Production process of biodiesel from the esterification of free faty acids

Abstract

This invention describes a process for the production of biodiesel from the alcohol esterification of free fatty acids, resulting from the refining of vegetable oils, rejects of industrial and frying oils, and animal fats and organic sewage, using niobic acid as a solid acid catalyst.

Description

BRIEF DESCRIPTION OF FIGURES

FIG. 1—Kinetics curve of reaction time versus yield or conversion for palm oil free fatty acids esterification with methanol at the temperature of 130° C., using powdered niobic acid (Nióbia HY®) as a solid acid catalyst and a commercial zeolite Y. Amount of catalyst: (a) 1% in weight; and (b) 2% in weight related to free fatty acids weight.

FIG. 2—Kinetics curve of reaction time versus yield or conversion for palm oil free fatty acids esterification with methanol at the temperature of 130° C., using niobic acid (Nióbia HY®) as tablet or pellet and a commercial zeolite Y. The amount of catalyst was of 2% in weight related to the free fatty acids weight.

FIG. 3—Kinetics curve of reaction time versus yield or conversion for palm oil free fatty acids esterification with methanol at the temperature of 130° C., using extrudates niobic acid (Nióbia HY®). The amount of catalyst was of 2% in weight related to free fatty acids weight.

FIG. 4—Kinetics curve of reaction time versus yield or conversion for palm oil free fatty acids esterification with methanol at the temperature of 130° C., comparing the performance of different forms of niobic acid (Nióbia HY®) and commercial zeolites. The amount of catalyst was of 2% in weight related to the free fatty acids weight.

Claims

1. A process for the production of Biodiesel characterized by the use of a solid niobic acid catalyst (Nb2O5.nH2O or hydrated niobium pentoxide) in the free fatty acids esterification with an alcohol.

2. A process for the production of Biodiesel according to claim 1, characterized in that the free fatty acids are from refining of vegetable oils such as soy, rape, palm, canola, olive, babaçu, peanut, coconut, castor, cotton and sunflower oils.

3. A process for the production of Biodiesel according to claim 1, characterized in that the free fatty acids are from disposals where free acidity is significant, such as used vegetable oils, rejects of industrial oils, animal fat and fat-enriched organic sewage.

4. A process for the production of Biodiesel according to claims 2 and 3, characterized in that the free fatty acids are long chain carboxylic acids containing 6 to 24 carbon atoms (C6 to C24) such as caproic, caprylic, capric, lauric, miristic, palmitic, palmitoleic, stearic, oleic, vaccenic, linoleic, linolenic, arachidic, gadoleic, arachidonic, behenic, erucic, linoceric acids or their mixtures.

5. A process for the production of Biodiesel according to claim 1, characterized in that the alcohol is methanol, ethanol, propanol, isopropanol, butanol or isobutanol.

6. A process for the production of Biodiesel according to claim 5, characterized in that the alcohol is preferably methanol and ethanol.

7. A process for the production of Biodiesel according to claim 1, characterized in that the alcohol is added in excess to the reaction mixture, with molar alcohol fatty acids ratio between 1,5 and 6.

8. A process for the production of Biodiesel according to claim 1, characterized in that the water content of niobic acid is within 5 to 25% in weight.

9. A process for the production of Biodiesel according to claim 1, characterized in that the niobic acid is calcined at a temperature of 100 to 300° C.

10. A process for the production of Biodiesel according to claim 9, characterized in that the niobic acid calcination is for a period of 1 to 3 hours.

11. A process for the production of Biodiesel according to claim 1, characterized in that the BET surface area of niobic acid is between 10 to 300 m2/g.

12. A process for the production of Biodiesel according to claim 11, characterized in that the preferred BET surface area is within 80 to 200 m2/g.

13. A process for the production of Biodiesel according to claim 1, characterized in that the niobic acid is used in powder, tablet or pellet and extrudates.

14. A process for the production of Biodiesel according to claim 13, characterized in that that the mechanical resistance of tablet/pellet and extrudates of niobic acid is within 10 to 40 N·mm−1.

15. A process for the production of Biodiesel according to claim 1, characterized in that the amount of niobic acid used in the reaction ranges from 1 to 2% in weight of the mixture of free fatty acids.

16. A process for the production of Biodiesel according to claim 1, characterized in that the reaction temperature is between 80 to 200° C.

17. A process for the production of Biodiesel according to claim 16, characterized in that that the preferred reaction temperature is between 120 to 170° C.

18. A process for the production of Biodiesel according to claim 1, characterized in that the pressure of reaction is endogenous and depends on the temperature and alcohol used.

19. A process for the production of Biodiesel according to claim 1, characterized in that the reaction configuration uses batch reactors.

20. A process for the production of Biodiesel according to claim 1, characterized in that the reaction configuration uses continuous reactors of fixed bed and perfect mixture.

21. A process for the production of Biodiesel according to claim 19, characterized in that the time of residence in the batch reactors ranges between 60 to 300 minutes of reaction.

22. A process for the production of Biodiesel according to claim 20, characterized in that the spatial time in the continuous reactions in relation to the fatty acids flow rate and volume of solid catalyst is between 15 and 160 minutes.

23. A process for the production of Biodiesel according to claim 22, characterized in that the preferred spatial time in continuous reactors in relation to fatty acids flow rate and the volume of solid catalyst is between 30 to 120 minutes.

24. A process for the production of Biodiesel according to claim 1, characterized in that the obtained Biodiesel is a mixture of fatty acids methyl esters.

25. A process for the production of Biodiesel according to claim 1, characterized in that the obtained Biodiesel is a mixture of fatty acids ethyl esters.