Methods of making 2,3,3,3-tetrafluoro-2-propene

Patent metadata

Field	Value
Publication number	US-9890096-B2
Application number	US-201113313649-A
Country	US
Kind code	B2
Filing date	Dec 7, 2011
Priority date	Jan 19, 2011
Publication date	Feb 13, 2018
Grant date	Feb 13, 2018

Abstract

Disclosed is a process for the manufacture of 1234yf from 1,1,2,3-tetrachloropropene, abbreviated herein as “TCP,” in three integrated steps:
(a) the R-1 hydrofluorination of TCP to form 1233xf in the vapor phase; (b) the R-2 hydrofluorination of 1233xf to form 244bb in either the liquid phase or in the liquid phase followed by the vapor phase; and (c) the R-3 dehydrochlorination of the 244bb in either the liquid or the vapor phase to produce 1234yf;

wherein the vapor phase hydrofluorination of TCP in step (a) is carried out at a higher pressure than the liquid phase hydrofluorination of 1233xf; and
wherein the HC1 generated during these steps is scrubbed with water to form an acid solution and the organic components are scrubbed with a caustic solution and then dried before further processing.

First claim

What is claimed is:

1. A process for the formation of 2,3,3,3-tetrafluoro-2-propene (HFO-1234yf) from 1,1,2,3-tetrachloropropene (TCP), wherein the reaction includes the following steps:
(a) conducting the hydrofluorination reaction of TCP with HF under conditions effective to provide at least 85%, conversion of TCP to 2-chloro-3,3,3-trifluoropropene (1233xf), where the mole ratio of HF to TCP is about 20:1, the reaction temperature is about 300° C. and the reaction pressure is about 120 psig;
(b) cooling the effluent from step (a) which contains 1233xf, HCl, HF and any unreacted TCP, and separating any unreacted TCP for recycle to step (a);
(c) feeding the mixture of 1233xf, HCl and HF from step (b) to a liquid phase reactor containing catalyst for hydrofluorination of the 1233xf to 2-chloro-1,1,1,2-tetrafluoropropane (244bb), under conditions effective to provide at least 98% conversion of 1233xf to 244bb, where the mole ratio of HF to 1233xf is about 20:1, the reaction temperature is about 85° C. and the reaction pressure is about 100 psig;
(d) feeding the mixture of 244bb, HCl, unreacted 1233xf and HF formed in step (c) to a catalyst stripper, from which unreacted HF and catalyst are recycled to the step (c) reactor;
(e) feeding the effluent from the catalyst stripper through a bed containing SbCl 5 /Carbon catalyst for further conversion of 1233xf to 244bb;
(f) feeding the effluent from the SbCl 5 /C catalyst bed in step (e) to a column to separate the HCl from the mixture of 244bb, 1233xf, HF and HCl;
(g) feeding the mixture of 244bb, 1233xf, HF from step (f) to an HF recovery system by subjecting the mixture to a phase separation to separate a stream rich in organic and a stream rich in HF;
(h) feeding the organic stream from step (g) to a dehydrochlorination reactor and dehydrochlorinating the 244bb mixture under conditions effective to provide 1234yf and unreacted 244bb and recycling unreacted 244bb to step (c).

2. The process of claim 1 , wherein the dehydrochlorination is conducted using a vapor phase reactor containing catalyst, where the reaction temperature is about 400° C. and the reaction pressure is about 15 psig.

3. The process of claim 2 , wherein the effluent from step (h) containing 1234yf, HCl and unreacted 244bb is deacidified, dried, compressed and distilled so that the 1234yf is recovered and unreacted 244bb is recycled to the dehydrochlorination reactor in step (h).

4. The process of claim 1 , wherein the dehydrochlorination is conducted in a liquid phase reactor in the presence of an aqueous base at a temperature of about 50° C.

5. The process of claim 4 , wherein the effluent from step (h) is dried, compressed and distilled, so that 1234yf is recovered and unreacted 244bb is recycled to the dehydrochlorination reactor in step (h).

6. The process of claim 4 , wherein any unreacted 244bb is recycled to the liquid phase reactor in step (c).

Assignees

• Cottrell Stephen A
• Chiu Yuon
• Kopkalli Haluk
• Tung Hsueh Sung
• Uhrich Kevin D
• Scheidle Peter
• Honeywell Int Inc

Inventors

• Cottrell Stephen A
• Chiu Yuon
• Kopkalli Haluk
• Tung Hsueh Sung
• Uhrich Kevin D
• Scheidle Peter

Classifications

• C07C17/383

  by distillation · CPC title

• C07C17/38

  Separation; Purification; Stabilisation; Use of additives · CPC title

• C07C17/25 Primary

  by splitting-off hydrogen halides from halogenated hydrocarbons · CPC title

• C07C19/10

  and chlorine · CPC title

• C07C17/21 Primary

  with simultaneous increase of the number of halogen atoms · CPC title