Integrated process for the co-production of trans-1-chloro-3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoropropene, and 1,1,1,3,3-pentafluoropropane
View Patent ↗Disclosed is an integrated process to co-produce trans-1-chloro-3,3,3-trifluoro-propene (1233zd (E)), trans-1,3,3,3-tetrafluoropropene (1234ze (E)), and 1,1,1,3,3-pentafluoropropane (245fa). Overall the co-production is a three-step process. The chemistry involves the steps of: (1) the reaction of 1,1,1,3-tetrachloropropene and/or 1,1,3,3-tetrachloropropene with anhydrous HF in excess in a liquid-phase catalyzed reactor in such a way as to co-produce primarily 1233zd (E) and 244fa (plus by-product HCl); an optionally (2) the 244fa stream can then be used to directly produce any (or all) of the following desired products; (a) the 244fa stream can be dehydrochlorinated to produce the desired second product 1234ze (E); and/or (b) the 244fa stream can be dehydrofluorinated to produce 1233zd (E) if more of that product is desired; and/or (c) the 244fa stream can be further fluorinated to form 245fa.
1. An integrated process for the production of trans-1-chloro-3,3,3-trifluoropropene (1233zd (E)), trans-1,3,3,3-tetrafluoropropene (1234ze (E)), and 1,1,1,3,3-pentafluoro-propane (245fa) from a starting material comprising 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene, or a mixture thereof, comprising the steps of:
(1) reacting the starting material with HF in a liquid-phase catalyzed reactor so as to co-produce at least about 40% 1233zd (E) and 244fa, plus by-product HCl; and
(2) further reacting the 244fa product stream in the following reactions:
(a) the 244fa stream is dehydrochlorinated to produce 1234ze (E); and
(b) the 244fa stream is dehydrofluorinated to produce 1233zd (E); and
(c) the 244fa stream is further fluorinated to produce 245fa.
2. The process of claim 1 , wherein the starting material comprises 1,1,3,3-tetrachloropropene.
3. The process of claim 1 , wherein the starting material comprises 1,3,3,3-tetrachloropropene.
4. The process of claim 1 , wherein the starting material comprises a mixture of 1,1,3,3-tetrachloropropene and 1,3,3,3-tetrachloropropene.
5. The process of claim 1 , wherein at least a portion of the 244fa stream is dehydrochlorinated to produce 1234ze (E).
6. The process of claim 1 , wherein at least a portion of the 244fa stream is dehydrofluorinated to produce 1233zd (E).
7. The process of claim 1 , wherein at least a portion of the 244fa stream is further fluorinated to produce 245fa.
8. The process of claim 1 , wherein at least a portion of the 244fa stream is dehydrochlorinated to produce 1234ze (E); and at least a portion of the 244fa stream is dehydrofluorinated to produce 1233zd (E); and at least a portion of the 244fa stream is further fluorinated to produce 245fa.
9. The process of claim 1 , wherein the step (1) fluorination reaction is conducted in a continuous mode with simultaneous removal of the by-product HCl and separation of the 1233zd (E) and 244fa.
10. The process of claim 1 , wherein the step (1) fluorination reaction is conducted in a batch mode with removal of the by-product HCl and separation of the 1233zd (E) and 244fa.
11. The process of claim 1 , wherein the liquid phase fluorination catalyst is selected from the group consisting of TiCl 4 , SnCl 4 , TaCl 5 , SbCl 3 , AlCl 3 , or SbCl 5 , alone or in combination.
12. The process of claim 1 , wherein step (b) is a vapor phase reaction using a dehydrofluorination catalyst.
13. The process of claim 12 , wherein the dehydrofluorination catalyst is selected from the group consisting of fluorinated metal oxides, metal fluorides, and supported metal catalysts.
14. The process of claim 13 , wherein the dehydrofluorination catalyst is fluorinated Cr 2 O 3 .
15. The process of claim 1 , further comprising one or more purification steps to recover the 1233zd (E), 245fa, and 1234ze (E) products.
16. The process of claim 15 , which further includes HCl recovery.
17. The process of claim 15 , which further includes an HF recycle step.
18. The process of claim 17 , which further includes recycle of unreacted 244fa.
19. An integrated process for the production of trans-1-chloro-3,3,3-trifluoropropene (1233zd (E)) and one or more of the following compounds, trans-1,3,3,3-tetrafluoropropene (1234ze (E)), and 1,1,1,3,3-pentafluoropropane (245fa); from a starting material comprising 1,1,3,3-tetrachloropropene, 1,3,3,3-tetrachloropropene, or a mixture thereof, comprising the steps of:
(1) reacting the starting material with HF in a liquid-phase catalyzed reactor so as to co-produce at least about 40% 1233zd (E) and 244fa, plus by-product HCl; and further reacting the 244fa product stream in at least one of the following reactions:
(a) the 244fa stream is dehydrochlorinated to produce 1234ze (E); or
(b) the 244fa stream is dehydrofluorinated to produce 1233zd (E); or
(c) the 244fa stream is further fluorinated to produce 245fa.