US008598377B2

(12) United States Patent (10) Patent No.: US 8,598,377 B2

Weidner et al. (45) Date of Patent: Dec. 3, 2013

(54) METHOD FOR PRODUCING FATTY ACID (56) References Cited

ESTERS OF MONOVALENT OR
POLYVALENT ALCOHOLS USING SPECIAL FOREIGN PATENT DOCUMENTS
HYDROXY-FUNC TIONAL QUATERNARY
AMMONIUM COMPOUNDS AS CATALYSTS DE 10245806 A1 4/2004
DE 102004004660 A1 9/2005
(75) Inventors: Eckhard Weidner, Bochum (DE); Axel DE 102006028560 A1 12/2007
Kraft, Oer-ErkenschWick (DE); Anna DE 60035109 T2 2/2008
GB 1313923 * 4/1973
Grevé, Bochum (DE); Reinhard WO 0112581 A1 2/2001
Broucek, Aschaffenburg (DE) WO 2004031119 A1 4/2004
WO 2005100306 A1 10/2005
(73) Assignees: Fraunhofer-Gesellschaft zur WO 2006029655 A1 3/2006
Foerderung der angeWandten WO WO2007111604 * 10/2007
WO 2007143803 A1 12/2007
Forschung e.V., Munich (DE); Balchem
Corporation, New Hampton, NY (U S) OTHER PUBLICATIONS

(*) Notice: Subject to any disclaimer, the term of this Abbott et a1 , Extraction of glycerol from biodiesel into a eutetic
patent is extended or adjusted under 35 based ionic liquid, 2007, Green Chem., vol. 9. p. 868-872.*
U.S.C. 154(b) by 188 days. Stecher et al, The Merck Index, an Encyclopedia of chemicals and
drugs, 8”’ ed., Merck & c0. , Inc., 1968, p. 972*
(21) Appl. No.: 13/125,387 International Search Report for Appln. No. PCT/EP2009/007544
mailed Feb. 16, 2010.
(22) PCT Filed: Oct. 21, 2009 Schuchardt et al., J. Bras. Chem. Soc., 9(3): 199-210 (1998).
Freedman et al., 3. Am. Oil. Chem. Soc., 63(19): 1375-1380 (1986).
(86) PCT No.: PCT/EP2009/007544 Chiu et al., AlChE Journal, 51(4): 1274-1278 (2005).
Vicente et al., Ind. Eng. Chem. Res., 44: 5447-5454 (2005).
§ 371 (0X1)’ Schuchardt et al., J. Mol., Catal., 109: 37-44 (1996).
(2), (4) Date: Jul. 21, 2011 Sercheli et al., J. Am. Oil. Chem. Soc., 78: 1207-1210 (1999).
Cerce et al., Ind. Eng. Chem. Res, 44(25): 9535-9541 (2005).
(87) PCT Pub. No.: WO2010/046100 Peter et al., Eur. J. Lipid Sci. Technol, 104: 324-330 (2002).
Peter et al., E., Eur. J. Lipid Sci. Technol, 109: 11-16 (2007).
PCT Pub. Date: Apr. 29, 2010 Kim et al., Catalysis Today, 93-95: 315-320 (2004).
CAS Registry No. 934234-70-5, May 2009.
(65) Prior Publication Data Liu et al., Journal of Catalysis 246(2): 428-433 (2007).
US 2011/0300281A1 Dec. 8,2011
* cited by examiner
(30) Foreign Application Priority Data
Primary Examiner * Taylor Victor Oh
Oct. 22, 2008 (DE) ....................... .. 10 2008 052 795 (74) Attorney, Agent, or Firm * Carter, DeLuca, Farrell &
Schmidt, LLP
(51) Int. Cl.
C11C3/02 (2006.01) (57) ABSTRACT
A23D 7/01 (2006.01) The present invention relates to a method for producing fatty
A23D 9/013 (2006.01) acid esters from fats and/or oils of biogenic origin by trans
(52) US. Cl. esteri?cation With monovalent or polyvalent alcohols in the
USPC .......... .. 554/161; 426/601; 426/608; 568/852 presence of a special hydroxy-functional quaternary ammo
(58) Field of Classi?cation Search nium compound as the catalyst.
USPC .......... .. 554/124, 161; 568/852; 426/601, 608
See application ?le for complete search history. 12 Claims, No Drawings
 US 8,598,377 B2
1 2
METHOD FOR PRODUCING FATTY ACID free fatty acids since the above described saponi?cation is
ESTERS OF MONOVALENT OR more intense in the presence of free fatty acids and increases
POLYVALENT ALCOHOLS USING SPECIAL the viscosity of the reaction mixture (see Freedman et al., J.
HYDROXY-FUNC TIONAL QUATERNARY Am. Oil Chem. Soc. 63(10): 1375-1380 (1986)).
AMMONIUM COMPOUNDS AS CATALYSTS The saponi?cation may be reduced by the use of sodium or
potassium methylate instead of sodium hydroxide or potas
The present invention relates to a method for producing sium hydroxide. HoWever, the production of the methylates is
fatty acid esters from fats and/or oils of biogenic origin by considerably more expensive. For optimum conversion rates
transesteri?cation With monovalent or polyvalent alcohols in the latter also require the, if possible, complete absence of
the presence of a special hydroxy-functional quaternary Water from the reaction system.
ammonium compound as the catalyst.
Fatty acid esters are commercially produced by transesteri Moreover, the ef?ciency of the base-catalyZed transesteri
?cation of oils and/or fats of biological origin, Which pre ?cation of fats and/or oils of biogenic origin With alcohols is
dominantly consist of triglycerides, With an alcohol. The also signi?cantly determined by the type of alcohol. For
triglycerides react With alcohol in the presence of a catalyst 5
example, even though it is basically possible to also use
thereby forming fatty acid esters and glycerol: ethanol as a monovalent alcohol When potassium hydroxide
or sodium hydroxide is employed as the catalyst, this trans
esteri?cation reaction proceeds at a markedly sloWer rate
H2C—OCOR' ROCOR' HZC —OH compared to the reaction With methanol.
I atalyst + I 20 Another factor Which signi?cantly in?uences the base
HC — OCOR" + 3 ROH ROCOR" + HC — OH
+ catalyZed transesteri?cation, in particular the yield, is the
H2C—OCOR'” ROCOR'” H2C—OH alcohol/triglyceride ratio. In general, the alcohol to be
exchanged is added in excess to obtain a high yield of desired
triglyceride alcohol fatty acid glyceride
ester
fatty acid esters. Depending on the employed fats and/ or oils
25 and catalyst, the optimum molar ratio usually varies from 6:1
to 45 :1 (in the case of a high concentration of free fatty acids).
Since the original ester, i.e. the triglyceride, is reacted With Along With the type of catalyst, the purity of the reactants
an alcohol in this reaction, this transesteri?cation reaction is (in particular the Water content), the quality of the initial oil
also referred to as an alcoholysis. The alcoholysis of fat and/or fat (in particular the content of free fatty acids) and the
and/or oil of biogenic origin is highly signi?cant for the alcohol (type of alcohol and Water content) as Well as the
economy and has become much more important in connec alcohol/triglyceride ratio, the effectiveness of the conven
tion With the production of biodiesel (fatty acid methyl ester) tional base-catalyzed transesteri?cation strongly depends on
by transesteri?cation of vegetable oil, in particular rapeseed the phase behavior during the reaction. At the beginning of the
oil, With methanol in the past feW years. reaction, the triglycerides and the alcohol form a tWo-phase
The transesteri?cation or alcoholysis is an equilibrium 35 reaction mixture. The contact of the reactants is initially con
reaction Which as a rule already proceeds When the starting ?ned by the mixing and the reaction is thus limited by the
products are mixed at a suitable temperature. HoWever, the substance transport resistances at the phase boundary of alco
reaction proceeds rather sloWly so that commercial methods hol and triglyceride. When the reaction time proceeds, partial
use catalysts to accelerate the reaction. In the majority of glycerides and fatty acid esters are formed Which improve the
cases, base-catalyzed methods are employed since they pro 40 solubility of the alcohol. In particular in the case of the esteri
ceed much faster than the acid-catalyZed methods using sul ?cation With monovalent alcohols, an amount of glycerol
fonic or sulfuric acid, Which are also knoWn in the art (as to a may ?nally be formed such that its solubility limit is achieved
revieW see eg Schuchardt et al., J. Bras. Chem. Soc. 9(3): and a separate glycerol phase precipitates. As a result, the
199-210 (1996)). The catalysts used in base-catalyzed trans conversion of the triglycerides sloWs doWn in the conven
esteri?cations, in particular in the production of fatty acid 45 tional catalysis since the catalyst is draWn into the glycerol
methyl esters used as a biodiesel, are usually potassium phase to a disproportionate extent. HoWever, the reactants are
hydroxide or sodium hydroxide or the corresponding methy predominantly in the triglyceride phase so that the reaction is
lates. It is thus possible to achieve conversion rates of >98%. noW limited by the substance transport and the unfavorable
HoWever, both catalysts leave their cationic constituent in the distribution of the catalyst (Chiu et al., AlChE Journal 51(4):
reaction system and in particular in the glycerol Which pre 50 1274-1278 (2005); Vicente et al., Ind. Eng. Chem. Res. 44:
cipitates as a separate phase When the reaction mixture is 5447-5454 (2005)).
alloWed to stand. As a result, costly and time-consuming In the light of the above-mentioned problems Which occur
separation by neutralization and Washing With Water becomes in the transesteri?cation With conventionally used catalysts
necessary. (NaOH, KOH; Na-methylate, K-methylate), a plurality of
In addition, a certain amount of Water is formed in the 55 organic bases have been studied With respect to their suitabil
alkaline transesteri?cation methods using sodium hydroxide ity as catalysts in the base-catalyzed transesteri?cation in the
or potassium hydroxide due to the reaction of hydroxide With past feW years. Scienti?c literature has described various
the alcohol employed. The presence of Water results in a amine, amidine, (alkyl)guanidine and triamino(imino)phos
saponi?cation, i.e. the hydrolysis of the fatty acid esters phorane compounds Which may be used as catalysts in the
formed and the formation of alkali salts of the released fatty 60 transesteri?cation of fats and/or oils (Schuchardt et al., J.
acids (What is called soaps). The fatty acid ester yield is thus Mol. Catal. 99: 65-70 (1995); Schuchardt et al., J. Mol. Catal.
reduced as a result of the catalyst consumption. In addition, 190: 37-44 (1996); Schuchardt et al., J. Bras. Chem. Soc. 9:
the soaps formed Which have an emulsifying effect compli 199-210 (1998); Sercheli et al., J. Am. Oil Chem. Soc. 76:
cate the separation of the produced glycerol from the fatty 1207-1210 (1999); Cerce et al., Ind. Eng. Chem. Res. 44(25):
acid esters formed. Therefore, the educts (fats and/or oils and 65 9535-9541 (2005); Peter et al., Eur. J. Lipid Sci. Technol. 104:
alcohols) used have to be as Water-free as possible and the 324-330 (2002); Peter, S. & Weidner, E., Eur. J. Lipid Sci.
starting fats and/or oils should also have a small amount of Technol. 109: 11-16 (2007)).
 US 8,598,377 B2
3 4
In addition, the use of compounds having an imino group, branched alkyl residue having 1 to 8 carbon atoms, preferably
tertiary amines, Wherein the tertiary amines have at least one 1 to 1, 6 or 8 and R is a straight-chain or branched hydroxy
OH group or NH2 group and are no amino acids or derivatives alkyl, hydroxyalkenyl or hydroxyalkynyl residue having 1 to
thereof, and butylamine as catalysts in the production of fatty 12, preferably 1 to 8, more preferably 2 to 8 and most pref
acid esters of monovalent alcohols by means of alcoholysis of erably 2 to 6 or 2 to 4 carbon atoms. The substituents may be
fat and/or oil of biological origin is knoWn from DE 102 45 straight-chain or branched alkyl, alkenyl, alkynyl, alkoxy,
806 A1 and WO 2004/031119 A1. DE 10 2004 044 660 A1 alkoxyalkyl, alkenyloxy and alkenyloxyalkyl groups having
and WO 2006/029655 A1 also disclose the use of carbonic 1 to 5, preferably 1 to 3, carbon atoms.
acid salts of guanidine or derivatives thereof, such as 1-ami It has been found surprisingly that compounds of the above
noguanidine, as basic catalysts in the transesteri?cation of shoWn general formula (I) are active as catalysts in the trans
fats and/or oils of biological origin by means of alcoholysis. esteri?cation of fats and/or oils of biogenic origin With
In addition, it is knoWn from WO 2005/ 100306 A1 to use monovalent or polyvalent alcohols. On the one hand, these
another guanidine derivative, namely the N,N',N"-tris-(3 compounds are distinguished by a quaternary ammonium
dimethylaminopropyl)-guanidine, in the transesteri?cation group and, on the other hand, by a saturation of a valence at
of sun?ower, soy bean and rapeseed oil. Finally, WO 2007/ the nitrogen atom of the quaternary ammonium group by a
143803 A1 describes a method for the reaction of fats and/or rather short straight-chain or branched hydroxyalkyl,
oils using a catalyst selected from salts of hydroxide (OHi) hydroxyalkenyl or hydroxyalkynyl residue. Using these cata
and alkoxides (alcoholates), such as methanolate (CH3i lysts, it is possible to obtain in an extremely e?icient Way a
Of) or ethanolate (CH34CH24Oi), With guanidine and fatty acid ester content Which complies With the European
N-alkylated derivatives thereof or With quaternary ammo 20 standard for biodiesel (DIN EN 14214) in a single process
nium compounds. step.
The catalysts described in the above mentioned scienti?c In the light of the structure of the catalytically active com
publications and the patent literature as mentioned shoW a pounds according to general formula (I), a skilled person
good catalytic activity in the transesteri?cation of triglycer could not expect these compounds to shoW surface-active
ides. HoWever, they do not function as a solubiliZer With the 25 properties Which considerably improve the mutual miscibil
conventionally used catalyst amounts and therefore cannot ity of alcohol and fat and/or oil. Surprisingly, only small
overcome the above explained problems associated With the amounts of the compound of general formula (I) are neces
phase behavior of the reaction mixture during the transesteri sary to signi?cantly improve the solubility of the alcohol in
?cation. the triglycerides. In the presence of the compound of general
In order to improve the phase behavior, literature has thus 30 formula (I), the alcohol and the triglycerides form a macro
proposed the use of a co-solvent. For example, Kim et al. scopically homogeneous, optically transparent and thermo
describe a method Where an additional component is used as dynamically stable mixture. It is presumably a microemul
a co-solvent, e.g. n-hexane or tetrahydrofuran, to minimiZe sion. The space-time-yield of the reaction is considerably
the substance transport resistances. These substances accelerated by the formation of such a microemulsion.
improve the solubility of the alcohol in fat and oil (Kim et al., 35 It has also been found surprisingly that catalytically active
Catalysis Today 93-95: 315-320 (2004)). Moreover, WO compounds according to general formula (I) result in a rapid
01/12581A1 describes a tWo-stage method for the production and complete segregation of the glycerol phase from the
of fatty acid methyl esters, Where in the second step triglyc biodiesel phase (fatty acid ester phase) after the conclusion of
erides are transesteri?ed using KOH or NaOH as basic cata the reaction and therefore it is possible to markedly reduce the
lysts in the presence of a co-solvent selected from the group 40 separation and Washing costs. Since the catalyst predomi
consisting of tetrahydrofuran, 1,4-dioxane, diethyl ether, nantly accumulates in the glycerol phase, it is thus also pos
methyl-tert-butyl ether and diisopropyl ether. sible to separate the catalyst substantially quantitatively With
HoWever, the use of a co-solvent as a solubiliZer has the the glycerol phase. As a rule, less than 1%, usually is less than
drawback that another component is introduced into the reac 0.1%, ofthe catalyst, e.g. choline, is left in the biodiesel phase
tion system, Which has to be separated in complicated fashion 45 and more than 99% or more than 99.9% is left in the glycerol
at a later date. phase.
Therefore, an object of the present invention is to provide a It has also been found surprisingly that it is possible to
method Which eliminates or minimiZes the above mentioned e?iciently convert triglycerides not only With methanol but
problems in the production of fatty acid esters by converting also With ethanol by means of the method according to the
to fat and/ or oil of biogenic origin With alcohols in the pres 50 invention. Thus, the above described dual function of the
ence of a catalyst. compounds of general formula (I) as a catalyst and solubiliZer
This object is achieved according to the invention by a is also observed in the transesteri?cation With ethanol. The
method in Which fat and/or oil of biogenic origin is reacted reaction With ethanol here proceeds at a rate comparable to
With monovalent and/or polyvalent alcohols in the presence the reaction With methanol. In addition, a skilled person could
of a catalyst, Wherein the catalyst is a hydroxy-functional 55 not foresee that by means of a compound of general formula
quaternary ammonium compound of the folloWing general (I) the transesteri?cation of triglycerides can also be cata
formula (I): lyZed With polyvalent alcohols. For example, glycerol
monoesters and diesters and the corresponding monoalcohol
and dialcohol esters of propanediol form e. g. from a mixture
60 of propanediol and triglycerides (i.e. fat and/or oil) When a
compound of general formula (I) is added.
Moreover, it has unexpectedly been found that the com
pounds of general formula (I) according to the invention still
have a high catalytic activity even in the presence of a rather
65 high Water concentration. This is surprising in so far as Water
in Which R1, R2 and R3 are equal or different and each actually shifts the balanced condition of the transesteri?ca
represents an unsubstituted or substituted straight-chain or tion reaction toWards the side of the educts. Even traces of
 US 8,598,377 B2
5 6
Water result in a drastic loss of yield When commercial basic in methanol and, along With choline as the main component,
catalysts (i.e. NaOH, KOH, Na-methylate, K-methylate) are also contains over-ethoxylated products of the main compo
used. nent as Well as an over-ethoxylated solvent, such as methoxy
The good Water tolerance is of considerable economic ethylene glycol, as by-products in an amount of up to 10% by
signi?cance since in this case the alcohol does not have to be Weight.
absolutiZed in an energy- and cost-intensive Way, or only has The catalysts of general formula (I), Which are used in the
to be absolutiZed to a minor extent, before it is used in the method according to the invention, may either be used in free
method according to the invention. The Water tolerance is of form or in the form of a salt, optionally dissolved in an organic
signi?cance eg for the production of “real” biodiesel by is solvent, such as methanol. Suitable salts comprise salts With
transesteri?cation of fats and/or oils of biogenic origin With organic or inorganic anions. Preferred examples are basic
biotechnologically produced bioethanol and enables the salts of the compounds of general formula (I), in particular
direct production of ethyl esters from an aZeotropic solution hydroxide, phosphate and carboxylic acid salts, such as
of alcohol and Water. As a result, the overall ef?ciency of the hydrogen carbonate and carbonate salts. Particularly pre
ethyl ester production is considerably improved. ferred salts for use in the method according to the invention
The compounds of general formula (I) thus combine in a are in particular choline salts, e.g. choline hydroxide, choline
unique Way the basicity required for the catalytic transesteri phosphate and choline carbonate.
?cation With the function of a solubiliZer for the multiphase According to a particular other embodiment of the present
system used in the method according to the invention. invention, the organic or inorganic anions are no hydroxide or
Another advantage of the presently described method is alcoholate anions.
that the main by-product accumulating in the transesteri?ca 20 In addition, the compounds of general formula (I) may also
tion method according to the invention, i.e. glycerol, may be be used based on the present invention in a form in Which they
employed in the animal feed industry, in particular When are supported on a carrier material or are bound thereto, i.e. in
choline or a derivative thereof is used as the catalyst accord heterogeniZed or supported form.
ing to general formula (I). Glycerol is knoWn to be usable eg The catalyst is preferably used in the method according to
in poultry farming as a feed additive up to a concentration of 25 the invention in an amount of 0.01 to 20% by Weight, in
about 5% by Weight (Cerrate et al., Int. J. Poultry Sci. 5(11): particular in an amount of 0.05 to 4.0% by Weight and more
1001 -1007 (2006)). HoWever, glycerol from conventional preferably to in an amount of 0.1 to 2.0% by Weight, based on
transesteri?cations is not suited as a feed additive due to the the total Weight of the employed fat and/or oil of biogenic
salt load since the electrolyte balance of the animals may be origin (or the employed triglycerides).
disturbed by it. When choline is used in the method according 30 Suitable monovalent alcohols for use in the method accord
to the invention for the production of fatty acid esters, these ing to the invention comprise methanol, ethanol, n-propanol,
problems do not exist. Choline is Widely used as a feed isopropanol and butanol but are not limited thereto. Preferred
additive to feed poultry, remnants and pigs. Choline com monovalent alcohols comprise methanol, Which is recovered
pound residues in the glycerol are therefore even advanta in large amounts from fossil raW materials, and ethanol Which
geous for use in the animal feed industry and along With the 35 is readily accessible from biotechnological processes. Suit
fatty acid esters represent another valuable product obtain able polyvalent alcohols are in particular divalent and, to a
able With the method according to the invention. minor extent, trivalent alcohols. Preferred divalent alcohols
In contrast to the commercially employed catalysts (i.e. comprise propanediol or butanediol, in particular 1,2-pro
NaOH, KOH, Na-methylate, K-methylate), the compounds panediol, but are not limited thereto. Both the monovalent and
of general formula (I), Which are used as catalysts, in particu 40 also the polyvalent alcohols may be used as such or in admix
lar choline, eg in the form of the choline base or in the form ture With one and/or more other monovalent or polyvalent
of a choline salt, such as choline carbonate, may also be alcohols. It is preferred to use in the method according to the
produced so as to be free from alkalis and alkaline earths or invention a monovalent alcohol selected from methanol and
other metal cations. Correspondingly, the glycerol accumu ethanol or a mixture thereof.
lating in the method according to the invention and enriched 45 As described above, the method according to the invention
With a catalyst may be combusted Without a catalyst-related is distinguished by a surprisingly good Water tolerance so that
(metal) salt formation occurring. the employed alcohols may have a Water content of up to
A catalyst particularly suited Within the scope of the about 10 to 15% by Weight and, depending on the employed
present invention is an above de?ned compound of general alcohol, a conversion rate of 50 to 80% can still be achieved.
formula (I), Wherein R1, R2 and R3 are equal or different and 50 For an ef?cient transesteri?cation (conversion rate >90%) the
each represents an unsubstituted er substituted straight-chain Water content is, hoWever, preferably less than 2% by Weight,
alkyl residue having 1 to 6 carbon atoms. in particular less than 1% by Weight.
Particularly suited catalysts for use in the method accord Fats and/ or oils Which may be used in the method accord
ing to the invention are also the above de?ned compounds of ing to the invention comprise all fats and/or oils of biogenic
general formula (I), Wherein R is a straight-chain hydroxy 55 origin as Well as any mixtures thereof. The term “biogenic
alkyl residue having 1 to 12 carbon atoms, preferably 1 to 8, origin” Which is used in the present invention means “of
more preferably 2 to 8 and most preferably 2 to 6 or 2 to 4 biological or organic origin”, i.e. not of chemical and syn
carbon atoms. It is preferred for R to have at least one, in thetic origin. Thus, the term “fats and/ or oils of biogenic
particular only one, hydroxyl group Which is preferably dis origin” comprises all fats and/ or oils Which are formed from
posed at position 2. It is particularly preferred for R to be 60 plants, animals or microorganisms (in particular fungi, algae
2-hydroxyethyl. It is most preferred for choline to be used as and bacteria). Fats and oils of biogenic origin consist of
a catalyst in the method according to the invention. glycerides (mono-, di- and triglycerides), and substantially of
The compounds of general formula (I), Which are used as triglycerides. In this description, the term “triglycerides” is
catalysts, can be produced in chemical and synthetic fashion thus sometimes also used synonymously for fat and/ or oil of
or be recovered from biological sources. In particular, it is 65 biogenic origin.
possible to use a choline compound Which can be obtained in It is preferred to use a fat and/or oil of vegetable origin in
the production of choline by ethoxylation of trimethylamine the method according to the invention. A “vegetable oil”
 US 8,598,377 B2
7 8
within the meaning of the present invention does not only ally below 2500 C. The reaction temperature is preferably
refer to a vegetable oil of a certain plant, such as rapeseed oil, adjusted so as to be approximately within the region of the
but also to any mixtures of different vegetable oils. Examples boiling temperature of the reaction mixture at atmospheric
of suitable vegetable oils are cotton seed oil, sa?Tower oil, pressure. However, it has been found surprisingly that the
jatropha oil, peanut oil, haZelnut oil, coconut oil, pumpkin transesteri?cation reaction even proceeds signi?cantly at
seed oil, linseed oil, corn oil, olive oil, palm oil, palm kernel lower temperatures, even at room temperature.
oil, rapeseed oil (also referred to as colZa oil), rice oil, soy According to a preferred embodiment of the method of the
bean oil, sun?ower oil, grape seed oil and wheat germ oil, in invention, the fat and/or oil of biogenic origin is initially
re?ned or cold-pressed form, and any mixtures thereof. Oils contacted with the monovalent and/or polyvalent alcohol and
recovered from algae may also be used. Vegetable oils pre then the catalyst is added to the resulting mixture. The catalyst
ferred in the present invention are rapeseed oil, palm oil, is here preferably dissolved in a solvent, wherein the solvent
sun?ower oil, soy bean oil or mixtures thereof, with rapeseed is preferably an alcohol, in particular the monovalent and/or
oil and sun?ower oil being particularly preferred. polyvalent alcohol used in the transesteri?cation reaction,
Starting fats and oils which are particularly suited foruse in such as methanol or ethanol. Alternatively, the catalyst may
the method according to the invention have an acid number of also be dissolved in the monovalent and/ or polyvalent alcohol
less than 1.0, which corresponds approximately to a concen to be esteri?ed and may then be mixed with the fat and/or oil
tration of free fatty acids of less than 0.5% by weight depend of biogenic origin in the reactor.
ing on the particular fat and oil. The fats and/or oils preferably After the conclusion of the conversion of fat and/ or oil of
contain an amount of free fatty acids of no more than 0.2% by biogenic origin with the monovalent and/ or polyvalent alco
weight. However, the method according to the invention may 20 hol in the presence of the catalyst described herein thereby
also use fats and/ or oils having a higher free fatty acid content. forming glycerol and fatty acid esters, the glycerol may be
In order to obtain a fat and/ or oil having a very small free fatty separated in a further method step. This may be done in the
acid content, it may be necessary for the starting fats and/or reaction vessel as such or in optionally subsequent treatment
oils to be subjected to a deacidi?cation treatment before they steps. Having concluded stirring, the glycerol collects as the
are used. 25 lower phase in the reaction vessel and can be withdrawn
As already explained in connection with the usable alco separately. Alternatively, the glycerol may also be withdrawn
hols, the fat or oil may also contain residual water amounts in downstream apparatuses and/ or methods utiliZing the den
without this negatively affecting the method according to the sity differences. The phase separation may be made by means
invention in a signi?cant manner. However, the residual water of gravity, i.e. by simply allowing it to stand. To this end, a
amount in the fats and/or oils, which are usually used in the 30 sedimentation container may be used, for example. However,
method according to the invention, is usually very small and it is also possible to use centrifugal forces, eg in hydrocy
is typically no more than about 1% by weight. clones or centrifuges.
In the method according to the invention, the alcohol is The excess alcohol, e.g. excess methanol or ethanol, can be
usually added in excess to obtain a high yield of desired fatty removed separately from each of the resulting glycerol phase
acid esters of monovalent or polyvalent alcohols. Here, the 35 and the resulting ester phase. This may be done by known
molar ratio of the monovalent and/ or polyvalent alcohol to the methods, e. g. by distillation. In an alternative embodiment of
fat and/or oil of biogenic origin is preferably at least 6:1. In the method according to the invention, the excess alcohol may
the case of monovalent alcohols, such as methanol or ethanol, also be removed before the separation of the glycerol and
this corresponds to a 2-fold stoichiometric excess because at ester phases. The recovered alcohol may be recycled to the
least 3 moles of methanol or ethanol are required to form 3 40 reaction. Due to the water tolerance of the method according
moles of methyl ester or ethyl ester from 1 mole of triglycer to the invention, a complex subsequent drying step of the
ides. In the case of polyvalent alcohols, the preferred molar alcohol may be omitted or the interval up to the use of fresh
ratio may also be smaller and in the case of divalent alcohols alcohol may be considerably prolonged.
it may be at least 2:1, for example. The glycerol and/or the glycerol phase contains substan
In addition to the above mentioned components, it is pos 45 tially the entire amount of the hydroxy-functional quaternary
sible to add to the reaction mixture, where appropriate, fur ammonium compound used as the catalyst, usually over 99%
ther substances, such as catalyst stabiliZers, which are com of the employed catalyst. The catalyst containing glycerol
patible with the reaction conditions and the intended use of may thus be used in a next reaction step, i.e. in a further
the reaction end products. transesteri?cation, to catalyZe the reaction between alcohols,
In standard stirred reactors, the transesteri?cation may be 50 in particular monovalent alcohols, such as methanol and/or
carried out without pressure and under re?ux. Alternatively, ethanol, and triglycerides. It has been found surprisingly that
the reaction control in tubular reactors is conceivable. First, the glycerol recycled in this way results in a considerable
the starting products, i.e. fats and/or oils of biogenic origin, formation of fatty acid esters. Such a recycling of the glycerol
and the catalyst are fed to the reactor and are all converted in produced in the transesteri?cation method markedly
the reactor at a suitable temperature into glycerol and the 55 improves the economic ef?ciency of the method according to
desired fatty acid ester of the employed monovalent and/or the invention since in this way more fatty acid esters than
polyvalent alcohol. After a contact time (hereinafter also formerly can be produced with a certain amount of overall to
“reaction time”) of some few minutes, the formation of glyc employed catalyst.
erol is observed, the transesteri?cation reaction being con After the separation of the excess alcohol, the catalyst
cluded after a reaction time of at least 15 minutes, typically 30 60 containing glycerol is also available for further uses. Depend
to 60 minutes. ing on the type of educts used, the employed catalyst and the
The reaction is usually carried out with stirring so as to intended use, further puri?cation steps known to a skilled
increase the substance transport and thus the reaction e?i person, such as bleaching, ?ltration, neutralization, etc., may
ciency. The temperature of the transesteri?cation reaction is optionally be required. The resulting glycerol may be used
above the melting temperature of the employed fat having the 65 materially or energetically. For example, the glycerol may be
highest melting temperature if fats are used. The reaction used with the catalyst enriched therein, as already described
temperature of the method according to the invention is usu above, optionally as a food supplement or feed additive in the
 US 8,598,377 B2
9 10
animal production industry or animal feed industry. Alterna by Weight of fatty acid methyl ester, <2% by Weight of trig
tively, the catalyst-containing glycerol may also be used to lycerides, 0.96% by Weight of diglycerides, 0.91% by Weight
recover energy by combustion, gasi?cation or pyrolysis or in of monoglycerides and 0.02% by Weight of glycerol.
fermentation processes and biogas systems.
When the fats and/ or oils used as the starting products are Example 3
carefully selected and pre-cleaned, the alcohol ester phase
produced is a clear phase Which under certain circumstances The transesteri?cation method according to Example 1
may have a slightly yelloW color. Depending on the intended Was carried out, hoWever, the reaction time Was 15 minutes.
use, the ester phase may be used as such. Alternatively, further The resulting upper lighter and loWer heavier phases had a
puri?cation steps may be necessary. Such puri?cation steps mass of 96.40 g and 11.06 g, respectively. The upper lighter
may be neutralization, discoloration, removal of trace com phase contained 93.7% by Weight of fatty acid methyl ester,
ponents, etc. This may be made eg by sorption processes <2% by Weight of triglycerides, 1.96% by Weight of diglyc
With solid or liquid auxiliary materials. erides, 1.30% by Weight of monoglycerides and 0.03% by
In the case of the fatty acid esters formed With monovalent Weight of glycerol.
alcohols, the esters formed may be used as a chemical raW
material, eg as a starting product for chemical syntheses or Example 4
as biofuel or biocombustible. For example, the end product of
the transesteri?cation With methanol, i.e. fatty acid methyl The transesteri?cation method according to Example 1
ester, has a markedly loWer viscosity than the employed fat Was carried out, hoWever, a mixture of 100 g rapeseed oil and
and/or oil and on account of its physical properties may be 20 14 g methanol (molar ratio of alcoholzoil of about 4.511) and
used as a substitute for diesel fuel. 5.0 g catalyst solution (choline base solution 44% in metha
The glycerol monoesters or glycerol diesters, Which are nol) Was used, and the reaction time Was 30 minutes.
formed in the transesteri?cation With polyvalent alcohols, The resulting upper lighter phase had a mass of 99.10 g and
such as propanediol, may be used as a mixture or after puri the loWer heavier phase had a mass of 10.6 g. The upper
?cation or fractionation eg as food emulsi?ers or as a chemi 25 lighter phase contained 90.6% by Weight of fatty acid methyl
cal raW material, eg in the detergent synthesis. ester, 2.19% by Weight of triglycerides, 2.63% by Weight of
The method according to the invention is explained in more diglycerides, 1.42% by Weight of monoglycerides and 0.02%
detail beloW by different examples. by Weight of glycerol.
EXAMPLES 30 Example 5
Example 1 This example illustrates the transesteri?cation of rapeseed
oil With ethanol into fatty acid ethyl esters and glycerol using
This example illustrates the transesteri?cation of rapeseed choline base as the catalyst.
oil With methanol into fatty acid methyl esters and glycerol 35 A mixture of 100 g rapeseed oil and 20 g ethanol (corre
using choline base as a catalyst. sponds to a molar ratio of alcohol to oil of about 4.211) Was
A mixture of 100 g rapeseed oil and 20 methanol (corre heated to the reaction temperature (boiling temperature)
sponds to a molar ratio of alcohol to oil of about 6:1) Was under stirring and With re?ux. Having reached the boiling
heated to reaction temperature (boiling temperature) under temperature, 4.8 g catalyst solution (choline base solution
stirring and With re?ux. Having reached the boiling tempera 40 44% in methanol) Was added. Some feW seconds after the
ture, 4.8 g catalyst solution (choline base solution 44% in addition of the catalyst solution, the initially turbid dispersion
methanol) Was added. Some feW seconds after the addition of of ethanol and oil converted into a clear mixture and the
the catalyst to solution, the initially turbid dispersion from precipitation of glycerol Was observed after some minutes.
methanol and oil changed into a clear mixture and the pre After a reaction time of 45 minutes, the reaction mixture
cipitation of glycerol Was observed after some minutes. 45 Was placed in a rotary evaporator to distill off excess ethanol
After a reaction time of 60 minutes, the reaction mixture (?nal pressure about 50 mbar). The residue from the distilla
Was placed in a rotary evaporator to distill off the excess tion Was then transferred to a separating funnel. The mixture
methanol (?nal pressure about 50 mbar). The residue from the separated into tWo phases at room is temperature.
distillation Was then transferred to a separating funnel. The The loWer heavier phase had a mass of 17.0 g and the
mixture separated into tWo phases at room temperature. 50 glycerol concentration Was about 43% by Weight. The upper
The loWer heavier phase had a mass of 11.76 g and a lighter phase had a mass of 95.80 g and contained 87.1% by
glycerol concentration of about 85% by Weight. The upper Weight of fatty acid ethyl ester (rapeseed oil ethyl ester), <1 %
lighter phase had a mass of 97.14 g and contained 96.4% by by Weight of triglycerides, 3.63% by Weight of diglycerides,
Weight of fatty acid methyl ester (rapeseed oil methyl ester), 1.5% by Weight of monoglycerides and 0.04% by Weight of
<2% by Weight of triglycerides, 0.96% by Weight of diglyc 55 glycerol, determined by means of gas chromatography
erides, 1.12% by Weight of monoglycerides and 0.04% by according to DIN EN 14103.
Weight of glycerol, determined by gas chromatography
according to DIN EN 14103 for fatty acid methyl esters and Example 6
according to DIN EN 14105 for partial glycerides and glyc
erol. 60 This example illustrates the transesteri?cation of rapeseed
oil With Water-containing methanol into fatty acid methyl
Example 2 esters and glycerol using choline base as the catalyst.
The employed method substantially corresponds to the
The transesteri?cation according to Example 1 Was carried method according to Example 2; hoWever, a total of 2 g Water
out, but the reaction time Was 45 minutes. The resulting upper 65 (corresponds to a Water content of 8.8% by Weight, based on
lighter and loWer heavier phases had a mass of 98.17 g and the total alcohol amount, i.e. 20 g methanol plus the amount
10.6 g, respectively. The upper lighter phase contained 96.1% of alcohol introduced into the system by the catalyst solution)
 US 8,598,377 B2
11 12
Was added to the mixture of 100 g rapeseed oil, 20 g methanol Was heated to the reaction temperature (boiling temperature)
(molar ratio of alcohol:oil of about 6:1) and 4.8 g catalyst under stirring and With re?ux. Having reached the boiling
solution (choline base solution 44% in methanol). temperature, 4.8 g catalyst solution (choline base solution
The resulting upper lighter phase had a mass of 97.50 g and 44% in methanol) Was added. Some feW seconds after the
contained 74.6% by Weight of fatty acid methyl ester, >20% addition of the catalyst solution, the initially turbid dispersion
by Weight of triglycerides, 5.24% by Weight of diglycerides, of 1,2-propanediol and oil converted into a clear mixture.
1.17% by Weight of monoglycerides and 0.02% by Weight of After a reaction time of 30 minutes, the excess 1,2-pro
glycerol. panediol Was separated With a rotary evaporator (?nal pres
sure 50 mbar). The residue (homogeneous phase) had the
Example 7 folloWing composition: 11% by Weight of monoglycerides,
21.7% by Weight of diglycerides, 1.2% by Weight of triglyc
This example illustrates the transesteri?cation of rapeseed erides, 4% by Weight of glycerol. In addition, small amounts
oil With Water-containing ethanol into fatty acid ethyl esters of methyl ester formed from the methanol portion Which Was
and glycerol using choline base as the catalyst. introduced by the methanolic solution of the catalyst.
The employed method substantially corresponds to the
method according to Example 5; hoWever, a total of 0.9 g Example 11
Water (corresponds to a Water content of 4.0% by Weight,
based on the total alcohol amount, i.e. 20 g ethanol plus the This example illustrates the transesteri?cation of rapeseed
amount of alcohol introduced into the system by the catalyst oil With methanol into fatty acid methyl esters and glycerol
solution) Was added to the mixture of 100 g rapeseed oil, 20 g 20 employing a reusable choline base-containing glycerol
ethanol (molar ratio of alcohol:oil of about 4.2:1) and 4.8 g phase.
catalyst solution (choline base solution 44% in methanol). In The transesteri?cation method according to Example 1
the case of ethanol, this Water content corresponds to that of Was initially carried out, hoWever, 200 g rapeseed oil, 24 g
aZeotropic ethanol. methanol and 20 g catalyst solution (choline base solution
The resulting upper lighter phase had a mass of 100.2 g and 25 20% in methanol) Were employed. The resulting heavier
contained 60.6% by Weight of fatty acid ethyl ester, 5.50% by phase (25 g choline base-containing glycerol phase) Was
Weight of triglycerides, 10.94% by Weight of diglycerides, separated and used Without further treatment as the catalyst
10.65% by Weight of monoglycerides and >0.55% by Weight for another transesteri?cation. To this end, a mixture of 200 g
of glycerol. rapeseed oil, 40 g methanol and 25 g of the choline base
30 containing glycerol phase from the ?rst transesteri?cation
Example 8 Was heated to the reaction temperature (boiling temperature)
under stirring and With re?ux. The test Was terminated after
This example illustrates the transesteri?cation of rapeseed 60 minutes and the product phases Were recycled as described
oil With methanol into fatty acid methyl esters and glycerol in Example 1.
using choline carbonate as the catalyst. 35 The resulting upper lighter and loWer heavier phases had a
The employed method substantially corresponds to the mass of 203.0 g and 30.44 g, respectively. The upper lighter
method according to Example 1, a to choline carbonate solu phase contained 67.58% by Weight of fatty acid methyl ester,
tion 74% in methanol being used as the catalyst solution. The 17.58% by Weight of triglycerides, 8.13% by Weight of dig
resulting upper lighter phase had a mass of 98.2 g While the lycerides, 2.28% by Weight of monoglycerides and 0.06% by
loWer heavier phase had a mass of 5.7 g. The upper lighter 40 Weight of glycerol.
phase contained 56.3% by Weight of fatty acid methyl esters, The invention claimed is:
>20% by Weight of triglycerides, 20.96% by Weight of dig 1. A method for producing fatty acid esters of monovalent
lycerides, 4.32% by Weight of monoglycerides and 0.1 1% by or polyvalent alcohols by means of a catalyst, comprising
Weight of glycerol. reacting fat and/or oil of biogenic origin With monovalent
45 and/or polyvalent alcohols in the presence of a catalyst,
Example 9 Wherein the catalyst is a hydroxy-functional quaternary
ammonium compound of the folloWing formula (I):
This example illustrates the transesteri?cation of rapeseed
oil With ethanol into fatty acid ethyl esters and glycerol using
choline carbonate as the catalyst. 50
The employed method substantially corresponds to the
method according to Example 5, hoWever, a choline carbon
ate solution 74% in methanol Was used as the catalyst solu
tion. The resulting upper lighter phase had a mass of 100.0 g
While the loWer heavier phase had a mass of 6.2 g. The upper 55
lighter phase contained 62.3% by Weight of fatty acid ethyl in Which R1, R2 and R3 are equal or different and each
ester, 12.95% by Weight oftriglycerides, 17.47% by Weight of represents an unsubstituted straight-chain alkyl residue
diglycerides, 5.22% by Weight of monoglycerides and 0.48% having 1 to 6 carbon atoms, and
by Weight of glycerol. R is a straight-chain or branched hydroxyalkyl, hydroxy
alkenyl or hydroxyalkynyl residue having 1 to 8 carbon
Example 10 atoms.
2. The method according to claim 1, Wherein R is a straight
This example illustrates the transesteri?cation of rapeseed chain hydroxyalkyl residue having 1 to 12 carbon atoms.
oil With 1,2-propanediol into fatty acid esters and glycerol 3. The method according to claim 1, Wherein R is 2-hy
using choline base as the catalyst. 5 droxyethyl.
A mixture of 50 g rapeseed oil and 10 g 1,2-propanediol 4. The method according to claim 1, Wherein choline or a
(corresponds to a molar ratio of alcohol to oil of about 2.5:1) salt thereof is used as the catalyst.
 US 8,598,377 B2
13 14
5. The method according to claim 1, wherein the catalyst is 12. A method of preparing a feed additive for use in the
used in an amount betWeen 0.01 and 4.0% by Weight, based animal feed industry, the feed additive including fatty acid
on the Weight of the employed fat and/or oil of biogenic esters of monovalent or polyvalent alcohols produced by
origin. means of a catalyst, the method comprising:
6. The method according to claim 1, Wherein the monova reacting fat and/or oil of biogenic origin With monovalent
and/or polyvalent alcohols in the presence of a catalyst,
lent alcohol is selected from the group consisting of metha
Wherein the catalyst is a hydroXy-functional quaternary
nol, ethanol, n-propanol, isopropanol, butanol and mixtures ammonium compound of the folloWing formula (I):
thereof and the polyvalent alcohol is a divalent alcohol
selected from the group consisting of propanediol, butanediol
and mixtures thereof.
7. The method according to claim 1, Wherein the employed
fat and/or oil of biogenic origin contains less than 0.5% by
Weight of fatty acids.
8. The method according to claim 1, Wherein the molar
ratio of the monovalent and/or polyvalent alcohol to the fat
and/or oil ofbiogenic origin is at least 6:1. in Which R1, R2 and R3 are equal or different and each
9. The method according to claim 1, further comprising the represents an unsubstituted straight-chain alkyl residue
puri?cation of the formed fatty acid ester of monovalent or having 1 to 6 carbon atoms, and
polyvalent alcohols by separation of the by-products formed. R is a straight-chain or branched hydroxyalkyl, hydroxy
10. The method according to claim 9, Wherein the by alkenyl or hydroxyalkynyl residue having 1 to 8 carbon
product formed is a glycerol product, comprising a catalyst atoms;
containing glycerol fraction. purifying of the formed fatty acid esters of monovalent or
11. The method according to claim 1, Wherein the hydroxy polyvalent alcohols by separating the catalyst contain
functional quaternary ammonium compound used as the cata ing the glycerol faction as a by-product, Wherein the
25
lyst is employed in the form of a glycerol fraction Which is catalyst is used in an amount of 0.01 to 2.0 percent by
obtainable according to a method as de?ned in claim 1 and in Weight, based on the Weight of the employed fat and/or
Which the hydroXy-functional quaternary ammonium com oil of biogenic origin.
pound used as the catalyst is enriched. * * * * *