Integrated process and methods of producing (E)-1-chloro-3,3,3-trifluoropropene

1. A process for the formation of a 1233zd reaction product having a majority of E-isomer comprising:

conducting a catalytic liquid phase reaction between HF and a mixture of organic hydrohalocarbons consisting of 1,1,1,3,3-pentachloropropane (HCC-240fa), 1,1,3,3-tetrachloropropene and 1,3,3,3-tetrachloropropene to create a first crude product stream comprising 1233zd(E);

wherein said hydrogen fluoride and said hydrohalocarbons are present in a HF:organic molar ratio of about 9:1;

wherein the catalyst comprises titanium tetrachloride;

wherein the temperature of the liquid phase reaction is maintained at from about 85° C. to about 120° C.;

wherein the E-isomer yield is further improved to above 94% by passing the liquid phase crude product stream through a stripping column as it leaves the reactor to reflux unreacted reactants back to the reactor; and

wherein the stripping column is operated to achieve an average stripping temperature of from about 10° C. to about 40° C. below the corresponding reaction temperature.

2. The method of claim 1 , wherein said reaction temperature is about 90° C. to about 110° C.

3. The method of claim 1 , wherein said reaction temperature is about 95° C. to about 100° C.

4. The method of claim 1 , further comprising:

distilling said crude product stream to produce;

a first recycle stream comprising unreacted hydrogen fluoride from said reaction product stream, unreacted one or more hydrohalocarbons and partially fluorinated intermediates from said crude product stream, and

an overhead stream comprising a majority of said (E)1-chloro-3,3,3-trifluoropropene, (Z)1-chloro-3,3,3-trifluoropropene, hydrogen chloride, and a portion of said hydrogen fluoride from said crude product stream; and

recycling said first recycle stream to said liquid reaction admixture.

5. The method of claim 1 , further comprising:

distilling said first crude product stream to produce;

a first by-product stream comprising a majority of said hydrogen chloride separated from said first crude product stream, and

a second crude product stream comprising a majority of said (E)1-chloro-3,3,3-trifluoropropene separated from said first crude product stream,

a majority of said (Z)1-chloro-3,3,3-trifluoropropene separated from said first crude product stream, and

a majority of said unreacted hydrogen fluoride separated from said first crude product stream.

6. The method of 5 , further comprising:

separating said second crude product stream into:

a recycle stream comprising a majority of said unreacted hydrogen fluoride separated from said second crude product stream, and

a third crude product stream comprising a majority of said (E)1-chloro-3,3,3-trifluoropropene separated from said second crude product stream, and a majority of said (Z)1-chloro-3,3,3-trifluoropropene separated from said second crude product stream, and a portion of said unreacted hydrogen fluoride separated from said second crude product stream; and

introducing said second recycle stream into said liquid reaction admixture.

7. The method of claim 6 , wherein said separating comprises:

contacting said second crude product stream with a stripping composition comprising sulfuric acid to produce a sulfuric acid-hydrogen fluoride admixture stream and said third crude product stream; and

separating at least a portion of the hydrogen fluoride from said admixture to form said second recycle stream and a sulfuric acid recycle stream.

8. The method of claim 6 , wherein said separating comprises:

cooling said second crude product stream to produce a composition having a hydrogen fluoride-rich top layer and an organic-rich bottom layer;

separating said top and bottom layers to form said second recycle stream,

wherein said second recycle stream comprises said top layer and said third crude product stream, and

wherein said third product stream comprises said bottom layer.

9. The method of claim 6 , further comprising:

distilling said third crude product stream to produce;

a purified product stream comprising a majority of said (E)1-chloro-3,3,3-trifluoropropene and a second by-product stream comprising said a majority of said (Z)1-chloro-3,3,3-trifluoropropene; and

contacting said second by-product stream with a heated surface maintained at a temperature of about 50° C. to about 350° C. and in the presence of an isomerization catalyst to produce a third recycle stream comprising (E)1-chloro-3,3,3-trifluoropropene isomerized from said (Z)1-chloro-3,3,3-trifluoropropene; and

introducing said third recycle stream to said third crude product stream.

10. A process for producing a hydrofluoroolefin comprising the following steps:

(a) providing one or more feed streams cumulatively comprising hydrogen fluoride and a hydrohalocarbon mixture of 1,1,1,3,3-pentachloropropane, 1,1,3,3-tetrachloropropene and 1,3,3,3-tetrachloropropene;

(b) providing a liquid phase reactor charged with a liquid phase fluorination catalyst and maintained at a first temperature of about 85° C. to about 120° C., wherein said liquid phase reactor is fluidly connected to said one or more feed streams;

(c) providing a stripping system comprising a stripping column having an average temperature maintained at a second temperature of about 10° C. to about 40° C. below said first temperature, a reflux stream fluidly connected to said stripping column, and a first crude product stream fluidly connected to said stripping column, wherein said reflux stream is fluidly connected to said liquid phase reactor;

(d) providing a hydrogen chloride removal system comprising a first distillation column, a hydrogen chloride by-product stream fluidly connected to said first distillation column, and a second crude product stream fluidly connected to said first distillation column, wherein said first distillation column is fluidly connected to said stripping column;

(e) providing a hydrogen fluoride recovery system comprising a sulfuric acid absorption and recycle system or a phase separation vessel, a second recycle stream comprising hydrogen fluoride fluidly connected to said sulfuric acid absorption and recycle system or a phase separation vessel, a third product stream comprising (E) and (Z) 1-chloro-3,3,3-trifluoropropene fluidly connected to said sulfuric acid absorption and recycle system or a phase separation vessel, wherein said sulfuric acid absorption and recycle system or a phase separation vessel is fluidly connected to said second crude product stream; and

(f) providing a 1-chloro-3,3,3-trifluoropropene purification system comprising a second distillation column fluidly connected to said third product stream; and

(g) generating from steps (a)-(f), a final product stream comprising (E)1-chloro-3,3,3-trifluoropropene fluidly connected to said second distillation column; and

(h) generating a second by-product stream fluidly connected to said distillation column;

(i) providing an isomerization reactor fluidly connected to said second by-product stream; and

(j) generating a product recycle stream fluidly connected to said isomerization reactor and said second distillation column.

11. An integrated process for producing a hydrofluoroolefin including the following steps:

(a) providing one or more feed streams cumulatively comprising hydrogen fluoride and a hydrohalocarbon mixture of 1,1,1,3,3-pentachloropropane, 1,1,3,3-tetrachloropropene and 1,3,3,3-tetrachloropropene;

(b) providing a vapor phase reactor with a vapor phase fluorination catalyst and maintained at a first temperature of about 200° to about 450° C. and a pressure of about 0 to about 160 psig, wherein said vapor phase reactor is fluidly connected to said one or more feed streams;

(c) providing a hydrogen chloride removal system including a first distillation column, a hydrogen chloride by-product stream fluidly connected to said first distillation column, and a crude product stream fluidly connected to said first distillation column wherein said first distillation column is fluidly connected to said vapor phase reactor;

(d) providing a hydrogen fluoride recovery system including a sulfuric acid stripping and recycle system or a phase separation vessel, a recycle stream comprising hydrogen fluoride fluidly connected to said sulfuric acid stripping and recycle system or a phase separation vessel, a product stream including (E) and (Z) 1-chloro-3,3,3-trifluoropropene fluidly connected to said sulfuric acid stripping and recycle system or a phase separation vessel, wherein said sulfuric acid stripping and recycle system or a phase separation vessel is fluidly connected to said crude product stream;

(e) providing a 1-chloro-3,3,3-trifluoropropene purification system including a second distillation column fluidly connected to said product stream;

(f) generating a final product stream including (E) 1-chloro-3,3,3-trifluoropropene fluidly connected to said second distillation column;

(g) generating a second by-product stream fluidly connected to said distillation column;

(h) providing an isomerization reactor fluidly connected to said second by-product stream; and

(i) generating a product recycle stream fluidly connected to said isomerization reactor and said second distillation column.