Integrated process to co-produce 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 240fa 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 byproduct HCl); (2) the 244fa stream can then be used to directly produce any of the three desired products; (3a) the 244fa stream can be dehydrochlorinated to produce the desired second product 1234ze(E); and/or (3b) the 244fa stream can be dehydrofluorinated to produce 1233zd(E) if more of that product is desired; and/or (3c) the 244fa stream can be further fluorinated to form 245fa.
1. An integrated process to co-produce trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), trans-1,3,3,3-tetrafluoropropene (1234ze(E)), and 1,1,1,3,3-pentafluoropropane (245fa) comprising the steps of:
(1) reacting 1,1,1,3,3-pentachloropropane (240fa) with HF in a liquid-phase catalyzed reactor wherein the catalyst comprises TiCl 4 so as to co-produce at least 40% 1233zd(E), and at least 5% 3-chloro-1,1,1,3-tetrafluoro-propane (244fa), plus byproduct HCl;
(2) further reacting the 244fa product stream as follows:
(3a) the 244fa stream is dehydrochlorinated to produce 1234ze(E); and
(3b) the 244fa stream is dehydrofluorinated to produce 1233zd(E); and
(3c) the 244fa stream is further fluorinated to produce 245fa.
2. The process of claim 1 , wherein the 244fa stream is dehydrochlorinated to produce 1234ze(E).
3. The process of claim 1 , wherein the 244fa stream is dehydrofluorinated to produce 1233zd(E).
4. The process of claim 1 , wherein the 244fa stream is further fluorinated to produce 245fa.
5. The process of claim 1 , wherein the step (1) fluorination reaction is conducted in a continuous mode with simultaneous removal of the byproduct HCl and separation of the 1233zd(E) and 244fa.
6. The process of claim 1 , wherein the step (1) fluorination reaction is conducted in a batch mode with removal of the byproduct HCl and separation of the 1233zd(E) and 244fa.
7. The process of claim 1 , wherein step (3b) is a vapor phase reaction using a dehydrofluorination catalyst.
8. The process of claim 7 , wherein the dehydrofluorination catalyst is selected from the group consisting of fluorinated metal oxides, metal fluorides, and supported metal catalysts.
9. The process of claim 7 , wherein the dehydrofluorination catalyst is fluorinated Cr 2 O 3 .
10. The process of claim 1 , further comprising one or more purification steps to recover the 1233zd(E), 245fa, and 1234ze(E) products.
11. The process of claim 6 , which further includes HCl recovery.
12. The process of claim 11 , which further includes an HF recycle step.
13. The process of claim 12 , which further includes recycle of unreacted 244fa to step (2) of the process.
14. An integrated process to co-produce trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and one or both of trans-1,3,3,3-tetrafluoropropene (1234ze(E)), and 1,1,1,3,3-pentafluoropropane (245fa), comprising the steps of:
(1) reacting 1,1,1,3,3-pentachloropropane (240fa) with HF in a liquid-phase catalyzed reactor wherein the catalyst comprises TiCl 4 so as to co-produce at least 40% 1233zd(E) and 3-chloro-1,1,1,3-tetrafluoropropane (244fa), plus byproduct HCl; and
(2) further reacting the 244fa product stream with one or more of the following reactions:
(3a) the 244fa stream is dehydrochlorinated to produce 1234ze(E);
(3b) the 244fa stream is dehydrofluorinated to produce 1233zd(E);
(3c) the 244fa stream is further fluorinated to produce 245fa.
15. The process of claim 14 , wherein the 244fa stream is dehydrochlorinated to produce 1234ze(E).
16. The process of claim 14 , wherein the 244fa stream is dehydrofluorinated to produce 1233zd(E).
17. The process of claim 14 , wherein the 244fa stream is further fluorinated to produce 245fa.
18. The process of claim 14 , which further includes recycle of unreacted 244fa to step (2) of the process.