Method for preparing caprolactam by using a microreactor under lewis acid catalysis

Patent metadata

Field	Value
Publication number	US-9624176-B2
Application number	US-201615192869-A
Country	US
Kind code	B2
Filing date	Jun 24, 2016
Priority date	Jul 8, 2015
Publication date	Apr 18, 2017
Grant date	Apr 18, 2017

Abstract

A method for preparing caprolactam by using a microreactor under Lewis acid catalysis, wherein a hydroxyl group in a cyclohexanone oxime is activated to obtain a cyclohexanone oxime sulfonates intermediate, then rearranged under Lewis acid catalysis to prepare the caprolactam. The method of this invention has a simple process and a high operation safety and selectivity, the reaction condition is mild, an efficient reaction can take place even at room temperature, the reaction time is short, the conversion of the cyclohexanone oxime can reach 100% within a short time, the selectivity of the caprolactam can reach 99%, the energy consumption is greatly reduced in the premise of maintaining a high yield, and the production cost is reduced, being an efficient and green and environmentally friendly method of for synthesizing the caprolactam.

First claim

What is claimed is:

1. A method for preparing caprolactam by using a microreactor under Lewis acid catalysis, comprising the following steps:
(1) cyclohexanone oxime is dissolved in an organic solvent, an organic acid binding agent is added, and homogeneously mixed, to obtain a homogeneous solution;
(2) a sulfonyl chlorides compound is dissolved in an organic solvent, and homogeneously mixed, to obtain a homogeneous solution;
(3) a Lewis acid is dissolved in an organic solvent, and homogeneously mixed, to obtain a homogeneous solution;
(4) the homogeneous solution obtained in step (1) and the homogeneous solution obtained in step (2) are concurrently and respectively pumped into a first microchannel reactor of a microreactor, and completely reacted, to obtain a cyclohexanone oxime sulphonates intermediate;
(5) a mixed system obtained in step (4) and the homogeneous solution obtained in step (3) are concurrently and respectively pumped into a second microchannel reactor of the microreactor, and completely reacted, a outflow liquid is collected, to obtain the caprolactam.

2. The method for preparing caprolactam by using a microreactor under Lewis acid catalysis according to claim 1 , characterized in that, in step (1), the organic solvent is acetonitrile, toluene, DMSO or dichloromethane, and the organic acid binding agent is pyridines acid binding agent and organic amines acid binding agent.

3. The method for preparing caprolactam by using a microreactor under Lewis acid catalysis according to claim 1 , characterized in that, in the homogeneous solution obtained in step (1), the concentration of the cyclohexanone oxime is 0.2-3.0 mol/L, and the concentration of the organic acid binding agent is 0.3-5.0 mol/L.

4. The method for preparing caprolactam by using a microreactor under Lewis acid catalysis according to claim 1 , characterized in that, in step (2), the sulfonyl chlorides compound is any one of sulfonyl chloride, methanesulfonyl chloride, benzenesulfonyl chloride, p-tolunesulfonyl chloride and p-nitrobenbenzenesulfonyl chloride or a combination thereof, the organic solvent is acetonitrile, toluene, DMSO or dichloromethane; in the homogeneous solution obtained in step (2), the concentration of the sulfonyl chlorides compound is 0.2-3.0 mol/L.

5. The method for preparing caprolactam by using a microreactor under Lewis acid catalysis according to claim 1 , characterized in that, in step (3), the Lewis acid is anhydrous aluminum chloride, boron trifluoride diethyl etherate, iron trichloride, stannic chloride or zinc chloride; the organic solvent is acetonitrile, toluene, DMSO or dichloromethane; in the homogeneous solution obtained in step (3), the concentration of the Lewis acid is 0.4-5.0 mol/L.

6. The method for preparing caprolactam by using a microreactor under Lewis acid catalysis according to claim 1 , characterized in that, a reaction mole ratio of the cyclohexanone oxime, the organic acid binding agent and the sulfonyl chlorides compound is 1:1-2.5:1-1.5, and the reaction mole ratio of the cyclohexanone oxime sulphonates intermediate and the Lewis acid is 1:1-5.

7. The method for preparing caprolactam by using a microreactor under Lewis acid catalysis according to claim 1 , characterized in that, in the first microchannel reactor of step (4), the reaction temperature is 25-50° C., the reaction residence time is 5-20 minutes; wherein, the flow rate for pumping the homogeneous solution obtained in step (1) into the first microchannel reactor is 0.1-2.0 ml/min, the flow rate for pumping the homogeneous solution obtained in step (2) into the first microchannel reactor is 0.15-2.5 ml/min.

8. The method for preparing caprolactam by using a microreactor under Lewis acid catalysis according to claim 1 , characterized in that, in the second microchannel reactor of step (5), the reaction temperature is 25-50° C., the reaction residence time is 5-25 minutes; wherein, the flow rate for pumping the homogeneous solution obtained in step (3) into the second microchannel reactor is 0.5-3.0 ml/min, the flow rate for pumping the mixed system obtained in step (4) into the second microchannel reactor is 0.25-4.5 ml/min.

9. The method for preparing caprolactam by using a microreactor under Lewis acid catalysis according to claim 1 , characterized in that, the volume of the first microchannel reactor is 5-15 ml, and the volume of the second microchannel reactor is 5-25 ml.

Assignees

• Nanjing Tech Univ (Cn)
• Nanjing University Of Technology

Inventors

• Guo Kai
• Li Xin
• Fang Zheng
• Zhang Kai
• Yu Qi
• Ouyang Pingkai

Classifications

• C07D223/10 Primary

  attached in position 2 · CPC title

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title