Integrated process for making 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd) from a mixture of high-boiling fluorinated components
The present disclosure provides a method for conversion of a mixture of high-boiling fluorinated components comprising 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa), 1,3,3-trichloro-1, 1-difluoropropane (HCFC-242fa), 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb), 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243fa), 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb), 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa), their isomers, and combinations thereof, to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd). Heavy impurities, such as oligomers and other high boiling impurities, that are present may be purged during the process to prevent yield loss and reduction of catalyst efficacy.
1. A method for conversion of a mixture of high-boiling fluorinated components to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), comprising:
contacting the mixture with hydrogen fluoride (HF) to produce a combined stream, the mixture comprising heavy impurities with a boiling point of greater than 140° C.;
vaporizing the combined stream in a vaporizer to produce vaporized reactant stream;
purging the heavy impurities from the vaporizer;
reacting the vaporized reactant stream in the presence of a catalyst to produce a product stream comprising E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)) and additional heavy impurities with a boiling point of greater than 140° C.;
condensing, and purging from the product stream, at least a portion of the additional heavy impurities; and
optionally purifying the product stream.
2. The method of claim 1 , wherein the high-boiling fluorinated components have a boiling point of greater than 39° C.
3. The method of claim 1 , wherein the mixture of high-boiling fluorinated components comprises 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa), 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa), 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb), 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243fa), 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb), 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa), and combinations thereof.
4. The method of claim 1 , wherein the vaporization step is conducted at a temperature of 220° C. or higher.
5. The method of claim 1 , wherein the reacting step is conducted at a temperature between 200° C. and 300° C.
6. The method of claim 1 , wherein the condensing step is conducted at a temperature of 10° C. or higher.
7. The method of claim 1 , wherein the catalyst is selected from the group consisting of chromium oxides, chromium oxyfluorides, and chromium halides.
8. The method of claim 1 , wherein the catalyst is a chromium oxyfluoride catalyst.
9. The method of claim 1 , wherein:
the vaporization step is conducted at a temperature of 220° C. or higher;
the condensing step is conducted at a temperature of 10° C. or higher; and
the catalyst is chromium oxide.
10. The method of claim 1 , wherein the catalyst is a zinc/chromium catalyst including 0.5 to 6.0 wt. % Zn, based on the total weight of the catalyst.
11. A method for conversion of a mixture of high-boiling fluorinated components to 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), comprising:
contacting the mixture with hydrogen fluoride (HF) to produce a combined stream, the mixture comprising heavy impurities with a boiling point of greater than 140° C.;
vaporizing the combined stream to produce a vaporized reactant stream and a heavy impurity stream;
separating the heavy impurity stream from the vaporized reactant stream;
reacting the vaporized reactant stream in the presence of a catalyst to produce a product stream comprising E-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd(E)) and additional heavy impurities with a boiling point of greater than 140° C.;
condensing, and purging from the product stream, at least a portion of the additional heavy impurities; and
optionally purifying the product stream.
12. The method of claim 11 , wherein the high-boiling fluorinated components have a boiling point of greater than 39° C.
13. The method of claim 11 , wherein the mixture of high-boiling fluorinated components comprises 1,1,3,3-tetrachloro-1-fluoropropane (HCFC-241fa), 1,3,3-trichloro-1,1-difluoropropane (HCFC-242fa), 1,1,3-trichloro-1,3-difluoropropane (HCFC-242fb), 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243fa), 1,3-dichloro-1,1,3-trifluoropropane (HCFC-243fb), 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa), and combinations thereof.
14. The method of claim 11 , wherein the vaporization step is conducted at a temperature of 220° C. or higher.
15. The method of claim 11 , wherein the reacting step is conducted at a temperature between 200° C. and 300° C.
16. The method of claim 11 , wherein the condensing step is conducted at a temperature of 10° C. or higher.
17. The method of claim 11 , wherein the catalyst is selected from the group consisting of chromium oxides, chromium oxyfluorides, and chromium halides.
18. The method of claim 11 , wherein the catalyst is a chromium oxyfluoride catalyst.
19. The method of claim 1 , wherein the mixture of high boiling fluorinated components comprises by-products derived from reacting HCC-240fa to form HFO-1233zd.
20. The method of claim 11 , wherein the mixture of high boiling fluorinated components comprises by-products derived from reacting HCC-240fa to form HFO-1233zd.