Process for producing chlorinated hydrocarbons in the presence of a polyvalent molybdenum compound
View Patent ↗The preparation of chlorinated hydrocarbons by reacting a chlorinated alkane substrate, such as 1,1,1,3-tetrachloropropane, with a source of chlorine, such as chlorine (Cl 2 ), in the presence of a polyvalent molybdenum compound, such as molybdenum pentachloride, is described. With the method of the present invention, the chlorinated alkane product has covalently bonded thereto at least one more chlorine group than the chlorinated alkane substrate, and the chlorinated alkane substrate and the chlorinated alkane product each have a carbon backbone structure that is in each case the same.
1. A method of preparing a chlorinated alkane product comprising,
reacting a chlorinated alkane substrate with a source of chlorine in the presence of a polyvalent molybdenum compound, thereby forming a product comprising said chlorinated alkane product,
wherein said chlorinated alkane product has covalently bonded thereto at least one more chlorine group than said chlorinated alkane substrate, and
said chlorinated alkane substrate and said chlorinated alkane product each have a carbon backbone structure that is in each case the same.
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 molybdenum compound is selected from the group consisting of a tetravalent molybdenum compound, pentavalent molybdenum compound, a hexavalent molybdenum compound, and combinations thereof.
4. The method of claim 3 , wherein said tetravalent molybdenum compound comprises one or more tetravalent molybdenum compounds represented by the following Formula (I),
Mo(R 1 ) a (Cl) b (I)
wherein the sum of a and b is 2, 3, or 4, provided that b is 0, 1, 2, 3, or 4; and
R 1 independently for each a is oxygen.
5. The method of claim 3 , wherein said tetravalent molybdenum compound is selected from the group consisting of MoO 2 , MoOCl 2 , MoCl 4 and mixtures thereof.
6. The method of claim 3 , wherein said pentavalent molybdenum compound comprises one or more pentavalent molybdenum compounds represented by the following Formula (II),
[Mo(R 1 ) c (Cl) d ] z (II)
wherein z is 1 or 2, the sum of c and d is 5, provided that d is 1, 2, 3, 4, or 5; and
R 1 independently for each c is oxygen.
7. The method of claim 3 , wherein said pentavalent molybdenum compound is selected from the group consisting of molybdenum pentachloride, and Mo 2 Cl 10 and mixtures thereof.
8. The method of claim 3 , wherein said hexavalent molybdenum compound comprises one or more hexavalent molybdenum compounds represented by the following Formula (III),
Mo(R 1 ) x (Cl) y (III)
wherein the sum of x and y is 3, 4, 5, or 6, provided that y is 0, 1, 2, 3, 4, 5 or 6; and
R 1 independently for each x is oxygen.
9. The method of claim 3 , wherein said hexavalent molybdenum compound is selected from the group consisting of MoCl 6 , Cs 2 (MoOCl 5 ), MoOCl 4 , Na 2 MoO 4 , CaMoO 4 , MgMoO 4 , Li 2 MoO 4 , Ag 2 MoO 4 , NiMoO 4 , Al 2 (MoO 4 ) 3 , Bi 2 (MoO 4 ) 3 , SrMoO 4 , K 2 MoO 4 , Cs 2 MoO 4 , ZnMoO 4 , CuMoO 4 , CoMoO 4 , CdMoO 4 , BaMoO 4 , MnMoO 4 , Ti 2 MoO 4 , MoO 3 and mixtures thereof.
10. The method of claim 3 , wherein said pentavalent molybdenum compound comprises molybdenum pentachloride.
11. The method of claim 1 , wherein said polyvalent molybdenum compound is supported on a solid support.
12. The method of claim 11 , wherein said solid support is selected from the group consisting of silica supports, alumina supports, zeolite supports, and combinations of two or more thereof.
13. The method of claim 1 , wherein said polyvalent molybdenum compound is present in a catalytic amount.
14. The method of claim 1 , wherein said method is performed as a batch method, a continuous method, or combinations thereof.
15. The method of claim 1 , wherein
said chlorinated alkane substrate is 1,1,1,3-tetrachloropropane, and
said chlorinated alkane product is 1,1,1,2,3-pentachloropropane.
16. The method of claim 15 , 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.
17. The method of claim 15 , wherein reacting 1,1,1,3-tetrachloropropane with said source of chlorine in the presence of said polyvalent molybdenum compound is conducted at a temperature of at least 20° C., and a pressure of at least 1 psia.
18. The method of claim 17 , wherein said temperature is from 20° C. to 150° C., and said pressure is from 1 psia to 500 psia.
19. The method of claim 15 , 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.