CN111517984B - Method for synthesizing cyclohexanone oxime by catalyzing cyclohexanone with titanium ammonium phosphotungstate - Google Patents
Method for synthesizing cyclohexanone oxime by catalyzing cyclohexanone with titanium ammonium phosphotungstate Download PDFInfo
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Abstract
The invention relates to a method for synthesizing cyclohexanone oxime by catalyzing cyclohexanone with titanium ammonium phosphotungstate. The method comprises the following steps: adding cyclohexanone, ammonia water, hydrogen peroxide and ammonium titanium phosphotungstate into a reactor, reacting for 3-7h under the condition of normal pressure of 20-60 ℃ and stirring in the presence of a solvent or in the absence of the solvent, and cooling to room temperature after the reaction is finished to obtain a product cyclohexanone-oxime; wherein the molar ratio of materials is cyclohexanone: ammonia water: hydrogen peroxide: ammonium titanium phosphotungstate =1:0.5-2.5:0.5-2.5:0.1 to 1; when the solvent exists, the volume ratio is as follows: cyclohexanone: solvent =1:3 to 8. The method has the advantages of high efficiency, environmental protection, mild reaction conditions, easy separation of the catalyst and the like.
Description
Technical Field
The invention relates to synthesis of organic chemical products, in particular to a process method for synthesizing cyclohexanone oxime by catalyzing cyclohexanone liquid-phase ammoximation by using titanium ammonium phosphotungstate as a catalyst.
Background
Cyclohexanone oxime (abbreviated as CHO) is an important organic intermediate for synthesizing epsilon-caprolactam, and caprolactam is one of important organic raw materials, and has been widely used in various fields of light and heavy industries such as synthetic fibers, nylon-6, plastics and resins (Li Da is, synthetic fibers industry, 2016 (4): 61-64). In recent years, with the increasing demand of cyclohexanone oxime, researchers have tried to synthesize cyclohexanone oxime by using different catalysts in order to reduce the preparation cost of the catalyst and optimize the production process.
A series of catalysts for catalyzing cyclohexanone to synthesize cyclohexanone oxime, such as silicide, heteropoly acid, heteropoly compound, etc., are developed at home and abroad. The research shows that the heteropoly acid has higher catalytic activity in the catalytic oxidation reaction. The heteropoly acid has the characteristics of greenness, no toxicity, high activity and selectivity and the like, but also has the problems that active components are easy to lose, the catalyst is difficult to separate from a reaction system after reaction and the like. In order to solve the above problems, a method of supporting a heteropoly acid on a porous carrier or converting the heteropoly acid into an insoluble heteropoly acid salt catalyst or the like has been adopted. Compared with the supported heteropoly acid, the heteropoly acid salt catalyst is easy to prepare and has wide application in the ammoximation reaction. Such as sodium, potassium and ammonium phosphotungstate salts (Zeng Xiang, etc., petro-chemical reports (petroleum processing), 2010 (5): 779-784), single transition metal substituted zirconium ammonium phosphotungstate salts, cobalt ammonium phosphotungstate salts, nickel ammonium phosphotungstate salts and copper ammonium phosphotungstate salts (Liu Biyu, etc., molecular catalysis, 2018, 28 (2): 140-147), as well as a series of novel organic-inorganic complex heteropolyacid salts (Zeng Yuanhui, shuozhi paper, hunan Tan university, 2010) such as quaternary ammonium phosphotungstate salts, pyridinium phosphotungstate salts, imidazolium phosphotungstate salts, etc., all of which can catalyze cyclohexanone ammoximation to synthesize cyclohexanone oxime. However, the single type heteropolyacid salt catalyst still has the defects of low catalytic activity, easy loss of active components, difficult catalyst recovery and the like.
Therefore, the development of a green, efficient, stable catalyst which is easy to separate from the reaction system and is used for the cyclohexanone ammoximation reaction and the optimization of the production process remains a problem to be solved by researchers in the field.
Disclosure of Invention
The invention provides a method for synthesizing cyclohexanone oxime by catalyzing cyclohexanone with titanium ammonium phosphotungstate, aiming at the problems that the prior production process of cyclohexanone oxime is complex, and the problems of low catalytic activity, easy loss of active components or difficult catalyst recovery and the like still exist when a single type heteropoly acid salt catalyst is used. The method realizes the synthesis of cyclohexanone oxime under mild conditions by using cyclohexanone as a raw material and ammonium titanium phosphotungstate as a catalyst for the first time. The method has the advantages of high efficiency, environmental protection, mild reaction conditions, easy separation of the catalyst and the like.
The specific technical scheme of the invention is as follows:
a method for synthesizing cyclohexanone oxime by catalyzing cyclohexanone with titanium ammonium phosphotungstate comprises the following steps:
adding cyclohexanone, ammonia water, hydrogen peroxide and titanium ammonium phosphotungstate into a reactor, reacting for 3-7h under the condition of stirring at the normal pressure of 20-60 ℃ under the condition of the existence of a solvent or without the solvent, and cooling to room temperature after the reaction is finished to obtain a product cyclohexanone oxime;
wherein the molar ratio of materials is cyclohexanone: ammonia water: hydrogen peroxide: ammonium titanium phosphotungstate =1:0.5-2.5:0.5-2.5:0.1 to 1; when the solvent exists, the volume ratio is cyclohexanone: solvent =1:3 to 8 percent;
the solvent is ethanol, acetonitrile, tert-butyl alcohol, cyclohexane or water;
the method also comprises the recovery of the ammonium titanium phosphotungstate catalyst, and comprises the following steps: after the reaction is finished, adding an extracting agent for extraction, and dividing the reaction liquid into two layers, wherein the upper layer is an organic phase containing the product cyclohexanone oxime, and the lower layer is a titanium salt phase containing ammonium phosphotungstate; distilling the lower layer liquid under reduced pressure to remove water, drying, and using for the next reaction;
wherein, the volume ratio is cyclohexanone: extractant =1:1 to 3.
The extractant is toluene.
The invention has the beneficial effects that:
(1) The method realizes that the ammonium titanium phosphotungstate is used as the catalyst for ammoximation of cyclohexanone to synthesize cyclohexanone oxime for the first time. The titanium ammonium phosphotungstate catalyst provided by the invention has a good keggin type structure, is excellent in catalytic performance, can effectively catalyze cyclohexanone ammoximation reaction, and is high in selectivity of cyclohexanone oxime.
(2) The catalyst has the advantages of easily obtained raw materials, low price, simple preparation process and high catalytic efficiency, after the reaction is finished, the reaction liquid is divided into two layers, the catalyst and the product are easy to separate, and the catalyst can be recycled and has good application prospect.
(3) Compared with the existing method for preparing cyclohexanone oxime by using cyclohexanone and titanium silicalite molecular sieve as catalysts, the method takes ammonium titanium phosphotungstate as a catalyst, the target product cyclohexanone oxime can be obtained by reacting at the normal pressure and the low temperature of 20-60 ℃ for 3-7h, the reaction conditions are mild (compared with the reaction in which titanium silicalite molecular sieve is used as a catalyst, the temperature can be reduced from 80 ℃ to 20 ℃), the decomposition of hydrogen peroxide can be effectively avoided, and the utilization rate of hydrogen peroxide is further improved. The method realizes that the ammonium titanium phosphotungstate is used as the catalyst for ammoximation of cyclohexanone to synthesize cyclohexanone oxime for the first time. The titanium ammonium phosphotungstate catalyst provided by the invention has a good keggin type structure, is excellent in catalytic performance, can effectively catalyze cyclohexanone ammoximation reaction, and is high in selectivity of cyclohexanone oxime. The conversion of cyclohexanone was 92.5% and the selectivity of cyclohexanone oxime was 91.0%.
Detailed Description
The essential features and the remarkable effects of the present invention can be obtained from the following examples, which are not intended to limit the present invention in any way, and those skilled in the art can make modifications and adjustments in some insubstantial ways in view of the present disclosure. The present invention will be further described with reference to the following embodiments.
The reaction mechanism of the invention is as follows:
the method realizes one-step clean synthesis of cyclohexanone oxime by using cyclohexanone as a raw material and ammonium titanium phosphotungstate as a catalyst.
The ammonium titanium phosphotungstate disclosed by the invention is a known substance and has a structural formula as follows: (NH) 4 ) 5 PW 11 TiO 39 . The preparation process comprises the following steps:
(1) Dissolving titanium sulfate, ammonium salt and sodium phosphotungstate in water to form a solution;
(2) And filtering and recrystallizing after reaction to obtain the ammonium titanium phosphotungstate.
Example 1
The preparation process of the ammonium phosphotungstate titanium salt catalyst comprises the following steps:
the titanium sulfate solution (6 mmol) was dissolved in 1mL of sulfuric acid (2M), added to an aqueous solution containing 6mmol of sodium phosphotungstate, and 1 mol. L was used -1 NaHCO 3 The pH of the solution is adjusted to 4.0-5.0. Stirring at 60 ℃ for 30 minutes, adding 0.01mol of NH 4 Stirring Cl for 2h, stopping reaction, filtering the obtained reaction product, and recrystallizing with water for 3 times to obtain the compound with the molecular formula of (NH) 4 ) 5 PW 11 TiO 39 Ammonium titanium phosphotungstate.
Example 2
Cyclohexanone (0.05 mol), ammonium titanium phosphotungstate (0.0125 mol), ammonia (0.075 mol-25% ammonia concentration) and hydrogen peroxide (0.025 mol-30% hydrogen peroxide concentration) were added to the flask, and the reaction was stopped after magnetically stirring and reacting at 30 ℃ under normal pressure for 3 hours. Cooling the reaction solution to room temperature, and extracting the reaction solution by using toluene (5 ml-15 ml); the reaction liquid is divided into two layers, the upper layer is an organic phase containing the product cyclohexanone oxime, and the lower layer is a titanium salt phase containing ammonium phosphotungstate; distilling the lower layer liquid under reduced pressure to remove water, drying, and using for the next reaction; taking the supernatant as an internal standard, and analyzing on a gas chromatograph, wherein the reaction result shows that the conversion rate of the cyclohexanone is 72.49 percent and the selectivity of the cyclohexanone oxime is 60.58 percent.
Example 3
The other steps are the same as example 2, except that solvent ethanol with 4 times of the volume of cyclohexanone is added into the system before the reaction, the reaction result is that the conversion rate of the cyclohexanone is 56.39 percent, and the selectivity of the cyclohexanone oxime is 39.53 percent.
Example 4
The other steps are the same as example 3, except that the added solvent is changed into acetonitrile, the reaction result is that the conversion rate of cyclohexanone is 48.86%, and the selectivity of cyclohexanone oxime is 36.23%.
Example 5
The other steps were the same as example 3 except that the solvent added was changed to cyclohexane, and the reaction result was that the conversion of cyclohexanone was 43.56% and the selectivity of cyclohexanone oxime was 34.78%.
Example 6
The other steps are the same as example 3 except that the solvent added is changed to tert-butanol, the conversion of cyclohexanone is 60.35% and the selectivity of cyclohexanone oxime is 40.26%.
Example 7
The other steps are the same as example 3, except that the added solvent is changed to water, the reaction result is that the conversion rate of cyclohexanone is 69.29%, and the selectivity of cyclohexanone oxime is 54.86%.
Example 8
The other steps are the same as example 2, except that the amount of titanium ammonium phosphotungstate added is 0.005mol, the conversion of cyclohexanone is 68.34% and the selectivity of cyclohexanone oxime is 56.23%.
Example 9
The other steps are the same as example 2, except that 0.025mol of titanium ammonium phosphotungstate was added, the conversion of cyclohexanone was 78.61%, and the selectivity of cyclohexanone oxime was 72.78%.
Example 10
The other steps are the same as example 2, except that the amount of titanium ammonium phosphotungstate added is 0.0375mol, the conversion of cyclohexanone is 78.82% and the selectivity of cyclohexanone oxime is 73.12%.
Example 11
The other steps are the same as example 2, except that the amount of titanium ammonium phosphotungstate added is 0.05mol, the reaction result is that the conversion of cyclohexanone is 79.03% and the selectivity of cyclohexanone oxime is 73.83%.
Example 12
The other steps are the same as example 9 except that 0.025mol of ammonia water is added, the conversion of cyclohexanone is 62.26% and the selectivity of cyclohexanone oxime is 46.38%.
Example 13
The other steps are the same as example 9, except that the ammonia added is 0.05mol, the conversion of cyclohexanone is 69.31% and the selectivity of cyclohexanone oxime is 54.23%.
Example 14
The other steps are the same as example 9, except that the ammonia added is 0.1mol, the reaction result is that the conversion rate of cyclohexanone is 73.47%, and the selectivity of cyclohexanone oxime is 64.22%.
Example 15
The other steps are the same as example 9, except that the amount of ammonia added is 0.125mol, the conversion of cyclohexanone is 69.92% and the selectivity of cyclohexanone oxime is 62.24%.
Example 16
The other steps are the same as example 9 except that 0.025mol of hydrogen peroxide is added, the conversion of cyclohexanone is 80.35% and the selectivity of cyclohexanone oxime is 76.28%.
Example 17
The other steps are the same as example 9, except that 0.075mol of hydrogen peroxide is added, the reaction result is a cyclohexanone conversion of 85.39% and cyclohexanone oxime selectivity of 80.34%.
Example 18
The other steps were the same as in example 9 except that 0.1mol of hydrogen peroxide was fed, the conversion of cyclohexanone was 80.02% and the selectivity of cyclohexanone oxime was 78.36%.
Example 19
The other steps are the same as example 9 except that 0.125mol of hydrogen peroxide is added, the conversion of cyclohexanone is 72.03% and the selectivity of cyclohexanone oxime is 73.32%.
Example 20
The other steps are the same as example 17 except that the reaction temperature is 20 ℃, the conversion of cyclohexanone is 75.32% and the selectivity of cyclohexanone oxime is 63.25%.
Example 21
The other steps are the same as example 17 except that the reaction temperature is 40 ℃, the conversion rate of cyclohexanone is 83.25% and the selectivity of cyclohexanone oxime is 79.96%.
Example 22
The other steps were the same as in example 17 except that the reaction temperature was 50 ℃ and the reaction result was 73.01% cyclohexanone conversion and 68.20% cyclohexanone oxime selectivity.
Example 23
The other steps were the same as in example 17 except that the reaction temperature was 60 ℃ and the reaction results in a cyclohexanone conversion of 60.13% and a cyclohexanone oxime selectivity of 53.68%.
Example 24
The other steps were the same as in example 17 except that the reaction time was 4 hours, the conversion of cyclohexanone was 86.35% and the selectivity of cyclohexanone oxime was 83.28%.
Example 25
The other steps are the same as example 17 except that the reaction time is 5 hours, the conversion of cyclohexanone is 90.36% and the selectivity of cyclohexanone oxime is 89.44%.
Example 26
The other steps are the same as example 17, except that the reaction time is 6h, the conversion of cyclohexanone is 91.17% and the selectivity of cyclohexanone oxime is 89.13%.
Example 27
The other steps are the same as example 17 except that the reaction time is 7 hours, the conversion of cyclohexanone is 92.5% and the selectivity of cyclohexanone oxime is 91.0%.
Example 28
The other steps are the same as in example 25 except that after the reaction mixture was cooled to room temperature, the titanium ammonium phosphotungstate was recovered and the recovered titanium ammonium phosphotungstate was compared with the newly prepared titanium ammonium phosphotungstate for catalyzing the ammoximation of cyclohexanone. The conversion rate of the cyclohexanone and the selectivity of the cyclohexanone oxime are basically unchanged, which shows that after the reaction is finished, the ammonium titanium phosphotungstate still has a keggin type structure, and the catalyst can be recycled, so that the environment-friendly synthesis process of the cyclohexanone oxime is realized.
Summary of 28 implementation examples
TABLE 1 Effect of solvents on Cyclohexanone Ammoximation
Table 1 Influence ofsolvent on ammoximation ofcyclohexanone
TABLE 2 influence of catalyst dosage on Cyclohexanone Ammoximation reaction
Table2 Influence ofthe amount ofcatalyst on ammoximation ofcyclohexanone
TABLE 3 influence of the amount of Ammonia addition on the cyclohexanone ammoximation reaction
Table3 Influence ofthe addition ofammonia on ammoximation ofcyclohexanone
TABLE 4 Effect of hydrogen peroxide addition on cyclohexanone ammoximation reaction
Table4 Influence ofthe addition ofhydrogen peroxide on ammoximation ofcyclohexanone
TABLE 5 Effect of reaction temperature on Cyclohexanone Ammoximation reaction
Table 5Influence ofthe reaction temperature on ammoximation ofcyclohexanone
TABLE 6 Effect of reaction time on Cyclohexanone Ammoximation reaction
Table 6Influence ofthe reaction time on ammoximation ofcyclohexanone
The examples show that titanium ammonium phosphotungstate as a catalyst has high catalytic activity for catalyzing cyclohexanone ammoximation reaction, reaction conditions such as material proportion, reaction temperature, reaction time and the like have great influence on the cyclohexanone ammoximation reaction, and the appropriate reaction conditions can obviously improve the yield of cyclohexanone oxime. In addition, for a reaction solvent, the catalytic effect is better under the condition of no solvent, and meanwhile, the use and subsequent separation of the solvent are avoided when no solvent exists, so that the cost is saved.
The invention is not the best known technology. It should be understood that although the present invention has been clearly illustrated by the foregoing examples, various changes and modifications may be made therein by those skilled in the art without departing from the spirit and scope of the invention, and it is intended to cover all such changes and modifications as fall within the scope of the appended claims.
Claims (2)
1. A method for synthesizing cyclohexanone oxime by catalyzing cyclohexanone with titanium ammonium phosphotungstate is characterized by comprising the following steps:
adding cyclohexanone, ammonia water, hydrogen peroxide and ammonium titanium phosphotungstate into a reactor, reacting for 3-7h under the condition of no solvent and under the condition of normal pressure of 20-60 ℃ and stirring, and cooling to room temperature after the reaction is finished to obtain a product cyclohexanone-oxime;
wherein the molar ratio of materials is cyclohexanone: ammonia water: hydrogen peroxide: ammonium titanium phosphotungstate =1:0.5-2.5:0.5-2.5:0.1 to 1;
the structural formula of the ammonium titanium phosphotungstate is as follows: (NH) 4 ) 5 PW 11 TiO 39 。
2. The method for synthesizing cyclohexanone oxime by catalyzing cyclohexanone with titanium ammonium phosphotungstate according to claim 1, wherein the method further comprises recovering the titanium ammonium phosphotungstate catalyst, and comprises the following steps: after the reaction is finished, adding an extracting agent for extraction, and dividing the reaction liquid into two layers, wherein the upper layer is an organic phase containing the product cyclohexanone oxime, and the lower layer is a titanium salt phase containing ammonium phosphotungstate; distilling the lower layer liquid under reduced pressure to remove water, drying, and using for the next reaction;
wherein, the volume ratio is cyclohexanone: extractant =1:1 to 3; the extractant is toluene.
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| US6121187A (en) * | 1995-12-02 | 2000-09-19 | Studiengesellschaft Kohle Mbh | Amorphous, microporous mixed oxide catalysts with controlled surface polarity for selective heterogeneous catalysis, adsorption and material separation |
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