Continuous low-temperature process to produce trans-1-chloro-3,3,3-trifluoropropene

Patent metadata

Field	Value
Publication number	US-9643903-B2
Application number	US-201414195893-A
Country	US
Kind code	B2
Filing date	Mar 4, 2014
Priority date	Sep 3, 2010
Publication date	May 9, 2017
Grant date	May 9, 2017

Abstract

Disclosed is process for the production of (E) 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)) by conducting a continuous reaction without the use of a catalyst. Also disclosed is an integrated system for producing hydrofluoro olefins, particularly 1233zd(E). The manufacturing process includes six major unit operations: (1) a fluorination reaction of HCC-240fa (in continuous or semi-batch mode) using HF with simultaneous removal of by-product HCl and the product 1233zd(E); (2) recycle of unreacted HCC-240fa and HF together with under-fluorinated by-products back to (1); (3) separation and purification of by-product HCl; (4) separation of excess HF back to (1); (5) purification of final product, 1233zd(E); and (6) isomerization of by-product 1233zd(Z) to 1233zd(E) to maximize the process yield.

First claim

What is claimed is:

1. An integrated system for producing (E)1-chloro-3,3,3-trifluoropropene, wherein the system comprises:
(a) one or more feed streams cumulatively comprising hydrogen fluoride and a reactant composition selected from the group consisting of 1,1,1,3,3-pentachloro-propane, or 1,1,1,3,3-pentachloropropane, and/or 1,1,3,3-tetrachloropropene, and/or 1,3,3,3-tetrachloropropene;
(b) a liquid phase reactor system consisting of a series of one or more agitated reactors, each fed by its predecessor, and wherein the liquid phase reactor series is fluidly connected to the one or more feed streams;
(c) recycle system comprising a recycle distillation column, a reflux stream fluidly connected to the top of the reactor and a combined first crude product stream fluidly connected to the top of the reactor, wherein the reflux stream is fluidly connected to a liquid phase reactor in the series;
(d) a hydrogen chloride removal system comprising a first distillation column, a hydrogen chloride by-product stream fluidly connected to the first distillation column, and a second crude product stream fluidly connected to the first distillation column, wherein the first distillation column is fluidly connected to a stripping column;
(e) a hydrogen fluoride recovery system comprising a sulfuric acid absorption and recycle system or a phase separation vessel, a second recycle stream comprising hydrogen fluoride fluidly connected to the sulfuric acid absorption and recycle system or a phase separation vessel;
(f) a third product stream comprising (E) and (Z) 1-chloro-3,3,3-trifluoro-propene fluidly connected to the sulfuric acid absorption and recycle system or a phase separation vessel, wherein the sulfuric acid absorption and recycle system or a phase separation vessel is fluidly connected to the second crude product stream and a 1-chloro-3,3,3-trifluoropropene purification system comprising a second distillation column fluidly connected to the third product stream and
(g) a final product stream comprising at least 50 wt. percent (E)1-chloro-3,3,3-trifluoropropene fluidly connected to the second distillation column; a second by-product stream fluidly connected to the distillation column, an isomerization reactor fluidly connected to the second by-product stream; and a product recycle stream fluidly connected to the isomerization reactor and the second distillation column.

2. The integrated system of claim 1 , wherein one or more of the reactors in part (b) is combined with an attached rectifying column supplied with low-temperature cooling, and maintained at a temperature of about 65° C. to about 175° C.

3. The integrated system of claim 1 , wherein the separating and recycling of HF is accomplished by phase separation.

4. The integrated system of claim 1 , wherein each reactor is maintained at a temperature range of 65° C. to 175° C.

5. The integrated system of claim 1 , wherein each reactor is maintained at a temperature range of 85° C. to 170° C.

6. The integrated system of claim 1 , wherein each reactor is maintained at a temperature range of 95° C. to 160° C.

Assignees

• Honeywell Int Inc

Inventors

• Pokrovski Konstantin A
• Merkel Daniel C
• Tung Hsueh Sung

Classifications

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C07C17/383

  by distillation · CPC title

• C07C21/18

  containing fluorine · CPC title

• C01B7/0706 Primary

  of hydrogen chloride · CPC title

• C01B7/0712

  by distillation · CPC title