Methods of making chlorinated hydrocarbons

1. A process for the manufacture of 1,1,2,3-tetrachloropropene, the process comprising;

(i) reacting carbon tetrachloride with ethylene in the presence of iron chlorides, iron metal, and a trialkylphosphate to produce a crude product containing 1,1,1,3-tetrachloropropane;

(ii) distilling said crude product to produce an overhead stream and a bottom stream, the overhead stream comprising 1,1,1,3-tetrachloropropane and unreacted carbon tetrachloride and the bottom stream comprising 1,1,1,3-tetrachloropropane;

(iii) reacting the overhead stream with chlorine in the presence of ferric chloride to produce crude 1,1,1,2,3-pentachloropropane;

(iv) adding crude 1,1,1,2,3-pentachloropropane from step (iii) to a reaction zone, which is part of a reactive distillation process equipment comprising a reaction zone, a separation zone, and a condensing zone, and dehydrochlorinating the crude 1,1,1,2,3-pentachloropropane to form hydrogen chloride and 1,1,2,3-tetrachloropropene, and removing hydrogen chloride and 1,1,2,3-tetrachloropropene from the reaction zone during the course of the dehydrochlorination by distillation, and

(v) collecting the 1,1,2,3-tetrachloropropene product.

2. The process of claim 1 , further comprising recycling at least a portion of the bottom stream of step (ii) into the reaction of step (i).

3. The process of claim 1 , wherein the crude 1,1,1,2,3-pentachloropropane liquid product of step (iii) is directly fed without substantial purification into the reaction zone of step (iv).

4. The process of claim 1 , wherein the 1,1,2,3-tetrachloropropene and hydrogen chloride of step (iv) are removed from the reaction zone via the separation zone and the condensing zone, whereby at least some of the 1,1,2,3-tetrachloropropene is separated as a liquid condensate from the hydrogen chloride vapor, producing a purified hydrogen chloride vapor and crude 1,1,2,3-tetrachloropropene.

5. The process of claim 1 , wherein at least a portion of the crude 1,1,2,3-tetrachloropropene is recycled to the separation zone.

6. The process of claim 1 , wherein at least a portion of the crude liquid 1,1,2,3-tetrachloropropene is subjected to one or more purification steps.

7. The process of claim 1 , wherein from about 30 to about 1000 ppm by weight of ferric chloride is maintained in the reaction zone of step (iii).

8. The process of claim 1 , wherein from about 30 to about 20000 ppm by weight of ferric chloride is maintained in the reaction zone of step (iv).

9. The process of claim 1 , wherein the liquid reaction mixture in the reaction zone of step (iv) contains unreacted 1,1,1,2,3-pentachloropropane and ferric chloride, and at least some of this liquid mixture is periodically or substantially continuously removed from the reaction zone.

10. The process of claim 9 , wherein at least a portion of the unreacted 1,1,1,2,3-pentachloropropane contained in the removed reaction mixture is substantially separated from at least some of the other components of the reaction mixture, and then recycled to the reaction zone.

11. A process for the manufacture of 1,1,2,3-tetrachloropropene, the process comprising;

(i) reacting carbon tetrachloride with ethylene in the presence of iron chlorides, iron metal, and a trialkylphosphate in a reactor to produce a crude product comprising 1,1,1,3-tetrachloropropane;

(ii) distilling said crude product to produce an overhead stream and a bottom stream, the overhead stream comprising a first 1,1,1,3-tetrachloropropane solution and unreacted carbon tetrachloride, and the bottom stream comprising 1,1,1,3-tetrachloropropane;

(iii) distilling the 1,1,1,3-tetrachloropropane solution from step (ii) to produce a substantially pure carbon tetrachloride stream, comprising about 90 weight percent or more of carbon tetrachloride, and a second 1,1,1,3-tetrachloropropane solution comprising no more than about 10 weight percent of carbon tetrachloride;

(iv) recycling a portion of the substantially pure carbon tetrachloride stream from step (iii) to the reactor of step (i);

(v) reacting the second 1,1,1,3-tetrachloropropane solution from step (iii) with chlorine in the presence of ferric chloride under conditions effective to produce 1,1,1,2,3-pentachloropropane;

(vi) adding the product from step (v) to reactive distillation process equipment comprising a reaction zone, a separation zone, and a condensing zone, and dehydrochlorinating the crude 1,1,1,2,3-pentachloropropane to form hydrogen chloride and 1,1,2,3-tetrachloropropene, and removing hydrogen chloride and 1,1,2,3-tetrachloropropene from the reaction zone during the course of the dehydrochlorinating by distillation, and

(vii) collecting the 1,1,2,3-tetrachloropropene product.

12. A process for the manufacture of 1,1,2,3-tetrachloropropene, the process comprising:

heating a reaction mixture comprising 1,1,1,3-tetrachloropropane, ferric chloride, and chlorine to produce 1,1,1,2,3-pentachloropropane; and

dehydrochlorinating the 1,1,1,2,3-pentachloropropane in the presence of the ferric chloride to produce 1,1,2,3-tetrachloropropene.

13. The process of claim 12 , further comprising subjecting at least a portion of the 1,1,2,3-tetrachloropropene to one or more purification steps.

14. The process of claim 12 , wherein from about 30 to 20000 parts per million by weight of ferric chloride is maintained in the reaction zone.

15. The process of claim 12 , where said step of dehydrochlorinating takes place within a reaction zone, and wherein a liquid reaction mixture that comprises unreacted 1,1,1,2,3-pentachloropropane, ferric chloride, non-volatile material, and high-boiling by-products, is periodically or substantially continuously removed from the reaction zone.

16. The process of claim 15 , wherein a solution comprising ferric chloride and 1,1,1,2,3-pentachloropropane is introduced periodically or substantially continuously into the reaction zone.

17. The process of claim 12 , wherein the process is performed using reactive distillation equipment, comprising a reaction zone, a separation zone, and a condensing zone.

18. The process of claim 17 , wherein 1,1,2,3-tetrachloropropene and hydrogen chloride are removed from the reaction zone via the separation zone and the condensing zone.

19. The process of claim 17 , wherein the temperature of the reaction zone is from about 120 to about 180° C. and the pressure of the separation zone is in the range from about 100 to about 600 torr.

20. The process of claim 19 , further comprising the step of condensing the 1,1,2,3-tetrachloropropene, after removal from the reaction zone, within a condensing zone, wherein the temperature of the condensing zone is such as to cause 1,1,2,3-tetrachloropropene distilled from the reaction zone to condense into liquid.

21. The process of claim 12 , where said step of dehydrochlorinating takes place within a reaction zone, and where said step of dehydrochlorinating also produces hydrogen chloride, wherein the 1,1,2,3-tetrachloropropene and the hydrogen chloride are removed from the reaction zone via distillation during the course of the dehydrochlorination reaction.

22. The process of claim 21 , wherein the 1,1,2,3-tetrachloropropene and the hydrogen chloride are removed from the reaction zone via distillation during the course of the dehydrochlorination reaction.