Method for preparing amide using nonhomogeneous phase oximation rearrangement

An amide and rearrangement technology, applied in chemical instruments and methods, preparation of organic compounds, preparation of carboxylic acid amides, etc., can solve the problems of high viscosity of materials, small reduction of by-products of multi-stage rearrangement, and high energy consumption. , to reduce the consumption of sulfuric acid and by-products, improve the quality of the reaction, and reduce the reaction temperature.

Active Publication Date: 2008-05-07
HUBEI JINXIANGNING CHEM ENG TECHENOLOGY CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0010] (1) The technological process is complicated and the energy consumption is large;
[0011] (2) Both distillation and extraction are carried out at relatively high temperatures, and the stability of the oxime solution is relatively poor, and trace impurities are generated in the subsequent rearrangement, which brings difficulties to the refining process;
[0012] (3) The material that enters the subsequent rearrangement is molten oxime. During production, the pipeline needs heat preservation and heat tracing, which is easy to block, which brings inconvenience to start-up and production operations.
[0016] (1) The decline of multi-stage rearrangement by-products is small. Under the conditions of low acid content and low temperature, the viscosity of the material is high, which is unfavorable for mass transfer and reaction
[0017] (2) Ammonium salt metathesis and sulfuric acid cycle process consume a lot of energy and cost, so they are not economical

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0044] Example 1: Add 45.0 g of n-hexane, 15.2 g of methyl ethyl ketone, and 1.5 g of titanium-silicon molecular sieve in advance in a 250 ml glass reactor with magnetic stirring. After mixing fully, the temperature is raised to 65° C., and 27.5% (by weight) hydrogen peroxide 28.0 g is slowly added dropwise. g and 25% (weight ratio) ammoniacal liquor 30.0g. Add dropwise at a constant speed for 2.5 hours, and continue to react for 1 hour. Stirring was maintained during the reaction, and the temperature was controlled at 65°C. After cooling and standing to separate the heavy phase, extract it three times with 45.0 g of n-hexane, and mix the extraction phase with the light phase of the reaction to obtain 105.6 g of methyl ethyl ketone oxime-n-hexane solution. %, the selectivity of methyl ethyl ketone oxime is 97.1%. Add SO to another 250ml reactor 3 Concentration is 5% oleum 15.8g, slowly add methyl ethyl ketoxime oxime solution dropwise. The reaction temperature is 68° C., a...

Embodiment 2

[0045] Embodiment 2: Add cyclohexane, cyclohexanone and titanium silicon molecular sieve catalyst in advance in the glass reactor of 250ml band magnetic stirring, cyclohexane consumption is cyclohexane: cyclohexanone=3.0: 1 (molar ratio, below Same), the mass percentage of titanium silicon molecular sieve is 2.2%. When the temperature rises to 70-71° C., hydrogen peroxide and ammonia water are added dropwise for oximation reaction. The total consumption of hydrogen peroxide and ammonia is hydrogen peroxide: ammonia: cyclohexanone=1.1:1.9:1. The dropwise addition time was 2 hours, and the reaction was continued for 1.1 hours after the dropwise addition was completed. Stirring was maintained during the reaction, and the temperature was controlled at 71°C. The aqueous phase product of the reaction is extracted three times with cyclohexane equivalent to the reaction volume, and the extract phase is mixed with the organic phase product of the reaction to obtain a cyclohexane solut...

Embodiment 3

[0047] Example 3: 39.2 g of cyclohexane, 15.1 g of cyclohexanone, and 3.8 g of titanium-silicon molecular sieve catalyst were added into a 250 ml glass reactor. Take 23.5 g of hydrogen peroxide and 33.2 g of ammonia water with a concentration of 27.5% (weight ratio) respectively, and add them dropwise into the reaction kettle at a uniform speed, and the feeding time is 2.1 hours. Magnetic stirring is adopted, the temperature is controlled by an oil bath, and the reaction temperature is about 72°C under normal pressure. After the addition, the reaction was continued for 1 hour, cooled and left to stand, and 55.1 g of the light phase was separated, and the heavy phase was extracted three times in equal parts with 39.0 g of cyclohexane, and the extracted phase was mixed with the light phase to obtain 95.3 g of cyclohexanone oxime solution. Add SO to another 250ml reactor 3 Concentration is 15.8g of fuming sulfuric acid of 8%, and cyclohexanone oxime solution is slowly added drop...

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PUM

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Abstract

The present invention discloses oximation and rearrangement process of preparing amide with aliphatic and / or cyclic aliphatic ketone as material. The preparation process includes catalytic reaction of ketone, hydrogen peroxide solution and ammonia inside inert solvent to produce ketoxime solution, Beckmann rearrangement of the oil phase product under the action of fuming sulfuric acid, and hydrolysis to neutralize and produce amide. The present invention has shortened technological process, lowered cyclohexyl ketoxime rearranging reaction temperature, lowered sulfuric acid consumption and reduced side product.

Description

technical field [0001] The invention relates to a method for preparing amides, and further illustrates that the amides are prepared by heterogeneous ammoximation and heterogeneous Beckmann rearrangement using ketones as raw materials. Background technique [0002] Amides are a class of compounds in which the hydroxyl groups in carboxylic acid molecules are replaced by amino or amino groups, and can also be regarded as acyl derivatives of ammonia, primary or secondary amines. Most of the amides with the general formula RCONH2 are crystalline at room temperature, have good water solubility, and are excellent solvents and polymer raw materials. The preparation of amides usually includes amine acylation, carboxylate ammonium salt dehydration, nitrile partial hydrolysis and ketoxime rearrangement and other methods. [0003] Aliphatic ketones or aromatic ketones can condense with ammonia derivatives such as hydroxylamine to generate corresponding ketoximes. Using acidic substanc...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C231/10
CPCC07C231/10C07C233/05
Inventor 罗和安吴剑刘国清朱亚玲
Owner HUBEI JINXIANGNING CHEM ENG TECHENOLOGY CO LTD
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