Process for preparing fatty acid esters of short-chain monohydric alcohols

• US 5,434,279 A
• Filed: 05/06/1994
• Issued: 07/18/1995
• Est. Priority Date: 11/06/1991
• Status: Expired due to Fees

• Current Assignee: Theodor Wimmer
• Original Assignee: Theodor Wimmer
• Inventors: Wimmer, Theodor
• Primary Examiner(s): Dees, Jose G.
• Assistant Examiner(s): Carr, Deborah D.
• Application Number:
  US08/232,285
• Time in Patent Office: 438 Days
• Field of Search: 554/167, 554/168, 554/169
• US Class Current: 554/169
• CPC Class Codes: C11C 3/04 by esterification of fats or fatty oils

Abstract

A process is disclosed for preparing fatty acid esters of short-chain monohydric aliphatic alcohols or monoalkylated diols by basically catalyzed esterification of natural, partially or totally synthetic fatty acid glycerides, as well as fatty acid glyceride-based waste products, such as used frying oils. The process is characterized in that the unpurified fatty acid glycerides, containing in particular high proportions of free fatty acids and phosphatides, (a) are esterified in one or several steps in the presence of a basic catalyst with an excess of short-chain alcohol or monoalkylated diol; (b) the glycerin phase produced after the first esterification step is at least partially added to the second or following step, after sterification has been carried out, and the mixture is stirred; (c) the glycerin phase is again separated, the supernatant fatty acid ester is cleared of excess alcohol or diol, then treated with a possibly diluted organic or anorganic acid, and if necessary filtered. This process, that is carried out without pressure and heat supply, is characterized by a technically simple implementation by means of simple equipment, and by a high degree of purity of the thus obtained fatty acid esters.

Claims

1. In a process for preparing fatty acid esters and mixtures of fatty acid esters of short-chain monohydric alcohols having from 1 to 5 carbon atoms or short-chain diols having from 2 to 5 carbon atoms, which are monoalkylated by alkyl radicals having from 1 to 3 carbon atoms, by trans-esterification of fatty acid glycerides with the alcohols or monoalkylated diols in the presence of a basic catalyst, in a plurality of steps, the improvement which comprises:

a) carrying out a trans-esterification in the presence of from 0.5% to 5.0% of a basic catalyst, based on the amount of fatty acid glyceride, and in the presence of a short-chain alcohol or monoalkylated diol in an excess over a stoichiometric quantity of from 10% to 200% per mol of glycerine-bound fatty acid; and

obtaining a relatively lighter fatty acid ester phase and a relatively heavier glycerine phase by settling and separating;

b) subjecting the relatively higher fatty acid ester phase obtained in step a) to transesterification in the presence of a basic catalyst and a short-chain alcohol or a monoalkylated diol;

c) adding at least one-tenth of the relatively heavier glycerine phase obtained in step a), while stirring; and

obtaining a fatty acid ester phase and a heavy glycerine phase by settling and separating;

d) removing excess short-chain alcohol or monoalkylated diol from the fatty acid ester phase obtained in step c, subsequently stirring in acid and, after a completed phase separation, removing the fatty acid ester phase.

2. The process according to claim 1, which further comprises filtering the fatty acid ester phase in the removing step.

3. The process according to claim 1, which further comprises introducing the acid in one of concentrated and semiconcentrated form in step d).

4. The process according to claim 1, which further comprises carrying out the trans-esterification of step a) in the presence of from 0.5% to 10% water based on the mass of the fatty acid glyceride used.

5. The process according to claim 1, which further comprises carrying out the trans-esterification in a temperature range between -25°

C. and +60°

C. and at atmospheric pressure.

6. The process according to claim 1, which further comprises introducing from four-tenths to ten-tenths of a total quantity of short-chain alcohol or monoalkylated diol in step a), and introducing from zero to six-tenths of the total quantity in a subsequent step.

7. The process according to claim 1, which further comprises introducing from four-tenths to nine-tenths of a total quantity of basic catalyst in step a), and introducing from one-tenth to six-tenths of the total quantity in a subsequent step.

8. The process according to claim 1, which further comprises introducing the same short-chain alcohol or the same monoalkylated diol and the same basic catalyst throughout all trans-esterification steps.

9. The process according to claim 1, which further comprises introducing a given basic catalyst, a given alcohol, a given monoalkylated diol, or a given mixture ratio of alcohols or diols in the first trans-esterification step, and introducing a basic catalyst different from the give basic catalyst, an alcohol or diol different from the given alcohol or diol, respectively, or a different mixture ratio of the alcohols and diols in a subsequent trans-esterification step.

10. The process according to claim 1, which further comprises carrying out the trans-esterification with monohydric aliphatic alcohols having from 1 to 5 carbon atoms, and aliphatic diols having from 2 to 5 carbon atoms and being monoalkylated by alkyl radicals having from 1 to 3 carbon atoms.

11. The process according to claim 9, which further comprises selecting the monohydric aliphatic alcohols from the group consisting of methanol, ethanol, butanols, fermentation amylalcohol, neopentyl alcohol and fusel oils, and selecting the aliphatic diols from the group consisting of ethylene glycol monomethyl ether, 1,2-propane diol monomethyl ether, ethylene glycol monoisopropyl ether, and mixtures thereof.

12. The process according to claim 1, which further comprises carrying out the trans-esterification steps with catalysts selected from the group consisting of basic alkaline and alkaline earth metal compounds.

13. The process according to claim 11, which further comprises selecting the basic catalyst from the group consisting of oxides, hydroxides, alcoholates, borates, carbonates, aluminates and silicates of lithium, sodium, potassium and calcium, in one of concentrated aqueous and alcohol solution.

14. The process according to claim 1, which further comprises carrying out a transesterification with fatty acid glycerides selected from the group consisting of naturally occurring vegetable and animal fats and oils, partly or fully synthetic fatty acid glycerides and used fatty acid glycerides;

used industrial fats and oils based on glyceride, in raw, uncleaned or arbitrarily cleaned quality, with contents of free fatty acids of up to 20% or phosphatide contents of up to 3%, and mixtures thereof.

15. The process according to claim 13, which further comprises carrying out the transesterification with fatty acid glycerides selected from the group consisting of used frying oils and fats;

soybean oil, sunflower oil, linseed oil, rapeseed oil, castor oil, palm oil, palm kernel oil, coconut oil, cottonseed oil, peanut oil, olive oil, beef tallow, used frying oil;

used hydraulic oil and lubricating oil.

16. The process according to claim 1, which further comprises stirring in the acid in step d) in the form of an acid selected from the group consisting of phosphoric, sulfuric, hydrochloric, nitric, boric, formic, acetic, lactic, gluconic, oxalic, succinic, maleic, tartaric, malic and citric acid;

organic sulfonic acids and sulfuric acid semiesters and concentrated solutions of acidic salts.

17. The process according to claim 1, which further comprises adding an acidic salt from the group consisting of potassium and sodium hydrogen sulfate, potassium and sodium dihydrogen phosphate, and monopotassium and monosodium hydrogen citrate, in step d).