Process for producing acrylonitrile

专利摘要:
Acrylonitrile is produced from propylene in an excellent percent conversion of propylene, percent selectivity to acrylonitrile and percent yield of acrylonitrile, by bringing, at an elevated temperature, a reaction feed containing propylene, molecular oxygen and ammonia, each in gas phase, into contact with a catalyst consisting essentially of an oxide composition of the empirical formula: MoaCobNicFedBieXdTigOh wherein X represents at least one atom of an element selected from vanadium and tellurium; the subscripts a, b, c, d, e, f and g respectively denote the numbers of the respective atoms of the elements, the ratio a:b:c:d:e:f:g being in the range of 10:0 to 10:0 to 10:1 to 7:0.08 to 1.1:0.01 to 1:1 to 15, and the ratio of a to the sum of b and c being in a range of 10:3 to 10, and; the subscript h represents the number of oxygen atoms which satisfies the average valency of the elements, the ratio a:h being in a range of 10:36.7 to 84.1.
公开号:SU957763A3
申请号:SU792820049
申请日:1979-09-12
公开日:1982-09-07
发明作者:Умемура Сумио；Охдан Киедзи；Матсузаки Токуо；Асада Хироюки；Цуруока Масао
申请人:Убе Индастриз Лтд (Фирма)；
IPC主号:

专利说明:

This invention relates to a process for the preparation of acrylonitrile, which is used especially in the manufacture of high molecular weight compounds, for example, butadiene nitrile rubber.
Acrylonitrile is used as a pro-intermediate in the synthesis of acrylic esters.
A known method of producing acrylonitrile by treating propylene with ammonia and oxygen-containing gas at 300-500 ° C in the presence of a catalyst Mo-Bi-Fe-Co-W-Ca-TiO 1.
However, under the conditions of this method, the target product is obtained with a yield of no more than 80% with a duration of up to 20 s. In addition, the formation of undesirable acrolein, which polymerizes and precipitates on the inner surface of the apparatus, takes place.
The closest to the technical essence of the proposed method is the production of acrylonitrile, which is based on the fact that propylene is treated with ammonia and molecular oxygen or air in the presence of water vapor at 330–470 ° C on a torch;
MoqCo, FegBia XeOf,
where X is vanadium or tellurium or their mixture, and 10; b 3-10; c 1-7; d 0.1-0.7; e 0.01-1;
ten
 - the number of oxygen atoms, determined by the h, the sum, g of the valences of the remaining elements of the catalyst; .
a: f 10: 34,6-54 ,.
15 The process is carried out at a molar ratio of propylene: NH3: 02 1: 0.5-2: 0.1-5.
This method allows to obtain relatively high rates of yield, conversion and selectivity,
20 which respectively are 78.982, 9%, 92.2-99.2%, 81-7-85.6%.
However, under the conditions of this method, up to 3.8% of 25 side acrolein is formed. The catalyst, in addition, has a low mechanical strength.
The aim of the invention is to reduce the formation of by-product in this process. The goal is achieved by the implementation of the method of obtaining acrylonitrile by treatment of sawn with ammonia and air at 39 p-430-s in the presence of a catalyst of the formula MOoYbFe BieXjTi "Oni. where Y is Co and / or Ni. X - V and / or Te a 10; b 2-14; d 1-7; c, 0.08-0.3; f 0.01-0.5; . g 1-15, n is a number that satisfies the average valence of the corresponding metals, with a molar ratio of propylene: ammonia:; AIR} water vapor, respectively, equal to lsl-1.5: 8-18:: 0.5-6 , as a catalyst, is used for a catalyst; the corresponding empirical formula is MOttY Fe BieXiTicOd where Y is Co or Co Ni. X - V and / or Te. a 10; . b 2-15; d 1-7; from 0.08-0.3; f 0.01-0.5; g 1-15; n is the number that satisfies the average valence of the corresponding metals, with a molar ratio of propylene: ammonia g of an air-vapor pair, respectively equal to 1: 1-1.5: 8-18: 0.5-6 and the process is carried out at the specified temperature, The proposed method allows to reduce the formation of secondary acrolein to 1%. The process is carried out for 1.7-2 s. B. The conditions of the proposed method after working on the specified catalyst for 500 hours. The main indicators of the process do not change. Productivity of the process reaches 280 g / l of catalyst per hour. Example 1. A solution is prepared by dissolving 166.1 ammonium molybdate tetrahydrate (NH 3 Mo-t-OHA HjO in 200 ml of hot water at 1.5 ml of tellurium dioxide (TeOj) and 37.6 are suspended in this solution. titanium dioxide (TiOj) with simultaneous stirring, the result is an aqueous pacTBOpi-suspension system. An aqueous solution prepared by dissolving 136.9 g of cobalt nitrate (CoCNO) bNgO),, 8 g; nickel nitrate (NiCNOg) -) and 76.1 g of nitrate iron (Fe (. 9HjO in 250 ml of hot water with, and a solution of 9.12 g of bismuth nitrate (Bi (N05) jSH20) in 10 ml in 15% - An aqueous aqueous solution of nitric acid is added individually, dropwise, into an aqueous solution-suspension system prepared as a yKa3aHOj, resulting in a suspension mixture. This suspension mixture is dried with simultaneous stirring, as a result of which it is converted into a dried solid, mixture. The resulting solid mixture is ground to a powder and this The powder is formed into EO tablets, each of which has a diameter of 5 mm and a thickness of 5 mm, and is molded using a pressing machine. The tablets are burned at 5 h in an atmosphere of air. These tablets are subjected to a crush strength test. tablets between plates. The pressure acting on the tablet increases until the tablet collapses. The crush strength of the test tablet is expressed in units of pressure at which the tablet is divided by Jaec. Such a measurement is repeated for five. Tablets, and the crush strength of the catalyst is expressed as the average crush strength of the fifty tablets. Catalysis: the torus used in this example has a crush strength of 7.4 kg / tab. These 8 ml catalyst tablets are placed in a U-shaped glass reaction tube having an internal diameter of 8 mm. The initial reaction product, containing propylene, ammonia, air and water vapor. In a molar ratio of 1: 1: 11: 2, is passed through this reaction tube at a flow rate of 282 ml / min at atmospheric pressure. The duration of contacting the starting material with the catalyst is 1.7 seconds. This operation is continued for two hours. As a result of the reaction, acrylonitrile is obtained with a propylene conversion of 97.4%, with an acrylonitrile activity of 85.7%, with an acrylonitrile yield of 83.5% and with a high percentage of acrylonitrile yield per unit of time per unit volume of contact space equal to 279 g / l of catalyst per hour. The output of acrolein is very small - 0.7%. The atomic ratio of the elements in the catalyst is presented in table. 1. Examples 2-15. Carry out the same operations as in Example 1.
The atomic ratio of the elements in the prepared catalyst and process indicators are presented in Table. one.
Comparative measures 1-7. The asteroid process of example 1. The atomic ratio of the elements of the catalyst used and the process values are presented in Table. 2.,
The data table. 2 shows that the use of a catalyst with an atomic ratio of elements beyond the limits specified in the claims has a negative effect on the main indicators of the process.
Examples 16-20 and с о п о with the good examples 8-10. In each of Examples 16-18, the process is carried out as in Example 1, but ammonium metavanadate is used instead of tellurium dioxide.
In Example 19, the same operations as described in Example 1 are performed, along with tellurium dioxide ammonium metavanadate is used.
In Example 20, the same operations as described in Example 1 were carried out. Moreover, 143 ml of an aqueous sol containing 30% by weight of silica was introduced into the suspension mixture, the prepared catalyst was applied to the silica (support) in an amount of 20% by weight .%.
In comparative examples 8-10, the same operations are carried out as in example 1, but ammonium metavanadate is used instead of tellurium dioxide.
The atomic ratio of the elements in the prepared catalyst and process indicators are presented in Table.
EXAMPLE 21 The process is carried out in the same manner as described in Example 1 for 500 hours using the same catalyst (CojNij Fcj Bio., Tiy) as described in Example 1. The decrease in catalytic activity of the catalyst does not decrease. is observed. After completion of the 500-hour process, it was found that propylene conversion was 97.8%, selectivity to acrylonitrile was 85.9%, the yield of acrylonitrile was 84.0%, and the yield of acrolein was 0.6%.
Examples 22-24. The process is carried out as in Example 1.
The molar ratio of propylene, ammonia, air and vapor in the reaction mixture and the process indicators are shown in Table. four. ,
Examples 25 and 26 and equivalent examples s 11-14 The process is carried out as in example 1.
The atomic ratio of the elements in the used catalyst and the process indices are shown in Table. five.
Examples 27-31. The process is carried out as in Example 1.
The atomic ratio of the elements in the catalyst and process indicators are presented in Table. 6
Examples 32-34. The process is carried out as in Example 1.
The molar ratio between propylene, ammonia, air and steam in the reaction mixture and the process indicators are given in table. 7
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权利要求:
Claims (1)
[1]
Claim d 1-7;
The method for producing acrylonitrile is 0.01-0.5;
the treatment of propylene with ammonia sp is the number / medium satisfying air at elevated temperatures of valence corresponding to the presence of water vapor and catalyzed metals;
mash, including molybdenum, iron, g 1-15, with molar ratio-bismuth, cobalt, oxygen, about propylene gas, ammonia: air;
due to the fact that with the product: water vapor, correspondingly reducing the formation of by-products but equal to 1; 1.5: 18: 0.5-6,
Comrade, the catalyst is used as the catalyst; at 390-430 C.
catalyst, appropriate sources of information,
empirical formula taken into account in the examination
MOgYj Fe jBicXfTigOn.1. Patent Linglia 1-436475,
where Y is Co or Co. + Ni; cl. C 2 C, pub. 05/19/76.
X - V and / or Te; 52 CllA 4070390,
a 10; cl. 260-465,3, published 24/01/76
b 2-15; (prototype).
from 0.08-0.3;

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同族专利:

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MX150969A|1984-08-30|

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GB2031878A|1980-04-30|

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JPS5538330A|1980-03-17|

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ES484125A1|1980-04-16|

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引用文献:

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RU2761968C1|2018-08-23|2021-12-14|Асахи Касеи Кабусики Кайся|Method for producing ammoxidation catalyst and method for producing acrylonitrile|JPS494452B1|1970-09-18|1974-02-01|

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KR100809463B1|2000-12-22|2008-03-03|니폰 가야꾸 가부시끼가이샤|Alkane oxidation catalyst, process for producing the same, and process for producing oxygen-containing unsaturated compound|

法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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JP11170078A|JPS575221B2|1978-09-13|1978-09-13|

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