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Process for preparing unsaturated nitrile

A technology of acrylonitrile and methacrylonitrile, applied in chemical instruments and methods, hydrocarbon ammoxidation preparation, metal/metal oxide/metal hydroxide catalysts, etc., can solve problems such as impossible and difficult maintenance, and achieve economical significant effect

Inactive Publication Date: 2003-01-29
ASAHI KASEI KK
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, research has found that, according to this method, since the catalyst contains metal elements other than molybdenum, some problems will be caused, such as the composition of the catalyst in the reaction system and the excessive additives are difficult to maintain, making it necessary to achieve stable and continuous acrylonitrile or formaldehyde for a long time. Acrylonitrile production becomes impossible

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0050] Embodiment 1 (the present invention)

[0051] Composed of Mo 12.0 Bi 0.20 Ce 0.40 Fe 2.0 Ni 5.6 Mg 2.2 K 0.07 Cs 0.04 A catalyst consisting of oxide supported on 50% by weight silica was prepared as follows. In this catalyst, x is 10.7 and the ratio y of molybdenum atoms is 1.12x.

[0052] to contain SiO 2 Be that a solution is added in the 3333.4g silica sol of 30% by weight, and this solution is made of 38.6g bismuth nitrate [Bi(NO 3 ) 3 5H2O], 69.0g cerium nitrate [Ce(NO 3 ) 3 6H2O], 321.2g iron nitrate [Fe(NO 3 ) 3 9H2O], 647.6g nickel nitrate [Ni(NO 3 ) 2 6H2O], 224.2g magnesium nitrate [Mg(NO 3 ) 2 6H2O], 2.82g potassium nitrate [K(NO 3 )] and 3.10g cesium nitrate [Cs(NO 3 )] dissolved in 755.4g concentration by weight of 17.9% nitric acid and formed, finally added by 842.4g ammonium paramolybdate [(NH 4 ) 6 Mo 7 o 24 4H 2 O] dissolved in 1696.6g of water to form a solution. The resulting mixed solution was sent to a co-current type spray...

Embodiment 2

[0061] Embodiment 2 (the present invention)

[0062] The catalyst is prepared in the same manner as in Example 1, except that the composition of the oxide is Mo 11.8 Bi 0.45 Ce 0.90 Fe 1.8 Ni 5.0 Mg 2.0 K 0.09 Rb 0.05 , The calcination process is calcination at 610°C for 2 hours. In this catalyst, x is 10.8 and the ratio y of molybdenum atoms is 1.09x.

[0063] Using this catalyst, the ammoxidation of propylene was carried out under the same normal reaction conditions as in Example 1, except that the contact time was 6.7 sec.g / ml. After about 100 hours of reaction, the conversion was 99.6%, and the yield of acrylonitrile was 81.8%. The ratio of molybdenum atoms in the catalyst sampled from the reactor was 11.8 (y=1.09x).

[0064] Then the reaction was run for two weeks under the same harsh reaction conditions as in Example 1, and then returned to the original normal reaction conditions. Analysis of the reaction gas showed that the conversion rate was 99.3% and the y...

Embodiment 3

[0069] From these results, it can be seen that by adding an activator to the reaction system, the yield of acrylonitrile can be increased without increasing the molar ratio of ammonia / propylene in the feed gas, and the yield of acrylonitrile can also be obtained than that of the same molybdenum atom without adding the additive. The ratio is higher acrylonitrile yield of the catalyst, and this high acrylonitrile yield can be maintained stably. Also, since no white particles were observed in the sampled catalyst, this indicated that the added activator was actually acting as a catalyst with little deposition on the internal structure of the reactor, etc. Embodiment 3 (the present invention)

[0070] The catalyst is prepared in the same manner as in Example 1, except that the composition of the oxide is Mo 11.4 Bi 0.60 Ce 1.20 Fe 1.6 Ni 4.8 Mg 1.9 K 0.11 Rb 0.05 , The calcination process is calcination at 600°C for 2 hours. In this catalyst, x is 11.0 and the ratio y of ...

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PUM

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Abstract

A process for producing acrylonitrile or methacrylonitrile, wherein a molybdenum compound, which is convertible to molybdenum oxide and not supported on a carrier is added to a fluidized bed reactor as an activator, in such a way that the ratio y of molybdenum atoms in the oxide catalyst represented by the formula:MoyBipFeqAaBbCcDdEeOfwill be maintained in the range of 1.02x to 1.12x (x=1.5p+q+a+c+1.5d+1.5e) during an ammoxydation reaction.

Description

technical field [0001] The invention relates to a method for preparing acrylonitrile or methacrylonitrile, which is realized by using a multi-component oxide catalyst containing molybdenum, bismuth and iron through fluidized bed ammoxidation reaction, wherein a molybdenum compound is used as a An activator is added to the fluidized bed reactor. Background technique [0002] In the presence of ammonia and molecular oxygen, the method of preparing acrylonitrile or methacrylonitrile by contacting propylene, isobutene or tert-butanol in the gas phase with a catalyst is a well-known olefin ammoxidation reaction method, and industrial production has been realized. Many multicomponent oxide catalysts containing molybdenum, bismuth and iron suitable for this type of reaction have been disclosed in JP-B-51-6649, JP-B-51-33888, JP-B-56-52013, JP-B- B-59-50667, JP-B-60-36812 and other patents. [0003] However, these catalysts have a problem that when they are used in the fluidized b...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/887C07C253/24C07C255/07
CPCC07C253/24B01J23/8876Y02P20/52C07C255/07C07C255/08B01J23/887B01J23/88
Inventor 绿川英雄染谷贤
Owner ASAHI KASEI KK
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