Mj. Haas et Km. Scott, DIESEL FUEL AS A SOLVENT FOR THE LIPASE-CATALYZED ALCOHOLYSIS OF TRIGLYCERIDES AND PHOSPHATIDYLCHOLINE, Journal of the American Oil Chemists' Society, 73(11), 1996, pp. 1497-1504
The abilities of three commercially available lipases-lipozyme IM 20,
Amano PS-30, and Amano CE-to synthesize fatty acid ethyl esters via th
e alcoholysis of soy triglycerides (TG) and phosphatidylcholine (PC) i
n grade No. 2 diesel fuel were investigated. All three enzyme preparat
ions were active in water-saturated diesel fuel, synthesizing fatty ac
id esters from both TC and PC. Response surface methodology, based on
a Modified Central Composite design, was employed to examine the coord
inate effects of lipid, water, and ethanol concentrations on enzyme ac
tivities and to identify conditions yielding maximum alcoholysis. For
all three enzymes, optimal activities toward TG occurred al added wate
r concentrations of less than 0.3 M. With PC as substrate, optimal enz
yme activities occurred at added water concentrations as much as tenfo
ld greater than this, and the amount of water required for maximum act
ivity was proportional to the substrate concentration. For both substr
ates the enzyme activities were generally reduced as ethanol concentra
tions rose. The exceptions to this were the Lipozyme-TG combination, w
here activity increased with increasing ethanol concentrations, and th
e PS-30-PC combination, where activity was roughly constant across the
range of water and ethanol concentrations examined. Hydrolytic activi
ties of the enzymes in aqueous reactions were poor predictors of trans
esterification activity in organic solvent: the aqueous hydrolytic act
ivities of CE and PS-30 toward TG were roughly comparable, and 25 to 5
0 times greater than that of IM 20. However, in the alcoholysis of TG
in diesel fuel the order of activities was PS-30 > IM 20 > CE. The act
ivities of Lipozyme and CE toward PC were similar to one another, and
PS-30 was considerably less active on this substrate. CE lipase was mo
re active toward PC than toward TG. Lipozyme displayed comparable acti
vity toward the two substrates. PS-30 was considerably more active on
TG than on PC: Degrees of conversion were consistent with the transest
erification of only one fatty acid of TG, and slightly greater than on
e fatty acid for PC. Preliminary studies indicated that for CE and PS-
30, but not for Lipozyme IM 20, the degree of conversion of TC, but no
t PC, could be significantly increased by the further provision of eth
anol. Expansion of this work could lead to a method for the production
of simple fatty acid esters, which are suitable as diesel fuels, from
multicomponent agricultural materials containing TC and PC.