• 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:
    In the production of a Mo-Bi-Na composite oxide catalyst by the process comprising incorporating compounds as respective element sources into a composite and subjecting the composite to heat treatment, a bismuth subcarbonate in which at least a part of required Na has been solid-dissolved is used as a Bi source compound. The activity of the catalyst is significantly improved by introducing Bi and Na in the form of the specified water insoluble compound into the catalyst.
    公开号:SU1665870A3
    申请号:SU874202265
    申请日:1987-03-23
    公开日:1991-07-23
    发明作者:Сарумару Кохеи；Ямамото Ецудзи；Саито Теруо
    申请人:Мицубиси Петрокемикал Компани Лимитед (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to methods for the preparation of catalysts for the oxidation of olefins, in particular propylene.
    The aim of the invention is to obtain a catalyst with increased activity due to the use of certain bismuth compounds.
    Example 1. In 400 ml of pure water, 94.1 g of ammonium paramolybdic acid is dissolved under heating, then 7.18 g of iron (3) nitrate, 25.8 g of cobalt nitrate and 35.7 g of nickel nitrate are dissolved in 60 ml pure water when heated. Both of these solutions are slowly mixed with sufficient stirring.
    To the mixed solution is added a solution in which 0.85 g of borax and 0.36 g of potassium nitrate are dissolved in 40 ml of pure water under heating conditions, and then the mixture is well mixed. 57.8 g of basic carbonate are added to the mixture. bismuth, in which 0.57 g of sodium is dissolved in solid solution, and 64 g of silicon dioxide, and all this is mixed with stirring. After thermally drying the suspension, it is subjected to heat treatment at 300 ° C for one hour in an air atmosphere. The solid mass is formed into tablets with a diameter of 5 mm and a height of 4 mm, using a small molding machine, and then they are burned in muO
    about ate
    00
    Vi o

    s
    stove at 500 ° C for 4 hours to obtain a catalyst.
    The ratio of the metal ingredients in the catalyst, calculated from the loaded raw materials, is shown on the example of a complex mixture, as follows; Mo: BI: Co: NI: Fe: Na: B: K: S): 0 412: 5: 2: 3: 0.4: 0.39: 0.2: 0.08: 24: 97.6.
    An amount of 20 ml of this catalyst is loaded into a stainless steel reaction tube, equipped with a jacket for the nitrate heating medium and having an inner diameter of 15 mm, and the raw material gas containing 10% propylene, 17% steam and 73% air, is passed through a fub with a contact time of 2.3 s at atmospheric pressure.
    At a reaction temperature of 310 ° C, the following reaction results are obtained,%: Conversion of propylene, 98.7
    The output of acrolein 90,6
    Acrylic outlet
    acids4,5
    Total output95.1
    PRI me R 2 (comparative). In 400 ml of pure water, 94.1 g of ammonium paramolybdate are dissolved under heating. Then, 7.18 g of iron (III) nitrate, 25.8 g of cobalt nitrate, and 38.7 g of nickel nitrate are dissolved in 60 ml of frequent water under heating conditions, by thorough mixing, both solutions are slowly mixed.
    To the mixed solution is added a solution in which 0.85 g of borax, f, 09 g of sodium nitrate and 0.36 g of potassium nitrate are dissolved in 40 ml of pure water with heating and then stirred.
    57.8 g of basic bismuth carbonate, obtained from an aqueous solution of bismuth nitrate and ammonium bicarbonate by the precipitation method, is added to the mixture, and it does not have Na dissolved in a solid solution, and 64 g of silica, and the whole is mixed by mixing. After that, a catalysis top is obtained as in Example 1.
    The ratio of metal components in the catalyst, calculated from the loaded raw materials. Corresponds to Example 1. The oxidation reaction of propylene was carried out under the conditions of Example 1 using 20 ml of catalyst.
    At a reaction temperature of 310 ° C, the following reaction results are obtained,%: Conversion of propylene 95.9
    Acrolein yield 87.1
    Acrylic outlet
    acid5,3
    Total output 92,4
    PrimerZ (comparative). 94.1 g of paramolybdum ammonium is dissolved in 400 ml of pure water when heated, Then 7.18 g of iron (III) nitrate, 25.8 g of cobalt nitrate and 38.7 g of nickel nitrate are dissolved in 60 ml of pure water heating up. Both of these solutions are slowly mixed with sufficient mixing. After this is added by sufficient stirring
    0 A solution in which 12 ml of nitric acid is added to 98 ml of pure water and in which 108 g of bismuth nitrate are dissolved.
    Then 64 g of silica are added to the mixture and mixed with stirring.
    5 A catalyst is obtained as in Example 1 by molding the mixture and firing the molded article in a muffle furnace at 480 ° C for 8 hours.
    The correlation of the metallic ingredients of the catalyst, calculated from the loaded starting materials, is shown by the example of a complex oxide: Mo: Bi: Co: Ni: Fe: Na: B: K: Si: 0 - 12: 5: 2: 3: 0.4 : 0.2: 0.08: 24: 97.6.
    5 Using this catalyst in an amount of 40 ml in the same reactor as in Example 1, the oxidation of propylene is carried out by passing a gas of the starting material consisting of 12% propylene,
    0 10% of steam and 78% of air, through a reactor with a contact time of 4.2 s at atmospheric pressure.
    At a reaction temperature of 290 ° C, the following reaction results are obtained,%:
    5 Propylene conversions97.2
    The output of acrolein88,0
    Acrylic outlet
    acid4.1
    Total output92.1
    0 Example 4. In 400 ml of pure water, 94.1 g of ammonium paramolybdate are dissolved under heating. Then, 18.0 g of iron (3) nitrate and 51, b g of cobalt nitrate are dissolved in 60 ml of pure water under heating conditions. Both
    5, these solutions are mixed slowly by sufficient mixing.
    To the mixed solution is added a solution in which 0.90 g of potassium nitrate
    0 is dissolved in 40 ml of pure water, and then 4.35 g of orthophosphoric acid is added and the mixture is thoroughly mixed. Then, 23.1 g of basic bismuth carbonate, in which Na is dissolved in a solid solution in an amount of 0.72 wt.% And 32 g of silica, are added, and the mixture is mixed by stirring. In a true embodiment, a catalyst having the composition Mo: BI: Co: Fe: P: Na: K: Sl: 0 12: 2: 4: 1: 1: 0.15: 0.2: 12: 97.5 is obtained.
    The catalyst is tested as in example 1, the following results are obtained at a reaction temperature of 310 ° C,%:
    Propylene Conversion98.2
    The output of acrolein 89,7
    Acrylic outlet
    acid4.1
    Total yield 93.8
    Example 5. In 400 ml of pure water, 94.1 g of ammonium paramolybdate is dissolved under heating. Then, 5.8 g of ammonium para-tungstate is added and the mixture is stirred. 7.18 g of iron (III) nitrate, 38.7 g of cobalt nitrate and 25.8 g of nickel nitrate are dissolved in 60 ml of pure water when heated. Both of these solutions are slowly mixed with sufficient stirring. To the mixed solution is added a solution in which 0.85 g of borax and 0.71 g of thallium nitrate are dissolved in 40 ml of pure water with heating, and the mixture is thoroughly mixed. Then, 57.8 g of basic bismuth carbonate, in which Na is dissolved in a solid solution in an amount of 0.45 wt.%, And 32 g of silica, are added, and the mixture is mixed by stirring. In a true embodiment, a catalyst is obtained having the composition: Mo: W: Bi: Co: Ni: Fe: Na: B: TI: SI: 0 12.0: 0.5: 5: 3: 2: 0.4: 0 , 33: 0.2: 0.06: 12: 75.1.
    The catalyst is tested in the oxidation reaction of propylene as in Example 1 and the following results are obtained at a reaction temperature of 310 ° C,%:
    Propylene Conversion98.4
    The output of acrolein 90,1
    Acrylic outlet
    acids4.8
    Total output 94.9
    Example 6. A stainless steel reaction tube having an inner diameter of 15 mm and jacketed for the nitrate heating medium was charged with 60 ml of the catalyst described in Example 1 and the acid-oxidation reaction was carried out by passing a source material gas containing 4.3% - propylene, 10.1% ammonia, 24.2% steam, and 51.4% air through a pipe with a contact time of 2.9 s.
    At a reaction temperature of 330 ° C, the following results were obtained,%:
    Propylene Conversion69,7
    The output of acrolonitrile65,7
    Acryl Nitrile 94.2 Selectivity
    PRI me R 7 (comparative). Using the catalyst described in example 3, the reaction of the ammoxidation of propylene is carried out under conditions similar to example 6. At the reaction temperature of 330 ° C, the following results are obtained,%:
    Propylene conversion 47,7
    The output of acrylonitrile 40,8
    5 Acrylonitrile selectivity 95.7
    Try on 94.1 g of ammonium paramolybdate are dissolved in 400 ml of pure water under heating. Then, 7.18 g of iron (III) nitrate, 25.8 g of cobalt nitrate and 38.7 g of 10 nickel nitrate are dissolved in 60 ml of pure water by heating. Both of these solutions are slowly mixed by mixing sufficiently.
    A solution is added to the mixed solution, in which 0.85 g of borax and 0.36 g of potassium nitrate are dissolved in 40 ml of pure water with heating, and the mixture is thoroughly mixed. Then, 58.1 white bismuth basic carbonate are added to the mixture, at 0 which 0.50% by weight of Na and 0.3% by weight of Ca form a complex, 32 g of silica are added to the mixture and mixed by stirring. After heat drying, the suspension is subjected to heat treatment at 300 ° C for one hour in an air atmosphere. Tablets with a diameter of 5 mm and a height of 4 mm are obtained from a granular solid material, using a small molding machine, and then they are calcined in a muffle furnace at 500 ° C for 4 hours to obtain a catalyst.
    The ratio of the metallic ingredients of the catalyst, calculated from the loaded raw materials, 5 shown in the example of a composite oxide, is the following: Mo: BI; Co: NI: Fe: Na: Ca: B: K: SI: 0 12: 5: 2: 3 : 0.3: 0.35: 0.1: 0.2: 0.08: 12: 73.6.
    An amount of 20 ml of this catalyst is loaded into a stainless steel reaction tube, equipped with a jacket for the heating environment of nitrate and having an inner diameter of 15 mm, and a feedstock gas containing 10% propylene, 17% steam and 73% is passed through the tube 5 air at the same time, the contact time is 2.3 s at atmospheric pressure. At a reaction temperature of 310 ° C., the following reaction results are obtained,%:
    Propylene Conversion 99.1
    0 Output acrolein90,8
    Acrylic acid4,5
    Total output95.3
    PRI me R 9 (comparative). In 400 ml of pure water, 94.1 g of paramolyb-5 ammonium is dissolved with heating. Then, 5.39 g of iron (III) nitrate, 25.8 g of cobalt nitrate and 38.7 g of nickel nitrate are dissolved in 60 ml of pure water when heated. Both of these solutions are mixed slowly by thorough mixing.
    To the mixed solution is added a solution in which 0.85 g of borax and 0.36 g of potassium nitrate are dissolved in 40 ml of pure water when heated, and the mixture is stirred sufficiently. 57.6 g of basic bismuth carbonate, obtained from an aqueous solution of bismuth nitrate and ammonium carbonate by means of a precipitation method and not having sodium dissolved in a solid solution, and 32 g of silicon dioxide, and all this is added to the mixture. After that, get a catalyst similar to that obtained in example 8.
    The ratio of the metal components of the catalyst, calculated from the loaded starting materials, is as follows: Mo; Bi: Co: Ni: Fe: Na: Ca: B: K: Si: 0 12: 5: 2: 3: 0.3: 0, 35: 0.1; 0.2; 0.08: 12; 73, b.
    The propylene oxidation reaction is conducted under the conditions of Example 8 using 20 ml of catalyst.
    At a reaction temperature of 310 ° C., the following results are obtained,%:
    Propylene Conversion95.4
    Acrolein yield 86,9
    Acrylic acid yield5.0
    Total output91.9
    Examples 10-13. Follow the method of example 8 except for the use of catalysts based on basic bismuth carbonate, in which, instead of Ca, X is included.
    Characteristics of the basic carbonate of bismuth are given in table 1.
    These catalysts are tested during the oxidation of propylene. The results obtained are presented in Table 2.
    Example 14. In 400 ml of pure water, 94.1 g of ammonium paramolybdate is dissolved under heating. Then, 5.8 g of ammonium para-tungstate is added, and the mixture is stirred. 18.0 g of iron nitrate (HI) and 51.6 g of cobalt nitrate are dissolved in 60 ml of pure water by heating. Both of these solutions are slowly mixed with sufficient mixing. Then, a solution in which 0.27 g of potassium nitrate is dissolved in 30 ml of pure water under heating conditions is added to the mixed solution, and the mixture is thoroughly mixed. 11.8 g of basic bismuth carbonate, in which Na and Ca form a complex in an amount of 0.5 wt.%: 0.3 wt.%, And 26.9 g of colloidal silicon dioxide with an Si02 content of 20 wt.% And 4.5 g of powder and mix it all up. Get the catalyst having the composition Mo: W: Bi: Co: Fe: Na: Ca: K: Sl: (AI): 0 -12: 0.5: 1: 4: 1: 0.5: 0.1: 0 , 06: 2: (5): 47.7.
    20 ml of catalyst are tested in the oxidation reaction of propylene as in Example 8. The following results are obtained,%: Propylene conversion 98.1
    The output of acrolein89,8
    Acrylic Acid Output 3.0
    Total output92.8
    Example 15 (comparative); In 400 ml of pure water, 94.1 g of paramolybdenum ammonium is dissolved with heating. 5.8 g of ammonium paratungstate is then added, and the mixture is stirred. 18.0 g of iron (III) nitrate and 51.6 g of cobalt nitrate are dissolved in pure water, acidified with nitric acid.
    5 and 21.5 g bismuth nitrate. Both solutions are slowly mixed with sufficient stirring.
    To the mixed solution is added a solution, 27 g of potassium nitrate, dissolved
    0 in 30 ml of pure water, with sufficient mixing. Then, 26.7 g of colloidal silicon dioxide with a SiOa content of 20 wt.% And 4.5 g of powder and AiaOs are added with stirring. A catalyst having the composition Mo: W: BI: Co: Fe: K: SI: (AI ): 0 12: 0.5: 1: 4: 1: 0.06: 2: 5: 47.7.
    This catalyst differs from the catalyst of Example 8 in the type of Bi source compound.
    0 20 ml of the catalyst is subjected to an oxidation test as in Example 8. The following results are obtained,%:
    Propylene Conversion 94.2
    Acrolein 86,6
    5 Output acrylic acid2,9
    Total output89.5
    EXAMPLE 16 In 400 ml of pure water, 94.1 g of ammonium paramolybdate are dissolved under heating. Then, 7.18 g of iron (III) nitrate, 25.8 g of cobalt nitrate and 38.7 g of nickel nitrate are dissolved in 60 ml of pure water when heated. Both of these solutions are slowly mixed by mixing sufficiently.
    five
    To the mixed solution is added a solution in which 0.85 g of borax and 0.36 g of potassium nitrate are dissolved in 60 ml of pure water under heating conditions, and the mixture is well stirred. Then, 58.1 g of basic bismuth carbonate, to which 0.80 wt.% Md is added, is added to the mixture and mixed. 32 g of silica are added. After heat drying the suspension is subjected to
    5 heat treated at 300 ° C for one hour in an atmosphere of air. Tablets with a diameter of 5 mm and a height of 4 mm are molded from the obtained powder of solid material using a small molding machine and then they are burned with
    500 ° C for 4 hours to obtain a catalyst.
    The ratio of the metallic ingredients of the catalyst, calculated from the loaded raw materials, shown in the example of the composite oxide, is the following: Mo: BI: Co: N: Fe: Na: Mg: B: K: Si: 0 12: 5: 2: 3: 0, 4: 0.1: 0.4: 0.2: 0.08: 24: 97.9,
    An amount of 20 ml of this catalyst is loaded into a stainless steel reaction tube, jacketed for the nitrate heating medium and having an inner diameter of 15 mm, and the raw material gas containing 10% propylene, 14% steam and 73% air is passed through the tube with a duration of contact 2.3 with at atmospheric pressure.
    At a reaction temperature of 310 ° C., the following results are obtained,%:
    Propylene Conversion98.1
    The output of acrolein90,0
    Acrylic acid3,8
    Total output93.8
    Examples 17-20. The method of example 16 is repeated with the exception of the use of a catalyst from basic carbonate of bismuth, which includes, instead of MD X. The characteristics of the basic carbonate of bismuth are given in Table 3.
    The resulting catalysts are tested in the oxidation reaction of propylene. Res 1t are presented in Table. four.
    Example21. 94.1 g of ammonium paramolybdate are dissolved in 400 ml of pure water under heating. Then, 5.8 g of ammonium paratungstate is added and the mixture is stirred. 5.39 g of iron (III) nitrate, 38.7 g of cobalt nitrate and 25.8 g of nickel nitrate are dissolved in 60 ml of pure water under heating. These two solutions are slowly mixed with sufficient stirring. A solution is then added to the mixed solution, in which 0.85 g of borax and 0.71 g of thallium nitrate are dissolved in 40 ml of pure water using heat, and the mixture is thoroughly mixed. After that, 58.0 g of basic bismuth carbonate are added to which Ca is added in an amount of 1.2% by weight and 32 g of silicon dioxide, and the mixture is stirred. Get the catalyst having the composition Mo: W: Bi: Co: Ni: Fe: Na: Ca: B: Ti: Si: 0 12: 0.5: 5: 3: 2: 0.3: 0.1: 0, 4: 0.2: 0.06: 12: 75.23.
    The catalyst is tested in the oxidation reaction of propylene as in Example 16. The following results are obtained at a reaction temperature of 310 ° C,%:
    Propylene Conversion98.1
    The output of acrolein91,0
    Acrylic acid4,1
    Total output95.1
    PRI me R 22 (comparative). In 400 ml of pure water, 94.1 g of paramolyb-5 ammonium is dissolved under heating. Then, 7.18 g of iron (III) nitrate, 25.8 g of cobalt nitrate and 38.7 g of nickel nitrate are dissolved in 60 ml of pure water when heated. The two solutions are mixed slowly by mixing.
    To the mixed solution (suspension) is added a solution in which 0.85 g of borax and 0.38 g of potassium nitrate are dissolved in 40 ml of pure water while heating, and the mixture is thoroughly mixed. Then, 57.6 g of basic bismuth carbonate, obtained by precipitation from bismuth nitrate and ammonium bicarbonate, and 64 g of silica are added to the mixture and mixed. 0 The catalyst has a composition similar to the catalyst of example 16.
    20 ml of the catalyst are tested in the oxidation reaction of propylene as in Example 16, the following results are obtained at a reaction temperature of 310 ° C,%:
    Propylene Conversion95.3
    The output of acrolein87,0
    Acrylic acid4.8
    Total output91.8
    0
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    The method of preparing an oxide catalyst for the oxidation of propylene 5 based on molybdenum and bismuth, corresponding to the empirical formula
    MoaBlbCocNIdFeeNafXgYhZiSljOk, where X is an element selected from the group consisting of magnesium, calcium, zinc, cerium 0 or samarium;
    Y is potassium or thallium; Z is phosphorus, boron and / or tungsten; B 1-5; 5 C 2-4;
    d 0-3, and with + d 4-5; e-0.3-1.0; f 0.035-0.5; d 0-0,6;
    0 h 0.06-0.2: 1 0.2-1.0; J 2-24;
    k is the number of oxygen atoms satisfying the valence of the incoming elements, 5 by mixing the compounds of these active components in an aqueous medium with subsequent heat treatment, characterized in that, in order to obtain a catalyst with increased activity, bismuth compounds are used as bismuth compounds
    bismuth basic carbonate with dissolved 0.45-1.0 wt.% sodium in solid solution, or a complex compound of basic bismuth carbonate with 0.4-0.6 wt.% sodium and 0.1-0.3 wt.% of element X, or a compound of basic bismuth carbonate with 0.8-2.0 wt.% of element X.
    Priority signs: 24.03.86 - use basic bismuth carbonate with sodium dissolved in it in solid solution.
    08/23/86 - complex compound of basic bismuth carbonate with sodium and element X and compound of basic bismuth carbonate with element X.
    Table
    table 2
    Table 3
    Table 4
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    法律状态:
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