Process for manufacturing a composition of fatty acid esters useful as gas oil substitute motor fuel with hydrated ethyl alcohol and the resultant esters composition

• US 4,695,411 A
• Filed: 02/18/1986
• Issued: 09/22/1987
• Est. Priority Date: 02/15/1985
• Status: Expired due to Fees

• Current Assignee: Institut Francais Du Petrole
• Original Assignee: Institut Francais Du Petrole
• Inventors: Gateau, Paul, Guibet, Jean-Claude, Hillion, Gerard, Stern, Robert
• Primary Examiner(s): Evans, J. E.
• Application Number:
  US06/830,169
• Time in Patent Office: 581 Days
• Field of Search: 260/410.9 E, 260/421
• US Class Current: 554/167
• CPC Class Codes: C10G 2300/1003 Waste materials
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10G 2400/04 Diesel oil
• CPC Class Codes: C10L 1/026 for compression ignition
• CPC Class Codes: C10L 1/143 mixtures of organic macromolecular compounds with organic non-macromolecular compounds
• CPC Class Codes: C10L 1/18 containing oxygen
• CPC Class Codes: C11C 3/04 by esterification of fats or fatty oils
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02P 30/20 using bio-feedstock

Abstract

The invention concerns a process for manufacturing a composition of fatty acid esters useful as gas oil substitute motor fuel, said composition containing at least one hydrated ethyl alcohol.

The process comprises:

(A) A first acid transesterification step in the presence of at least one aliphatic, linear or branched monoalcohol of 1 to 5 carbon atoms, consisting at least partly of hydrated ethyl alcohol containing 1 to 60% by weight of water, said step leading to the formation of a phase mainly containing ethyl esters after removal of the produced glycerol phase,

(B) A second step wherein the initial free acidity or that formed during the first step in the phase containing the esters is decreased to a value at most equal to about 2%; and

(C) A third step of basic transesterification of the phase resulting from step B, in the presence of at least one aliphatic, linear or branched monoalcohol of 1 to 5 carbon atoms, with the recovery of the so-formed ester composition.

The composition of the invention can be used for combustion in Diesel engines.

Claims

1. A process for manufacturing a composition of fatty acid esters, useful as motor fuel substitute for gas oil, said composition comprising a major proportion of ethyl esters, by transesterification of a starting material oil or grease of vegetable or animal origin, or a mixture thereof, which starting material may contain free acids, said process comprising the following steps:

(a) in a first acid transesterification step, reacting said starting material oil or grease with ethyl alcohol containing from 1 to 60% by weight of water, in the presence of an acid catalyst, at 70°

-150°

C. for a time sufficient to transesterify at least 75% of said oil or grease to ethyl ester, and recovering a raw ethyl ester phase containing free fatty acids and a glycerol phase and separating said phases from each other,

(b) in a second step, reacting said separated raw ethyl ester phase at an acid pH with an alcohol selected from the group consisting of methanol, ethanol, propanol and butanol and simultaneously distilling water from the reaction mixture, so as to form additional ester from said free fatty acids present in said separated raw ethyl ester phase, while decreasing the content of said free fatty acids to at most about 2% by weight of said raw ethyl ester phase,

(c) in a third step, reacting resultant reaction product of said second step with at least one aliphatic, linear or branched monoalcohol of 1 to 5 carbon atoms in the presence of a basic catalyst, thereby further reducing the content of said free fatty acid in the product of step (b) and forming a purified composition of fatty acid esters.

2. A process according to claim 1, wherein the first transesterification step is performed with hydrated ethyl alcohol containing 4 to 50% by weight of water.

3. A process according to claim 1, wherein said first acid transesterification step is conducted for a time of 30 minutes to 24 hours.

4. A process according to claim 1, wherein the first acid transesterification step is performed in the presence of an amount of alcohol of 1 to 2.5 times the stoichiometrical amount.

5. A process according to claim 1, wherein the first transesterification step is performed in the presence of a soluble acid catalyst used in a proportion of 0.1 to 3% by weight or of an insoluble acid catalyst used in a proportion of 1 to 20% by weight with respect to the oil or to the grease.

6. A process according to claim 1, wherein the oil or the grease has an acidity content of at most about 50%.

7. A process according to claim 1, wherein, in the first step, hydrated alcohol is continuously introduced in a reactor with reflux so as to maintain the reaction temperature between 85°

and 125°

C.

8. A process according to claim 1, wherein, in the second step, the free acidity, initial or formed during the first step, is decreased to a value of at most 1%.

9. A process according to claim 1, wherein, in the second step, the acidity is decreased by esterification with an alcohol in the presence of an alcohol drying agent.

10. A process according to claim 1, wherein, in the second step, the acidity is decreased by esterification with substantially anhydrous methyl, propyl or butyl alcohol.

11. A process according to claim 1, wherein, in the second step, the acidity is decreased by esterification in the presence of an azeotropic mixture containing a third solvent.

12. A process according to claim 1, wherein the third step is conducted at a temperature of 20°

C. to 100°

C., in the presence of an amount of alcohol of from 2 to 5 times the total stoichiometrical amount of unconverted oil or grease, in the presence of a basic catalyst used in a proportion from 0.1 to 1% by weight with respect to the oil or to the grease and for a time ranging from 5 minutes to 1 hour.

13. A process according to claim 1, wherein the esters recovered in the third step are subjected to a final purification by successive washings with water followed with a drying step, by successive washings with water followed with alcohol addition, by passage over cationic ion exchange resins or by passage over activated clay.

14. A process according to claim 1, wherein in step (a) the reaction of said oil or grease with ethyl alcohol is conducted for a time sufficient to transesterify at least 95% of said oil or grease.

15. A process according to claim 1, wherein the first transesterification step is performed with hydrated ethyl alcohol containing 7% by weight of water.

16. A process according to claim 1, wherein the time sufficient to transesterify at least 75% of said oil or grease is 0.5-24 hours.

17. A process according to claim 1, wherein in step (b) the alcohol is that alcohol which remains in the raw ethyl ester phase separated in step (a).