USOO6500974B2

(12) United States Patent (10) Patent No.: US 6,500,974 B2

Thengumpillil et al. (45) Date of Patent: Dec. 31, 2002

(54) PROCESS FOR THE PREPARATION OF A (65) Prior Publication Data

MONOGLYCERIDE US 2002/0120159 A1 Aug. 29, 2002
(75) Inventors: Narayana Balagopala Kaimal (51) Int. Cl." .................................................. C11C 3700
Thengumpilil, Andhra Pradesh (IN); (52) U.S. Cl. ....................................................... 554/161
Vijayalakshmi Penumarthy, Andhra (58) Field of Search .......................................... 554/161
Pradesh (IN); Ananta Laxmi Ayyagari,
Andhra Pradesh (IN)
Primary Examiner Deborah D. Carr
(73) ASSignee: Council of Scientific and Industrial (74) Attorney, Agent, Or Firm-Darby & Darby
Research, New Delhi (IN) (57) ABSTRACT
(*) Notice: Suitsystic little An improved proceSS for the preparation of a monoglyceride
U.S.C. 154(b) by 82 days by reacting a fatty acid and glycerol in the presence of a food
a -- grade polar Solvent and avoiding the use of catalysts is
ided.
(21) Appl. No.: 09/796,083 provide
(22) Filed: Feb. 28, 2001 8 Claims, No Drawings
 US 6,500,974 B2
1 2
PROCESS FOR THE PREPARATION OFA gen at atmospheric pressure using a glass Vessel equipped
MONOGLYCERIDE with a stainless steel stirrer at 200-250 C. Monoglycerides
to an extent of 40 and 60% were obtained by using approxi
mately 20 and 45% glycerol respectively with sodium
FIELD OF THE INVENTION hydroxide as catalyst. Higher yields of monoglycerides are
reported with Soaps of iron, nickel, chromium or manganese
The present invention relates to a process for the prepa as catalysts (U.S. Pat. No. 2,628,967). Choudhury reported
ration of a monoglyceride. The present invention particu glycerolysis of various oils for the preparation of monoglyc
larly relates to a catalyst free improved process for the erides and found that the maximum amount of monoglyc
preparation of a monoglyceride by reaction of fatty acids eride formed by glycerolysis was about 45% (J. Am. Oil.
with glycerol in the presence of Solvent, under conditions Chem. Soc., 1960, 37, 483).
that favour the predominant formation of monoglycerides. A commercial non-Solvent method of production involv
BACKGROUND OF THE INVENTION ing glycerolysis of hydrogenated cottonseed oil with 40%
glycerol (based upon the weight of fat used) at 250° C.
Monoglycerides constitute an important group of com 15 yields about 60% of monoglycerides (J. Am. Oil. Chem.
mercial derivatives which are used in food, cosmetic, Soc., 1979, 56, 752A). Castor oil glycerolysis was claimed
pharmaceutical, lubricant and chemical industries. to give 82% alpha-monoglycerides after 2 hours at 240 C.
Monoglycerides find many applications as Surfactants, with 800gm of oil and 2000 gm of glycerol, in the presence
mainly as emulsifiers, in a wide range of foods, cosmetics of carbon dioxide at 100 psi as a coblanketing catalytic
and pharmaceuticals. Monoglycerides are used in yeast agent. Under Similar conditions coconut oil gave 74 and
raised foods for retarding Staling, cakes, icings and in the peanut oil 73% of monoglyceride. (Indian patent 71,979).
manufacture of margarine. Overall, this group of Surfactants Recently glycerolysis of methyl Stearate and tristearin has
is the Single most important one for food uses, representing been carried out in the presence of alkyl guanidines, Strong
about 75% of total emulsifier production. (Bailey's Indus non-ionic baseS as catalyst. The reaction was carried out at
trial Oil Fat Products, Vol. 3, 5' Edition; J. Am. Oil. Chem. 25 10 mol % of 1,5,7-tri-azabicyclo(4.4.0)de-5-ene, 1,2,3-
Soc., 1976, 53,400; J. Am. Oil. Chem. Soc., 1984, 61, 255; tricyclohexylguanidine or 1,3-decyclohexyl-2-n-
Angew. Chem. Int. Ed., 1988, 27, 42). Surfactants have a octylguanidine resulting in monoglycerides in more than
wide field of application in all those processes that involve 90% selectivity at 50% conversion at 110° C. and 16 mbar
working with interfaces. Nonionic Surfactants especially pressure. They found that a higher conversion of about 80%
esters of hydrophillic polyols, Such as glycerine with fatty resulted in lower selectivity (50-60%) for monoglycerides
acids are of great interest (Fallbe, J., Surfactants in Consumer (J. Am. Oil. Chem. Soc., 1998, 75, 755).
Products. Theory, Technology and Applications, Springer Choudhury also studied direct esterification of fatty acids
Verger New York, 1988). The most important commercial with glycerol for preparation of monoglycerides in optimum
products are glycerol monoStearate, monooleate, and yield and carried out reactions with excess glycerol at 180
monoricinoleate. Owing to their ability to form stable 35 C. in the presence or absence of alkaline catalysts and
emulsions, monoglycerides Such as monooleates are Suitable reported a maximum yield of 55-60% of monoglyceride (J.
as emulsifying components in aqueous fiber finishes, lubri Am. Oil. Chem. Soc., 1960, 37, 483). Selective esterification
cant components, fine mechanical oils, water displacing oils of glycerine to glycerol monooleate using a slightly basic
and in grinding and polishing pastes (J. Am. Oil. Chem. Soc., ultrastable Y-Zeolite as catalyst was reported to give
1984, 61,255). Monoglycerides are also reported to possess 40 monoglycerides with a selectivity of about 90% (Ind. Eng.
antibacterial properties. (Kabara, J. J., The Pharmacological Chem. Res., 1997, 36, 1524). Esterification of oleic acid with
Effect of Lipids, 2" Edition, The American Oil Chemist's glycerol in the presence of Superacidic Sulfated iron oxide
Society, Illinois, 1985). Recent developments include their catalyst was reported (J. Am. Oil. Chem. Soc., 1996, 73,
use as drug delivery facilitators and bioadhesives (Int. J. 347). Monoglycerides were also obtained by esterification
Pharma, 1997, 147, 135; Biomaterials, 1997, 18, 63). They 45 reaction over an acid catalyst. High pressure and tempera
are reported to have a preventive effect on cardiovascular tures were used to shift the equilibrium forward towards
diseases. (J. Am. Oil. Chem. Soc., 1993, 70, 745). monoglyceride production. The product obtained was a
Many methods are described in prior art for the prepara complex mixture of 35-60% monoglyceride, 35-50%
tion of monoglycerides. Commercial manufacture of diglyceride, 1-20% triglyceride, 1-10% glycerine and fatty
monoglycerides involves either glycerolysis of oils and fats 50 acids. The amount of monoglyceride was raised to 90-95%
at high temperature or direct esterification of fatty acids and with 7-10% of 2-monoglyceride by molecular distillation.
glycerol with or without catalysts. Various types of homog The advantage of pressure in carrying out glycerolysis is
enous and heterogenous catalysts are reported (J. Am. Oil. noteworthy. It appears to aid in the attainment of homoge
Chem. Soc., 1976, 53,400; J. An Oil Chem. Soc., 1982, 59, neity and thus yields were improved.
795A; Nature, 1960, 188, 56; J. Am. Oil. Chem. Soc., 1962, 55 Although the yields of monoglycerides by usual non
39, 345; J. Am. Oil. Chem. Soc., 1964, 41, 727; Chem Rev. solvent methods of production are limited to about 60% of
1958, 58,845; J. Am Oil. Chem. Soc., 1966,43,536; J. Org. total glycerides, the use of Solvents for the glycerolysis
Chem. 1997, 62,749; J. Am. Oil. Chem. Soc., 1998, 75,755). reaction enables a much higher conversion. Immiscibility of
In all these processes the yields are typically in the range of glycerol in fat like phases was overcome by carrying out the
50%. Pure monoglycerides (over 90%) are obtained by 60 reaction in a Solvent medium. Solvents like phenol, creSols,
molecular distillation which Sometimes is a part of industrial 1,4 dioxane, pyridine, chloroform and dimethyl formamide
process (Fette. Seifen. Anstrichmittel, 1983, 85,443; Chem etc were used (J. Am. Oil. Chem. Soc., 1982, 59,795A; Fat.
Abstr 1995, 123, 202772c). Sci. Technol., 1995, 97, 347; Chem Abst, 1990, 112,
Feuge and Gross (J. Am. Oil. Chem. Soc., 1950, 27, 117) 197639a). Solvents offer the prospects of high yields at
described preparation and purification of technical 65 relatively low temperature but disadvantages in their
monoglycerides by modification of vegetable oils. They handling, toxicity, noxious odors etc and the need to remove
carried out reaction between fat and glycerol under hydro them completely from products explains the very limited
 US 6,500,974 B2
3 4
efforts directed towards the synthesis in solvents. For methyl esters. In this process the reaction is carried out with
example, Sunflower oil 10 parts, was reacted with glycerol, excess of glycerol at 130–160° C. and a vacuum of 200-400
20 parts at 120° C. with 0.3 parts of sodium bicarbonate in mbar in the presence of alkaline catalysts. The reaction is
excess pyridine yielding 83% of total monoglycerides con Stopped by fast cooling of the reaction mixture. The glycerol
taining about 8% of 2-monoglyceride. In the absence of and methyl ester were separated by distillation at 230 C.
solvent, the reaction yielded 58% total monoglyceride con and 4 mbar pressure in laboratory thin film evaporator.
taining 6% of beta-monoglyceride (J. Am. Oil. Chem. Soc., During the distillation the reaction proceeded further at
1979, 56,751A). Kinetics of esterification reaction between resident time estimated at about 4-5 min. The residue
glycerol and oleic acid in the presence of pyridine for contained 80% monoglyceride and 18% diglyceride.
production of partial glycerides was studied (Fat. Sci. The main difficulty in achieving high yields of monoglyc
Technol, 1995, 97,347). The authors found pyridine to be a erides either by glycerolysis or by direct esterification of
good Solvent for the formation of partial glycerides. fatty acids with glycerol is ascribed to the lack of Sufficient
The use of enzymes for the synthesis of MG was exten degree of homogeneity of the reactants resulting in a product
sively studied (Enzyme Microb. Technol., 1995, 17,578; J. consisting of monoglycerides, diglycerides and triglycer
Am. Chem. Soc., 1999, 76, 701). U.S. Pat. No. 5,153,126 15 ides. Thus, many efforts were directed towards increasing
describes a method for continous preparation of highly pure the yields of monoglycerides. All the above procedures for
monoglycerides. The method comprises of esterification of the Synthesis of monoglycerides are carried out in the
fatty acid dissolved in a non-polar Solvent at the interface presence of alkaline or acidic catalyst, which requires neu
between the nonpolar Solvent phase and a polar Solvent tralization Step. Glycerolysis reaction also generally requires
phase containing glycerol, water and dispersed lipase. The two Stringent conditions like Very low levels of moisture and
non-polar Solvent phase is continuously taken out cooled, very low levels of FFA. And also the solvents reported may
and the precipitated monoglycerides are isolated. The not be acceptable to production of food grade monoglycer
remaining Solution is recycled back to the esterification ides. Hence there is need for an alternative catalyst free
System. process, but at the same time under homogenous
The enzymatic esterification of glycerol with dicarboxylic 25 environment, which gives high yields of monoglyceride.
acids or esters was Studied to produce mono-and/or dies To Summarize, two methods are generally used for com
terified glycerol adducts as Synthons for biodegradable poly mercial production of monoglycerides. The first, non
merS and Surfactants. They reacted glycerol or isopropy Solvent method requires high temperatures and generally
lidene glycerol with Sebacic or adipic acid esters. Reaction results in a mixture of mono, di and triglycerides with low
of dimethyl Sebacate with isopropylidene glycerol gave the Selectivity towards monoglycerides formation. Those pre
monoester in >95% yield, while reaction of glycerol Sup pared with heterogenous catalyst Such as molecular Sieves
ported on silica with dimethyl adipate gave only 40% yield have questionable applicability if the product is intended for
of glycerol-mono-methyl adipate ester. Direct reaction of food use. The Second method involving Solvents which
free glycerol with diester in the presence of water (<4%) offers better Selectivity have also major disadvantage in that
gave a product containing 70% of glycerol-mono-methyl 35 the Solvents employed are not food grade. Development of
adipate ester (J. Am. Oil. Chem. Soc., 1998, 75, 1545). a simple proceSS which may be carried out in the presence
Lipase G catalyzed Synthesis of monoglycerides in of Solvent to provide the homogenous atmosphere would be
advantageous.
organic Solvent hexane and water are reported (J. Am. Oil.
Chem. Soc., 1992, 69,257). U.S. Pat. No. 5,270,188 claims OBJECTS OF THE INVENTION
40
preparation of glycerides having a high content of The main object of the present invention is to provide a
monoglycerides with Lipase G. U.S. Pat. No. 5,508,182 catalyst free proceSS for the preparation of monoglycerides
describes esterification of hydrophilic polyol by adsorption in presence of a Solvent that is acceptable to the food
onto a Solid Support and employing a Substrate immiscible industry and that also functions as a Suitable Solvent for
solvent like hexane or t-butylmethyl ether. In this process the 45 glycerol.
hydrophilic Substrates were adsorbed on Solid Supports Such Another object of the present invention is to use the
as Silica gel, diatomaceous earths or activated charcoals in monoglycerides thus obtained as emulsifiers in food, cos
order to promote the dispersions of the hydrophilic Sub metics and pharmaceutical preparations.
Strates within hydrophobic Substrates and Solvents. Enzymes Yet another object of the invention is to use solvents
used include lipases from Mucor miehei, and Pseudomonas 50 which are completely Safe, nontoxic and biodegradable.
fluorescens, glycosidases Such as beta-galactosidase, pro Another object of the invention is to avoid the generation
teaseS Such as chymotrypsin and acid or alkaline phos of aqueous effluents as in the case of homogeneous catalysts,
phatases. thereby resulting in an environmentally friendly process.
A process for the production of high purity beta Another object of the invention is to provide a process that
monoglycerides by lipase catalyzed transesterification (1,3- 55 has enhanced Selectivity for monoglyceride over diglycer
regiospecific lipase) is described in U.S. Pat. No. 5,316,927. ide.
Yield of monoglycerides is enhanced by means of enzymatic
transesterification of triglycerides with aliphatic alcohols in STATEMENT OF THE PRESENT INVENTION
a medium of Supercritical carbon dioxide, with Accordingly the present invention provides a process for
NOVOZYME 435TM enzyme. Aliphatic primary and sec 60 the preparation of a monoglyceride which comprises react
ondary alcohols of 1-8 carbon atoms were used at lower ing a fatty acid and glycerol in a molar ratio in the range of
reaction temperatures of 50-80 C., and a pressure of 3000 1:1 to 1:10, in the presence of a food grade polar Solvent at
psi to 5000 psi diminishing the production of undesired side a temperature in the range of 130-150° C. for a time period
products thus increasing the reaction efficiency (U.S. Pat. in the range of 3–6 hours to obtain Said monoglyceride.
No. 5,747,305). 65 In one embodiment of the invention, the fatty acid used is
U.S. Pat. No. 6,127.561 describes a process for the a Straight or branched chain fatty acid of acyl chain length
production of monoglycerides based on the glycerolysis of C-8 to C-22.
 US 6,500,974 B2
S 6
In a further embodiment of the invention, the fatty acid glycerol) at 130-140°C., for 5 hours. After the reaction the
used is Selected from lauric acid and Stearic acid. mixture was cooled, dissolved in diethyl ether and washed
In a further embodiment of the invention, the food grade with water to remove unreacted glycerol and methyl lactate.
polar Solvent used is Selected from methyl lactate and lactic The Solvent was removed under reduced preSSure, and
acid. product was dried under Vacuum and was analyzed by GC
In yet another embodiment of the invention, the molar as trimethylsilyl derivative to determine the individual com
ratio of said fatty acid to alcohol varies from 1:2 to 1:10. position of fatty acid, monoglyceride, diglyceride, and trig
In yet another embodiment of the invention, the unreacted lyceride in the product. (FA, 26%; MG, 59%; DG, 10%; TG,
glycerol and fatty acid are removed by dissolving the 1%; LMG, 4%)
reaction mixture in diethyl ether and washing with water. The conversion of fatty acid was found to be 75% and
In still another embodiment of the invention, the conver Selectivity of monoglyceride over diglyceride was found to
be 85%.
sion of said fatty acid is between 60-80%.
In yet another embodiment of the invention, the selectiv EXAMPLE 3
ity of monoglyceride over diglyceride is between 60-98%. 15
DETAILS OF THE PRESENT INVENTION
Lauric acid and glycerol were reacted in a ratio of 1:4 in
presence of methyl lactate (50% of total wt of fatty acid and
For achieving high yields of monoglycerides at low glycerol) at 130-140° C., for 5 hours. After the reaction the
temperature, it is necessary to create a homogenous envi mixture was cooled, dissolved in diethyl ether, and washed
ronment in the reaction medium. Hence the use of co-Solvent with water to remove unreacted glycerol and methyl lactate.
was Suggested by many workers in literature. The literature The Solvent was removed under reduced pressure, product
methods involves the use of pyridine, 1,4-dioxane, was dried under vacuum and was analyzed by GC as
chloroform, phenols, cresols, and dimethyl formamide etc. trimethylsilyl derivative to determine the individual com
as Solvents in the presence of acidic or alkaline catalyst. position of fatty acid, monoglyceride, diglyceride, and trig
These Solvents are toxic and moreover the use of catalyst 25 lyceride in the product. (FA, 24%; MG, 64%; DG, 7%; TG,
requires a neutralization Step. Hence it would be more 1%; LMG, 4%)
advantageous to carry out the reaction in a Solvent which The conversion of fatty acid was found to be 76% and
provides a homogenous atmosphere and at the same time is Selectivity of monoglyceride over diglyceride was found to
very Safe to use the resultant monoglyceride in food grade be 90%.
preparations.
The present invention relates to a catalyst free process for EXAMPLE 4
Synthesis of monoglycerides in presence of polar food grade Lauric acid and glycerol were reacted in the ratio of 1:4
Solvents like methyl lactate and lactic acid, leading to high in presence of lactic acid (50% of total wt of fatty acid and
conversion and Selectivities of monoglycerides over diglyc glycerol) at 140-150° C., for 5 hours. After the reaction the
erides. These Solvents are completely Safe, non-toxic and 35
mixture was cooled, dissolved in diethyl ether, and washed
biodegradable. with water to remove unreacted glycerol and lactic acid. The
A minor percentage of the formed monoglycerides are Solvent was removed under reduced preSSure, the product
converted under the process conditions to lactylated dried under vacuum and was analyzed by GC as trimethyl
monoglycerides (5-20%) which are also permitted food silyl derivative to determine the individual composition of
emulsifiers. The enhanced Surface activity of the lactylated 40 fatty acid, monoglyceride, diglyceride, and triglyceride in
monoglycerides offers a product that is functionally Superior the product. (FA, 25%; MG, 56%; DG, 9%; TG, not present;
to monoglyceride alone. AS far as the authors are aware, LMG, 10%) The conversion of fatty acid was found to be
lactic acid and alkyl lactates have not been used as a Solvent 75% and selectivity of monoglyceride over diglyceride was
for Such reactions. found to be 86%.
The following examples are given by the way of illustra 45
tion and therefore should not be construed to limit the Scope EXAMPLE 5
of the present invention. Stearic acid and glycerol were reacted in a ratio of 1:3 in
EXAMPLE 1. presence of methyl lactate (50% of total wt of fatty acid and
Lauric acid and glycerol were reacted in a ratio of 1:2 in 50 glycerol) at 130-140°C., for 5 hours. After the reaction the
the presence of methyl lactate (10% of total wt of fatty acid mixture was cooled, dissolved in diethyl ether, and washed
and glycerol) at 130-140°C., for 5 hours. After the reaction with water to remove unreacted glycerol and methyl lactate.
the mixture was cooled, dissolved in diethyl ether and The Solvent was removed under reduced pressure, the prod
washed with water to remove unreacted glycerol and methyl uct dried under vacuum and was analyzed by GC as trim
lactate. The Solvent was removed under reduced pressure, 55 ethylsilyl derivative to determine the individual composition
of fatty acid, monoglyceride, diglyceride, and triglyceride in
product was dried under vacuum and was analyzed by GC the product. (FA, 38%; MG, 46%, DG, 6%; TG, 2%; LMG,
as trimethylsilyl derivative to determine the individual com 8%)
position of fatty acid, monoglyceride, diglyceride, and trig
lyceride in the product. Fatty acid (FA), 22%; Monoglyc The conversion of fatty acid was found to be 62%and
eride (MG), 52%; Diglyceride (DG), 22%; Triglyceride 60 Selectivity of monoglyceride over diglyceride was found to
(TG), 1%; Lactylated monoglyceride (LMG), 3%). be 88%.
The conversion of fatty acid was found to be 78% and EXAMPLE 6
selectivity of monoglyceride over diglyceride was 70%.
EXAMPLE 2
Stearic acid and glycerol were reacted in a ratio of 1:3 in
65 presence of lactic acid (50% of total wt of fatty acid and
Lauric acid and glycerol were reacted in a ratio of 1:2 in glycerol) at 140-150° C., for 5 hours. After the reaction the
presence of methyl lactate (50% of total wt of fatty acid and mixture was cooled, dissolved in diethyl ether and washed
 US 6,500,974 B2
7 8
with water to remove unreacted glycerol and lactic acid. The We claim:
Solvent was removed under reduced pressure, the product 1. A process for the preparation of a monoglyceride which
dried under vacuum and was analyzed by GC as trimethyl comprises reacting a fatty acid and glycerol in a molar ratio
silyl derivative to determine the individual composition of in the range of 1:1 to 1:10, in the presence of a food grade
fatty acid, monoglyceride, diglyceride, and triglyceride in 5 polar solvent at a temperature in the range of 130-150° C.
the product. (FA, 37%; MG, 26%; DG, 14%; TG, 4%; LMG, for a time period in the range of 3–6 hours to obtain Said
20%) monoglyceride.
2. A process as claimed in claim 1, wherein the fatty acid
The conversion of fatty acid was found to be 63%and is a Straight or branched chain fatty acid of an acyl length
Selectivity of monoglyceride over diglyceride was found to between C-8 to C-22.
be 65%. 3. A process as claimed in claim 2, wherein the fatty acid
The main advantages of the present invention are: is Selected from lauric acid and Stearic acid.
1. The present invention is a catalyst free proceSS for the 4. A process as claimed in claim 1, wherein the food grade
preparation of monoglycerides by esterification between polar Solvent is Selected from methyl lactate and lactic acid.
fatty acids and glycerol. 15 5. A proceSS as claimed in claim 1, wherein the fatty acid
2. The reaction is carried out with the Solvents which are and glycerol is in a molar ratio in the range of 1:2 to 1:10.
completely safe, non-toxic and biodegradable. 6. A process as claimed in claim 1 wherein unreacted
3. AS no catalyst is used, there is no generation of aqueous glycerol and fatty acid are removed by dissolving the
effluents as in the case of homogeneous catalysts. Hence reaction mixture in diethyl ether and washing with water.
the proceSS is more environmentally friendly. 7. A process as claimed in claim 1, wherein between
4. The reaction is carried out at relatively milder conditions 60-80% of the fatty acid is converted.
than earlier reported methods. 8. A process as claimed in claim 1, wherein the process
5. The presence of minor concentrations of lactylated yields a Selectivity of monoglyceride over diglyceride
monoglycerides may provide a functionally Superior between 60-98%.
product than monoglycerides alone.