 1.6; thorium oxide 3.7; the oxide herma- 5 thief above {) is kept dry on a water bath 1.4; oxide oxide 1.0; oxide of iron. The dried product (catalyst) left 1,1; cobalt oxide 1.1; zinc oxide 1.1; titanium oxide 1.1; lead tetraxide 3.2; rhenium oxide 3.4;
    50
    zirconium oxide 1.7; bismuth oxide 3,2; The acid is 1.9, respectively, and dry products (catalysts) are obtained. Then the process is carried out using the following examples: the composition of Mo, V P, Oz, H .. The study of X-ray diffraction on a sample of a catalyst isator shows Diffraction peaks, 0; 8.9; 9.3, etc. due to a heteropoly acid consisting of phosphanate-momolybdic acid, and fuzzy diffraction peaks, 6; 10.8
    under the same reaction conditions, 55, etc. due to the potassium salt of the het- ation, as in Example 1. poly-acid. With this received
    All dried products (catalysts) by x-ray diffraction peaks the catalyst is a mixture of heteropolyacids, mainly
    sky rays at, 0; 8.9; 9.3, etc. identified as heteropoly acid.
    Examples 16-22. Dried up
    products (catalysts) are obtained under the same conditions as in example 1. The process is carried out using the listed catalysts under the same conditions as in example 1. These
    catalysts for x-ray diffraction peaks at, 0, 8.9, 9.3, etc. identified as heteropoly acid.
    EXAMPLE: l -22 (comparative). The procedures of Examples 1-22 are repeated with the exception that isobutylene (IB) is not introduced into the reactor.
    Examples -22 (comparative). The procedures of Examples 1-22 are repeated with the exception that methacrolein (MA.L) is not introduced into the reactor.
    The compositions of the catalysts and the results of the tests in examples 1-22, - 22 comparative, 1 -22 comparative are given in table. one.
    The consumption of methacrylic acid, obtained by EI example 1, is higher than the sum of the costs of separate oxidation of methacrolein and isobutylene (cf.Ifl f
    a good example of t and 1), which confirms the effect of coexistence of isobutyl, ene. The same comparison made in all the examples shows this effect.
    Example 23: 100 g of molybdenum trioxide, 6.3 g of thioxide yanadi, 1 j1 g of copper oxide and 8.0 g of orthophosphoric acid are dispersed or dissolved in 1000 ml of deionized water.
    and after 3 hours of heating and stirring, 0.45 potassium hydroxide is added to the resulting solution. The mixture is refluxed for 1 hour at reflux. Thus obtained water growth
    the thief was superior {) and kept dry in a water bath. Dried product (catalyst)
    has the composition of Mo, V P ,, Oz, H... The study of X-ray diffraction on a sample of a catalytic converter shows Diffraction peaks, 0; 8.9; 9.3, etc. due to a heteropoly acid consisting of phosphanate-momolybdic acid, and fuzzy diffraction peaks, 6; 10.8
    the catalyst is a mixture of heteropoly acids, mainly composed
    from phosphanovadomolybdic acid and its potassium salt.
    Using this catalyst, the process is carried out under the same reaction conditions as in Example 1.
    Examples 24-30. Catalysts were prepared analogously to example 23. The process was carried out using the indicated catalysts under the same reaction conditions as in example 1.
    X-ray diffraction study on a sample of catalysts
    8.0;
    shows diffraction peaks, 0;
    8.9; 9.3, etc. due to heteropoly acid, mainly consisting of phosphanovadomolybdic acid, and fuzzy diffraction peaks, 6; 10.8, etc. thanks to the hetero-polyacid salt. In addition, each of the catalysts is a mixture of a heteropoly acid, mainly consisting of phosphanomeadomolybdenum ACID and its salt.
    And p and mery 23-30 (comparative). The procedures of Examples 23-30 are repeated with the exception that isobutylene is not introduced into the reactor.
    And p and mery 23 -ZO (comparative). The procedures of Examples 23-30 are repeated with the exception that methacrolein is not introduced into the reactor.
    The results of the tests in examples 23-30, 23-30 and 23 -ZO are given in table. 2
    Examples 31-35. The catalysts are prepared analogously to example 1. Using the catalysts thus obtained, the process is carried out under the same conditions as in example 1.
    Examples 31 -35 (comparative). The procedures of Examples 31-35 are repeated except that isobutylene is not introduced into the reactor.
    Examples 31 -35 (comparative). The procedures of Examples 31-35 are repeated, except that methacrolein is not introduced into the reactor.
    The compositions of the catalysts and the results of the tests in examples 31-35, 31-35 and 31 -35 are given in table. 3
    Examples 36-38. Using catalysts prepared analogously to example 16, the process is carried out
    analogous to example 1,. but with a change in the consumption of isobutylene (in the range of 0.1-0.15 l / h), the ratio of methacrolein.
    to
    five
    0 5
    Q
    d
    0
    five
    0
    five
    isobutylene, ci (hydrogen, nitrogen and water vapor in example 36 is 0.49: 0.01: 1.5: 8: 5, and in example 38 0.35: 0.15 1.5: 8: 5 .
    Example s zb-sr (comparative). The procedures of Examples 36-38 are repeated, except that isobutylene is not introduced into the reactor.
    Examples -38 (comparative). The procedures of Examples 36-38 are repeated with the exception that methacrolein is not introduced into the reactor. The compositions of the catalysts and the results of tests according to examples 36-38, 36-38 and 36-38 are given in table. four.
    Examples 39-41. Using catalysts prepared analogously to example 1, 15 and 27, the process is carried out under the same conditions as in example 1 with the exception that tertiary butanol (TBA) is introduced into the reactor instead of isobutylene.
    PRI me R s 39 - i1 (comparative). The procedures of Examples 39-41 are repeated, except that methacrolein is not introduced into the reactor, I The catalyst compositions and the test results for Examples 39-4J, 39-4 l and 39 -41 are given in Table 5.
    EXAMPLE 42 The procedure of Example 39 is repeated using the catalyst used in Examples 2-15, 17-26 and 28-30.
    In all cases, almost the same results are obtained as in Examples 2-15, 17-26 and 28-30, and the effect of coexistence of tertiary butanol is observed.
    Examples 43-44, The process is carried out analogously to Example 1 using the same catalyst, but at different temperatures and flow rates: in example 42, temperature is 280 ° C, volume velocity is 1000 hours, in example 43 temperature is 370 ° C, volume speed 2500
    Examples 45-46, The catalyst is prepared analogously to example 1. The process is carried out analogously to example 1 at volumetric feed rates of methacrolein and isobutylene, respectively, 0.475 and 0.025 l / h.
    Example 47 The process described in the respective examples 1-12, 14-18, 20, 23-26, 29-36, 38 and 43-46 is carried out for 30 days.
    The results of the processes in examples 42-47 are given in table. 6,
    Examples 48 and 49. The process is carried out analogously to example 1 for 30 days, with the difference that the catalyst described in example 16 is used (molar ratio of methacrolein, isobutylene, oxygen, nitrogen and water vapor in example 48 0.475: 0.025: 1 : 10: 1, and in example 49 49575: 0.025: 2: 8: 2).
    The test results for Primaran 48 and 49 are given in Table. 7.: PRI me R 50. The process is carried out as in Example 1 for 30 days. using a catalyst according to example 1, P Cuj, 0.5-2, with the difference that the volumetric rate is 500, and the reaction temperature is 250 C. The results of this reaction are illustrated in Table 8.
    The analysis of the obtained results testifies to the stability of the catalyst operation for 1 month by the proposed method, in contrast to the well-known one, where the catalyst activity significantly deteriorates after 10 days. work.
    Table 1
    Continuation of table
    Continuation of table
    Table3
    Continuation of table 6
    Continued table. 6
    500
    500
    one
    thirty
    VNIIPI
    Order 4029/59
    Random polygons pr-tie, Uzhgorod, st. Project, 4
    Continued table. 6
    nzraiziz:
    Table

    93.1 93.9
    80.5 80.3
    74.9 75.3
    Circulation 379 Subscription
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING METACRYLIC ACID by vapor-phase oxidation of methacrolein with molecular oxygen in the presence of isobutylene and / or tertiary butanol at 250 360 ° С in the presence of water vapor at a molar water vapor ratio of £ methacrolein + (isobutylene or tertiary butanol)], equal to (2-10): 1 , and a volumetric feed rate of 500
    2500 h ~ 'in the presence of a catalyst containing phosphorus, molybdenum and oxygen, characterized in that, in order to increase the stability of the process, a catalyst of the general formula M % V 0.5-2 P ° .5 -3 is used as a catalyst. X 0.04 Y a.-4 ° f 'having a heteropoly acid structure or a mixed heteropoly acid structure and a heteropoly acid salt, where X is one or more elements selected from the group consisting of copper, tin, thorium, germanium, nickel, iron, cobalt, zinc, titanium, lead, rhenium, zirconium, bismuth and arsenic;
    Y - one or more elements selected from the group including potassium., Rubidium, cesium and thallium;
    f is a number determined depending on the valency and atomic ratio of other elements.
    SU H1 , 1246889
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP3232379A|JPS55124734A|1979-03-22|1979-03-22|Preparation of methacrylic acid|
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