• 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 novel catalyst composition is disclosed which comprises a catalytically-active metal oxide component containing the oxides of cobalt, molybdenum, bismuth, and iron corresponding to the empirical formula:
    公开号:SU791205A3
    申请号:SU772521791
    申请日:1977-09-14
    公开日:1980-12-23
    发明作者:Дома Жан-Клод；Деррьен Жан-Ив；Ван Ден Буш Франсис
    申请人:Рон-Пуленк Эндюстри (Фирма)；
    IPC主号:
    专利说明:

    calcination at 450-500С, followed by cooling to room temperature and second calcination at 350-500С.
    Depending on the calcination conditions, the catalysts based on oxides of molybdenum, cobalt, iron, and bismuth contain a new crystalline phase, telling catalysts properties that are significantly superior to those of known catalysts with the same general formula. The higher the double calcined temperature rises, the more the specific surface area decreases. Phase B i2 MO. appears at double calcination temperatures of 450 and 520 ° C, approximately. Thus, the ideal double calcination temperature will be one that allows you to simultaneously obtain phase B iri. maximum possible specific surface. Thus, the most effective temperature is 475-485 ° C.
    If the pre-calcination is carried out at 4bO ° C, in the case of preparing a catalyst based on the powder obtained after the preliminary calcination, it takes the form of small grains when applied to the balls, which does not occur at the pre-calcination temperature less than 460 ° C.
    Example 1. Obtaining a catalyst with the active phase according to the SoHo formula (y is the valence) deposited on enamelled alumina balls.
    The precursor of the active phase is obtained by the reaction between an ammonium heptamolybdate solution and a solution of Co, Bi and Fe nitrate. Each solution is prepared separately as follows.
    In 450 cm of water is dissolved at room temperature 1938, 15 g of hydrated cobalt nitrate according to the formula: Co (NO,) 2 eHjO; The pH of the solution is 1.8.
    In 450 cm of water, 268.87 g of hydrated iron nitrate according to the formula Fe (NO03) 2 is dissolved at room temperature. The pH of the solution is 0.7.
    In 240 cm of water, 323.3 g of hydrated bismuth nitrate according to the formula B i (NO) 2-5H20 and 32.5 cm of concentrated nitric acid are dissolved at room temperature to better dissolve bismuth nitrate; The pH of the solution is 0.6.
    A mixture of these three solutions leads to a solution of L nitrate of bismuth, cobalt and iron.
    A solution of heptamolybdag is obtained; a solution at room temperature of 1411.2 g of ammonium heptamolybdate in
    6.75 liters of distilled water; The pH of the solution is 5.6 (solution in).
    To obtain the precursor of the active phase to the solution B of heptamolybdate slowly, at 10 ml per minute,. a solution of nitrate A is added. There must be strong mixing during this addition.
    At the end of stirring, a salmon-colored suspension is obtained, which is stirred for 1/2 hour at room temperature. During this mixing, the pH stabilizes to 1.1.
    Heated with stirring to 80 ° C to evaporate the water; according to Prostest5 VII 2 h, a non-flowing mass is obtained; mixing and heating stop. Thus, the resulting mass, decomposed with a thickness of 2 cm, is dried in air with during
    0 6h Get a solid - the precursor of the active phase.
    Before calcination, the solid is cut into pieces 1 cm in size and placed in a 5-lane kiln with a 2–3 cm thickness. Pre-calcination is carried out at 450 s for b. The temperature rise of the furnace should not be too fast due to the exothermic decomposition reaction around
    230 ° C. Temperature rise rate -
    azo / h
    The solid obtained after calcining 5 is crushed to obtain a smaller particle size composition. Then a water-glucose solution, a solution of 10 g of glucose in 100 ml of water at room temperature is prepared. Then 95 g of a crushed solid is added to this solution, and then heated to 70 s with vigorous stirring. within 30 min. In the box, Contents.
    burning 250 g of enameled rough balls of gshyumini oxide with
    with a diameter of 4., 8 mm and heated to 70 ° C, the previously obtained solution is poured. The box was rotated at 80 ° C until all the water evaporated. In this way.
    the coated beads are dried when
    140 ° C for 2 hours. Then they are placed in a kiln on a gasket 2-3 cm, and then calcined at 480 s for b under a closed
    5 atmosphere. The first calcination leads to the elimination of glucose. This is followed by slow cooling and second calcination at 480 ° C. Thus, a final catalyst is obtained, which contains about 2.4 wt.% Of the active phase.
    The X-ray spectrum of phase B i, 0, obtained on the final catalyst is given below.
    where OS is very strong; C - strong; with weak {; OOS - very very weak.
    Example 2. Preparation of the catalyst in the mass with the formula 8 Oy (y is the valence).
    The predecessors are prepared according to example 1.
    The precursor is directly subjected to the first calcination at, followed by slow cooling and then the second calcination at 48 ° C. Then molding is carried out.
    Example 3-8. Examples 3-8 show the improved properties of the proposed catalysts and the effect of various fits.
    Various catalysts are tested for the preparation of acrolein, starting from propylene, air, water or hydrogen in a reactor 50 cm high and 2.1 cm in diameter, containing 100 cm of catalyst formed in the case when the active phase is applied to the substrate (examples 3-8) with rough enameled . alumina balls with an average diameter of 4.8 mm covered with 23.1 wt.% of the active phase (O ,,) with respect to the aggregate active phase - base. The specific surface is 8.5 m / g, and the pore volume is 0.6 CMVr; example 8 illustrates the case of a massive catalyst H h Oy. obtained in example 2 in the form of tablets e 3 mm high and 3 mm in diameter.
    The gases leaving the reactor are a mixture of nitrogen, oxygen, water, propene, acrolein, acrylic acid, acetic acid and carbon monoxide (CO and C Od).
    XQ represents the degree of transformation, i.e. the ratio
    The number of moles of reacted propylene
    .: X 100
    The number of moles of propylene at the entrance
    Sy represents product selectivity X, i.e. the ratio
    The number of formed moles of product X
     100
    The number of moles of propene transformed
    5 p represents the yield of product X. It is equal to the product XQ "
    The results of experiments 3-8 are given
    in table.1.
    The catalyst in example 3 is prepared
    o by a known method, i.e. with calcination for 6 h at.
    The proposed catalysts in example 4 and 5 previously. calcined at 450 ° C for 6 hours, the first
    5 calcination at 450 ° C and the second at, each for 6 hours; the catalyst according to example b and 7 is also preliminarily calcined at 450 for 6 hours, the first and second calcinations are carried out at 480 ° C for 6 hours.
    Massive catalyst according to example 8 is subjected to double calcination at 480C for b h
    Improved yields of acrolein are obtained, since they range from 68.3% (Example 3) to 80%.
    The degree of conversion increases in the same way as the selectivity for acrolein.
    0 Comparison of example 3 and example 5 shows that to obtain a uniform degree of conversion (about 91%), using a known catalyst, much more
    5 high maximum temperature (40 ° C large). This well underlines the high activity of the proposed catalysts.
    in examples b and 7, better results are achieved due to the fact that double calcination is carried out under the most favorable conditions
    getting the phase better texture.
    The results of example 5 show that a massive catalyst in the form of tablets has a very good activity, but less good yield
    0 and selectivity for acrolein. This is mainly due to the strong combustion (17.5%), which explains the large temperature difference between the hot spot and
    f baths. Such a temperature difference makes it difficult to control the reaction. In order to smooth out the effects of strong combustion, it is useful to use a catalyst supported on a substrate.
    Examples 9-19. Acrolein, starting from propylene, is prepared using the proposed catalysts in examples 9, 10, 12, 13, 15, 16 and 18, and a known catalyst in
    5 examples 11, 14 and 19 proposed
    7 791205о
    catalyst - for example b and 7, of the results from the table. 2 confirms - in example 3). Low active active known
    Experiments are performed in a pro-catalyst reactor with respect to
    4 m tall and of the proposed type, which are insufficient
    25 mm meter, containing 2 liters catalyzed to overdraft. .- to sow under industrial conditions. 2 shows the propene preparations of 192 and 215 g / h / l of catalysts, of the mash.
    权利要求:
    Claims (2)
    [1]
    1. US patent 3380931, cl. 252-432, pub. 1968.
    [2]
    2. The patent of France No. 1604942, d cl. C 07 C, publ. 1972 (about. Totype).
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    同族专利:
    公开号 | 公开日
    NL7710033A|1978-03-16|
    ES462361A1|1978-06-01|
    FR2364061A1|1978-04-07|
    BE858643A|1978-03-13|
    SE436618B|1985-01-14|
    BR7706111A|1978-06-27|
    SE7710271L|1978-03-15|
    DE2741132C3|1981-06-11|
    JPS5628180B2|1981-06-30|
    DE2741132A1|1978-07-27|
    IT1116109B|1986-02-10|
    MX159804A|1989-08-31|
    DE2741132B2|1980-04-03|
    NL188932B|1992-06-16|
    DE2759531C2|1990-10-18|
    US4166808A|1979-09-04|
    JPS5348095A|1978-05-01|
    FR2364061B1|1981-07-31|
    CA1090771A|1980-12-02|
    CH624587A5|1981-08-14|
    GB1548328A|1979-07-11|
    NL188932C|1992-11-16|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    FR7627531A|FR2364061B1|1976-09-14|1976-09-14|
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