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1. (WO2006020234) CONVERSION OF A MULTIHYDROXYLATED-ALIPHATIC HYDROCARBON OR ESTER THEREOF TO A CHLOROHYDRIN
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WHAT TS CLAIMED IS:

1. A process for producing a chlorohydrin, an ester of a chlorohydrin, or a mixture thereof comprising the step of contacting a multihydroxylated-aliphatic hydrocarbon, an ester of a multihydroxylated-aliphatic hydrocarbon, or a mixture thereof with a source of a superatmospheric partial pressure of hydrogen chloride, in the presence of a catalyst to produce a chlorohydrin, an ester of a chlorohydrin, or a mixture thereof, said contacting step carried out without substantial removal of water.

2. The process of Claim 1 carried out in the presence of a catalyst and a co-catalyst.

3. The process of Claim 2 where the co-catalyst is a source of chloride, bromide or iodide.

4. The process of Claim 1 wherein the hydrogen chloride source is at least 50 mole% hydrogen chloride.

5. The process of Claim 1 wherein the hydrogen chloride source is hydrogen chloride gas.

6. The process of Claim 1 wherein the chlorohydrin is a dichlorohydrin, an ester of a dichlorohydrin, or a mixture thereof.

7. The process of Claim 6 wherein the dichlorohydrin is
l,3-dichloropropan-2-ol, or 2,3-dichloropropan-l-ol, or a mixture thereof.

8. The process of Claim 1 wherein the multihydroxylated-aliphatic hydrocarbon is crude glycerol.

9. The process of Claim 8 wherein the crude glycerol contains less than 25 weight % water, and less than 25 weight % alkali or alkaline earth metal salts.

10. The process of Claim 1 wherein the multihydroxylated-aliphatic hydrocarbon is 1,2,3-propanetriol.

11. The process of Claim 1 wherein the multihydroxylated-aliphatic hydrocarbon is selected from the group consisting of 1,2-ethanediol; 1,2-ρropanediol;
1,3-propanediol; l-chloro-2,3-propanediol; 2-chloro-l,3-propandiol; and 1,2,3-propanetriol; and mixtures thereof.

12. The process of Claim 1 wherein the catalyst is selected from the group consisting of a carboxylic acid, an anhydride, an acid chloride, an ester, a lactone, a lactam, an amide, a metal organic compound, a metal salt, any compound convertible to a carboxylic acid under the reaction conditions of the process, or a combination thereof.

13. The process of Claim 1 wherein the catalyst is a carboxylic acid or precursor thereof containing from 1 to about 60 carbon atoms.

14. The process of Claim 1 where in the catalyst is a carboxylate derivative having from two to about 20 carbon atoms and containing at least one functional group including an amine, an alcohol, a halogen, a sulfhydryl, an ether, an ester, or combination thereof, wherein the functional group is attached no closer to the acid function than the alpha carbon; or a precursor thereto.

15. The process of Claim 1 wherein the catalyst is selected from the group consisting of acetic acid, propionic acid, hexanoic acid, heptanoic acid, stearic acid, butyric acid, valeric acid, 4-methylvaleric acid, phenylacetic acid, cinnamic acid, succinic acid, polyacrylic acid, polyethylene grafted with acrylic acid, epsilon-caprolactone, delta-valerolactone, gamma-butyrolactone, epsilon-caprolactam, 6-chlorohexanoic acid, 4-hydroxyphenylacetic acids, 4-aminobutyric acid, 4-dimethylaminobutyric acid,
4-trimethylammoniumbutyric acid chloride, 4-hydroxyphenylacetic acid,
4-aminophenylacetic acid, 5-chlorovaleric acid, 5-hydroxyvaleric acid,
4-hydroxybutyric acid, 4-chlorobutyric, 5-chloropentanoic acid, and mixtures thereof.

16. The process of Claim 1 wherein the catalyst is selected from the group consisting of acetic acid, propionic acid, butyric acid, 4-methylvaleric acid, hexanoic acid, heptanoic acid, stearic acid, epsilon-caprolactone, gamma-butyrolactone,
6-chlorohexanoic acid, 4-aminobutyric acid, 4-dimethylaminobutyric acid,
4-trimethylammoniumbutyric acid chloride, 4-hydroxyphenylacetic acid,
4-aminophenylacetic acid, and mixtures thereof.

17. The process of Claim 1 wherein the catalyst is selected from the group consisting of acetic acid, epsilon caprolactone, 6-chlorohexanoic acid, delta-valerolactone, 5-chloropentanoic acid, 4-chlorobutyric acid, 4-hydroxyphenylacetic acid, 4-aminophenylacetic acid, 4-aminobutyric acid, and mixtures thereof.

18. The process of Claim 1 wherein the catalyst is acetic acid or a derivative of acetic acid.

19. The process of Claim 1 wherein the catalyst is caprolactone or a derivative of caprolactone.

20. The process of Claim 1 wherein the catalyst is an ester of glycerin, an ester of ethylene glycol or an ester of propylene glycol derived from a compound selected from the group consisting of acetic acid, propionic acid, hexanoic acid, heptanoic acid, stearic acid, butyric acid, valeric acid, 4-methylvaleric acid, phenylacetic acid, cinnamic acid, succinic acid, benzoic acid, polyacrylic acid, polyethylene grafted with acrylic acid, epsilon caprolactone, delta-valerolactone, gamma-butyrolactone, epsilon-caprolactam, 6-chloroheχanoic acid, 4-hydroxyphenylacetic acids, 4-aminobutyric acid,
4-dimethylaminobutyric acid, 4-trimethylammoniumbutyric acid chloride,
4-hydroxyphenylacetic acid, 4-aminophenylacetic acid, 5-chlorovaleric acid,
5-hydroxyvaleric acid, 4-hydroxybutyric acid, 4-chlorobutyric, 5-chloropentanoic acid, and mixtures thereof

21. The process of Claim 1 wherein the catalyst is an ester selected from the group consisting of glycerin monoacetate, glycerin diacetate, glycerin distearate, l~chloro-2,3-propanediolmonoacetate, a glycerin ester of a polycarboxylic acid, and mixtures thereof.

22. The process of Claim 1 wherein the catalyst is an insoluble polymer containing carboxylic acid moieties or esters thereof.

23. The process of Claim 22 wherein the insoluble polymer or copolymer is a polyester, polyacrylic acid, polyamide, polyacrylate and copolymers thereof and mixtures thereof.

24. The process of Claim 1 wherein the catalyst has a vapor pressure lower than the chlorohydrin or its azeotrope with water.

25. The process of Claim 1 which is carried out at a hydrogen chloride partial pressure of from about 15 psia to about 1000 psia.

26. The process of Claim 1 which is carried out at a hydrogen chloride partial pressure of from about 35 psia to about 600 psia.

27. The process of Claim 1 which is carried out at a hydrogen chloride partial pressure of from about 55 psia to about 150 psia.

28. The process of Claim 1 which is carried out at a hydrogen chloride partial pressure of from about 20 psia to about 120 psia.

29. The process of Claim 1 which is carried out at a temperature of from about 25 0C to about 300 0C.

30. The process of Claim 1 which is carried out at a temperature of from about 25 °C to about 200 0C.

31. The process of Claim 1 which is carried out at a temperature of from about 30 0C to about 160 0C.

32. The process of Claim 1 which is carried out at a temperature of from about 40 0C to about 150 0C.

33. The process of Claim 1 which is carried out at a temperature of from about 50 0C to about 140 0C.

34. A process for preparing a chlorohydrin comprising the step of contacting together at a hydrogen chloride partial pressure of from about 15 psia to about 1000 psia and at a temperature in the range of from about 25° C to about 300° C; (a) a multihydroxylated-aϊiphatic hydrocarbon; (b) a catalyst that facilitates the conversion of the multihydroxylated-aliphatic hydrocarbon to a chlorohydrin; and (c) hydrogen chloride gas; said contacting step carried out without substantial removal of water.

35. A process for preparing a chlorohydrin comprising the step of contacting together at a hydrogen chloride partial pressure of from about 15 psia to about 1000 psia and at a temperature in the range of from about 25 0C to about 300 0C: (a) an ester of a multihydroxylated-aliphatic hydrocarbon; and (b) hydrogen chloride; said contacting step carried out without substantial removal of water.

36. A process for preparing an epoxide comprising the steps of:

(a) contacting a multihydroxylated-aliphatic hydrocarbon, an ester of a multihydroxylated-aliphatic hydrocarbon, or a mixture thereof with hydrogen chloride source at superatmospheric pressure to produce a chlorohydrin, said contacting step carried out without substantial removal of water; and

(b) contacting the chlorohydrin formed in step (a) above with a base to form an epoxide.

37. A process for preparing an epichlorohydrin comprising the steps of:

(a) contacting glycerin, an ester of glycerin, or a mixture thereof with hydrogen chloride source at superatmospheric pressure to produce a dichlorohydrin, said contacting step carried out without substantial removal of water; and

(b) contacting the dichlorohydrin formed in step (a) above with a base to form an epichlorohydrin.

38. A process for preparing an epoxide comprising the steps of:

(a) contacting a multihydroxylated-aliphatic hydrocarbon, an ester of a multihydroxylated-aliphatic hydrocarbon, or a mixture thereof with a hydrogen chloride source at superatmospheric pressure to produce a desired chlorohydrin, said contacting step carried out without substantial removal of water;

(b) separating the desired chlorohydrins from unreacted multihydroxylated-aliphatic hydrocarbon, undesired chlorohydrins and their esters, and catalyst; and (c) contacting the desired chlorohydriris separated in step (b) above with a base to form an epoxide.

39. The process of Claim 38 including the step of recycling the separated unreacted multihydroxylated-aliphatic hydrocarbon, monochlorohydrins and their esters, and catalyst to step (a).

40. A process for preparing an epichlorohydrin comprising the steps of:

(a) contacting glycerin, an ester of glycerin, or a mixture thereof with hydrogen chloride source at superatmospheric pressure to produce a dichlorohydrin, said contacting step carried out without substantial removal of water;

(b) separating the dichlorohydrins from unreacted glycerin,
monochlorohydrins and their esters, and catalyst; and

(c) contacting the dichlorohydrins separated in step (b) above with a base to form an epichlorohydrin.

41. A process for preparing an epoxide comprising the steps of:

(a) contacting a multihydroxylated-aliphatic hydrocarbon, an ester of a multihydroxylated-aliphatic hydrocarbon, or a mixture thereof with chloride ion source at superatmospheric pressure to produce a desired chlorohydrin and an ester thereof, said contacting step carried out without substantial removal of water;

(b) reacting the product of step (a) with multihydroxylated-aliphatic hydrocarbon to convert the desired chlorohydrin esters to the desired chlorohydrins;

(c) separating the desired chlorohydrins from unreacted multihydroxylated-aliphatic hydrocarbon, undesired chlorohydrins and their esters, and catalyst; and

(d) contacting the desired chlorohydrin separated in step (c) above with a base to form an epoxide.

42. A process for preparing an epichlorohydrin comprising the steps of: (a) contacting glycerin, an ester of grycerϊh'"or a mixture tnereoi wim chloride ion source at superatmospheric pressure to produce a dichlorohydrin and an ester thereof, said contacting step carried out without substantial removal of water;

(b) reacting the product of step (a) with glycerin to convert the
dichlorohydrin esters to dichlorohydrins;

(c) separating the dichlorohydrins from unreacted glycerin ,
monochlorohydrins and their esters, and catalyst; and

(d) contacting the dichlorohydrin separated in step (c) above with a base to form an epichlorohydrin.

43. The process of claim 40 wherein the base is a carbonate, bicarbonate or hydroxide of sodium, potassium, calcium, magnesium or mixtures thereof.

44. The process of Claims 34-43 wherein the multihydroxylated-aliphatic hydrocarbon is crude glycerol.

45. The process of Claims 34-43 wherein the multihydroxylated-aliphatic hydrocarbon is 1,2,3-propanetriol.

46. A process for producing a high yield of a chlorohydrin, an ester of a chlorohydrin, or a mixture thereof comprising the step of contacting a multihydroxylated-aliphatic hydrocarbon, an ester of a multihydroxylated-aliphatic hydrocarbon, or a mixture thereof with a source of a superatmospheric partial pressure of a hydrogen chloride and in the presence of a catalyst to produce a chlorohydrin, an ester of a chlorohydrin, or a mixture thereof without the substantial removal of water.

47. A process comprising the step of contacting a multihydroxylated-aliphatic hydrocarbon, an ester of a multihydroxylated-aliphatic hydrocarbon, or a mixture thereof with hydrochloric acid gas at superatmospheric pressure to produce a chlorohydrin, said contacting step carried out without substantial removal of water.

48. A composition comprising a dichlorohydrin containing: glycerol and its esters of from about 0.1 mole% to about Tmole%; monocnioronydrins and their esters of from about 4 mole% to about 10 mole%; 1,3-dichlorohydrin and its esters of greater than about 80 mole%; 2,3-dichlorohydrin and its esters of from about 1 mole% to about 4 mole%; 1,2,3-trichloropropane of less than about 1 mole%; and chlorinated glycerol ethers and their esters of less than 0.3 mole%; and wherein the 1,3-dichlorohydrin to 2,3-dichlorohydrin ratio in the composition is greater than about 8:1.
49. The composition of Claim 48 wherein the chlorinated glycerol ethers and their esters is less than about 0.2 mole%.
50. The composition of Claim 48 wherein the chlorinated glycerol ethers and their esters is less than about 0.15 mole%.
51. The composition of Claim 48 wherein the chlorinated glycerol ethers and their esters is less than about 0.1 mole%.
52. The composition of Claim 48 wherein the 1,2,3-trichloropropane is less than about 0.1 mole%.
53. The composition of Claim 48 wherein the 1,2,3-trichloropropane is less than about 0.05 mole%.
54. The composition of Claim 48 wherein the 1 ,2,3-trichloropropane is less than about 0.02 mole%.
55. A process for producing a chlorohydrin, an ester of a chlorohydrin, or a mixture thereof comprising the step of contacting a multihydroxylated-aliphatic hydrocarbon, an ester of a multihydroxylated-aliphatic hydrocarbon, or a mixture thereof with a source of a superatmospheric, atmospheric or subatmospheric partial pressure of hydrogen chloride to produce a chlorohydrin, an ester of a chlorohydrin, or a mixture thereof, in the presence of a catalyst wherein the catalyst: (i) is a carboxylate derivative having from two to about 20 carbon atoms and containing at least one functional group selected from the group comprising an amine, an alcohol, a halogen, an sulfhydryl, an ether, an ester, or a combination thereof, wherein the functional group is attached no closer to the acid function than the alpha carbon; or a precursor thereto; (ii) is less volatile than the desired chlorohydrin, the ester of a chlorohydrin or the mixture thereof; and (iii) contains heteroatom substituents.

56. The process of Claim 55 wherein the carDoxylate derivative catalyst has the following general Formula (a):



Formula (a)

wherein "R'" includes a functional group comprising an amine, an alcohol, a halogen, a sulfhydryl, an ether: or an alkyl, an aryl or alkaryl group of from 1 to about 20 carbon atoms containing said functional group; or a combination thereof; and wherein "R" includes hydrogen, alkali, alkali earth or transition metal or hydrocarbon functional group.

57. The process of claim 55 wherein the carboxylate derivative catalyst is selected from the group consisting of lactones, esters, lactams, amides and functionalized carboxylic acids.

58. The process of Claim 55 wherein the carboxylate derivative catalyst is selected from the group consisting of a caprolactone, a carboxylic acid amide, a carboxylic acid lactone, a caprolactam, and combinations thereof.

59. The process of Claim 55 wherein the carboxylate derivative catalyst is selected from the group consisting of 6-hydroxyhexanoic acid, 6-chIorohexanoic acid, caprolactone, ε-caprolactam, and γ-butyrolactam; γ-butyrolactone, δ-valerolactone, and ε-caprolactone; 6-aminocaproic acid; 4-aminophenylacetic acid, 4-aminobutyric acid, 4-dimethylaminobutyric acid, 4-hydroxyphenylacetic acid, 4-dimethylaminophenylacetic acid, aminophenylacetic acid, lactic acid, glycolic acid, 4-dimethylaminobutyric acid, 4-trimethylammoniumbutyric acid, and combinations thereof.
60. The process of Claim 55 where the multihydroxylated-aliphatic hydrocarbon is glycerol or a crude glycerol.