HFO-1234ZE, HFO-1225ZC and HFO-1234YF compositions and processes for producing and using the compositions
A fluoropropene composition comprising Z-1,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene, 2,3,3,3-tetrafluoropropene, and optionally 1,1,1,3,3-pentafluoropropane wherein the 2,3,3,3-tetrafluoropropene being present in an amount of 0.00001 to 1.0%. A method of producing the fluoropropene, methods for using the fluoropropene and the composition formed are also disclosed.
1. A method of producing a fluoropropene of formula CF 3 CH═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.
2. The method of claim 1 , wherein step (a) comprises preheating the starting feed mixture at a temperature sufficient to vaporize the starting feed mixture prior to step (b).
3. The method of claim 1 , the method further comprising at least one of:
i. recovering the Z-HFO-1234ze of step (c), and recycling the Z-HFO-1234ze to step (a);
ii. recovering the Z-HFO-1234ze and unreacted HFC-245fa of step (c), and recycling the Z-HFO-1234ze and unreacted HFC-245fa to step (a);
iii. recovering the HF of step (b); and
iv. recycling the HF to step (a).
4. The method of claim 1 , wherein an oxygen containing gas is added to the gas phase reactor during step (b).
5. The method of claim 4 , wherein said oxygen containing gas is oxygen.
6. The method of claim 1 , the method further comprising providing the E-HFO-1234ze to one of (i) a refrigerant system and (ii) a foam forming system.
7. The method of claim 1 further comprising including the recovered E-1,3,3,3-tetrafluoropropene of step (e) as a component of a composition selected from the group consisting of:
(a) a composition comprising E-1,3,3,3-tetrafluoropropene and at least one additional member selected from the group consisting of R32, R125, R134, R134a, 227ea, and R1336mzz(E),
(b) a composition comprising E-1,3,3,3-tetrafluoropropene, HFO-1225zc, HFO-1234yf and at least one compound selected from the group consisting of: HFO-1234ye, HFO-1243zf, HFC-32, HFC-125, HFC-134, HFC-134a, HFC-143a, HFC-152a, HFC-161, HFC-227ea, HFC-236ea, HFC-236fa, HFC-245fa, HFC-365mfc, R1336mzz(E), propane, n-butane, isobutane, 2-methylbutane, n-pentane, and cyclopentane, and
(c) a composition selected from the group consisting of R444A, R444B, 446A, R446B, R447B, R448A, R450A, R456A, R459A, R459B, R460A, R460B, R460C, R464A, R515A and R515B.
8. The method of claim 1 , wherein the amount of Z-1,3,3,3-tetrafluoropropene in the product mixture is at most about 0.6 mol. % greater than the amount of Z-1,3,3,3-tetrafluoropropene in the starting feed mixture.
9. The method of claim 1 , wherein the contacting is conducted at one of: (i) a temperature held between 275° C. and 350° C.; or a temperature held at about 300° C.
10. A composition comprising E-HFO-1234ze produced by the method of claim 1 and at least one additional refrigerant member selected from the group consisting of R-32, R-125, R-134, R-134a, R-227ea, and R-1336mzz(E).
11. The composition of claim 10 , wherein an amount of the at least one additional refrigerant member is selected from the group consisting of about 5 to about 95 wt. %, about 50 to about 90 wt. %, and about 60 to about 80 wt. %, based on a total amount of the composition such that the total amount of the composition is 100 wt. %.
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 Cr 2 O 3 , 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).
13. The method of claim 12 , wherein the amount of Z-HFO-1234ze in the product mixture is at most about 0.6 mol. % greater than the first level of Z-HFO-1234ze in the starting feed mixture.
14. The method of claim 12 , wherein the isomeric selectivity of the conversion of the HFC-245fa to E-HFO-1234ze is selected from one of: at least 94 mol % and at least 98 mol %.
15. The method of claim 12 , further comprising one of:
(a) recovering the Z-HFO-1234ze and recycling the Z-HFO-1234ze to the reactor; or
(b) recovering a mixture of the Z-HFO-1234ze and unreacted HFC-245fa and recycling the mixture to the reactor; or
(c) recovering the mixture of Z-HFO-1234ze and E-HFO-1234ze and converting the Z-HFO-1234ze in the mixture to additional E-HFO-1234ze.
16. The process of claim 12 , wherein said hydrogen fluoride produced in step (a) is separated and recovered.
17. The process of claim 12 , wherein said oxygen containing gas is oxygen or air.
18. The method of claim 12 , wherein the contacting is conducted at a temperature selected from one of: held at a temperature between 275° C. and 350° C. and held at a temperature at about 300° C.
19. The method of claim 12 , the method further comprising formulating a blend selected from the group consisting of R444A, R444B, R446A, R446B, R447B, R448A, R450A, R456A, R459A, R599B, R460A, R460B and R460C, using the recovered E-HFO-1234ze of claim 12 .
20. A composition comprising the E-HFO-1234ze produced by the method of claim 12 and at least one additional refrigerant member selected from the group consisting of R-32, R-125, R-134, R-134a, R-227ea, and R-1336mzz(E).
21. The composition of claim 20 , wherein an amount of the at least one additional refrigerant member is selected from the group consisting of about 5 to about 95 wt. %, about 50 to about 90 wt. %, and about 60 to about 80 wt. %, based on a total amount of the composition.