Preparation method of cyclohexanone-oxime

A technology of cyclohexanone oxime and cyclohexanone, which is applied in the field of preparation of cyclohexanone oxime, can solve the problems of high difficulty, high consumption of cyclohexane, large waste lye treatment load, etc., and achieve reduction of material consumption and energy consumption, Reduction of land occupation and investment, the effect of land occupation and investment reduction

Active Publication Date: 2020-05-15
XIANGTAN UNIV
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  • Abstract
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Problems solved by technology

This method mainly has the following disadvantages: one is that the yield of phenol is low (72-75%), and there are many by-products; the other is that the separation and purification device of phenol and acetone is complicated and the energy consumption is high; Price affects the production cost of phenol
The main advantage of this method is that the complete hydrogenation of benzene to cyclohexane is a mature technology with low difficulty and high yield, but there are three major disadvantages in the oxidation process of cyclohexane: (i) In order to maintain a high selectivity, the cyclohexane The one-way cyclohexane conversion rate of hexane air oxidation can only be controlled at 3-5%, and a large amount of unconverted cyclohexane needs to consume a lot of energy to separate and circulate it. Even so, the final cyclohexane calculated The total yield of KA oil (a mixture of cyclohexanone and cyclohexanol) can only reach about 83%, which shows that the consumption of cyclohexane is high and the amount of by-products is large
(ii) The main product of the uncatalyzed oxidation reaction of cyclohexane is cyclohexyl hydroperoxide, and its decomposition process needs to consume NaOH. In addition, the by-products of the oxidation reaction of cyclohexane are mainly acids, esters, ethers, etc., which also need to pass Saponification and removal of alkaline aqueous solution requires the consumption of a large amount of NaOH and the generation of a large amount of saponification waste lye, not only the production cost is high, but also the environmental pressure is relatively high
(iii) Since the target product is cyclohexanone, it is necessary to further separate KA oil into cyclohexanone and cyclohexanol through rectific

Method used

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  • Preparation method of cyclohexanone-oxime
  • Preparation method of cyclohexanone-oxime
  • Preparation method of cyclohexanone-oxime

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0057] Preparation of cobalt-cerium composite oxide catalyst: Weigh 4.4g of cerium nitrate hexahydrate and 1.5g of cobalt nitrate hexahydrate respectively, then add 250ml of deionized water, stir to dissolve completely, obtain solution A, add NaBH at room temperature 4 , to partially reduce the cobalt ions and cerium ions in the A solution. Then weigh 3.1 g of potassium carbonate and place it in a 100 ml beaker, add 50 ml of deionized water and stir to completely dissolve the potassium carbonate to obtain solution B. Then slowly add solution B to solution A under ultrasonic conditions, carry out co-precipitation reaction at 40°C, then add ammonia water dropwise to the mixture containing the precipitate under stirring conditions to adjust the pH value of the solution, and keep stirring to make the pH of the solution The value was stable at 10, and the obtained precipitate was filtered, washed, dried at 120°C for 12 hours, and then calcined in a muffle furnace at 400°C for 2 hou...

Embodiment 2

[0060] Amination of KA oil with ammonia and hydrogen: In a fixed-bed device, load a 6 cm high (1.2 g) amination catalyst NiCu / MgAlO, feed the KA oil obtained in Example 1, at 170 ° C, in normal Under pressure condition, pass into ammonia and hydrogen to carry out ammoniation reaction, wherein KA oil feeding liquid volume space velocity is 0.3h-1, the feeding speed of ammonia is 50mL / min, ammonia and KA oil molar ratio is 13: 1. The hydrogen feed rate is 10mL / min, the reaction product is condensed, and the product is collected every 6 hours for gas chromatography analysis. The conversion rate of cyclohexanol is 98.8%, the conversion rate of cyclohexanone is 100%, and the conversion rate of cyclohexanone is 100%. The selectivity of the amine was 98.5%, and the catalyst activity did not decrease after 200 hours of reaction.

Embodiment 3

[0062] Partial oxidation of cyclohexylamine: take by weighing 15 grams of cyclohexylamine (purity is 99.9%) and 0.5 gram of TiO produced by the method described in Example 2 2 / MCM-41 catalyst were added together into a 100ml reaction kettle, and oxygen was introduced (the pressure was maintained at 1.0 MPa), and the reaction was carried out at 100°C for 4 hours. After the reaction, the solid catalyst was separated by filtration to obtain 16.25 grams of oxidation reaction liquid. This solution was qualitatively characterized by a gas spectrometer, and accurately quantified by a gas chromatography internal standard method (chlorobenzene was used as an internal standard). The measured cyclohexylamine was 8.78 grams, cyclohexanone oxime was 6.42 grams, and the by-product nitrate 0.45 gram of cyclohexane, 0.15 gram of cyclohexanone, 0.07 gram of cyclohexyl imine, 0.03 gram of N-cyclohexyl cyclohexyl imine, the conversion rate of cyclohexylamine in this process is 41.6%, the selecti...

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Abstract

The invention relates to a preparation method of cyclohexanone-oxime, which mainly comprises the following steps: (1) oxidizing cyclohexane and molecular oxygen under the action of a solid catalyst, carrying out one-step reaction to generate KA oil, and performing separation to obtain the KA oil; (2) directly aminating the KA oil with ammonia and hydrogen under the action of a solid catalyst to generate cyclohexylamine and a small amount of byproduct-A, and performing separation to obtain cyclohexylamine; (3) carrying out partial oxidation on cyclohexylamine and molecular oxygen under the action of a solid catalyst to obtain an oxidation product mainly composed of cyclohexanone-oxime, a small amount of byproduct-B and cyclohexylamine which may not be completely converted; and (4) aminatingthe oxidation product, namely, directly carrying out amination reaction on the oxidation product obtained in the step (3), ammonia and hydrogen under the action of a solid catalyst without separation, converting the byproduct-B into cyclohexylamine, and performing separation to obtain cyclohexanone-oxime. The method is short in technological process, small in occupied area and investment, low incost and environmentally friendly.

Description

technical field [0001] The invention relates to the preparation of cyclohexanone oxime, in particular to a preparation method of cyclohexanone oxime. Background technique [0002] Cyclohexanone oxime is an intermediate of ε-caprolactam, an important raw material (the main purpose is to produce polyamide chips through polymerization to further produce nylon fibers, engineering plastics, plastic films, etc.). [0003] Currently known cyclohexanone oxime production methods mainly contain two: cyclohexanone-hydroxylamine method and cyclohexanone ammoximation method. These two methods are the most commonly used, and both use benzene as the starting material to synthesize cyclohexanone oxime through the intermediate cyclohexanone. [0004] There are currently three industrial methods for synthesizing cyclohexanone from benzene: phenol method, cyclohexane oxidation method and cyclohexene hydration method. The phenol method has a long history. The earliest cyclohexanone oxime prod...

Claims

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Application Information

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IPC IPC(8): C07C251/44C07C249/04C07C249/14
CPCC07C249/04C07C249/14C07C209/26C07C45/33C07C2601/14C07C251/44C07C211/35C07C49/403
Inventor 罗和安游奎一傅尚军倪文金魏亚南刘平乐艾秋红
Owner XIANGTAN UNIV
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