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-242sfa), 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 reactant stream;
vaporizing the combined reactant stream to produce 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 heavy impurities;
condensing at least a portion of 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 composition further comprises heavy impurities with a boiling point of greater than 140° C.
10 . The method of claim 9 , further comprising at least of one the following additional steps:
purging the heavy impurities from the vaporizer; and
purging the heavy impurities from the partial condenser.
11 . 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.
12 . 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.
13 . 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 reactant stream;
vaporizing the combined reactant 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
optionally purifying the product stream.
14 . The method of claim 13 , wherein the high-boiling fluorinated components have a boiling point of greater than 39° C.
15 . The method of claim 13 , 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.
16 . The method of claim 13 , wherein the vaporization step is conducted at a temperature of 220° C. or higher.
17 . The method of claim 13 , wherein the reacting step is conducted at a temperature between 200° C. and 300° C.
18 . The method of claim 13 , wherein the condensing step is conducted at a temperature of 10° C. or higher.
19 . The method of claim 13 , wherein the catalyst is selected from the group consisting of chromium oxides, chromium oxyfluorides, and chromium halides.
20 . The method of claim 13 , wherein the catalyst is a chromium oxyfluoride catalyst.