A kind of method of directly synthesizing cyclohexanol by cyclohexylamine

Abstract

The invention discloses a method for directly synthesizing cyclohexanol from cyclohexylamine. The method comprises the following steps: putting the cyclohexylamine, a catalyst, water and tert-butyl alcohol in a high-pressure reaction kettle, charging N2 for replacement, raising the temperature to 140-200 DEG C, not charging hydrogen or charging hydrogen under the pressure of 0.1-7MPa, keeping the pressure, stopping charging the hydrogen after reacting for 4-16h, cooling to room temperature, filtering under the reduced pressure to separate the catalyst from a reaction solution, and performing extraction separation on the reaction solution to obtain an organic phase containing the cyclohexanol, wherein the molar ratio of the cyclohexylamine to the catalyst to the water to the tert-butyl alcohol is equal to 1:(0.0005-0.05):(1-10000):(0.01-10). The method has the characteristics of simple synthesis and environmental friendliness, and the yield of the cyclohexanol is approximate to 100 percent.

Description

technical field

[0001] The invention relates to a new method for directly synthesizing cyclohexanol from cyclohexylamine, specifically a process for directly synthesizing cyclohexanol by using cyclohexylamine as a raw material and using a supported metal catalyst to catalyze the hydration deamination of cyclohexylamine. Chemical technology field. Background technique

[0002] Cyclohexanol is an important organic chemical raw material and an important intermediate for the synthesis of caprolactam, adipic acid, and fine chemicals such as medicine, paint, and dye.

[0003] At present, there are generally three methods for the synthesis of cyclohexanol. (1) Using phenol as a raw material, one-step catalytic hydrogenation to prepare cyclohexanol is relatively simple, but it is limited due to the high price of phenol. (2) Using benzene as a raw material, complete hydrogenation to obtain cyclohexane, and further oxidation to obtain cyclohexanol or cyclohexanone. This is currentl...

Examples

Embodiment 1

[0025] In the autoclave, 1.6g of cyclohexylamine, 0.41g of 2% (wt) Ru / MCM-41 (molecular sieve) catalyst, 170ml of water and 10ml of tert-butanol (the molar ratio of which is 1:0.005:583:6.5) were successively added into the autoclave. Pass N 2 Make a replacement. Then the temperature was raised to 180°C, and the pressure of 3.0 MPa of hydrogen gas was introduced and maintained. After 8 hours of reaction, the hydrogen gas flow was stopped, and the temperature was lowered to room temperature. The catalyst and the reaction solution were separated by filtration under reduced pressure, and the reaction solution was extracted and separated by toluene to obtain an organic phase, which was analyzed by gas chromatography. The yield of the product cyclohexanol by quantitative calculation is 97.8%.

Embodiment 2

[0027] 1.6 g of cyclohexylamine, 0.41 g of 2% Ru / AC catalyst, 170 ml of water and 10 ml of tert-butanol (the molar ratio of which is 1:0.005:583:6.5) were successively added into the autoclave. Pass N 2 Make a replacement. Then the temperature was raised to 180° C., and the pressure of hydrogen was 2.0 MPa and maintained. After 8 hours of reaction, the hydrogen flow was stopped and the temperature was lowered to room temperature. The catalyst and the reaction solution were separated by filtration under reduced pressure, and the reaction solution was extracted and separated by toluene to obtain an organic phase, which was analyzed by gas chromatography. The yield of the product cyclohexanol by quantitative calculation is 99.5%.

Embodiment 3

[0029] Add cyclohexylamine 1.6g, 2%Ru / SiO 2 Catalyst 0.41g, water 170ml and tert-butanol 10ml (the molar ratio is 1:0.005:583:6.5). Pass N 2 Make a replacement. Then the temperature was raised to 180°C, and the pressure of 3.0 MPa of hydrogen gas was introduced and maintained. After 8 hours of reaction, the hydrogen gas flow was stopped, and the temperature was lowered to room temperature. The catalyst and the reaction solution were separated by filtration under reduced pressure, and the reaction solution was extracted and separated by toluene to obtain an organic phase, which was analyzed by gas chromatography. The yield of product cyclohexanol was 98.9% according to quantitative calculation.

technical field

[0001] The invention relates to a new method for directly synthesizing cyclohexanol from cyclohexylamine, specifically a process for directly synthesizing cyclohexanol by using cyclohexylamine as a raw material and using a supported metal catalyst to catalyze the hydration deamination of cyclohexylamine. Chemical technology field. Background technique

[0002] Cyclohexanol is an important organic chemical raw material and an important intermediate for the synthesis of caprolactam, adipic acid, and fine chemicals such as medicine, paint, and dye.

[0003] At present, there are generally three methods for the synthesis of cyclohexanol. (1) Using phenol as a raw material, one-step catalytic hydrogenation to prepare cyclohexanol is relatively simple, but it is limited due to the high price of phenol. (2) Using benzene as a raw material, complete hydrogenation to obtain cyclohexane, and further oxidation to obtain cyclohexanol or cyclohexanone. This is currentl...

Examples

Embodiment 1

[0025] In the autoclave, 1.6g of cyclohexylamine, 0.41g of 2% (wt) Ru / MCM-41 (molecular sieve) catalyst, 170ml of water and 10ml of tert-butanol (the molar ratio of which is 1:0.005:583:6.5) were successively added into the autoclave. Pass N 2 Make a replacement. Then the temperature was raised to 180°C, and the pressure of 3.0 MPa of hydrogen gas was introduced and maintained. After 8 hours of reaction, the hydrogen gas flow was stopped, and the temperature was lowered to room temperature. The catalyst and the reaction solution were separated by filtration under reduced pressure, and the reaction solution was extracted and separated by toluene to obtain an organic phase, which was analyzed by gas chromatography. The yield of the product cyclohexanol by quantitative calculation is 97.8%.

Embodiment 2

[0027] 1.6 g of cyclohexylamine, 0.41 g of 2% Ru / AC catalyst, 170 ml of water and 10 ml of tert-butanol (the molar ratio of which is 1:0.005:583:6.5) were successively added into the autoclave. Pass N 2 Make a replacement. Then the temperature was raised to 180° C., and the pressure of hydrogen was 2.0 MPa and maintained. After 8 hours of reaction, the hydrogen flow was stopped and the temperature was lowered to room temperature. The catalyst and the reaction solution were separated by filtration under reduced pressure, and the reaction solution was extracted and separated by toluene to obtain an organic phase, which was analyzed by gas chromatography. The yield of the product cyclohexanol by quantitative calculation is 99.5%.

Embodiment 3

[0029] Add cyclohexylamine 1.6g, 2%Ru / SiO 2 Catalyst 0.41g, water 170ml and tert-butanol 10ml (the molar ratio is 1:0.005:583:6.5). Pass N 2 Make a replacement. Then the temperature was raised to 180°C, and the pressure of 3.0 MPa of hydrogen gas was introduced and maintained. After 8 hours of reaction, the hydrogen gas flow was stopped, and the temperature was lowered to room temperature. The catalyst and the reaction solution were separated by filtration under reduced pressure, and the reaction solution was extracted and separated by toluene to obtain an organic phase, which was analyzed by gas chromatography. The yield of product cyclohexanol was 98.9% according to quantitative calculation.

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