Process for the manufacture of 2,3,3,3-tetrafluoropropene by gas phase fluorination of pentachloropropane

Patent metadata

Field	Value
Publication number	US-2016145175-A1
Application number	US-201615008896-A
Country	US
Kind code	A1
Filing date	Jan 28, 2016
Priority date	Jan 21, 2011
Publication date	May 26, 2016
Grant date	—

Abstract

The present invention provides a process of catalytic fluorination in gas phase of product 1,1,1,2,3-pentachloropropane or/and 1,1,2,2,3-pentachloropropane into product 2,3,3,3-tetrafluoropropene in presence of a catalyst.

First claim

1 . Process of catalytic fluorination in gas phase of product 1,1,1,2,3-pentachloropropane and/or 1,1,2,2,3-pentachloropropane into product 2,3,3,3-tetrafluoropropene.

2 . Process according to claim 1 , carried out in a single stage, preferably in one reactor, more preferably in one catalytic bed.

3 . Process according to claim 1 or 2 , wherein the product 2,3,3,3-tetrafluoropropene is present at a concentration of at least 1%, preferably more than 2%, more preferably more than 3%.

4 . Process according to any one of claims 1 to 3 , wherein said catalyst is a chromium catalyst, supported or unsupported, preferably unsupported.

5 . Process according to any one of claims 1 to 4 , wherein said catalyst further comprises a co-catalyst selected from Ni, Co, Zn, Mn, Mg or mixtures thereof, preferably nickel or magnesium, and wherein said co-catalyst is preferably present in an amount from about 1-10 wt % of said fluorination catalyst.

6 . Process according to any one of claims 1 to 5 , carried, out in the presence of a catalyst comprising Ni—Cr, preferably supported.

7 . Process according to any one of claims 1 to 6 , wherein said catalyst is supported on a support selected from fluorinated alumina, fluorinated chromia, fluorinated activated carbon or graphite carbon.

8 . Process according to any one of claims 1 to 7 , wherein said fluorination catalyst is activated with a fluorine-containing compound, preferably hydrogen fluoride.

9 . Process according to one of the claims 1 to 8 , in which the 1,1,1,2,3-pentachloropropane contains up to 40 mol % of isomer 1,1,2,2,3-pentachloropropane.

10 . Process according to any one of claims 1 to 9 , which is Carried out at a pressure from 3 to 20 bars, preferably 5 to 15 bars, more preferably 7 to 10 bars.

11 . Process according to any one of claims 1 to, carried out at a temperature of from 200 to 450° C., preferably from 300 to 4.30° C., more preferably from 320 to 420° C.

12 . Process according to any one of claims 1 to 11 , carried out with a contact time from 6 to 100 sec, preferably from 10 to 80 sec, more preferably from 15 to 50 sec.

13 . Process according to any one of claims 1 to 12 , carried out with a molar ratio HF: 240 from 3:1 to 150:1, preferably 4:1 to 70:1, more preferably' 5:1 to 50:1.

14 . Process according to any one of claims 1 to 13 , carried out in the presence of a polymerization inhibitor, preferably chosen from the group consisting of p-methexyphenol, t-amylphenol, limonene, quinones, hydroquinones, epoxides, amines and mixtures thereof.

15 . Process according to any one of claims 1 to 14 , carried out in the presence of oxygen and/or chlorine

16 . Process according to claim 15 , carried out in the presence of oxygen and/or chlorine in an amount of from 0.05 to 15 mole %, more preferably 0.5 to 10 mole % of oxygen or chlorine per pentachloropropane molecule.

17 . Process according to any one of claims 1 to 16 , comprising the steps of:
(i) contacting 1,1,1,2,3-pentachloropropane (HCC 240db) and/or 1,1,2,2,3-pentachloropropane (HCC 240aa) with hydrogen fluoride HF in gas phase in the presence of a fluorination catalyst under conditions sufficient to produce a reaction mixture comprising 2,3,3,3-tetrafluoropropene (1234yf);
(ii) separating the reaction mixture into a first stream comprising 2,3,3,3-tetrafluoropropene (1234yf) and a second stream comprising 2-chloro-3,3,3-trifluoro-l-propene (1233xf) and 1,1,1,2,2-pentafluoropropane (245cb);
(iii) recycling at least a part of the second stream at least in part back to step (i).

18 . Process according to any one of claims 1 to 16 , comprising the steps of:
(i) contacting 1,1,1,2,3-pentachloropropane (HCC 240db) and/or 1,1,2,2,3-pentachloropropane (HCC 240aa) with hydrogen fluoride HF in gas phase in the presence of a fluorination catalyst under conditions sufficient to produce a reaction mixture comprising 2,3,3,3-tetrafluoropropene (1234yf);
(ii) separating the reaction mixture into a first stream comprising HCl, 2,3,3,3-tetrafluoropropene (1234yf) and a second stream comprising HF, 2-chloro-3,3,3-trifluoro-1-propene (1233xf) and 1,1,1,2,2-pentafluoropropane (245cb);
(iii) recycling at least a part of the second stream at least in part back to step (i).

19 . Process according to claim 18 , wherein the first stream is further separated into HCl and 2,3,3,3-tetrafluoropropene (1234yf), preferably in a distillation step.

20 . Process according to any one of claims 1 to 16 , comprising the steps of:
(i) contacting 1,1,1,2,3-pentachloropropane (HCC 240db) and/or 1,1,2,2,3-pentachloropropane (HCC 240aa) with hydrogen fluoride HF in gas phase in the presence of a fluorination catalyst under conditions sufficient to produce a reaction mixture comprising 2,3,3,3-tetrafluoropropene (1234yf);
(ii) separating the reaction mixture into HCl and a stream containing the fluorinated products;
(iii) separating said stream containing the fluorinated products into a first stream comprising 2,3,3,3-tetrafluoropropene (1234yf) and a second stream comprising HF, 2-chloro-3,3,3-trifluoro-l-propene (1233xf) and 1,1,1,2,2-pentafluoropropane (245cb);
(iv) recycling at least a part of the second stream at least in part back to step (i).

21 . Process according to any one of claims 17 to 20 , wherein the separating step is a distillation step.

22 . The process according to any one of the preceding claims which is continuous.

Assignees

• Arkema France

Inventors

• Deur-Bert Dominique
• Pigamo Anne
• Doucet Nicolas
• Wendlinger Laurent

Classifications

• C07C17/25

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

• C07C17/383 Primary

  by distillation · CPC title

• C07C17/206 Primary

  the other compound being HX · CPC title

• C07C21/18

  containing fluorine · CPC title

• B01J27/125

  with scandium, yttrium, aluminium, gallium, indium or thallium · CPC title