US 12,292,213 B2
HFO-1234ZE, HFO-1225ZC and HFO-1234YF compositions and processes for producing and using the compositions
Sheng Peng, Hockessin, DE (US); and Mario Joseph Nappa, Leesburg, FL (US)
Assigned to THE CHEMOURS COMPANY FC, LLC, Wilmington, DE (US)
Filed by THE CHEMOURS COMPANY FC, LLC, Wilmington, DE (US)
Filed on Sep. 16, 2024, as Appl. No. 18/886,068.
Application 18/886,068 is a continuation of application No. 18/414,971, filed on Jan. 17, 2024, granted, now 12,123,631.
Application 18/414,971 is a continuation of application No. 18/220,777, filed on Jul. 11, 2023, granted, now 11,913,681, issued on Feb. 27, 2024.
Application 18/220,777 is a continuation of application No. 18/102,007, filed on Jan. 26, 2023, granted, now 11,732,932, issued on Aug. 22, 2023.
Application 18/102,007 is a continuation of application No. 17/733,563, filed on Apr. 29, 2022, granted, now 11,592,217, issued on Feb. 28, 2023.
Application 17/733,563 is a continuation of application No. 17/536,970, filed on Nov. 29, 2021, granted, now 11,365,908, issued on Jun. 21, 2022.
Application 17/536,970 is a continuation of application No. 17/193,021, filed on Mar. 5, 2021, granted, now 11,209,196, issued on Dec. 28, 2021.
Application 17/193,021 is a continuation of application No. PCT/US2020/029690, filed on Apr. 24, 2020.
Application 17/193,021 is a continuation of application No. 17/270,654, granted, now 11,702,379, issued on Jul. 18, 2023, previously published as PCT/US2019/057999, filed on Oct. 25, 2019.
Application PCT/US2020/029690 is a continuation in part of application No. PCT/US2019/057999, filed on Oct. 25, 2019.
Claims priority of provisional application 62/750,991, filed on Oct. 26, 2018.
Prior Publication US 2025/0003647 A1, Jan. 2, 2025
This patent is subject to a terminal disclaimer.
Int. Cl. C07C 19/08 (2006.01); C07C 17/357 (2006.01); C07C 21/18 (2006.01); F25B 13/00 (2006.01)
CPC F25B 13/00 (2013.01) [C07C 17/357 (2013.01); C07C 19/08 (2013.01); C07C 21/18 (2013.01)] 21 Claims
 
1. A method of producing a fluoropropene of formula CF3CH═CHF (HFO-1234ze), the method comprising:
(a) providing a starting feed mixture of 1,1,1,3,3-pentafluoropropane (HFC-245fa) and an amount of Z-1,3,3,3-tetrafluoropropene (Z-HFO-1234ze) sufficient to suppress formation of additional Z-HFO-1234ze in the gas phase;
(b) contacting the starting feed mixture with a pretreated chromium oxide catalyst in a gas phase reactor and converting the HFC-245fa to a product mixture comprising at least about (i) E-HFO-1234ze and Z-HFO-1234ze, (ii) hydrogen fluoride (HF), (iii) at least one additional compound selected from the group consisting of HFO-1234yf, 3,3,3-trifluoropropyne (TFP), HFC-143a, HFC-152a, HCFO-1233xf, HCFO-1233zd(E), HFC-245cb, HFO-1243zf and HFO-1225zc (iv), optionally at least one additional compound selected from the group consisting of HFC-236fa, HFO-1225zc, E-HFO-1225ye, Z-HFO-1225ye, E-HFO-1234ye, Z-HFO-1234ye, HFO-1234zc, and (v) optionally an amount of unreacted HFC-245fa;
(c) separating the E-HFO-1234ze from the Z-HFO-1234ze and any unreacted HFC-245fa, if present; and
(d) recovering the E-HFO-1234ze.
 
12. A method comprising:
(a) contacting a starting feed mixture of 1,1,1,3,3-pentafluoropropane (HFC-245fa) and Z-1,3,3,3-tetrafluoropropene (Z-HFO-1234ze) at a first level, in the gas phase with a catalyst comprising fluorinated Cr2O3, in the presence of an oxygen containing gas in a reactor, under conditions to facilitate isomeric selectivity to E-1,3,3,3-tetrafluoropropene (E-HFO-1234ze) and suppress formation of additional Z-HFO-1234ze and form a reactor product mixture, the reactor product mixture comprising (i) E-HFO-1234ze, (ii) Z-HFO-1234ze, (iii) hydrogen fluoride (HF), (iv) at least one additional compound selected from the group consisting of HFO-1234yf, 3,3,3-trifluoropropyne (TFP), HFC-143a, HFC-152a, HCFO-1233xf, HCFO-1233zd, (v) optionally at least one additional compound selected from the group consisting of HFC-236fa, HFO-1225zc, E-HFO-1225ye and Z-HFO-1225ye, E/Z-1,2,3,3-tetrafluoropropene (HFO-1234ye +HFO-1234ye), 3,3,1,1-tetrafluoropropene (HFO-1234zc), and (vi) optionally unreacted HFC-245fa;
(b) separating the HF and then separating the E-HFO-1234ze from the Z-HFO-1234ze and any unreacted HFC-245fa, if present;
(c) recovering the E-HFO-1234ze from (b); and
(d) optionally operating one of a heat transfer system, foaming system, or blending system with the recovered E-HFO-1234ze of (c).