Catalytic purification of fatty acid alkyl esters used in fuels
View Patent ↗The process of this invention removes impurities from transesterification products comprising primarily fatty acid alkyl esters (FAAE) that are being processed for final fuel products, such as biodiesel. The inventive process is catalytic, and the resulting ester is suitable for use as biodiesel. Metal oxide and mixed metal oxide catalysts are particularly suitable. The invention is particularly suitable for treating fatty acid alkyl ester compositions comprising impurities such as glycerin, sterol glycosides, and/or triglyceride, diglyceride and/or monoglyceride. The invention is particularly useful in treating FAAE transesterification products made using homogeneous alkali catalysts. The treated ester exhibits improved performance under cold weather conditions, which can be measured by methods such as ASTM 7501 Cold Soak Filtration Test (CSFT).
1. A process for treating a fatty acid alkyl ester-containing stream comprising impurities, and at least ninety percent by weight fatty acid alkyl ester, and optionally alcohol, the process for treating the feed stream comprising:
(a) contacting the stream with a catalyst comprising metal oxide, wherein the metal is selected from the group of metals consisting of those in Groups 3, 4, 5, 13 and 14, and optionally, alcohol under catalytic conditions to convert the impurities in the stream to a product or by product, and
(b) recovering a fatty acid alkyl ester stream having reduced amounts of impurities and having improved cold flow properties.
2. A process according to claim 1 , comprising contacting the fatty acid alkyl ester-containing stream in (a) with a catalyst comprising mixed metal oxide of two or more metals selected from the group of metals consisting of those in Groups 3, 4, 5, 13 and 14.
3. A process according to claim 1 , wherein the mixed oxide comprises magnesium oxide and alumina.
4. A process according to claim 1 , wherein the mixed oxide further comprises alkaline earth aluminate spinel.
5. A process according to claim 4 , wherein the alkaline earth aluminate spinel is magnesium aluminate spinel, and the catalyst further comprises rare earth oxide and an oxide of a Group 5 metal.
6. A process according to claim 5 , wherein the rare earth oxide is ceria, and the Group 5 metal oxide is vanadium oxide.
7. A process according to claim 1 , wherein the catalyst comprises alumina and an oxide of metal selected from the group of metals consisting of those in Groups 3, 4, 5 and 14.
8. A process according to claim 7 , wherein the metal selected is zirconium.
9. A process according to claim 1 , wherein the impurities are selected from the group consisting of monoglycerides, glycerin, sterol glycosides, triglycerides, diglycerides and mixtures thereof.
10. A process according to claim 1 comprising contacting the fatty acid alkyl ester-containing stream in (a) with a catalyst under catalytic conditions that comprise a temperature of at least 100° C.
11. A process according to claim 1 , wherein feed stream in (a) comprises alcohol, and/or additional alcohol is contacted with said stream in (a), wherein the alcohol is selected from the group consisting of methanol, ethanol, propanol, butanol, and mixtures thereof.
12. A process comprising:
(a) introducing triglyceride-containing feedstock and an alcohol as reactants into a reactor selected from the group consisting of continuous fixed bed reactor, a continuous tank reactor, and a batch reactor,
(b) contacting the reactants in the reactor with a catalyst in liquid, granulated or powder form;
(c) subjecting the feedstock and catalyst to transesterification conditions sufficient to convert triglycerides to products comprising alkyl ester derivatives of the triglycerides, and glycerin, wherein the alkyl ester derivatives of the triglycerides and impurities are present in an oil phase, wherein the oil phase comprises at least 90% by weight alkyl ester derivatives, and glycerin is present in a water soluble phase;
(d) performing product separation to remove glycerin product from the oil phase;
(e) contacting the oil phase separated by (d) and, optionally, any residual unreacted alcohol, with a catalyst comprising metal oxide, wherein the metal is selected from the group of metals consisting of those in Groups 3, 4, 5, 13 and 14, and, optionally, additional alcohol, under catalytic conditions to convert the impurities in the oil phase to a product or by product, and
(f) recovering a fatty acid alkyl ester stream having reduced amounts of impurities.
13. A process according to claim 12 wherein methanol is removed from the oil phase from (d) comprising fatty acid alkyl ester, or, during the recovery of the fatty acid alkyl ester stream in (f) or wherein methanol is removed during both steps.
14. A process according to claim 12 , wherein the catalyst in step (b) is a liquid homogeneous catalyst comprising soluble alkali catalyst and step (c) further comprises neutralizing the liquid catalyst prior to the separation of the oil phase in step (d).
15. A process according to claim 14 , wherein the catalyst in step (b) is selected from the group consisting of alkali methoxides, alkali hydroxides, and mixtures thereof.
16. A process comprising:
(a) introducing triglyceride-containing feedstock and an alcohol as reactants into a reactor selected from the group consisting of continuous fixed bed reactor, a continuous tank reactor, and a batch reactor,
(b) contacting the reactants in the reactor with a catalyst in liquid, granulated or powder form;
(c) subjecting the feedstock and catalyst to transesterification conditions sufficient to convert triglycerides to products comprising alkyl ester derivatives of the triglycerides, and glycerin, wherein the alkyl ester derivatives of the triglycerides and impurities are present in an oil phase, wherein the oil phase comprises at least 90% by weight alkyl ester derivatives, and glycerin is present in a water soluble phase;
(d) performing product separation to remove glycerin product from the oil phase;
(e) removing residual alcohol from the oil phase recovered in (d),
(f) contacting the oil phase with adsorbent or filter, and
(g) further contacting the alkyl ester-containing oil phase recovered from (f) and any impurities therein with a catalyst comprising a metal oxide, wherein the metal is selected from the group of metals consisting of Groups 3, 4, 5, 13 and 14, and, optionally alcohol, under catalytic conditions to convert impurities in the alkyl ester-containing oil phase to a product or by product, and
(h) recovering a fatty acid alkyl ester stream having reduced amounts of impurities.
17. A process according to claim 16 wherein methanol is removed from the oil phase from (d) comprising fatty acid alkyl ester, or during the recovery of the fatty acid alkyl ester stream in (h) or wherein methanol is removed during both steps.
18. A process comprising:
(a) introducing triglyceride-containing feedstock and an alcohol as reactants into a reactor selected from the group consisting of continuous fixed bed reactor, a continuous tank reactor, and a batch reactor,
(b) contacting the reactants in the reactor with a catalyst in liquid, granulated or powder form;
(c) subjecting the feedstock and catalyst to transesterification conditions sufficient to convert triglycerides to products comprising alkyl ester derivatives of the triglycerides, and glycerin, wherein the alkyl ester derivatives of the triglycerides, and impurities are present in an oil phase, and glycerin is present in a water soluble phase;
(d) performing product separation to remove glycerin product from the oil phase;
(e) subjecting the oil phase to further transesterification in one or more reactors with additional alcohol under conditions sufficient to convert triglycerides, diglycerides and monoglycerides to products comprising alkyl ester derivatives of and optionally glycerin;
(f) recovering the alkyl ester derivatives in an oil phase with one or more product separation steps; and
(g) contacting the recovered oil phase comprising at least 90% alkyl ester derivatives, and any impurities therein and unreacted alcohol, with a catalyst comprising a metal oxide, wherein the metal is selected from the group of metals consisting of those in Groups 3, 4, 5, 13 and 14, and, optionally, additional alcohol, under catalytic conditions to convert the impurities in the recovered oil phase to a product or by product, and
(h) recovering a fatty acid alkyl ester stream having reduced amounts of impurities.
19. A process according to claim 18 , comprising contacting the recovered oil phase with a catalyst comprising mixed oxide.
20. A process according to claim 18 , wherein the catalyst contacting the recovered oil phase comprises magnesium oxide and alumina.
21. A process according to claim 18 , wherein catalyst contacting the recovered oil phase comprises mixed oxide that further comprises alkaline earth aluminate spinel, rare earth oxide, and an oxide of a Group 5 metal.
22. A process according to claim 21 , wherein the rare earth oxide is cerin, and the Group 5 metal oxide is vanadium oxide.
23. A process according to claim 18 wherein the catalyst contacting the recovered oil phase comprises alumina and an oxide of metal selected from the group of metals consisting of those in Groups 3, 4, 5 and 14.
24. A process according to claim 18 , wherein the impurities comprise glycerin, sterol glycosides, and/or triglyceride, diglyceride and/or monoglyceride.
25. A process according to claim 18 comprising contacting the recovered oil phase with a catalyst under catalytic conditions comprising a temperature of at least 100° C.
26. A process according to claim 18 , wherein the recovered fatty acid alkyl ester stream has properties such that the ester meets the cold flow specification for use as a biodiesel fuel such as the ASTM method D7501.
27. A process according to claim 21 , wherein the alkaline earth aluminate spinel is magnesium aluminate spinel.
28. A process according to claim 18 , wherein the catalyst in (b) is an alkali catalyst.
29. A process according to claim 17 , wherein methanol is removed during the recovery of the fatty acid alkyl ester stream in (h).
30. A process according to claim 1 , wherein the catalyst in (a) comprises alumina.
31. A process according to claim 18 wherein the catalyst contacting the recovered oil phase comprises alumina.
32. A process according to claim 12 , comprising contacting the oil phase with a catalyst comprising mixed oxide.
33. A process according to claim 12 , wherein the catalyst contacting the oil phase comprises magnesium oxide and alumina.
34. A process according to claim 12 , wherein catalyst contacting the oil phase comprises mixed oxide that further comprises alkaline earth aluminate spinel, rare earth oxide, and an oxide of a Group 5 metal.
35. A process according to claim 34 , wherein the rare earth oxide is ceria, and the Group 5 metal oxide is vanadium oxide.
36. A process according to claim 12 , wherein the impurities comprise glycerin, sterol glycosides, and/or triglyceride, diglyceride and/or monoglyceride.
37. A process according to claim 12 comprising contacting the oil phase with a catalyst under catalytic conditions comprising a temperature of at least 100° C.
38. A process according to claim 12 , wherein the recovered fatty acid alkyl ester stream has properties such that the ester meets the cold flow specification for use as a biodiesel fuel such as the ASTM method D7501.
39. A process according to claim 34 , wherein the alkaline earth aluminate spinel is magnesium aluminate spinel.
40. A process according to claim 12 wherein the catalyst contacting the oil phase comprises alumina.
41. A process according to claim 16 , comprising contacting the recovered oil phase in (g) with a catalyst comprising mixed oxide.
42. A process according to claim 16 , wherein the catalyst contacting the recovered oil phase in (g) comprises magnesium oxide and alumina.
43. A process according to 16 , wherein catalyst contacting the recovered oil phase in (g) comprises mixed oxide that further comprises alkaline earth aluminate spinel, rare earth oxide, and an oxide of a Group 5 metal.
44. A process according to claim 43 , wherein the rare earth oxide is ceria, and the Group 5 metal oxide is vanadium oxide.
45. A process according to claim 16 , wherein the impurities comprise glycerin, sterol glycosides, and/or triglyceride, diglyceride and/or monoglyceride.
46. A process according to claim 16 comprising contacting the recovered oil phase in (g) with a catalyst under catalytic conditions comprising a temperature of at least 100° C.
47. A process according to claim 16 , wherein the recovered fatty acid alkyl ester in step (h) has properties such that the ester meets the cold flow specification for use as a biodiesel fuel such as the ASTM method D7501.
48. A process according to claim 43 , wherein the alkaline earth aluminate spinel is magnesium aluminate spinel.
49. A process according to claim 16 , wherein the catalyst in (b) is an alkali catalyst.
50. A process according to claim 16 wherein the catalyst contacting the recovered oil phase in (g) comprises alumina.