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    • 专利摘要:
    A process for producing methacrolein and methacrylic acid by oxidizing isobutyl aldehyde with molecular oxygen or molecular oxygen-containing gas in the vapor phase characterized by the use of a catalyst of heteropoly-acid or a mixture of heterpoly-acid and its salt which has the general formula: MoaVbPcXdYeOf wherein Mo, V, P and O represent respectively molybdenum, vanadium, phosphorus and oxygen, X represents one or more elements selected from the group consisting of copper, tin, thorium, aluminum, germanium, nickel, iron, cobalt, zinc, titanium, lead, rhenium, zirconium, cerium, chromium, bismuth and arsenic, Y represents one or more elements selected from the group consisting of potassium, rubidium, cesium and thallium and a, b, c, d, e and f represent the atomic ratio of the elements where, a is 10, b is a number of 6 or less than 6 excluding 0, c is a number of 0.5 to 6, d is a number of 3 or less than 3 excluding 0, e is a number of 0 to 0.8, f is a number determined depending on the valency and atomic ratio of other elements.
    公开号:SU1055329A3
    申请号:SU802873603
    申请日:1980-01-22
    公开日:1983-11-15
    发明作者:Мацумото Муцуми；Вада Коуити
    申请人:Ниппон Каяку Кабусики Кайся (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a process for the preparation of methacrolein and m-acrylic acid, which is used in the production of fibers and films. A known method of producing methacrylate and methacrylic acid by oxidizing isobutyl aldehyde in the gas phase with molecular oxygen or oxygen-containing gas in the presence of water vapor and a catalyst containing molybdenum, vanadium phosphorus, thallium and oxygen, at 200-VOO C l. The disadvantage of this method is the relatively low yield of the desired product. The purpose of the invention is to increase the yield of the target product. This goal is achieved by producing methacrolein and methacrylate acid by oxidizing isobutyl aldehyde in the gas phase with molecular oxygen or oxygen-containing gas in the presence of water vapor and a catalyst containing molybdenum, vanadium, thallium and oxygen as a catalyst and using a heteropoly acid or a mixture of heteropoly acid and its salts with the following empirical formula ,, XjJeO. MOqV, Vjp, 0 - molybdenum, vanadium, where Mo is phosphorus and oxygen, respectively; X - one or two elements selected from the group consisting of copper, tin, thorium, aluminum, germanium, nickel, iron, cobalt, zinc titanium, lead, rhenium zirconium, chromium, cerium bismuth and mine; 7 potassium, rubidium, cesium thallium; About aj 10; B bj. 0.5-3; With ci 0.5-3; d 0.01-1.0; d, 0.01-1.8 0 0, l-rO, 5; {, i are determined depending on the valence and atomic ratio of other elements. The catalyst used is the catalyst of the following formula I LO I dJinO rt I,; Oa Vbjfc, (Id, 6, or, Mos, ПP where Mcr, V, M, Lu, u - molybdenum, vanad1Zh phosphorus, copper and oxygen, respectively; X - tin, thorium, aluminum, germanium, nickel, iron, cobalt zinc , titanium, lead, rhenium, zirconium, chromium, cerium, bismuth and mouse; 7 - potassium, rubidium, cesium, thallium; 10; C)) -0.5-3; 0.5-3; d d 0.01-1.0 62 64 0.01-1.0 h 0.1-0.5; Determined depending on the valence and atomic ratio of other elements. The main structure of the catalyst used is phosphonated ad-molybdic acid. In the case when the element He is present, the catalyst is a catalyst in which a part of the structure formed by phosphor-vanadom molybdic acid is occupied by element X. In the case when the element Y is present, the catalyst is a catalyst in which a part of the structure formed together by the phosphofand-molybdic acid and its metal salt Y, is occupied by the element X, If the element Y is not present, the catalyst is A heteropoly acid, consisting mainly of phosphanovadomolybdic acid, and in the case when the element Y is present, the catalyst is a mixture of heteropolyacid consisting mainly of phosphofadadomolybdenum acid and its. metal salt U. Element X. takes part of the structure of the hegeteroacid and its salt if it occurs. The x-ray diffraction pattern of this catalyst exhibits their maxima, 0; 8.9; 9.3 ° Typical for diffraction maxima of the heteropoly acid. In the case where the heteropoly acid salt is present, maxima are also observed, 6 °; 10.8 °, etc. characteristic for diffraction maxima of metal salts V of heteropoly acid. However, in the area of the catalyst where the amount is simultaneously present in a great salt, only maxima are observed, corresponding to acid. Those catalysts in which the amount of the Y component is too large, that only the maxima are observed, the heteropoly acids associated with the f Y salt do not give positive results. Therefore, it is important to control the amount of Y component added.
    Although the catalyst used is a heteropoly acid or a mixture of heteropoly acid and its salt, it may additionally contain other compounds, such as oxides of its constituent components.
    The catalyst is suitable for industrial use, as it has high activity, high selectivity and a long service life. In this case, the process can be carried out with a high volumetric rate, since increasing the volumetric rate has almost no effect on the results of the reaction, c. which use the specified catalyst. The catalyst used is soluble in water and can be easily applied to a carrier, as well as easily regenerated by dissolving it in water after it has lost its activity as a result of prolonged operation.
    Although the catalyst can be prepared using conventional methods. For preparing a heteropoly acid and its metal salt Y, it is necessary to avoid the formation in it of the structure of the ammonium salt of a heteropoly acid.
    The catalyst can be obtained by reacting the starting materials of the constituents in water or an organic solvent, followed by evaporation of the water or organic solvent to dryness.
    The most preferred methods for the preparation of a catalyst are dispersion or dissolution of the initial material, for example oxides or phosphates of elements included in the catalyst, in water, their interaction during heating with optional addition of hydrogen peroxide, removal of insoluble components, if necessary, followed by evaporation of the solution to dryness, or the interaction of phosphanadom-molybdenum
    Acids with oxides, hydroxides of phos
    veils, carbonates of other elements, the entrance of T1 to the composition of the catalyst.
    Starting materials suitable for the molybdenum-containing component include, for example, molybdenum trioxide, molybdic acid or its salt, heteropolymolybdic acid or its salt, metallic molybdenum.
    The raw materials suitable for the phosphorus-containing component include phosphoric acid, phosphorous acid, hypophosphorous acid or their salts, phosphorus pentoxide.
    Starting materials suitable for the vanadium-containing component include vanadium pentoxide, vanadium oxalate, vanadium sulfate, vanadic acid or its salts, phosphate ado. molybdic acid or its salt, metallic vanadium.
    Raw materials suitable for the component containing X and Y include the corresponding 1, oxides, phosphates, nitrates, sulfates, carbonates, molybdates, salts of organic acids, halides, hydroxides of the elements X and Y in the form of metals.
    Although the catalyst in accordance with the invention has a high catalytic activity, a preferable action in terms of improving thermal stability and catalyst life, as well as increasing the yield of methacrylic acid, can be expected when applied to a suitable carrier. Preferred carriers include silicon carbide. Of, - aluminum oxide, aluminum powder, diatomaceous earth, titanium oxide. It is also undesirable. To use active carriers, which interact, with TV with heteropoly acid.
    In most cases, the calcination process in the preparation of a catalyst is eliminated; therefore, it is easy to prepare and the cost of such a catalyst can be reduced.
     The reagents used for the oxidation reaction are isobutyl aldehyde and molecular oxygen or gas containing molecular oxygen, with a molar ratio of oxygen to isobutyl aldehyde of about 0.5-20, more preferably 1-10.
    It is preferable to add water vapor to the feed gas stream in a quantity of € 1-2, more preferably 2-15 in terms of molar δ per capita and double aldehyde. The feed gas stream may also contain other inert gases, such as nitrogen, carbon dioxide, and saturated hydrocarbons. The reaction temperature should preferably be 250-400 ° C, more preferably 250-370 ° C. The volumetric flow rate of the feed gas should preferably be 100-6000 hours from C, more preferably 400-3000 hours, calculated on normal conditions (temperature and pressure. Since the rate of space velocity does not significantly affect the results of the reaction, the reaction can be carried out at high volumetric rates. Although the process can be carried out at or below atmospheric pressure, it is usually convenient to carry out the reaction at an atmospheric pressure 1-5 atm. The process can be carried out in any type of reactor, such as a fixed bed, a fluidized bed or a moving catalyst bed. In the examples there is no specific indication of the oxygen content in the catalytic composition, since it is determined according to the atomic the ratio and valency of the remaining elements: Conversion of isobutyl aldehyde, methacrolein yield, methacrylic acid yield, and selectivity to methacrolein + methacrylic acid are determined as follows. Conversion of the reacted isobutyl alisobutyl aldehyde, mol of aldehyde,% aliquity of isobutyl alcohols, mol of obtained metaExit of mecrolein, mol of tacrolein,% of isobutyl aldehyde, of mol, Exit mpacs, acacryl acrylate, acylacryl aldehyde, mol Exit, acacrylate, acacrylate, acacryl, aldehyde, moles, tacrolein, aldehyde Selectivity per methacrolein + methacrylic acid |% The yield of metaconversion of isobutylocrolein- + the yield of meso apdetacrylic acid guide ExampleA. 100 g of molybdenum trioxide 6.3 g of vanadium hydroxide; 1.1 g of copper oxide and 8.0 g of orthophosphoric acid are dispersed or dissolved in 1000 ml of deionized water. The resulting mixture was heated under reflux with stirring for about 6 hours, resulting in a clear orange-red solution. After a small amount of insoluble compounds is removed, it is evaporated to dryness in a hot bath. The dry product catalyst obtained in this way) has the following composition: and, as confirmed by the X-ray diffraction pattern, is a heteropoly acid (diffraction peaks are observed at 20 ° -8.0, 8, 9.3 °). The catalyst is crushed to 0.3-0.7 mm and diluted with the same amount of silica sand with the same dimensions, and then loaded into a tubular reactor, made of 18 mm glass of internal diameter, the reactor is immersed in a fluidized bed. The feed gas stream is passed through the reactor with the following composites - isobutyl aldehyde: oxygen: nitrogen: water, 5: 10: 7 (molar ratio) with a flow rate of 1000 hours (under standard conditions) and the oxidation reaction is carried out at a reaction temperature of 325 C for 60 days. The results are shown in Table A. 1. After the reaction was carried out continuously for 60 days, the catalyst was examined by X-ray diffraction, and it was confirmed that molybdenum trioxide did not form and the structure of the catalyst did not change. Examples A2-A17. 1.1 g of copper oxide in Example A1 is replaced in each of the following examples, respectively, with 1.6 g of tin oxide; 3.7 g of thorium oxide, 0.7 g of alumina, 1.4 g of germanium oxide, 1.0 g of nickel oxide, 1.1 g of iron oxide, 1.1 g of cobalt oxide; 1, 1 -th zinc oxide, 1.1 g of titanium oxide; 3.2 g of lead tetroxide (three); 3.4 g of rhenium oxide; 1.7 g of circoia; 2.4 g of cerium oxide; 1.4 g of chromium oxide; 3.2 g of bismuth oxide and 1.9. g mouse sislots, resulting in products / catalysis, after drying; the compositions of which are listed in Table A. 1. The products obtained, as confirmed by observing the X-ray diffraction peaks at, 0 °; 8, 9.3 °, etc., are heteropolyacids. Using these catalysts under the reaction conditions of Example P1, a series of continuous reactions are carried out. The results are shown in Table A. After carrying out continuous reactions for 60 days, the results of an analysis of the diffraction of X-rays by these catalysts showed that the structure of the catalysts did not change. Examples A18-A22. The dried products, listed in Table A2, are prepared as in Example 1 and using X-ray diffraction analysis, it is confirmed that they are heteropolyacids. Using these catalysts under the conditions of Example 1, continuous reactions are carried out. The results are shown in Table A2. After 60 days, X-ray diffraction analysis was performed by these catalysts. It was confirmed that the structure of these catalysts did not change. And p and me R A 23. 100 g of molybdenum trioxide; 6.3 g vanadium thioxide; 1.1 g of copper oxide and 8.0 g of orthophosphoric acid are dispersed or dissolved in 1000 ml of deionized water and after three hours of heating and stirring the resulting mixture, 0.45 potassium hydroxide is added to the resulting solution. This mixture is heated under reflux for about 3 hours. The resulting aqueous solution is evaporated to dryness in a water bath. The composition of the dried product (catalyst) was as follows:. ;, R . X-ray diffraction patterns show maxima at, 0 °; 3.9 °; 9, etc., are corresponding to a heteropoly acid, consisting mainly of phosphanovadomic-molybdenum acid, and 98 weak maxima at, 6 °; 10.8, etc., corresponding to the potassium salt of the heteropoly acid. This shows that the catalyst obtained is a mixture of a heteropoly acid, consisting essentially of phosphanovadomolybdic acid and its potassium salt. Using this catalyst, a continuous reaction is carried out under conditions of Example A1. The results are shown in Table. A3. After continuous reaction, the X-ray diffraction analysis by the catalyst was proclaimed; it was confirmed that the structure of the catalyst did not change. Examples A24-A26. 0.45 g of potassium hydroxide in Example A23 is replaced in each of the following examples, respectively, with 0.7 g of rubidium hydroxide; 1.0 g cesium hydroxide; 1.5 g of hydroxide and, after drying, the products (catalysts) of the composition of which are listed in Table 2 are obtained. A 3. In the diffraction patterns of scattered x-rays, catalysts observe maxima at, 0; 8.9;, 9.3 °, etc., corresponding to a heteropolyacid consisting mainly of phosphovioadomolybdic acid, and weak maxima at, 10.8, correspond to the salt of the heteropolyacid. This is for now. It appears that each of the obtained catapacizers is a mixture of heteropoly acid, mainly consisting of phosphanovadomolybdic acid and its salt. Using these catalysts, a series of continuous reactions is carried out, under the conditions of Example A1. The results are shown in Table A3. After continuous reactions, analysis of X-ray diffraction and X-ray catalysts was carried out, and it was found that the structure of the catalyst did not change. Example A27-A42. Dried products (catalysts) listed in Table A4 are prepared as in Example A23. In the diffraction patterns, X-ray diffraction by these catalysts is visible at a maximum at, 8.9 °; 9.3 °, etc., corresponding to a heteropoly acid, mainly consisting of phosphanovadomolybdeic acid, and weak maxima at, 6; 10.8 °, etc., corresponding salts of the heteropolyacid. This indicates that each of these catalysts is a mixture of a heteropolyacid, consisting mainly of phosphanic acid, Odonic acid, and its salt. Using the indicated catalysts, a series of continuous reactions are carried out under conditions corresponding to the conditions of Example A1. The results are shown in tabl.A4. After continuous reactions, an analysis of x-ray diffraction by these catalysts was carried out, and it was confirmed that these catalysts did not change. Example A43-A45, Dried products / catalysts shown in Table 5 were prepared as in Example I, using X-ray diffraction, and shown to be hetero-polyacids. Using the indicated catalysts, continuous reactions were carried out under the conditions of Example 1. The results are shown in the following table. AZ. After continuous reactions, the X-ray diffraction analysis of the indicated catalysts was carried out, it was confirmed that the structure of these catalysts did not change. Examples A46-52. The dried products (catalysts) listed in Table 5 obtained in Example 23 using X-ray diffraction confirmed that they are mixtures of hetero-polyacids, mainly phosphono-ad-molybdic acid and its salt. Using the indicated catalysts, continuous reactions were carried out under the conditions indicated in Example 1. The results obtained are shown in Table AZ. After continuous reactions, the diffraction of X-rays by these catalysts was carried out, and the structure of the catalyst was not changed. PRI me R A53. The oxidation of isobutyl aldehyde is carried out as in Example 1, but the reaction temperature is changed. 11 obtained results are given in tab. Ab. EXAMPLE 54. The oxidation with isomeric aldehyde is carried out according to Example 1, with the exception of the reaction temperature and the space velocity. The condition and results of this reaction are given in Table A7. 910 PRI me R s A 55-A 58. For example, A1 or A23, the catalysts indicated in Table A, were used, and the reactions of Example A1 were carried out using the corresponding catalysts thus prepared. The results of this reaction are also given in the table. AZ. Examples A59-A62. Analogously to example 23, catalysts having the corresponding compositions shown in Table 9 are prepared, using appropriate catalysts, the reaction is similar to that given by the action of Example 1, the results are also shown in Table A9. ExampleB 100 g of molybdenum trioxide; 6.3 g vanadium thioxide; 1.1 g of copper oxide; 8.0 g of orthophosphoric acid and 1.9 g of mycic acid are dispersed or dissolved in 1000 ml of deionized water. The crawled mixture is heated to reflux with stirring for about 6 hours to obtain a clear orange-red solution. After removing a small amount of insoluble material, the solution is evaporated to dryness in a hot bath. The dried product (catalyst) obtained in this way has the following composition: P, Si., FLOX according to the position of the maxima in the diffraction pattern of x-ray scattering at, 0 °; 8.9; 9.3 °, etc. it is confirmed to be heteropoly acid. The product is crushed to 0.3-0.7 mm and diluted with the same amount of silica sand with the same particle size, and then loaded into a tubular reactor made of glass (18 mm inner diameter), the reactor is immersed in a fluidized bed. Gas of the following composition is supplied (in molar ratio: isobutyl aldegyl, oxygen, nitrogen, water vapor (; 2; 5; 10J7). This gas is passed through a tubular reactor with a bulk velocity of -1500 h (at standard temperature and pressure) and wire The oxidation reaction at the reaction temperature for 60 days. The results are shown in Table B. After the reaction, an x-ray diffraction catalyst was analyzed for 60 days, it was confirmed that molybdenum trioxide did not form, and the catalyst wall did not
    changed 4.
    Examples B2-B16, 1.9 g of the mouse acid acid of Example B1 is replaced in
    each of the following examples, respectively, of 3.7 g of thorium oxide; 0.72 g of alumina; 1.4 g of germanium oxide
    1.0g of nickel oxide; 1 g of iron oxide; 1.1 g of tetraoxide (three) cobalt
    1.1g of zinc oxide; 1.1 g of titanium oxide; 3.2 g of tetraoxide. three) lead 3.4 g of rhenium heptaoxide; 3.2 g of zirconium oxide; 2.4 g of cerium oxide, 3.2 g of bismuth oxide; 2.1 g of tin oxide and
    1, A g of chromium oxide, as a result of which, after drying, products (catalysts) are obtained, the compositions of which are given in Tab. S, As was shown using a diffraction maximum of 5v in the scattering of x-rays at, 0 °; 8.9 °; 9, etc., the dried products thus obtained are heteropolyacid,
    Using the indicated catalysts under the conditions of Example B1, continuous reactions are carried out. The results obtained are BT abl.V.
    After reaction for 60 days, X-ray diffraction analysis of these catalysts was carried out, it was confirmed that the structure was catalyzed; congestion has not changed.
    P p and measures B17. 100 g of trioxide: molybdenum; 6.3 g vanadium thioxide; 1.1 g of copper oxide; 1.9 g of mouse acid 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 the mixture, O, 45 g of potassium hydroxide is added to the solution obtained. The mixture was heated under reflux for about 3 hours. The resulting aqueous solution was heated to dryness in a water bath. The composition of the dried product (catalyst) is as follows:, ,,. In the diffraction pattern of the X-ray catalyst scatter, maxima are observed at, 00; 8.9 °; 9.3 °, etc., associated with a heteropolyacid, consisting mainly of phosphanovadomolybdic acid, and weak maxi: b,
    10.8, etc. somums at 20 "
    the corresponding potassium salt of the heteropoly acid. These data indicate that the catalyst obtained is a mixture of heteropolyacids consisting mainly of phosphanovadomolybdic acid and its salt.
    Using the specified catalyst under conditions similar to Example BI, a continuous reaction is carried out. The results are given in Table. AT 2.
    After continuous reaction, an X-ray diffraction analysis with a catalyst was performed; it was confirmed that the structure of the catalyst did not change.
    5 EXTERNAL B18-B20. 0.45 g of hydroxy potassium in example B17 is replaced in the following examples with 0.7 g hydro-. rubidium oxides; 1.0 g hydroxide 1.5 g hydroxide thallium, respectively, and get dried products (catalysts), the composition of which is listed in tab. B2,
    The diffraction pattern scatters x-ray catalysts whose maxima are observed at 20 ° -8.0 °; 8.9 °; 9, ZRi, etc., corresponding to phosphanic acid and molybdic acid, and weak maxima at, 10.8, etc., the corresponding salts of the heteropoly acid. This data shows that each of the catalysts is a mixture of a heteropoly acid, consisting mainly of phosphate and molybdic acid, and its salt.
    Using the indicated catalysts under the conditions of Example BI, continuous reactions are carried out. The results are shown in Table B2,
    After continuous reactions, an X-ray diffraction analysis of the indicated catalysts was performed, it was confirmed that the catalysts did not change.
    Examples B21-B25. Sugary
    5 products (the catalysts given in the table. B3 are obtained according to the line B17, confirmed by analyzing the diffraction patterns, that they are a mixture of a heteropoly acid, consisting mainly of phosphovay adiomolybdic acid and its salt.
    Using the indicated catalysts under the conditions of Example B1, continuous reactions are carried out. The resulting results will be given in Table 5.
    After continuous reactions, x-ray diffraction analysis of these catalysts was carried out, it was confirmed that the structure of the catalysts did not change.
    Examples B26-B29. Dried products (catalysts given in the table. VD are prepared according to Example B17.
    Using the indicated catalysts in ycddfe x of Example B1, continuous reactions are carried out. The results are shown in Table B4.
    Examples VZO-B31. Nspol Eu IQ is a catalyst of Example B17, isobutyl aldehyde is oxidized in Example B1 with the exception of the space velocity. The results obtained are listed in Table III. show
    that an increase in space velocity does not significantly affect the results of the reaction.
    Analogously to example B 1 or J 7, catalysts are prepared, and the corresponding compositions listed in Table B are prepared and the reaction is similar to Example B 1 using the corresponding catalysts, the results are also given in Table B. jj
    Example I (comparative). The dried product of composition f is taught according to example A1, without adding 1.1 g of copper oxide. Using the catalyst obtained, a continuous reaction is carried out in a manner analogous to the reaction of Example A1. The results obtained are shown in Table C.
    PRI me R 2 (comparative). The catalyst is prepared according to Example A23, but instead of 0, D5 g of potassium hydroxide, 9 g of hydroxide is used. Calcium and get a catalyst of composition: V P Sits Kj. Using the catalyst obtained, isobutyl aldehyde is oxidized under conditions analogous to Example A1. The results are shown in Table C. Since the activity of the catalyst was low, it was necessary to raise the reaction temperature, but the overall yield was low. An X-ray diffraction study of this catalyst showed that the potassium salt of the heteropoly acid prevailed in the catalyst.
    Examples 3-4 (comparative Dried products (the catalysts listed in Table C1 are prepared according to Example 2 comparative and using these catalysts under the conditions of Example A1), continuous reactions are carried out. The results are shown in Table C.
    It a b l and n a A1.
    .2
    , 2
    , Tlo,
    All, 0, Pbo
    A12
    , P, re
    A13
    . A14
    A15.
    , A16
    Mo o fP4Bo, 2 A17
    M fO lff O.
    nineteen
    A23
    about "0 | P4% hl1
    A24
    ,,
    A25
    o 0 ff V4
    A26
    .i
    1055329
    20 i A b l and c a A2
    T a b e c i a A3
    60 320
    79.5
    100
    60.0
    19.5
    ..
    Q PI CU (, p
    ,.five
    .Ta blitsa A6.
    . Table A7.
    T a b e and c a AS
    27
    VI
    ,,
    82
    3
    AW
    AT 4
    %
    AT 5
    w «iC« «« (u

    AT 7
    AT 8
    28 Table A9
    1055329
    Tablcz Bt
    BI7
    % 4 / V% n
    81v
    . "
    B19
    IN 20
    .f
    Herodo hashm table. Bt
    Table B2.
    VZO Mo, oV, P ,, Ko, i 500
    315 B3J, CUo ,, Aeo, Ko., 3000
    340
    Selectivity per methacrylene "methacrylate acid
    18.2 "4.9
    83.1
    18,563,8 82,3
    Table qi B6
    35
    105532936
    table c-1 (sravpitevn)
    Table D.
    权利要求:
    Claims (2)
    [1]
    1. METHOD FOR PRODUCING METAK-, ROLEIN AND METACRYLIC ACID by oxidation of isobutyl aldehyde in the gas phase with molecular oxygen or an oxygen-containing gas in the presence of water droplets < steam and catalysis - τόρδ containing molybdenum, vanadium, phosphorus and oxygen at 200-370¾, characterized in that, in order to increase the yield of the target product, a heteropoly acid or a mixture of heteropoly · acid 'with its salt, expressed as the following empirical formula
    WVt Х а 0 £ or Μο · ά < ν ^ P C1 X 1 е where Μο, ν, Ρ, Ο are molybdenum, vanadium, phosphorus and oxygen, respectively;
    X’ is one or two elements selected from the group consisting of copper, tin, thorium, aluminum, germanium, nickel, same. Lezo, cobalt, zinc, titanium, lead, rhenium, zirconium, chromium, cerium, bismuth and arsenic;
    U - potassium, rubidium, cesium, thallium; “C = a g ” 10;
    V = B t = 0.5-3;
    C = cj = 0.5-3;
    d = 0.01-1.0;
    d "= 0.01-1.8; β = 0.1-0.5;
    f, f {are determined depending on the valency and atomic ratio of other elements.
    [2]
    2. A method according to claim 1, characterized in that as catalyst is used catalyst was ka isleduyuschey formula · '' But v bi si s2 p x P u di «Moq / 'b p s" ChtsHe, ¥ In Λ, wherein Mo, V, P, Cu, 0 - molybdenum, vanadium ,;
    phosphorus, copper and sour rocks, respectively;
    X - tin, thorium, aluminum, germanium, nickel, iron,. cobalt, zinc ',, ti-, tan, lead, rhenium zirconium, chromium, 1 cerium, bismuth, arsenic;
    Y - potassium, rubidium, cesium, thallium. O r = a 3 = 10;
    • bg = oz = 0.5-3;
    . g 2 = c 3 = 0.5-3;
    = 0.01 —G 1ё] = = 0.01-1.0 ~ G = 0.1-0.5;
    £ 2 and f3 - are determined depending on the valency and atomic ratio
    SU <w 1055329 wearing other items. Priority on points;
    01/23/79 by π.1
    01/26/79 according to claim 2.
    >
    ι 1055329 2
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    JP3146486B2|2001-03-19|Method for producing catalyst for producing methacrylic acid
    同族专利:
    公开号 | 公开日
    SE8000535L|1980-07-24|
    GB2045635A|1980-11-05|
    IT1129709B|1986-06-11|
    ES488611A0|1980-12-16|
    RO80120A|1983-02-15|
    DE3001911A1|1980-07-31|
    CA1125785A|1982-06-15|
    GB2045635B|1983-02-23|
    YU41495B|1987-08-31|
    YU310979A|1982-08-31|
    NL8000441A|1980-07-25|
    FR2447364A1|1980-08-22|
    IT8019363D0|1980-01-22|
    RO80120B|1983-02-28|
    ES8101533A1|1980-12-16|
    FR2447364B1|1984-05-11|
    SE437150B|1985-02-11|
    CS226406B2|1984-03-19|
    US4320227A|1982-03-16|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP558479A|JPS55100324A|1979-01-23|1979-01-23|Preparation of methacrolein and methacrylic acid|
    JP719279A|JPS55100325A|1979-01-26|1979-01-26|Preparation of methacrolein and methacrylic acid|
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