• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    A process for the preparation of acrylonitrile by the ammoxidation reaction of propylene, characterized by using an oxide type catalyst which contains, as active ingredients, molybdenum, bismuth, iron and at least one element selected from potassium, rubidium and cesium in specifically limited proportions and which may further contain sodium and/or phosphorus. By the use of such a specific catalyst, the selectivity for the desired acrylonitrile is remarkably improved, and there can be attained high yield of the product. In the process of the present invention, the catalyst can maintain a high activity and a high selectivity for a long time, without undergoing attrition. The catalyst is well prevented from sublimation-escaping of the ingredient molybdenum therefrom.
    公开号:SU1056898A3
    申请号:SU782704546
    申请日:1978-12-29
    公开日:1983-11-23
    发明作者:Аоки Кунитоси；Хонда Макото；Дозоно Тецуро；Кацумата Путому
    申请人:Асахи Касеи Когио Кабусики Кайся (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for producing acrylonitrile, which is used in the synthesis of polymers. A known method for producing acrylonitrile by reacting propylene with ammonia and oxygen in the gas phase in the presence of a catalyst, which can be represented as the following empirical formula:. AT . where H is at least one metal selected from the group including calcium, barium and qing X is a metal selected from the group including titanium, zirconium, niobium, tantalum, vanadium, chromium, manganese, iron, cobalt and nickel, or two metals selected from the group comprising titanium and niobium, titanium and .. zirconium, chromium and titan, chromium and zirconium, chromium and niobium; . a - 0.3-10; B - 0.05-3.0; C - 0.1-6.0; d - 0-5.0; e is the number of oxygen atoms selected in accordance with the valence of the components entering the catalyst. The process is carried out at 300-550 ° C and the contact time is -O ,, 3-20 s, the conversion of propylene is 96%, the selectivity is 89.1%, the yield of the target product is 85% l. There is also known a method of producing acrylopitrile by reacting propylene with ammonia and oxygen in the gas phase at 200 ° C in the presence of a catalyst, which can be represented as the following empirical formula aA, CsGe 8 еМо „0, where X is a metal, selected from the group comprising germanium, tin, copper, silver, chromium, ruthenium tungsten, beryllium, boron, gallium, indium, manganese, thorium, zirconium, yttrium, or a mixture of them; A - alkali metal, or alkaline earth metal, or a rare milling metal, or niobium, or scandium, or yttrium, or tantalum, or phosphorus, or dung to; C is a metal selected from the group comprising nickel and cobalt; magnesium, zinc, cadmium, calcium, or their mixture; a - 0.01-4; L - 0-4;.; c - 0.01-12; d - 2-3; e - 0.01-6; X is the number of oxygen atoms selected in accordance with the valence of the components entering the catalyst. The propylene conversion is 99.6%, the selectivity is 82%, the catalyst yield in a single pass is 81.8% 2j. The disadvantage of these methods is that acceptable results on the yield of the target product (81-85%) are obtained only when the process is conducted in a fixed, catalyst bed. When conducting the process in a fluidized bed of catalyst, the yield of the target product is markedly reduced (see Table 1). Closest to the invention is a method for producing acrylonitrile by reacting propylene with ammonia and oxygen in the gas phase at 300-500 ° C at a pressure of 0.3-10 atm and contact time of 0.250 s in the presence of a catalyst on silica carrier, 30- 95% by weight of the catalyst. The oxide catalyst used in this method can be represented as the following empirical formula. Fo 0.03 - ° x where X is the number of oxygen atoms selected according to the valence of the components included in the catalyst. The propylene conversion is 92%, the selectivity is 81%, the yield of acrylonitrile is 74.8% of the CP. The disadvantages of this method are the relatively low yield of the target product and the selectivity of the process. The purpose of the invention is to increase the yield of the target product. This goal is achieved by the proposed method of producing acrylonitrile by the interaction of propylene with ammonia and g.leuk1 with oxygen with a volume ratio of 1:11, 3: 9-10, 440-480 ° C, and pressure from. atmospheric up to 2 kg / cm and a contact time of 2-10 s in the presence of an oxide catalyst, which can be represented as the following empirical formula AdMo 3 ib FefOjj, where A is potassium, or rubidium, or cesium, or their mixture; a - 0.002-0.02; q is the number of oxygen atoms selected in accordance with the valence of those entering the cat. component lizator; b, f-numbers found by the following formulas: h (1-X) (1-Y), X (1-Y) D y -, 1-Y ™ where X, Y are the numbers inside the region, bounded by an even triangle, formed by lines connecting respectively dots (0.45; 0.35), (0.45; 0.65 (0.85; 0.50) and (0.85; 0.6 on the graph in the coordinate system XY, shown in the q program, or catalyst, which can be represented by the following empirical formula: AdMoB ifaFef where A, a, q - have the indicated values; D is sodium or phosphorus, or their mixture; d is a number, found by the following formleg dp + p, where n is a number 0-0.3, indicating the number sodium, p is a number 0–0.2, indicating the amount of phosphorus; b, f are numbers found using the following formulas: Jj-X) (1-Y) (1-Z) l, p., X (1 -Y) (1-Z) f -, where X and Y have the indicated values Z is a number equal to 2n, where n has the indicated value. The drawing shows a triangular diagram of the values of X. and Y. The proposed method allows to obtain acrylonptril as in in the catalyst free bed and in the fluidized bed of the catasizer with a yield of 81-85.3%, which remains stable under the conditions of use of the catalyst for 15 days, Kytalizator with additional content sodium or phosphorus, or a mixture thereof, has increased strength and service life. The catalyst used in the proposed process is prepared according to the method of preparing slurry of raw materials, spray drying the resulting slurry, and calcining the spray-dried product. The following starting materials are used to prepare the catalyst: phosphoric acid, ammonium salt of molybdate, nitrates of bismuth, iron, sodium, kg, rubidium, and cesium. Example 1, Preparation of catalysts, 85% solution of phosphoric acid, then a solution of ammonium tetrahydrate ammonium heptamolybdate in water are added with stirring as a source of silica, with a stirring a solution of bismuth nitrate pentahydrate, iron nitrate nitrate, sodium nitrate and potassium nitrate (or rubidium, or cesium, or their mixture) in 15% nitric acid. Then, the resulting slurry is dried at 200 ° C using a parallel flow spray dryer. The raw materials slurry is sprayed using a centrifugal spray apparatus equipped with a plate-type rotor located in the center of the top of the spray dryer. The resulting dry powder is transferred to a tunnel-type furnace, where it is calcined at 620-710 ° C for 1-20 hours to obtain a catalyst. According to this method, 82 catalysts were prepared with a different composition, given in Table 2, Example 2, Acrylonitrile Production. A, Process in a fluidized bed of a catcher, Into a 3-inch-diameter stainless steel reactor, having 16 mesh stainless steel inside the grid, 1400 g of catalyst are loaded. A propylene-ammonia-air gas in a volume ratio of 1: (1-1.3) :( 9-10) is passed through the reactor at a rate of 420 l / h, considering the volume at normal temperature and pressure, maintaining the reaction temperature 440-480 0 and pressure from atmospheric to 2 kg / cm. The contact time of the gas mixture with the catalyst is set. from 2 to 10 sec., B, a fixed-bed catalyst process, a silica glass reactor having an internal diameter of 8 mm is loaded with 2 g of catalyst and a catalyst bed with its ends is closed with glass wool. A gaseous propylene-ammonia-oxygen mixture is passed through the reactor in a volume ratio of 1: (1.2.1.9: 12.7 at a rate of 1.2 l / h, considering the volume under normal conditions, maintaining the reaction temperature at 460s and atmospheric pressure. The contact time of the gas mixture with the catalyst is set to 2.2 s.
    The reaction products are analyzed by gas chromatography. The results are shown in Table. 3 (fixed bed) and 4 (fluidized bed) along with the .. weight of reacted propylene carbon ,, nn General conversion of propylene weight: feed carbon propylene
    The selectivity ic acrplohptplus g ° carbon of the acrylonitrile x formed, the selectivity of acrylonitrile g. carbon of the reacted propylene weight of carbon Output of acrylonitrile weight of carbon
    As can be seen from the table. 4, the catalyst has the highest activity during the operation with a strictly limited composition of the active components.
    Froze The effect of KjpHTaKTa time on the yield of acrylonitrile and reaction by-products. weight of carbon yield of carbon by-product As can be seen from the table. 5, in the case of catalyst 5, the high selectivity to acrylonitrile is maintained even with an increase in total propylene conversion, while using comparative catalyst 28 decreases markedly with an increase in total propylene conversion, which is associated with the secondary decomposition of the formed acrylonitrile. And p and mep 4. Loss of molybdenum catalyst during operation. The test to assess the loss of molybdenum is carried out as follows. About 10 g of the catalyst is precisely weighed into a porcelain dish and left standing in the presence of air at 750 ° C for 100 hours and then weighed again. The loss (in percent by weight of the catalyst) of molybdenum is calculated from the decrease in the weight of the catalyst. Elemental analysis after testing confirms that the decrease in the weight of the catalyst is due to the loss of MoOD-distillation. In tab. b shows the test results. I As can be seen from the table. b, the catalysts according to the proposed method effectively prevent the loss of injected molybdenum. In addition, the introduction of sodium (for example, 2) leads to a further decrease in the effect of loss of molybdenum. -Example 5. Abrasion. Rolling mash during operation. Tests to assess the abrasion of the catalyst are carried out as follows ... Precisely weigh about 50 g of the catalyst and place it in a vertical tube 5 ,. inward diammed rum
    catalyst used. The total conversion of propylene, the selectivity to acrylonitrile and the yield of acrylonitrile are calculated by the following formulas :.
    l 100
    In tab. 5 shows the obtained data on the yield of the products of the process in a fluidized bed of catalyst with different time of contact of the gas mixture with the catalyst. In this case, the by-product yield I is calculated by the formula of the formed acrylonitrile propylene by-product supply n in the propylene supply ° ° 1, 5 inches and 30 inches high, the lower end of which is closed by a perforated disk with three holes of 1/64 inch diameter each. Air is introduced into the tube through holes in the disk at a rate of 15 and the catalyst is rapidly fluidized. The degree of catalyst attrition is defined as the percentage of the weight of the catalyst emitted in the form of fine particles from the top of the tube over a period of 5-20 hours. 7 shows the test results, as well as the warning effect against abrasion, provided by the introduction of phosphorus. ; As can be seen from the table. 7, comparative catalysts 40 and 41 containing a small amount of silica are subject to abrasion to a significant extent, while catalysts containing the optimum amount of silica are subject to abrasion only to a small extent. Example 6. The change in the stability of the catalyst during operation. The change in catalyst stability over time is estimated as the change in the yield of acrylonitrile over a period of time during which the process of formation of the target product in the fluidized bed of the catalyst proceeds. In tab. 8 shows the test results. As can be seen from the table. 8, the output of acrylonitrile using kata-. lysators containing neither phosphorus nor sodium / lower by 1.2-1.4% after 15-d1; evanie carrying out the reaction, while the yield of acryloyitrile with a catalyst containing phosphibr and / or sodium is reduced by 0-0 , 5% after a 15-day reaction, which results in an effect of phosphorus and / or
    Sodium on the service life of the catalyst. Moreover, even catalysts that ne contain neither phosphorus nor
    sodium, is still superior in time stability to known catalysts.
    Table 1
    catalyst
    The reaction temperature, ° C;
    The output of Acrylonitrile,%
    1 day
    2 days
    5 days 10 days 15 days
    6.6 Vl 4.5
    81 moow
     i OK Sz READO
    420
    78.5
    75.3 73.4 72.5
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    oh oh
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    Table 3
    Continued table. four
    Continued table. four
    Note. Comparative compositions of the catalyst.
    il en me and e
    Comparative natashizator.
    Continued table. four
    Table 5
    Note. Comparative catalyst.
    Table b
    Table 8
    权利要求:
    Claims (1)
    [1]
    1. METHOD FOR PRODUCING ACRYLONITRILE by reacting propylene with ammonia and molecular oxygen at a volume ratio of 1: 1-1.3: 9-10, respectively, at 440-480 “s, at atmospheric pressure to 2 kg / cm g and contact time 2-10 s in the presence of an oxide catalyst including molybdenum, iron, bismuth oxygen on a silica support, which is related to the fact that, in order to increase the yield of the target product, a catalyst is used, additionally containing component A and in the form of the following empirical formula (I):
    A q Mo8i b Fe ^ Og 1 where A is potassium, or rubidium, or cesium, or a mixture thereof;
    .a - 0.002-0.02;
    η is the number of oxygen atoms selected in accordance with the valency of the components included in the catalyst;
    b, f -numbers found by the following formulas:
    (1-X) (1-Y) —V— ’
    X (1-Y) —where Χ, Υ are numbers inside the region bounded by a quadrilateral formed by lines connecting the points (6,45; 0,35), (0,45; 0,65), (0 85; 0.50) and (0.85; 0.65) on a graph in a coordinate system ΧΥ shown on the diagram, or a catalyst of formula (1), supplemented 0 tively containing component a, <g or sodium or phosphorus , or a mixture thereof and presented in the form of the following empirical formula
    AqMoB i Fe £ 0 ^ Og-, where where
    A, a, q have the indicated meanings; D is sodium or phosphorus, or a mixture thereof;
    d - means the number found by the following formula:
    d = n * p, n is the number 0-0.3, indicating. amount of sodium;
    p is the number 0-0.2, indicating the amount of phosphorus;
    f - mean numbers found by the following formulas b,
    X (l-Y) (1-Z) 'V where Χ, Υ have the indicated values; Ζ is a number equal to 2n, where n has the indicated value.
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    同族专利:
    公开号 | 公开日
    CA1119192A|1982-03-02|
    IE47641B1|1984-05-16|
    NL7812589A|1979-07-03|
    NL186154B|1990-05-01|
    DE2856413A1|1979-07-05|
    FR2413365A1|1979-07-27|
    JPS5495513A|1979-07-28|
    NL186154C|1990-10-01|
    GB2013183B|1982-06-16|
    IE782583L|1979-06-30|
    DE2856413C2|1984-08-30|
    FR2413365B1|1981-09-11|
    IT7831439D0|1978-12-29|
    JPS582232B2|1983-01-14|
    GB2013183A|1979-08-08|
    US4228098A|1980-10-14|
    IT1102800B|1985-10-07|
    引用文献:
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    CA975382A|1971-02-04|1975-09-30|Arthur F. Miller|Process for the manufacture of acrylonitrile and methacrylonitrile|
    US3907859A|1972-10-25|1975-09-23|Standard Oil Co Ohio|Coproduction of acrylonitrile and acrylic acid|
    US3993680A|1973-09-04|1976-11-23|The Standard Oil Company |Ammoxidation using chromium-containing catalysts|
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    JPH0134222B2|1981-10-26|1989-07-18|Asahi Chemical Ind|
    JPS6158462B2|1983-05-06|1986-12-11|Asahi Chemical Ind|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP52159797A|JPS582232B2|1977-12-31|1977-12-31|
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