Process for catalytic conversion of mixtures of HCFO-1233zd(Z) and HCFC-244fa into HCFO-1233zd(E)
A method for conversion of a composition containing HCFO-1233zd(Z) and HCFC-244fa to form HCFO-1233zd(E) by reacting a mixture including HCFO-1233zd(Z) and HCFC-244fa in a vapor phase in the presence of a catalyst to simultaneously isomerize HCFC-1233zd(Z) to form HCFO-1233zd(E) and dehydrohalogenate HCFC-244fa to form HCFO-1233zd(E). The catalyst may be a chromium-based catalyst such as chromium trifluoride, chromium oxyfluoride, or chromium oxide, for example.
1. A method for simultaneous conversion of a mixture of HCFO-1233zd(Z) and HCFC-244fa to form HCFO-1233zd(E), comprising:
providing a mixture including HCFO-1233zd(Z) and HCFC-244fa; and
reacting the HCFO-1233zd(Z) and HCFC-244fa mixture in a vapor phase in the presence of a catalyst selected from the group consisting of chromium trifluoride (CrF 3 ), chromium oxide (Cr 2 O 3 ), chromium oxyfluoride, aluminum fluoride, and combinations thereof to simultaneously isomerize HCFO-1233zd(Z) to form HCFO-1233zd(E) and dehydrohalogenate HCFC-244fa to form HCFO-1233zd(E),
wherein said reacting step is conducted at a temperature between 80° C. and 275° C., and wherein said reacting step achieves a conversion of HCFO-1233zd(Z) to HCFO-1233zd(E) of 88% or greater.
2. The method of claim 1 , wherein the catalyst comprises a catalyst selected from the group consisting of chromium trifluoride (CrF 3 ), chromium oxide (Cr 2 O 3 ), and chromium oxyfluoride, and combinations thereof.
3. The method of claim 1 , wherein said reacting step is conducted at a temperature between 80° C. and 170° C.
4. The method of claim 1 , wherein said reacting step is conducted at a temperature between 100° C. and 275° C.
5. The method of claim 1 , wherein a contact time between the composition and the catalyst is between 1 second and 150 seconds.
6. The method of claim 1 , wherein a pressure in the reactor is between 0 psig and 100 psig.
7. The method of claim 1 , wherein during the reacting step, the reactor includes less than 50 ppm water.
8. The method of claim 1 , wherein in the providing step, total impurities are present in an amount less than 10 wt. %, based on the total weight of the composition.
9. The method of claim 1 , wherein in the providing step, any compounds other than HCFO-1233zd(Z) and HCFC-244fa are present in an amount less than 6 wt. %, based on the total weight of the composition.
10. The method of claim 1 , wherein in the providing step, any compounds other than HCFO-1233zd(Z) and HCFC-244fa are present in an amount less than 1.5 wt. %, based on the total weight of the composition.
11. The method of claim 1 , wherein said reacting step achieves a conversion of HCFO-1233zd(Z) to HCFO-1233zd(E) between 88% and 96%, and wherein the catalyst is selected from the group consisting of chromium trifluoride (CrF 3 ), chromium oxide (Cr 2 O 3 ), and chromium oxyfluoride and combinations thereof.
12. The method of claim 1 , wherein said reacting step achieves a selectivity to HCFO-1233zd(E) between 90% and 97%, and wherein the catalyst is selected from the group consisting of chromium trifluoride (CrF 3 ) chromium oxide (Cr 2 O 3 ), chromium oxyfluoride, and combinations thereof.
13. The method of claim 1 , further comprising, after the reacting step, the additional steps of:
distilling the composition in a distillation column;
removing an overhead stream from the distillation column, the overhead stream concentrated in HCFO-1233zd(E); and
removing a bottoms stream from the distillation column, the bottoms stream concentrated in HCFO-1233zd(Z) and HCFC-244fa.
14. The method of claim 13 , further comprising, after the removing the bottoms stream step, the additional steps of:
recycling the bottoms stream back to the reactor.
15. The method of claim 1 , wherein the catalyst is an aluminum fluoride.
16. The method of claim 1 , wherein said reacting step achieves a selectivity to HCFO-1233zd(E) 90% or greater.