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April 1997
V Medikonduru
Department of Chemical Engineering, University of Nebraska-Lincoln
Noureddini, Hossein and Medikonduru, V, "Glycerolysis of Fats and Methyl Esters." (1997). Papers in Biomaterials. 11.
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Clycerolysis of Fats and Methyl Esters
H. Noureddini* and V. Medikonduru
Department of Chemical Engineering. bniversity of Neblarka, Lincoln, Nebraska G85RR-0126
ABSTRACT: The glycerolysis of methyl esters and triglycerides During the last decade, enzymatic synthesis of MG by var-
with crude glycerol. a coproduct from the transesterification of ious lipase catalysts has received a lot of attention due to
triglycerides, was studied. Three procedures were followed ior lower energy requirements and selectivity of the catalyst
this conversion. The first procedure was a one-step glycerolysis (7-10). Although enzyrnatic synthesis of MG offers perhaps
with methyl esters. The second procedure was a two-step the greatest potential for future production of MG, cursent in-
process. This proced~~re involved an initial partial glycerolysis
dustrial processes are based on the physicochemical glycerol-
with methyl esters, followed by fat glycerolysis. The third pro-
cedure u,as a simultaneous glycerolysis n,ith methyl esters and ysis of fats and oils.
triglycerides. In the glycerolysis with methyl esters, the removal Fatty acid ~lycerideshave also been prepared by direct es-
of methanol is vital to the production of mono- and diglyc- terification of fatty acids or their alkyl esters with glycerol.
erides. Methanol was removed either by drawing vacuum on The chemical reactions involved are reversible and result in
the reactor or by stripping methanol out by means of an inert formation of MG, DG, and possibly triglycerides (TG). Water
carrier gas (nitrogen]. Different molar ratios of methyl esters to or alcohol is also formed in the reaction. Masuyama and
glycerol were tested in the first two processes. At low concen- coworkers ( I I) transesterified methyl esters (ME) of various
tration of methyi esters, total conversion oi methyl esters to vegetable oils with glycerol and potassium hydroxide catalyst
mono- and diglycerides was achieved. As the concentration oi and reported 50-55% conversion to MG. Takeda et al. (12)
methyl esters was increased, the conversion of methyl esters to used both fatty acids and their alkyl esters in a two-step rzac-
m o n o and diglvcerides was decreased. Furthermore, the ratio
tion to prepare MG. The fatty acid or alkyl ester was first re-
of mono- to diglycerides was also higher at lower roncentra-
tions of methyl esters. The conversion of triglycerides in the acted with glycerol in the presence of an alkaline catalyst. The
two-step process with crude glycerol was similar to a one-step second step, which involved further addition of catalyst and
fat glycerolysis with pure glycerol. The composition of different an organic solvent. had a significant increase in the yield of
coniponents and the ratio of mono to diglycerides were also MG. Use of organic solveots in the production of fatty acid
comparable. MG from the glycerolysis of fatty acids with glycerol has also
IAOCS W11 9-425 (1 9973. been reported in other studies (13,14). In both studies. zinc
compounds were used as the catalyst.
KEY WORDS: Biodiesel, diglycerides, f a y acid methyl esters, Glycerol. Natural glycerol is the process coproduct in the
glycerol. glycerolysis, monoglycerides, transesterification, conversion of fats and oils to fatty acids (fat splitting) or fatty
triglycerides. acid esters (transesterification). Crude glycerol from fat split-
ting is a 15-20% solution of glycerol in water. The transes-
terification process results in a 75-90% solution of glycerol
Glycerolysis of fats and oils produces industrially import:int in alcohol, depending on the initial ratio of the alcohol to the
mono- (MG) and diglycerides (DG). Fatty acid MG and their fat or oil and the catalyst concentration. The coproducts from
derivatives have many applications as surfactants and emulsi- botli processes are further purified to different purities. Sev-
fiers in a w-ide range of foods, cosmetics, and pharmaceutical eral grades of refined and cmde glycerol with such names as
products (l,2). MG are commercially manufactured by the sweetwater, soap-lye cmde, saponification crude, alcoholysis
glycerolysis reaction in which fats and oils undergo a transes- crude. high-gravity, dynamite, and CPS are marketed (15).
terification reaction with glycerol. This is a physicochemical Over the last few years, fatty acid methyl esters have as-
process and requires high temperatures (216260C) and the sumed importance as research intensifies on the utilization of
iise of an inorganic cataiyst, such as sodium, potassium, or vegetable oils and animal fat derivatives as liquid fuels (bet-
calcium hydroxide (3-6). Glycerolysis of fats and oils with ter known as hiodiesel). Fatty acid methyl esters are the prod-
glycerol has been intensively patented as widening industrial uct of the oils' transesterification reaction. Crude glycerol
uses were found for MG in the 1940s and 1950s. Sonntag (3) from the transesterificalion process contains methanol, ,ME.
has a complete collection of these patents in his review. inlpulities from the raw material, and an insignificant amount
of glycerides. Because of the presence of fatty acid esters in
.*Towhom correspondence s h o ~ ~he
l d addressed the crude glycerol, utilization of crude glycerol in the fat glyc-
erolysis process would require its removal prior to or after the Table I shows the composition of the ME and glycerol as an-
process. The alternative to its removal is its possible conver- alyzed in our laboratory.
sion to M C and DC. Equipment. A bench-top mini reactor (model number
The objective of this article was to explore utilization of 4562; Parr Instrument Company, Moline, 1L) was used for the
c n ~ d eglycerol froin the t~nnsesterificationprocess in the pro- glycerolysis reactions. The reactor assembly was constn~cted
duction of M C and DC. Three different physiocher~licaltreat- from type 3 16 stainless steel with a 450-mL bomb. The reac-
ments were considered. The first approach was a one-step tor was equipped with a magnetic stirrer. a four-blade, down-
glycerolysis with ME. The second approach was a two-step ward-thrust impeller, and a l l l l - h p . variable-speed motor
glycerolysis: an initial glycerolysis with ME, followed by a with a pulley arrangement to turn the stirrer at speeds from 0
second glycerolysis with TG. The third procedure was a si- to 800 rpm. A heating mantle and internal cooling loop pro-
multaneous glycerolysis with M E and TG. The concentra- vided the heating and cooling requirements. A Parr4843 con-
tions of the glycerolysis products were monitored in the ex- troller was used for controlling as well as mouitoring the re-
periments, and the feasibility of the utilization of crude glyc- action temperature and the impeller speed. The reactor was
erol in the glycerolysis process was studied. Throughout this equipped with a rake-off condenser; which was attached to
manuscript, these three procedures will be referred to as Pro- the head assembly. A nitrogen cylinder provided the purge
cedure A, B, and C for the first, second and, third procedures, gas for the process. The purse gas was introduced into the
respectively bottom of the reactor bomb and was also used for stripping
methanol during the reaction. An airlvacuudpressure pump,
made by Fisher Scientific Company, provided the vacuum in-
EXPERIMENTAL PROCEDURES
side the reactor homh up to 600 mm Hg of vacuum.
Mater.inir. Pure glycerol (99.86) was obtained from Fisher A metering pump (E plus series; Pulsafeeder Company,
Scientific Company (Fair Lawn, NJI. Soyhean oil, which was Rochester, h'Y)was attached to the head assembly of the
refined and bleached. was provided by .Archer Daniels Mid- reactor to provide for the injection of material into the bomb.
land Company (Lincoln. KE). The free fatty acid content of The flow chart for the experimental set-up is presented in
the oil was determined to be 0.09%; according to AOCS Figure I.
method #Ca 5a-40 (Ref. 16). Sodium hydroxide (98.4%) and P~.ocedi~re A-glycerolysis of ME. In the presence of an al-
phosphoric acid (85%) were both obtained from Fisher Sci- kaline catalyst; glycerol (G) and M E of fatty acids form
entific Con~pany.The standards for M E were from Sigma methanol (hleOH), and a mixture of M C and DC. Theoreti-
Chemical Company (St. Louis. XIO). cally, TG may also form in this reaction, but none was de-
Crude ME and glycerol were prepared in a one-step batch tected in the reaction products. The reactions involved are re-
transesterification process (17). A 10: 1 molar ratio of alcohol versible, and simultaneous removal of methanol from the re-
to soybean oil was used in this process. Sodium hydroxide action environment will shift the equilibrium toward the
(0.10 wt% based on the vegetable oilj was the catalyst. The glycerides. The reaction steps are:
reaction was carried out for 1 h under total reflux. Gpon grav-
ity settling, the reaction products separated into an upper layer
of crude ME and a lower layer of crude glycerol. Excess
methanol was removed from both product layers under vac-
uum distillation. No additional purification or neutralization
was carried out. The amount of sodium hydroxide was mea-
surcd in both product layers hy titration. The titration results
show 3.29 g of NaOH per LOO0 g of methanol-free glycerol
and 0.281 g of S a O H per 1000 g of methanol-frec ME.
TABLE 1
Crude Methyl Esters and Crude Glycerol Composition
Crude methyl estersd Crude glycerol
Compounds !wt%) ~bb:~.,.!
Figures 4 and 5 show that the reactions under constant nitro- M E (Procedure A) were considered for further glycrrolysis
gen purge were sljghtly lower in the concentration of MG and with TG. In the previous section, it was shown that glycerol-
DG than reactions under vacuum distillation. This may have ysis under vacuum distillation results in a slightly higher
been due to the reversibility of the glycerolysis reaction and product formation than reactions under continuous purge with
the fact that vacuum is more effective in removing methanol nitrogen. Therefore, the product from Procedure A under vac-
from the reaction medium than continuous nitrogen purge. uum distillation, for which the initial molar ralio of M E to
Consequently, equilibrium conditions at larger product con- glycerol varied from 0.035:l.O to 0.313:l.O. was considered
centrations are reached when vacuum distillation is used. in these experiments. The reaction results are summarized in
However, because the reaction temperature was relatively Figure 7 . When an initial molar ratio of 0.035: 1.0 was used in
high (200-24O0C), the shift in equilibrium concentrations was Procedure A. the composition of the final products from Pro-
not significant. cedure B was identical to one-step fat glycerolysis with pure
The technical MG are not pure monoesters, but a mixture glycerol. and no significant amounts of RIE were detected in
of MG, DG; triglycerides, and glycerol. The percentage of the final products. When larger concentrations of ME were
MG is of particular importance in the mixture, because of its used in the initial step (Procedure A), the concentration of
emulsification properties. Moreover, pure MG find many uses MG was slightly lower in the products than for one-step fat
in the food industry. Therefore. for the purpose of comparing glycerolysis with pure glycerol. For these experiments. the
quality of the glycerolysis products, the ratio of MG to DG unreacted M E from Procedure A appeared unchanged in the
(RMD) was considered. This ratio will provide a convenient final product. This was expected because the glycerolysis of
parameter for analysis and comparison of results. ME is reversible and tends to reach and stay at equilibrium if
The effect of the initial ME concentration on RMD was ex- at least one of the reaction products (preferably methanol) is
amined next. At the lower ratios of .ME to glycerol, the prod- not removed from the reaction medium. The calculated RMD
uct is more concentrated in MG. The product is primarily MG was also co~nparableto one-step fat glycerolysis with pure
at 0.035: 1.0 ratio. This is consistent with the collision theory glycerol.
and the probability of collision between functional groups. Procedure C. The reaction results for one-step glyceroly-
For all experiments (Figs. 2-~5),when the molar ratio of RIE sis of crude glycerol with TG under vacuum distillation (Pro-
to glycerol was increased, the RMD decreased. The RMD re- cedure C! are also shown in Figure 7 (shaded marks). The
sults are summarized in Figure 6 for all four sets of experi- molar ratio of ME to glycerol in this experiment was
ments. Compared to our reference point for fat glycerolysis 0.035:l.O. Compared to Procedure B, the reaction products
with pure glycerol. which resulted in an RMD of 1.39, RMD from Procedure C were much lower in concentrations of MG
values for the glycerolysis of ME were much higher at the and DG. The amount of unreacted ME was also higher than
lower ME concentrations. This characteristic makes RRlD a the results from Procedure B, which showed no unreacted !VIE
reaction variable in ME glycerolysis. rather than a fixed pa- in the product. This may be due to the higher solubility of ME
rameter in fat glycerolysis. in TG. With the transfer of ME to the glycerides layer, addi-
Procedure B. The reaction products from glycerolysis of tional resistance for the diffusion of M E through the TG layer
4
"
W
Simultaneous glycerolysis with M E and T G (Procedure C) re- R. Schomacher, Lipase-Catalysed Ester Synthesis in Oil-Con-
sulted in a significant reduction in the amount of-MGad-D-DG: ~ t i n u ~ ~ ~ ~ M i ~ m e m u J s i o nBiophys. ~ ~ B i Acra
~ ~ h912:278-282
im,
T h e experimental investigations are conclusive in that the (1987).
8. McNeil. G.P.. S. Shimiru, and T. Yamane. Hioh-Yield Enzy-
glycerolysis of ME is an effective technique for the conver- matic Glycerolysis of Fats and 011s, I . Am. 6 i i Chetn. 30-c.
sion of ME to M G and D G . W h e n crude glycerol with a low 68:l-5 (1991).
concentration of M E is considered, glycerolysis of M E may 9. Yamaguchi, S., and T. Mase, High-Yield Synthesis of Mono-
b e performed prior t o fat glycerolysis o r as a single step. glyceride by M o n o and Diacylglycerol Lipase from Penicillium
camemberrii C-150, J. Ferment. Bioeng. 72:162-167 (1991).
Glycerolysis of M E occurs at considerably lower tempera-
10. HoImberg, K., B. Lassen, and M.B. Stark, Enzymatic Prepara-
ture, 200-21O0C, compared t o about 240-260C f o r fat tion of Monoolvcerides in Microemulsion. I . Am. Oil Chem.
glycerolysis, which may result in significant thermal energy Soc. 661796-7800 (1989).
savings. 11. Masuvama, S., >Takasaeo. l. K. Horikawa. F. Fuiiwara. and C.
~ugimoto,Glycerolysis ofPatty Acid Methyl ~ s t & s11. . Synthe-
sis of Pure I-Monopalmitin, Kagaku to Kogyo /Osnko)
ACKNOWLEDGMENTS 42:242-248 (1 968).
The authors express their gratitude to U.S. Department of Agricul- 12. Takeda, Y., R. Yasue, and Y. Miyawaki, Preparation of Mono-
ture Cooperative State Research Service and Nebraska Soybean glycerides by Two-Step Reaction, JP patent 1,268,663 (1989).
Board for their support of this work. 13. Kassern, T.K.. M.M. Soliman, A.A. El-sawy, andM. Sadek,Po-
tential for Partial Glvcerides as Emulsifiers. H u n ~J.. Ind. Chem.
12:347-353 (1984).
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