Process for producing chlorinated hydrocarbons
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 forming an alkene product 1,1,2,3-tetrachloropropene comprising,
(1) reacting carbon tetrachloride with ethylene in the presence of an iron chloride, iron metal, and a trialkylphosphate to form 1,1,1,3-tetrachloropropane;
(2) reacting the 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;
(3) performing a dehydrochlorination reaction comprising,
heating a chlorinated alkane substrate the 1,1,1,2,3-pentachloropropane in the presence of ferric chloride and a polyvalent antimony compound comprising a pentavalent antimony compound and a trivalent antimony compound, thereby forming a product comprising said alkene product 1,1,2,3-tetrachloropropene, wherein
said alkene product optionally has at least one chlorine group covalently bonded thereto, and
said chlorinated alkane substrate and said alkene product each have a carbon backbone structure that is in each case the same
ferric chloride and the polyvalent antimony compound in each of steps (2) and (3) are each independently present in a catalytic amount.
2. The method of claim 1 , wherein said polyvalent antimony compound comprises said pentavalent antimony compound and optionally a trivalent antimony compound, in step (3)
said pentavalent antimony compound comprising 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, and
said trivalent antimony compound comprising comprises 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.
3. The method of claim 2 , wherein in step (3)
said pentavalent antimony compound comprises antimony pentachloride, and
said trivalent antimony compound comprises antimony trichloride.
4. The method of claim 1 , wherein ferric chloride and said polyvalent antimony compound are each independently present in a catalytic amount.
5. The method of claim 1 , wherein said method is performed as a batch method, a continuous method, and combinations thereof.
6. The method of claim 1 wherein,
said chlorinated alkane substrate is 1,1,1,2,3-pentachloropropane, and
said alkene product is 1,1,2,3-tetrachloropropene.
7. The method of claim 6 1, wherein heating 1,1,1,2,3-pentachloropropane in the presence of ferric chloride and said polyvalent antimony compound is conducted at a temperature of from 50° C. to 200° C., and a pressure of from 0.6 psia to 215 psia.
8. The method of claim 6 1, wherein heating 1,1,1,2,3-pentachloropropane in the presence of ferric chloride and said polyvalent antimony compound is conducted with a mole ratio of ferric chloride to polyvalent antimony compound of from 1000:1 to 1:1000.
9. The method of claim 1 , wherein, heating the chlorinated alkane substrate 1,1,1,2,3-pentachloropropane in the presence of ferric chloride and the polyvalent antimony compound comprising the pentavalent antimony compound and the trivalent antimony compound, thereby forming the product comprising said alkene product 1,1,2,3-tetrachloropropene, is performed in a liquid phase.
10. The method of claim 1, wherein said source of chlorine is selected from chlorine (Cl 2 ), sulfuryl chloride, and combinations thereof.
11. 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.
12. The method of claim 1, wherein in step (2) 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.
13. The method of claim 12, wherein step (2) further comprises forming at least a portion of said pentavalent antimony compound from a precursor of said pentavalent antimony compound.
14. The method of claim 12, wherein in step (2) said trivalent antimony compound is selected from the group consisting of antimony trichloride, triphenyl antimony, and combinations thereof.