Process for producing dichloropropanol from glycerol, the glycerol coming eventually from the conversion of animal fats in the manufacture of biodiesel

• US 20070112224A1
• Filed: 11/18/2004
• Published: 05/17/2007
• Est. Priority Date: 11/20/2003
• Status: Active Grant

• Current Assignee: Solvay SA (Solvac SA)
• Original Assignee: Solvay SA (Solvac SA)
• Inventors: Krafft, Philippe, Claessens, Sara, Gosselin, Benoit, Gilbeau, Patrick
• Granted Patent: US 8,415,509 B2
• Time in Patent Office: Days
• US Class Current: 568/841
• CPC Class Codes: C01B 7/0712 by distillation
• CPC Class Codes: C07C 29/62 by introduction of halogen; by substitution of halogen atoms by other halogen atoms
• CPC Class Codes: C07C 31/36 the halogen not being fluorine
• CPC Class Codes: C07D 303/08 with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
• CPC Class Codes: C08G 59/04 of polyhydroxy compounds with epihalohydrins or precursors thereof
• CPC Class Codes: C11C 3/003 by esterification of fatty acids with alcohols C11C3/02 takes precedence
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials
• CPC Class Codes: Y02P 20/584 Recycling of catalysts

Abstract

Use of glycerol obtained from renewable raw materials, as starting product for producing organic compounds. Process for producing dichloropropanol, according to which glycerol is subjected to a reaction with a chlorinating agent, with the exception of a batch reaction carried out in the presence of acetic acid or its derivatives.

Claims

1. A process for producing dichloropropanol, according to which glycerol is subjected to a reaction with a chlorinating agent, with the exception of a reaction carried out in the presence of acetic acid or its derivatives.

2. The process according to claim 1, wherein the reaction is carried out continuously.

3. The process according to claim 1, wherein the chlorinating agent comprises substantially anhydrous hydrogen chloride.

4. The process according to claim 1, wherein the chlorinating agent is an aqueous solution of hydrogen chloride with a hydrogen chloride content higher than or equal to 4% by weight.

5. The process according to any of claim 1, wherein the reaction is carried out in the liquid phase.

6. The process according to claim 1, wherein a carboxylic acid, a carboxylic acid anhydride, a carboxylic acid chloride, a carboxylic acid salt or a carboxylic acid ester is used as the catalyst.

7. The process according to claim 6, wherein the catalyst is adipic acid, adipic acid anhydride, adipic acid chloride, adipic acid salt or adipic acid ester.

8. The process according to claim 6, wherein the acid concentration in the reaction medium expressed in mole of acid and of acid esters derivatives per kg of liquid reaction medium is higher than or equal to 0.1 and lower than or equal to 10.

9. The process according to claim 1, wherein the reaction is carried out in the presence of at least one organic solvent.

10. The process according to claim 9, wherein the solvent comprises chloropropanediol and/or dichloropropanol and/or heavy by-products of the reaction.

11. The process according to claim 10, wherein the water concentration in the reaction mixture is lower than or equal to 15% by weight.

12. The process according to claim 1, wherein reaction conditions are adjusted in such a way that the concentration of hydrogen chloride in the gas phase above the liquid reaction mixture remains lower than the concentration of hydrogen chloride in the binary azeotropic hydrogen chloride-water mixture.

13. The process according to claim 1, wherein continuous or periodic withdrawal of a fraction comprising at least water with a hydrogen chloride content equal to or less than 10% by weight relative to the total weight of the fraction comprising water and optionally dichloropropanol is carried out, and the reaction medium is optionally fed with water.

14. The process according to claim 1, wherein the reaction is carried out in a reactor made of materials that are resistant, under the conditions of reaction, to the chlorinating agent and are selected from the group consisting of enameled steel, polymers, coatings by means of resins, metals or alloys, ceramics and metalloceramics and refractory materials.

15. The process according to claim 1, wherein a reactor is fed, in a continuous or batch mode, with glycerol via a first line and catalyst via a second line, the feed of hydrogen chloride, anhydrous or in aqueous solution, is carried out continuously or in batch-mode via a third line, a distillation column is fed via a fourth line with vapor produced from the reactor, a stream is withdrawn from the distillation column via a fifth line and optionally fed to a decantor in which aqueous and organic phases are separated.

16. The process according to claim 1, wherein a reactor is continuously or batch fed with glycerol via a first line and catalyst via a second line, the feed of hydrogen chloride, anhydrous or in aqueous solution, is carried out continuously or in batch-mode through a third line, a distillation column is fed via a fourth line with the vapor produced from reactor, the residue from the distillation column is recycled via a fifth line to the reactor, a purge from the reactor bottom is fed via a sixth line into a stripper wherein a partial stripping operation is carried out, the gas phase containing most of the hydrogen chloride from a stream is recycled via line to the distillation column or via line to the reactor, a distillation or stripping column is fed with the liquid phase arising from the stripper via a seventh line, the main fraction of dichloropropanol is collected from the top of the column through an eighth line and the column residue is recycled via a nine line to the reactor.

17. The process according to claim 15, wherein

(a) a liquid phase is withdrawn from the reactor;

(b) a hydrogen chloride/water mixture is added to the liquid phase and the resulting mixture is then heated; and

(c) the acid is recovered from this resulting mixture.

18. The process according to claim 17, wherein water is added to the resulting mixture from step (b) and the acid catalyst is recovered by crystallization and recycled to the reactor.

19. The process according to claim 1, wherein 1,3-dichloropropan-2-ol is obtained with a selectivity of at least 50%.

20. The process according to claim 1, wherein the glycerol used has at least partially been produced from renewable raw materials.

31. A process for producing epichlorhydrin wherein

(a) dichloropropanol is produced in accordance with a process according to claim 1;

(b) at least one fraction of the obtained dichloropropanol is subjected to a dehydrochlorination reaction.

33. A process for producing epoxy resins according to which epichlorohydrin derived from the process according to claim 31 is used as starting material.

35. The process according to claim 6, wherein the catalyst is a dicarboxylic acid, a dicarboxylic acid anhydride, a dicarboxylic acid chloride, a dicarboxylic acid salt or a dicarboxylic acid ester.

21. A pseudo-azeotropic composition consisting essentially of dichloropropanol, hydrogen chloride and water.

22. A process for producing organic compounds comprising

(a) a first step wherein glycerol is produced from renewable raw materials;

and

(b) a second step wherein organic compounds are produced from glycerol obtained in the first step.

23. The process according to claim 22, wherein the glycerol used in the second step is a crude product comprising besides, water and a metal salt.

24. The process according to claim 23, wherein the crude product comprises from 40 to 99% by weight of glycerol, from 5 to 50% by weight of water and from 1 to 10% by weight of metal salt.

25. The process according to claim 22, wherein the glycerol used during the second step is a purified product.

26. The process according to claim 25, wherein the purified product comprises from 80 to 99.9% by weight of glycerol and from 0.1 to 20% by weight of water.

27. The process according to claim 22, wherein the glycerol is obtained by conversion of animal fats or has been obtained during the manufacture of biodiesel.

28. The process according to claim 27 according to which

(a) a plant oil is subjected to a trans-esterification reaction with an alcohol other than glycerol, preferably methanol or ethanol, so as to recover at least biodiesel and a crude product containing glycerol;

(b) the crude product is optionally subjected to a purification operation such as distillation; and

(c) glycerol formed in step (a) is subjected to the process for producing an organic compound.

29. The process according to claim 28, according to which the steps of production of glycerol and of production of the organic compound are carried out on the same production site.

30. The process according to claim 28, according to which the steps of production of glycerol and of production of the organic compound are carried out on different production sites.

32. The process according to claim 22, wherein glycerol is contacted with at least one condensing agent or with epichlorohydrin, possibly in the presence of a base, and polyglycerol is obtained.

34. A process for producing epoxy resins wherein dichloropropanol containing at least 50% by weight of 1,3-dichloropropane-2-ol relative to the total dichloropropanol is used as the starting material.

36. A process for separation of a mixture containing at least water, dichloropropane and hydrogen chloride wherein the mixture is separated in a distillation step wherein the sum of materials fed to said distillation step has a hydrogen chloride concentration which is lower than the hydrogen chloride concentration in the binary azeotropic composition hydrogen chloride/water at the pressure of the distillation.