Process for producing chlorinated hydrocarbons
View Patent ↗The preparation of chlorinated hydrocarbons, such as pentachloropropanes, such as 1,1,1,2,3-pentachloropropane, from tetrachloropropanes, such as 1,1,1,3-tetrachloropropane, in the presence of a polyvalent antimony compound that includes a pentavalent antimony compound, such as antimony pentachloride, is described. Also described are methods for preparing optionally chlorinated alkenes, such as, tetrachloropropenes, from chlorinated alkanes, such as pentachloropropanes, in the presence of ferric chloride and a polyvalent antimony compound that includes a pentavalent antimony compound.
1. A method of preparing 1,1,1,2,3-pentachloropropane comprising,
reacting 1,1,1,3-tetrachloropropane with a source of chlorine in the presence of a polyvalent antimony compound comprising a pentavalent antimony compound, thereby forming a product comprising 1,1,1,2,3-pentachloropropane.
2. The method of claim 1 , wherein said source of chlorine is selected from chlorine (Cl 2 ), sulfuryl chloride, and combinations thereof.
3. The method of claim 1 , wherein said polyvalent antimony compound comprises said pentavalent antimony compound and optionally a trivalent antimony compound,
said pentavalent antimony compound comprising one or more pentavalent antimony compounds represented by the following Formula (I),
Sb(R 1 ) a (Cl) b (I)
wherein the sum of a and b is 5, provided that b is at least 2, and
R 1 independently for each a is selected from the group consisting of linear, branched, or cyclic alkyl, and aryl, and
said trivalent antimony compound comprising one or more trivalent antimony compounds represented by the following Formula (II),
Sb(R 2 ) c (Cl) d (II)
wherein the sum of c and d is 3, and
R 2 independently for each c is selected from the group consisting of linear, branched, or cyclic alkyl, and aryl.
4. The method of claim 3 further comprising, forming at least a portion of said pentavalent antimony compound from a precursor of said pentavalent antimony compound.
5. The method of claim 4 , wherein said precursor of said pentavalent antimony compound comprises said trivalent antimony compound represented by Formula (II).
6. The method of claim 5 , wherein said precursor of said pentavalent antimony compound is selected from the group consisting of antimony trichloride, trialkyl antimony, triaryl antimony, and combinations of two or more thereof.
7. The method of claim 6 , wherein said precursor of said pentavalent antimony compound is selected from the group consisting of antimony trichloride, triphenyl antimony, and combinations thereof.
8. The method of claim 1 , wherein said polyvalent antimony compound is supported on a solid support.
9. The method of claim 8 , wherein said solid support is selected from the group consisting of silica supports, alumina supports, zeolite supports, and combinations of two or more thereof.
10. The method of claim 1 , wherein said polyvalent antimony compound is present in a catalytic amount.
11. The method of claim 1 , wherein said method is performed as a batch method, a continuous method, and combinations thereof.
12. The method of claim 1 , wherein said source of chlorine is chlorine (Cl 2 ), and reacting 1,1,1,3-tetrachloropropane with said source of chlorine is conducted with a mole ratio of chlorine (Cl 2 ) to 1,1,1,3-tetrachloropropane of 0.2:1 to 1.5:1.
13. The method of claim 1 wherein, reacting 1,1,1,3-tetrachloropropane with said source of chlorine in the presence of said polyvalent antimony compound is conducted at a temperature of at least 40° C., and a pressure of at least 1 psia.
14. The method of claim 13 , wherein said temperature is from 40° C. to 200° C., and said pressure is from 1 psia to 500 psia.
15. The method of claim 1 , wherein said 1,1,1,3-tetrachloropropane is formed from reacting carbon tetrachloride with ethylene in the presence of an iron chloride, iron metal, and a trialkylphosphate.
16. A method of preparing 1,1,2,3,-tetrachloropropene comprising:
reacting, in a first reaction, 1,1,1,3-tetrachloropropane with a source of chlorine in the presence of a polyvalent antimony compound comprising a pentavalent antimony compound, thereby forming a crude product comprising 1,1,1,2,3-pentachloropropane and said pentavalent antimony compound; and
heating, in a second reaction, said crude product in the presence of ferric chloride, thereby forming a product comprising 1,1,2,3-tetrachloropropene.
17. The method of claim 16 , wherein said pentavalent antimony compound comprises one or more pentavalent antimony compounds represented by the following Formula (I),
Sb(R 1 ) a (Cl) b (I)
wherein the sum of a and b is 5, provided that b is at least 2, and
R 1 independently for each a is selected from the group consisting of linear, branched, or cyclic alkyl, and aryl.
18. The method of claim 17 , wherein said pentavalent antimony compound comprises antimony pentachloride.
19. The method of claim 18 , wherein said product comprising 1,1,2,3-tetrachloropropene further comprises 1,1,1,2,3-pentachloropropane and antimony trichloride, and
said method further comprises distilling said product thereby forming,
a tops product comprising 1,1,2,3-tetrachloropropene, and
a bottoms product comprising 1,1,1,2,3-pentachloropropane and antimony trichloride.
20. The method of claim 19 further comprising, introducing at least a portion of said bottoms product into said first reaction.
21. The method of claim 16 , wherein said second reaction is conducted at a temperature and a pressure whereby at least a portion of said product is converted to a vaporous product comprising vaporous 1,1,2,3-tetrachloropropene, and
said method further comprises,
removing vaporous product comprising vaporous 1,1,2,3-tetrachloropropene from said second reaction, and
condensing said vaporous product removed from said second reaction into liquid product comprising liquid 1,1,2,3-tetrachloropropene.
22. The method of claim 16 , wherein said method is performed as a batch method, a continuous method, and combinations thereof.
23. The method of claim 16 , wherein said 1,1,1,3-tetrachloropropane is formed by reacting carbon tetrachloride with ethylene in the presence of an iron chloride, iron metal, and a trialkylphosphate.
24. A method of preparing 1,1,2,3,-tetrachloropropene comprising:
reacting, in a first reaction, 1,1,1,3-tetrachloropropane with a source of chlorine in the presence of a pentavalent antimony compound comprising antimony pentachloride, thereby forming a crude product comprising 1,1,1,2,3-pentachloropropane, 1,1,1,3-tetrachloropropane, antimony pentachloride, and antimony trichloride;
distilling said crude product thereby forming,
a tops product comprising 1,1,1,3-tetrachloropropane and antimony pentachloride, and
a bottoms product comprising 1,1,1,2,3-pentachloropropane and antimony trichloride;
introducing a source of chlorine into said bottoms product, thereby converting at least a portion of the antimony trichloride to antimony pentachloride, thereby forming a modified bottoms product; and
heating, in a second reaction, said modified bottoms product in the presence of ferric chloride, thereby forming a product comprising 1,1,2,3-tetrachloropropene.
25. The method of claim 24 , wherein said modified bottoms product is substantially free of said source of chlorine.
26. The method of claim 24 further comprising, introducing at least a portion of said tops product into said first reaction.
27. The method of claim 24 , wherein said second reaction is conducted at a temperature and a pressure whereby at least a portion of said product is converted to a vaporous product comprising vaporous 1,1,2,3-tetrachloropropene, and
said method further comprises,
removing said vaporous product comprising vaporous 1,1,2,3-tetrachloropropene from said second reaction, and
condensing said vaporous product removed from said second reaction into liquid product comprising liquid 1,1,2,3-tetrachloropropene.
28. The method of claim 24 , wherein said method is performed as a continuous method, a batch method, and combinations thereof.
29. The method of claim 24 , wherein said 1,1,1,3-tetrachloropropane is formed by reacting carbon tetrachloride with ethylene in the presence of an iron chloride, iron metal, and a trialkylphosphate.