Process for preparing dichloropropanol

Patent metadata

Field	Value
Publication number	US-9850190-B2
Application number	US-201615263727-A
Country	US
Kind code	B2
Filing date	Sep 13, 2016
Priority date	Dec 18, 2015
Publication date	Dec 26, 2017
Grant date	Dec 26, 2017

Abstract

Provided is a process of preparing dichloropropanol, DCP. The process includes the step of: subjecting a three-carbon material to a first chlorination reaction with an aqueous hydrochloric acid solution in the presence of a carboxylic acid catalyst; adding the three-carbon material into the first mixture solution to undergo a second chlorination reaction and obtain a second mixture solution containing less than 13 wt % of hydrochloric acid; distilling the second mixture solution; and purifying the overhead product by oil-water separation to obtain DCP from the oil phase. By lowering the concentration of the hydrochloric acid contained in the mixture to be distilled, the DCP product can be straightly obtained via distillation and oil-water separation, thereby effectively simplifying the process of preparing DCP.

First claim

What is claimed is:

1. A process of preparing dichloropropanol, comprising steps of:
step (a): subjecting a three-carbon material to a first chlorination reaction with an aqueous hydrochloric acid solution in the presence of a carboxylic acid catalyst, to obtain a first mixture solution, the three-carbon material comprising glycerin, glycerin ester, monochloropropanediol, monochloropropanediol ester or their combination;
step (b): adding the three-carbon material into the first mixture solution to undergo a second chlorination reaction, to obtain a second mixture solution, the second mixture solution containing hydrochloric acid in a concentration less than 13 wt %;
step (c): distilling the second mixture solution to obtain an overhead product; and
step (d): separating the overhead product into an oil phase and an aqueous phase, to collect the dichloropropanol from the oil phase.

2. The process as claimed in claim 1 , wherein a molar ratio of the three-carbon material relative to the hydrochloric acid contained in the aqueous hydrochloric acid solution ranges from 1:2 to 1:6.

3. The process as claimed in claim 1 , wherein a molar ratio of the three-carbon material relative to the carboxylic acid catalyst ranges from 1:0.1 to 1:1, and the carboxylic acid catalyst is a carboxylic acid having 1 to 8 carbon atoms, a carboxylic acid anhydride having 1 to 8 carbon atoms, or a carboxylic acid ester having 1 to 8 carbon atoms.

4. The process as claimed in claim 3 , wherein the carboxylic acid catalyst is acetic acid.

5. The process as claimed in claim 1 , wherein a concentration of the aqueous hydrochloric acid solution is equal to or more than 20 wt % and less than 40 wt %.

6. The process as claimed in claim 1 , wherein the first chlorination reaction in step (a) and the second chlorination reaction in step (b) are conducted at a temperature equal to or more than 80° C. and equal to or less than 150° C.

7. The process as claimed in claim 1 , wherein the concentration of the hydrochloric acid contained in the second mixture solution is less than 11 wt %.

8. The process as claimed in claim 7 , wherein the concentration of the hydrochloric acid contained in the second mixture solution is less than 10 wt %.

9. The process as claimed in claim 1 , wherein the process comprises repeating a cycle of steps (a) to (d) for at least one time.

10. The process as claimed in claim 1 , wherein the three-carbon material is a recycled crude glycerin, and the recycled crude glycerin is collected from a saline wastewater from epichlorohydrin saponification.

11. The process as claimed in claim 1 , wherein step (c) comprises:
step (c 1 ): distilling the second mixture solution to obtain the overhead product and a bottom product, the bottom product containing an unchlorinated three-carbon material, the aqueous hydrochloric acid solution, and dichloropropanol; and
step (c 2 ): increasing a concentration of the hydrochloric acid contained in the bottom product to equal to or more than 20 wt % and less than 40 wt %, to obtain a recycled hydrochloric acid solution.

12. The process as claimed in claim 11 , wherein step (c 2 ) comprises:
collecting the bottom product; and
feeding a gaseous hydrochloric acid into the bottom product to increase the concentration of the hydrochloric acid contained in the bottom product to equal to or more than 20 wt % and less than 40 wt %, to obtain the recycled hydrochloric acid solution.

13. The process as claimed in claim 11 , wherein step (c 2 ) comprises:
collecting the bottom product;
dehydrating the bottom product to obtain a dehydrated bottom product; and
feeding an aqueous hydrochloric acid supplement into the dehydrated bottom product to increase the concentration of the hydrochloric acid to equal to or more than 20 wt % and less than 40 wt %, to obtain the recycled hydrochloric acid solution.

14. The process as claimed in claim 11 , wherein the process comprises repeating a cycle of steps (a) to (d) for at least one time, and the aqueous hydrochloric acid solution used in step (a) of the repeated cycle is the recycled hydrochloric acid solution.

15. The process as claimed in claim 12 , wherein the process comprises repeating a cycle of steps (a) to (d) for at least one time, and the aqueous hydrochloric acid solution used in step (a) of the repeated cycle is the recycled hydrochloric acid solution.

16. The process as claimed in claim 13 , wherein the process comprises repeating a cycle of steps (a) to (d) for at least one time, and the aqueous hydrochloric acid solution used in step (a) of the repeated cycle is the recycled hydrochloric acid solution.

17. The process as claimed in claim 1 , wherein the process comprises repeating a cycle of steps (a) to (d) for at least one time, and step (c) of the repeated cycle comprises distilling the second mixture solution and the aqueous phase to obtain the overhead product.

18. The process as claimed in claim 14 , wherein step (c) of the repeated cycle comprises distilling the second mixture solution and the aqueous phase to obtain the overhead product.

19. The process as claimed in claim 15 , wherein step (c) of the repeated cycle comprises distilling the second mixture solution and the aqueous phase to obtain the overhead product.

20. The process as claimed in claim 16 , wherein step (c) of the repeated cycle comprises distilling the second mixture solution and the aqueous phase to obtain the overhead product.

Assignees

• Chang Chun Plastics Co Ltd

Inventors

• Huang Chien-Fu
• Chan Cheng-Hui

Classifications

• C07C29/86

  by liquid-liquid treatment · CPC title

• C07C29/62 Primary

  by introduction of halogen; by substitution of halogen atoms by other halogen atoms · CPC title

• C07C29/80

  by distillation · CPC title

• C07C31/42

  Polyhydroxylic acyclic alcohols · CPC title

• C07C31/36

  the halogen not being fluorine · CPC title