• 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 process for the production of antimony-containing metal oxide catalysts, comprising preparing a slurry containing as essential components an antimony component, a polyvalent metal compound, and silica sol, heating and drying the slurry to form a solid product, and then calcining the solid product, wherein the antimony component is a mixture of (A) at least one of antimonic acid, polyantimonic acid and the salts thereof and (B) antimony trioxide, and is prepared by mixing (A) and (B) in such a manner that the antimony provided by the (B) constitutes from 0.1 to 70 atomic % of the total amount of antimony and further in an aqueous slurry state. These antimony-containing metal oxide catalysts have superior activity and physical properties, and further reproducibility in the preparation thereof. Thus they are useful for production of aldehydes and acids through oxidation, nitriles through ammoxidation, and dienes, unsaturated aldehydes and unsaturated acids through oxidative dehydrogenation.
    公开号:SU1428180A3
    申请号:SU843796134
    申请日:1984-09-27
    公开日:1988-09-30
    发明作者:Сасаки Ютака；Утсуми Хироси；Мори Кунио；Ямамото Хироси；Накамура Есими；Мория Киеси；Мории Акимитеу；Нода Микио；Кунитани Мики
    申请人:Нитто Кемикал Индастри Ко,Лтд (Фирма)；
    IPC主号:
    专利说明:


    cm
    The invention relates to methods for preparing catalysts for the oxidative ammonolysis of propylene, in particular antimony-containing catalysts.
    The purpose of the invention is to obtain a catalyst with an increased selectivity due to the use of an antimony-containing component in the preparation of sludge of certain compounds of antimony.
    The invention is illustrated by the following examples.
    Example 1. A catalyst that has an empirical formula of Ray Sbie WiiTOfts-.g CsiOtlso. prepared as follows.
    54.9 g of powdered metal antimony are added in small portions in 230 ml of nitric acid heated to (specific gravity 1.38). After all the antimony has been added and the release of brown gas has ended, the mixture is kept at room temperature for 16 hours. The excess nitric acid is removed and the precipitate is washed three times in 100 ml of water,
    11.2 g of powdered electrolytic iron is added in small parts and completely dissolved in a mixture of 81 ml of nitric acid (specific gravity 1.38) and 100 ml of water at
    1.3 g of para-tungsten-acid ammonium is dissolved in 50 ml of water.
    180 g of silica sol (SiOa 20% by mass) is weighed.
    The prepared ingredients are thoroughly mixed and the pH of the mixture is adjusted to 2 by adding aqueous ammonia solution (28% by weight) in small quantities, with stirring. The resulting mixture was kept at 100 ° C for 5 h.
    In this case, most of the antimony turned into a pyvalent form and the resulting mixture contains antimony acid and iron antimonate.
    7.3 g of antimony trioxide was added to this sludge and the mixture was kept at room temperature for 30 minutes while stirring. Part of the sludge is removed and subjected to X-ray diffraction analysis, which indicates that crystalline antimony trioxide has disappeared.
    The mixture is dried and calcined at 200 ° C for 2 hours and then
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    400 ° C for 2 hours. Water is then added and the mixture is stirred and shaped into cylinders 2 mm in length and 2 mm in diameter. These molded articles are dried for 16 hours and then calcined at 800 seconds for 3 hours.
    Example 2 The catalyst of the empirical formula Sbas-WO, ES-Of.e CsiOjj is prepared in Example 1, except that the amount of antimony trioxide added to the sludge is reduced to 1/5 of the amount of Example 1.
    PRI me R 3. The catalyst of the empirical formula Fe, о Sbjs о, к Ob5,) is prepared as in example 1, except that the amount of antimony trioxide added to the sludge is reduced to 1/2 of the amount of example 2.
    Comparative example 1,
    The catalyst of empirical formula, as in Example 1, is prepared as follows.
    61 g of powdered metal antimony are added in small portions to 230 ml of nitric acid, heated to 80 ° C (specific gravity 1.38). The mixture was kept at room temperature for 16 hours. Then, excess nitric acid was removed and the resulting precipitate was washed three times with 100 ml of water.
    11.2 powdered electrolytic iron was added in small portions and the specific gravity of 1.38 and 100 ml of water at 80 was completely dissolved in a mixture of 81 ml of nitric acid.
    1.3 para-tungsten-acid ammonium is dissolved in 50 ml of water.
    180 g of silica dioxide ash is weighed in at 20% by weight.
    The prepared ingredients are thoroughly mixed and the pH of the mixture is adjusted to 2 by adding 28% by weight of an aqueous solution of ammonia in small amounts with stirring. The mixture was incubated for 5 hours.
    The reaction mixture is dried and calcined for 2 hours and then at 400 ° C for 2 hours. Water is then added and the resulting mixture is stirred and shaped into cylinders 2 mm long and 2 mm in diameter. Molded products are dried at 130 ° C for. 16 hours and then calcined for 3 hours.
    31428180
    Comparative Example 2, an empirical catalyst as in Example 1, is prepared as follows.
    54.9 g of powdered metallic antimony are added in small portions to 230 ml of nitric acid heated to (specific gravity 1.38). The mixture is kept at room temperature for 16 hours. Then, excess nitric acid is removed and the resulting precipitate is washed three times with 100 ml of water.
    11.2 powdered electrolytic iron is added small-. 15 parts and completely dissolved in a mixture of 81 ml of nitric acid (specific gravity 1.38) and 100 ml of water at 80 ° C. 1.3 g of para-tungsten-acid ammonium are dissolved in 50 ml of water; 20
    180 g of silica dioxide ash (SiO 20% by weight) are weighed.
    The prepared ingredients are thoroughly mixed and the pH of the mixture is adjusted to 2 by adding aqueous 25 ammonia solution (28% by weight) in small amounts with stirring. The resulting mixture was incubated for 5 hours.
    The reaction mixture is dried and 0
    calcined for 2 hours and then for 2 hours. Then, 7.3 g of antimony trioxide and water are added, and the mixture is stirred and shaped into cylinders 2 mm long and 2 mm in diameter. The molded articles are dried at TZO C for 16 hours and then calcined at 2 hours.
    Example 4, The empirical catalyst for the formula SbjQ (3102) 50 is prepared as follows.
    1550 g of sludge of antimony acid (a mixture of antimony acid and polysuronic acid (SbjOj - 10% by weight) and 30.1 g of powdered tin dioxide are mixed and kept at 100 ° C under reflux conditions for 2 hours. There 35 g of antimony trioxide are added and the mixture is kept at the same temperature of CBbEue for 20 minutes.
    X-ray diffraction analysis of the sludge showed that crystalline antimony trioxide disappeared.
    180 g of silica sol (SiOs 20% by weight) are added to this sludge and the mixture is evaporated dry with continuous stirring. Polug {ech
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    The solid mass thus obtained is calcined for 2 hours and then for 2 hours. Then water is added and the mixture is stirred and shaped into cylinders 2 mm long and 2 mm in diameter. These molded articles are dried at 130 ° C. for 16 hours and then calcined at 2 hours.
    Comparative example 3. A catalyst having the same empirical formula as described in example 4 is prepared in the same manner as in example 4, but the entire component of antimony is added as an antimony acid sludge, and antimony trioxide is not used.
    EXAMPLE 5 The catalyst of the empirical formula, Vw Sbjo Wa, i QUS (210g), is prepared as follows.
    1130 g of sludge containing a mixture of antimony acid and polyisurmy acid (SbjOy, 10% by weight) are weighed.
    100 g of uranyl nitric acid are dissolved in 100 g of water.
    0.52 g of para-tungsten-acid ammonium is dissolved in 30 ml of water.
    1.3 g of powdered metallic tellurium are dissolved in 60 g of nitric acid (specific gravity 1.38).
    Weigh 361 g of ash dioxide
    silicon (SiOg. 20% by weight).
    Cooked. Ingredients are mixed and the mixture is kept at for 2 hours.
    To the sludge prepared in this way, 43.7 g of antimony trioxide are added and the mixture is stirred for 30 minutes.
    The mixture was evaporated to dryness and calcined at 200 ° C for 2 hours and then at 400 ° C for 2 hours. Then 5 water was added and the mixture was stirred and shaped into cylinders 2 mm long and 2 mm in diameter. Such molded articles are dried at 130 ° C for 16 hours and then calcined for 5 hours.
    Comparative Example 4. A catalyst of empirical formula as in Example 5 is prepared in the same manner as in Example 5, except that the entire antimony component is added as antimony acid slurry, and antimony trioxide is NOT USED.
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    Example The empirical catalyst is Gead SbeyWo jTe, o Obt, & , (SiOg) 3o is prepared as follows.
    0.98 kg of powdered metal antimony is weighed, and gradually it is added to 7.2 g of nitrogen nitride (specific gravity 1.38) heated to 80 ° C. After complete oxidation of antimony, the residue of nitric acid is removed. Obtained in this way using
    nitric acid. antimony oxide
    It is sold five times .. 2 l of water and then.
    placed in a ball mill and grind ™ for 3 hours.
    Weigh About 358-kg Powder ™ of the Electrolytic Iron Gland, .3l of Nitric Acid (specific gravity 1.38)
    mixed with 4 liters of water and the resulting
    the mixture is heated to:.
    41.8 g of para-tungsten-acid ammonium solution in 2 l of water,
    147 g of telluric acid is dissolved in 1 liter of water.
    5.76 kg silica fume (SO2, 20% by weight) is weighed.
    The prepared ingredients are mixed and the pH of the mixture is adjusted to 2 by the gradual addition of an aqueous solution of ammonia (15% by weight) with good cross-feed. The sludge prepared in this way is heated to within 4 hours. As a result, most of the antimony falls to the pyvalent metal and the resulting mixture contains antimony acid and iron antimonite. The slurry is then cooled and 1168 g of antimony trioxide is added to it, and the mixture is stirred for 30 minutes.
    with
    The mixture is then dried by spraying in the usual way using spray 1G (its device). The fine spherical particles thus obtained are calcined at 200 ° C for 4 hours and at 400 ° C for 4 hours and additionally at 800 s for 8 hours in a stream air in a calcining furnace fluidized bed.
    Comparative Example 5. The empirical catalyst as described in Example 6 is prepared in the same manner as in Example 6, except that the entire antimony component is added simultaneously as metallic antimony and the final calcination is carried out. at for 8h.
    Example 7 The empirical catalyst of Cuj Te (8102) 55 is prepared as described in Example 6,
    but copper-nitrate is used, paramolybdenum-acid ammonium, powdered metallic tellurium dissolved in nitric acid, 5 at. % of the total antimony is
    antimony, introduced with antimony trioxide, the final calcination is carried out at 4 hours.
    PRI me R 8. Catalyst
    the empirical formula of Re Cujj-Sbji3 Mool Woli Zno, Bc ,, r PO, I Rel, t (, prepared as described in Example 6, but using copper nitrate, paramolybdenum-acid ammonium, para-tungsten-acid ammonium, zinc nitrate, orthoboric acid, orthophosphoric acid, telluric acid.
    . 10 at. % of the total antimony is szgrma,
    introduced using antimony trioxide, and the final calcination is carried out at 4 hours.
    Comparative Example 6. The empirical catalyst as in Example 8 is prepared in the same manner as in Example 6, except that the entire antimony component is added simultaneously as metallic antimony and the final calcination is carried out at 775 ° C. 4h
    The bulk density of the catalyst is 1.16 g / ml, whereas the catalyst of the example is 81.05 g / ml. In this way,
    the bulk density of the catalyst of this comparative example is about 10% Bbmie than that of the catalyst in Example 8. This characteristic of the fluidized bed of the crystallizer is unfavorable when using a foam layer in the reaction.
    Example 9. The empirical catalyst Feio Vj SbzfMoo, 0:} (j5- (810g) 55) is prepared in the same manner as in Example 6, but using ammonium paramolybdenum acid and telluric acid.
    15 at. % of the total antimony is antimony contributed by
    using antimony trichloride, and the final calcination is carried out for 5 hours. Example 10. Catalyst of the empirical formula Fe; o 5po, g Sbj
    R
    Tio.s Hoo,: f Vo, 4 Fe, 5. Oea.g (10g) is prepared in the same way as in Example 6, except for using nickel nitrate, powdered metal tin, oxidized with bicarbonate acid, powdered titanium dioxide, paramolybdenum-acid ammonium, metavanadic acid ammonium and
    Nb uses niobium oxalate, and bismuth nitrate is used as a starting material for Bi.
    The resulting slurry is found at 5 hours. After that, the slurry is cooled to room temperature (18 ° C), antimony trioxide is added to it, so that 10 atm. % total number15
    20
    powdered metallic tellurium, oxide- honest honest antimony was antimony added using nitric acid
    10 at. % of the total antimony is antimony added with antimony trioxide, with the final calcination being carried out for 4 hours.
    Comparative Example 7. A catalyst having the same empirical formula as in Example 10 is prepared in the same manner as described in Example 6, except that the entire antimony component is added simultaneously as metallic antimony.
    Example 11. Catalyst of empirical formula Ray Sgsu Sbjj Mog
     088.6 (Og) bo is obtained as in Example 6, with the exception that chromium nitrate is used as the starting material for chromium and ammonium paramolybdate is used as the starting material for molybdenum.
    The resulting sludge is cooled to after heat treatment and then antimony trioxide is added so that 5 at. % of the total amount of antimony was antimony, added with antimony trioxide. After that, the resulting mixture is stirred for 3 hours
    The mixture is spray dried.
    25
    thirty
    35
    40
    with antimony trioxide. After that, the resulting mixture is stirred for 1 h.
    The mixture is spray dried, and then calcined at 200 ° C for -4 h, at 400 ° C for 4 h, and additionally at 700 ° C for 5 h.
    Comparative Example 9. The catalyst of the empirical formula, as in Example 12, is prepared as in Example 12, except that the entire antimony-containing component is added to the slurry from the very beginning and the final calcination is carried out for 5 hours at 710 ° C.
    Example 13. The catalyst of the empirical formula is Gay CU (o Mnqf Ssgv. Mg ,, o Teg, O5 (510g), they are obtained as in Example 6, except that copper nitrate is used as the starting material for Cu the material for the production of Mn is manganese nitrate, the starting material for the production of Mo is ammonium paramolybdate, and the starting material for the production of Mg is magnesium nitrate.
    The psham obtained is cooled to 20 ° C after hot working, and then antimony trioxide is added to it, so that 10. at.% Of the total amount of antimony is antimony added with antimony trioxide. After that, the resulting mixture is stirred for 20 hours
    then calcined at a temperature for 4 hours, with - for. 4 hours and additionally at 600 ° C for 4 hours.
    Comparative Example 8 “The catalyst of the empirical formula, as in Example 11, is prepared as in Example 11 ,. with the exception that all the antimony component is added from the very beginning, and the final calcination is performed for 4 hours.
    Example 12. The catalyst of the empirical formula Sbj (j Moj Nbo B1CTHESO9 (510g) zo is obtained as in Example 6, except that as a starting material for Mo, ammonium paramolybdate is used as a starting material for
    Nb uses niobium oxalate, and bismuth nitrate is used as a starting material for Bi.
    The resulting slurry is found at 5 hours. After that, the slurry is cooled to room temperature (18 ° C), antimony trioxide is added to it, so that 10 atm. % total if
    honest antimony was antimony introduced
    with antimony trioxide. After that, the resulting mixture is stirred for 1 h.
    The mixture is spray dried, and then calcined at 200 ° C for -4 h, at 400 ° C for 4 h, and additionally at 700 ° C for 5 h.
    Comparative Example 9. The catalyst of the empirical formula, as in Example 12, is prepared as in Example 12, except that the entire antimony-containing component is added to the slurry from the very beginning and the final calcination is carried out for 5 hours at 710 ° C.
    Example 13. The catalyst of the empirical formula is Gay CU (o Mnqf Ssgv. Mg ,, o Teg, O5 (510g), they are obtained as in Example 6, except that copper nitrate is used as the starting material for Cu the material for the production of Mn is manganese nitrate, the starting material for the production of Mo is ammonium paramolybdate, and the starting material for the production of Mg is magnesium nitrate.
    The psham obtained is cooled to 20 ° C after hot working, and then antimony trioxide is added to it, so that 10. at.% Of the total amount of antimony is antimony added with antimony trioxide. After that, the resulting mixture is stirred for 20 hours
    The mixture is spray dried, and then calcined at 200 ° C for 4 hours, at 400 ° C for 4 hours and additionally at 740 ° C for 3 hours.
    Comparative Example 10. The catalyst of the empirical formula as in Example 13 is obtained in the same manner as in Example 13, with the exception that all the antimony component is added at the beginning and the final calcination is carried out at 740 seconds for 3 hours.
    Example 14, The catalyst of the empirical formula SbjjMoo, 2Gd, o, (Og) m is obtained as in Example 6, except that ammonium paramolybdate is used as the starting material for the production of Mo, and zirconium oxynitrate is used as the starting material for obtaining 2g ,
    The resulting slurry is heated for 5 hours. The slurry is then cooled until fpexoKHCb antimony is added to it, so that 10 atm. % of the total amount of antimony is antimony from antimony trioxide. After that, the resulting slurry is mixed with IOT for 1 hour.
    i Then the mixture is spray dried and calcined for 4 hours at 400 seconds for 4 hours and additionally at 760 ° C for 4 hours, j Comparative Example 11. The catalyst of the empirical formula, as in trpHMepe 14, is obtained as in Example 14, except that ammonium paramolybdate is used as the starting material for the production of Mo, and aluminium nitrate as the starting material for the production of A1.
    The resulting slurry is heated for 6 hours, and antimony trioxide is added to it, so that 15 atomic percent of the total amount of antimony is
    we are antimony trioxide
    antimony. The resulting mixture is stirred for 2 hours at this temperature,
    The mixture is dried by splitting, and then calcined at 200 ° C for 4 × 5; At 400 ° C - for 4 hours and additionally at 850 ° C for 2 hours,
    Comparative example 12. The catalyst of the same empirical formula as in example 15 is prepared as in example 15, with the exception that all the antimony component is added to the mixture at the very beginning, and the final calcination is carried out at 850 ° C for 2 hours
    Example 16. Catalyst of the empirical formula Fe, o CojCeo, Sbjo Wo, 5
    Theod (SiOg) 6o is obtained as described in Example 6, except that cobalt nitrate is used as the starting material for Co, and
    0 5 o

    b
    Q

    five
    for preparing Ce, ammonium cerium nitrate is used,
    The resulting flame was heated at 110 ° C for 10 hours and trioxide was added to it. antimony, so that 10 atomic percent of the total antimony was antimony, derived from antimony trioxide. The resulting mixture is stirred for 0.1 h at this temperature.
    The mixture is dried by pulverization, and then calcined at a temperature for 4 hours, with - for 4 hours and additionally at 890 ° C - for 0.5 hours.
    Comparative Example 13, an empirical catalyst as in Example 16, is prepared as in Example 16, with the exception that all of the antimony component is added at the beginning and the final calcination is carried out at 0.5 hours.
    The catalyst of Examples 1-16 and Comparative Examples are subjected to an activity test according to the activity test conditions.
    Test condition I is as follows.
    In a V-shaped steel pipe with an inner diameter of 16 mm, 50 ml of catalyst, molded in a cylindrical form, 2 mm in length and 2 mm in diameter, are placed. This pipe is placed in a fluidized bed and heated.
    The gas mixture is introduced into the pipe at a rate of 10 liters per hour (normal temperature and pressure) and the reaction is carried out at atmospheric pressure. The molar ratio of Og (supplied in. Air): propylene is 2.2: 1, W: propylene 1.3: 1,
    The conditions of test II are as follows.
    The catalyst is placed in the catalytic part (inner diameter 2, 3 cm and height 40 cm) of a fluidized bed reactor and a gas mixture having the composition shown below is introduced into it, the reaction is carried out at atmospheric pressure: Og (fed in air): propylene 2 , 2: 1, NH: propylene 1.1: 1,
    The yield of the desired product in the examples and comparative examples is determined as follows:
    II1
    The mass of carbon in the resulting desired product, g
    . Yield 100%.
    The mass of carbon in the initially supplied initial organic compounds, g
    . The test results are presented in the table.
    From the results of the table it can be seen that the catalysts obtained in accordance with the proposed method are superior to those known in terms of production of the required product and catalytic activity.
    权利要求:
    Claims (1)
    [1]
    Invention Formula
    A method for preparing a catalyst for oxidative ammonolysis of antimony-based propylene by preparing a water slurry containing an antimony-containing component,
    28180. 12
    from one of phosphorus, boron, iron, tungsten, tin, uranium, tellurium, copper, molybdenum, zinc, nickel, titanium, vanadium, chromium, niobium, bismuth, manganese, magnesium, zirconium, aluminum, cobalt, cerium or a mixture of them, and a silica sol, holding the sludge at 10-110 ° C for
    Q 0.1–20 h, drying to form a solid product and calcining the obtained solid product at 660–890 ° C for 0.5–8 h, characterized in that, in order to obtain a catalyst with increased selectivity, As the antimony-containing component in the preparation of sludge, a mixture of antimony trioxide and
    antimycic acid with polysurmy KIS
    2Q acid. or iron antimonate, 1 whereby the amount of antimony applied with antimony trioxide is 2.0-50.0 at.% of the total amount of antimony in the sludge.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US30545A|1860-10-30|Eugene m |
    NL291063A|1960-04-26|
    BE633452A|1962-06-11|
    US3198750A|1962-12-26|1965-08-03|Standard Oil Co|Mixed antimony oxide-uranium oxide oxidation catalyst|
    US3397153A|1965-12-23|1968-08-13|Du Pont|Process for manufacturing sintered silica gel of lowered bulk density and catalyst containing same|
    US3445521A|1966-11-17|1969-05-20|Standard Oil Co|Promoted antimony-iron oxidation catalyst|
    US3933751A|1967-05-15|1976-01-20|The Standard Oil Company|Promoted catalysts for the oxidation of olefins|
    US3504266A|1968-03-21|1970-03-31|Westinghouse Electric Corp|Inverter apparatus operative with variable input sources|
    DE1939633C3|1968-08-05|1975-03-13|Nitto Chemical Industry Co. Ltd., Tokio|Process for the production of abrasion-resistant, solid catalysts containing an antimony oxide which are suitable for fluidized bed reactions|
    BE741001A|1968-11-02|1970-04-01|
    JPS493962B1|1969-08-02|1974-01-29|
    GB1286292A|1969-10-13|1972-08-23|Bp Chem Int Ltd|Catalyst composition and oxidation processes using the same|
    JPS4818723U|1971-07-12|1973-03-02|
    GB1461284A|1974-02-19|1977-01-13|Vnii Reaktivov I Khim Chistykh|Preparation of oxygen-containing compounds of antimony and another metal|
    GB1553801A|1977-05-13|1979-10-10|Nitto Chemical Industry Co Ltd|Process for production of attrition resistant antimony oxide containing fluidized bed catalyst having controlled particle size distribution|
    US4374759A|1978-09-05|1983-02-22|The Halcon Sd Group, Inc.|Catalysts and process for unsaturated aldehydes|
    USRE30545E|1979-10-18|1981-03-10|Halcon Research And Development Corporation|Catalyst|
    JPH0247263B2|1982-11-12|1990-10-19|Nitto Chemical Industry Co Ltd|US4837233A|1986-07-21|1989-06-06|The Standard Oil Company|Catalyst system for ammoxidation of paraffins|
    JPH0763628B2|1987-02-24|1995-07-12|日東化学工業株式会社|Method for producing metal oxide catalyst containing antimony and tellurium|
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    申请号 | 申请日 | 专利标题
    JP58178314A|JPH0249130B2|1983-09-28|1983-09-28|
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