EP1465969A1 - Method for transesterifying fat and/or oil by heterogeneous catalysis - Google Patents

Method for transesterifying fat and/or oil by heterogeneous catalysis

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Publication number
EP1465969A1
EP1465969A1 EP02792891A EP02792891A EP1465969A1 EP 1465969 A1 EP1465969 A1 EP 1465969A1 EP 02792891 A EP02792891 A EP 02792891A EP 02792891 A EP02792891 A EP 02792891A EP 1465969 A1 EP1465969 A1 EP 1465969A1
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EP
European Patent Office
Prior art keywords
catalyst
oil
transesterification
fat
amino acid
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP02792891A
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German (de)
French (fr)
Inventor
Siegfried Peter
Eckhard Weidner
Hans-Peter Neuner
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Peter Siegfried Prof Dr
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Peter Siegfried Prof Dr
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Publication of EP1465969A1 publication Critical patent/EP1465969A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange

Definitions

  • the present invention relates to a process for the production of fat and / or oil with a modified fatty acid distribution by heterogeneously catalyzed transesterification.
  • Transesterification reactions are known per se, they are a commercially important class of industrial organic reactions.
  • the transesterification reaction is a transfer of an ester by exchange of the alcohol or acid group to another ester instead.
  • This type of reaction includes different types of transesterification, which can be differentiated from one another by different reactants (ester with alcohol, ester with acid, ester with ester).
  • two different esters react with one another to form two new esters (redistribution).
  • Such reactions usually take place under catalytic conditions in the presence of acids or bases.
  • the last-mentioned transesterification reaction is of particular interest in connection with the modification of fats and oils, in particular in the case of fats and oils of biological origin, which mainly consist of glycerides (mono-, di- and triglycerides).
  • fats and oils of biological origin which mainly consist of glycerides (mono-, di- and triglycerides).
  • glycerides mono-, di- and triglycerides
  • the properties of these materials can be changed in a wide range.
  • the melting point, the viscosity and other functional characteristics can be customized.
  • This method can be used instead of the classic hardening of fats or other conventional methods for changing the material properties of fats and oils.
  • the transesterification process is used particularly in the USA to refine lard.
  • greases with completely new properties can be tailored.
  • the melting point of a fat mixture after the transesterification may be higher or lower than that of the original mixture.
  • Large-scale transesterification also takes place in the margarine industry for the production of fats with changed properties.
  • alkali metals or their methylates are predominantly used as catalysts in the transesterification of fats and oils. These are either finely divided or suspended in the fat (0.1-0.2% by weight).
  • Alkaline alcoholates (0.1-0.3% by weight) are added in powder form.
  • K>Na>Li> Mg the catalytic activity is highest for potassium.
  • the fats must be deacidified (content of free fatty acids ⁇ 0.1% by weight) and dried before the transesterification, since free fatty acids, which are always contained in fats and oils of biological origin, and water inactivate the catalyst.
  • the reaction mixture turns orange-brown, which is seen as a first test for the quality of the process.
  • the reaction is usually complete about 30 minutes after the color has appeared. Investigations showed that there is an equilibrium in the distribution of the fatty acid molecules on the glycerol (KF Carlson and JD Scott, Inform. 1991, 2 (12), 134).
  • Controlled transesterification is based on the thermodynamic state of equilibrium, which is deliberately disturbed by causing existing, or by transesterification, higher melting and poorly soluble triglycerides to crystallize and to be removed from the equilibrium.
  • Both methods can be operated in batch, semi and full batch mode.
  • the transesterification must be preceded by drying and degassing so that all moisture is safely removed.
  • the catalyst must be dispersed in an extremely fine distribution. This is important for a smooth reaction process. Its particle size should be less than 50 ⁇ .
  • the reaction generally takes place in the temperature range between 70 and 120 ° C.
  • the reaction time can be less than 1 hour and up to 24 hours.
  • the catalyst is inactivated.
  • the catalyst is deactivated by adding water, dilute mineral acid or even water and carbon dioxide. Inactivation with water and carbon dioxide produces not only alkali soap but also soda ('The transesterification of fats', joint work of the German Society for Fat Science e.V., Industrieverlag von Hernatoryn KG, Hamburg, 1973).
  • fatty acid monoesters or alkali soaps are formed from the alkali alcoholates and the alkali metals. These are removed in the course of the subsequent refining process, especially during deodorization. They fall in the aqueous part of the condensate and must be disposed of. Since there is normally a residue of soap in the oil, the mixture is washed and the wash water is separated from the oil by centrifugation. The oil is then dried, bleached and deodorized in the usual way.
  • a reactor which is similar in design to that of hydrogenation is used for the unguided transesterification.
  • the transesterification with fatty acid esters can be carried out either in batch operation, usually in a closed deacidifying and bleaching apparatus, or continuously. In continuous work, the catalyst and grease are brought into contact with one another in suitable flow-through apparatus.
  • the fat In the controlled transesterification, the fat is z. B. cooled in a scratch cooler. A sufficiently long dwell time is then necessary to allow the higher-melting glycerides to crystallize, in accordance with the equilibrium. Inoculation facilitates crystallization. With physically refined oil, difficulties often arise with regard to the effectiveness of the transesterification, since a low level of free fatty acids must be present for a successful reaction.
  • An alternative method of increasing interest is the transesterification using enzymes as catalysts. This process is generally used for palm oil-based materials such as cocoa butter substitute and coconut oil.
  • the present invention is therefore based on the object of providing a simple and efficient method for producing fats and / or oils of biological origin with a modified fatty acid distribution in the glycerides.
  • the new process should avoid any waste water that has to be disposed of.
  • This object is achieved with a method according to claim 1.
  • metal salts of basic amino acids or amino acid derivatives are surprisingly suitable as catalysts for the production of fats and / or oils with changed fatty acid distribution in the glycerides by transesterification.
  • fats and / or oils of biological origin can thus be reacted in the presence of these salts, fats and / or oils being formed which differ in their fatty acid distribution in the glycerides from the corresponding starting materials.
  • changing the fatty acid distribution in the glycerides means both a change in the direction of a uniform arrangement of the fatty acids and a change to a statistical distribution of the fatty acids.
  • the use of these salts, which are insoluble in the reaction mixture, allows heterogeneously catalyzed transesterification reactions to be carried out, which are distinguished in particular by the fact that no waste water to be disposed of is obtained.
  • the fats and oils used in the process according to the invention have to be deacidified (content of free fatty acids ⁇ 0.1% by weight) and dewatered before the transesterification, so that good results can be achieved with regard to the speed of the transesterification reaction with the catalysts according to the invention.
  • catalysts are used whose amino acid components have a quaternary nitrogen or a guanidino group.
  • Metal salts of arginine or camitin are particularly preferred.
  • the metal ions preferably used in the process according to the invention are alkaline earth metal ions, in particular calcium, strontium or barium ions, heavy metal ions, in particular silver, copper, zinc, manganese, iron, nickel or cobalt ions or rare earth metal ions, in particular lanthanum ions. Zinc or lanthanum ions are particularly preferred.
  • Catalysts used with very particular preference in the context of the invention are the zinc or lanthanum salts of arginine or carnitine.
  • the catalysts can also be used in the process according to the invention.
  • the catalysts are used in an amount of 5-25% by weight, preferably 10-20% by weight. Due to the thermal stability of the catalysts, the process can be carried out at temperatures of about 60 to 200 ° C, preferably it is carried out at temperatures of 100 to 150 ° C, particularly preferably at about 125 ° C.
  • the heterogeneously catalyzed process according to the invention can be operated in a batch, semi or fully continuous mode.
  • the arginates preferably used in the process according to the invention can be pressed into pills and filled into a tubular reactor.
  • the powdery, finely crystalline metal arginate is suspended in the fat or oil.
  • the catalyst is filtered off or separated off with a centrifuge and recirculated.
  • the catalyst according to the invention can also be applied to a suitable support in order to improve the hydrodynamic conditions in a continuously operating reactor. In this way, there is no need to separate the powdery catalyst from the products by filtration.
  • the carrier can be cylindrical or any other shape that is favorable for the continuous course of the reaction. A high porosity is useful if the shape stability of the contact does not suffer too much.
  • the invention also relates to fat and / or oil of biological origin, which is produced by the method explained above.
  • This fat and / or oil according to the invention has a different fatty acid distribution than the corresponding starting material, and is usually also characterized by new material properties such as Distinguish melting point or viscosity from the starting material.
  • the attached single figure shows graphically the change in the fatty acid distribution after the transesterification.
  • FIG. 1 using the example of a mixture of sunflower oil and coconut oil in a ratio of 1: 1, it is shown that in the presence of zinc arginate in powder form (5% by weight) as a catalyst, a noticeable shift in the triglyceride spectrum occurred at 125 ° C. in the course of 8 hours is. The change of a peak area is in
  • composition of the fats before and after the transesterification depending on the retention time in% of the peak area
  • the retention time of 32.0 minutes corresponds to the tripalmitin component, that of 34.1 minutes to the tristearin component.
  • the softening temperature of the lard had increased slightly by about 1 ° C.

Abstract

The invention relates to a method for producing fat and/or oil with a modified fatty acid distribution in the glycerides by heterogeneously catalyzed transesterification. According to the inventive method, the fat and/or oil of biological origin to be transesterified is/are reacted in the presence of a catalyst from a metal salt of an alkaline amino acid or an amino acid derivative. By using the catalyst, the drawbacks of conventional transesterification methods can be eliminated.

Description

Verfahren zur Umesterung von Fett und/oder Öl durch heterogene Katalyse Process for the transesterification of fat and / or oil by heterogeneous catalysis
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Fett und/oder Öl mit geänderter Fettsäureverteilung durch heterogen katalysierte Umesterung.The present invention relates to a process for the production of fat and / or oil with a modified fatty acid distribution by heterogeneously catalyzed transesterification.
Umesterungsreaktionen sind an sich bekannt, sie stellen eine kommerziell bedeutsame Klasse industrieller organischer Reaktionen dar. Bei' der Umesterungsreaktion findet eine Überführung eines Esters durch Austausch der Alkohol- oder Säuregruppe in einen anderen Ester statt. Dieser Klasse von Reaktionen gehören verschiedene Arten der Umesterung an, die sich durch jeweils unterschiedliche Reaktanden (Ester mit Alkohol, Ester mit Säure, Ester mit Ester) voneinander abgrenzen lassen. Bei einer dieser Arten der Umesterungsreaktionen reagieren zwei verschiedene Ester unter Bildung zweier neuer Ester (Neuverteilung) miteinander. Solche Reaktionen laufen üblicherweise unter katalytischen Bedingungen in Gegenwart von Säuren oder Basen ab.Transesterification reactions are known per se, they are a commercially important class of industrial organic reactions. In 'of the transesterification reaction is a transfer of an ester by exchange of the alcohol or acid group to another ester instead. This type of reaction includes different types of transesterification, which can be differentiated from one another by different reactants (ester with alcohol, ester with acid, ester with ester). In one of these types of transesterification reactions, two different esters react with one another to form two new esters (redistribution). Such reactions usually take place under catalytic conditions in the presence of acids or bases.
Die zuletzt genannte Umesterungsreaktion ist vor allem im Zusammenhang mit der Modifikation von Fetten und Ölen von Interesse, insbesondere bei Fetten und Ölen biologischen Ursprungs, die überwiegend aus Glyceriden (Mono-, Di- und Triglyceri- de) bestehen. Durch die Neuverteilung der Fettsäuren in den Fetten und Ölen, d.h. durch Änderung der Fettsäureverteilung in den Glyceriden, können die Eigenschaften dieser Materialien in einem weiten Bereich verändert werden. So lassen sich z.B. der Schmelzpunkt, die Viskosität und andere funktioneile Charakteristika maßgeschneidert verändern. Dieses Verfahren kann anstelle der klassischen Härtung von Fetten oder anderen konventionellen Verfahren zur Änderung von Materialeigenschaften von Fetten und Ölen angewendet werden.The last-mentioned transesterification reaction is of particular interest in connection with the modification of fats and oils, in particular in the case of fats and oils of biological origin, which mainly consist of glycerides (mono-, di- and triglycerides). By redistributing the fatty acids in the fats and oils, i.e. by changing the fatty acid distribution in the glycerides, the properties of these materials can be changed in a wide range. For example, the melting point, the viscosity and other functional characteristics can be customized. This method can be used instead of the classic hardening of fats or other conventional methods for changing the material properties of fats and oils.
Die Umesterung wird besonders in den USA zur Veredelung von Schweineschmalz angewendet. Durch geeignete Auswahl der Umesterungskomponenten können Fette mit völlig neuen Eigenschaften maßgeschneidert werden. Je nach Wahl der Komponenten kann z.B. der Schmelzpunkt eines Fettgemisches nach der Umesterung höher oder tiefer liegen als der des ursprünglichen Gemisches. Großtechnische Umesterun- gen finden auch in der Margarine-Industrie zur Herstellung von Fetten mit geänderten Eigenschaften statt. In der Praxis werden bei der Umesterung von Fetten und Ölen überwiegend Alkalimetalle oder deren Methylate als Katalysatoren verwendet. Diese werden entweder fein verteilt oder im Fett suspendiert (0,1 - 0,2 Gew.-%) zugegeben. Alkalialkoholate (0,1 - 0,3 Gew.-%) werden in Pulverform zugesetzt. In der Reihenfolge K > Na > Li > Mg ist die katalytische Aktivität bei Kalium am höchsten. Die Fette müssen vor der Umesterung entsäuert (Gehalt an freien Fettsäuren < 0,1 Gew.-%) und getrocknet werden, da freie Fettsäuren, die in Fetten und Ölen biologischen Ursprungs immer enthalten sind, und Wasser den Katalysator inaktivieren. Während der Reaktion verfärbt sich das Reaktionsgemisch orange-braun, was als ein erster Test für die Qualität des Prozesses gewertet wird. Etwa 30 min nach Auftreten der Färbung ist die Reaktion in der Regel beendet. Untersuchungen ergaben, daß ein Gleichgewicht der Verteilung der Fettsäuremoleküle auf dem Glycerin besteht (K.F. Carlson und J.D. Scott, Inform. 1991, 2(12), 134).The transesterification process is used particularly in the USA to refine lard. By selecting the transesterification components appropriately, greases with completely new properties can be tailored. Depending on the choice of components, the melting point of a fat mixture after the transesterification may be higher or lower than that of the original mixture. Large-scale transesterification also takes place in the margarine industry for the production of fats with changed properties. In practice, alkali metals or their methylates are predominantly used as catalysts in the transesterification of fats and oils. These are either finely divided or suspended in the fat (0.1-0.2% by weight). Alkaline alcoholates (0.1-0.3% by weight) are added in powder form. In the order K>Na>Li> Mg, the catalytic activity is highest for potassium. The fats must be deacidified (content of free fatty acids <0.1% by weight) and dried before the transesterification, since free fatty acids, which are always contained in fats and oils of biological origin, and water inactivate the catalyst. During the reaction, the reaction mixture turns orange-brown, which is seen as a first test for the quality of the process. The reaction is usually complete about 30 minutes after the color has appeared. Investigations showed that there is an equilibrium in the distribution of the fatty acid molecules on the glycerol (KF Carlson and JD Scott, Inform. 1991, 2 (12), 134).
Verfahrenstechnisch wird zwischen ungelenkter (zufälliger) und gelenkter Umesterung unterschieden. Bei der gelenkten Umesterung wird vom thermodynamischen Gleichgewichtszustand ausgegangen, der gezielt gestört wird, indem vorhandene bzw. durch Umesterung sich bildende, höherschmelzende und schwerlösliche Trigly- ceride zum Kristallisieren gebracht und aus dem Gleichgewicht entfernt werden.In terms of process engineering, a distinction is made between unguided (random) and directed transesterification. Controlled transesterification is based on the thermodynamic state of equilibrium, which is deliberately disturbed by causing existing, or by transesterification, higher melting and poorly soluble triglycerides to crystallize and to be removed from the equilibrium.
Beide Verfahren, d.h. ungelenkte und gelenkte Umesterung, können in diskontinuierlicher, halb- und vollkontinuierlicher Arbeitsweise betrieben werden. In jedem Fall hat der Umesterung eine Trocknung und Entgasung voranzugehen, damit alle Feuchtigkeit sicher entfernt ist. Der Katalysator muß in äußerst feiner Verteilung dispergiert werden. Das ist für einen glatten Reaktionsverlauf wichtig. Seine Teilchengröße sollte unter 50 μ liegen. Die Umsetzung erfolgt im allgemeinen im Temperaturbereich zwischen 70 und 120°C. Die Reaktionszeit kann weniger als 1 Stunde und bis zu 24 Stunden betragen. Nach beendeter Reaktion wird der Katalysator inaktiviert. Die Inaktivierung des Katalysators geschieht durch Zugabe von Wasser, verdünnter Mineralsäure oder auch Wasser und Kohlendioxid. Bei der Inaktivierung mit Wasser und Kohlendioxid entsteht neben Alkaliseife auch Soda ('Die Umesterung von Fetten', Gemeinschaftsarbeit der Deutschen Gesellschaft für Fettwissenschaft e.V., Industrie- verlag von Hernhaussen KG, Hamburg, 1973).Both methods, i.e. unguided and steered transesterification, can be operated in batch, semi and full batch mode. In any case, the transesterification must be preceded by drying and degassing so that all moisture is safely removed. The catalyst must be dispersed in an extremely fine distribution. This is important for a smooth reaction process. Its particle size should be less than 50 μ. The reaction generally takes place in the temperature range between 70 and 120 ° C. The reaction time can be less than 1 hour and up to 24 hours. When the reaction has ended, the catalyst is inactivated. The catalyst is deactivated by adding water, dilute mineral acid or even water and carbon dioxide. Inactivation with water and carbon dioxide produces not only alkali soap but also soda ('The transesterification of fats', joint work of the German Society for Fat Science e.V., Industrieverlag von Hernhaussen KG, Hamburg, 1973).
Aus den Alkalialkoholaten und den Alkalimetallen entstehen äquivalente Mengen an Fettsäuremonoester bzw. Alkaliseifen. Diese werden im Verlaufe des anschließenden Raffinationsprozesses, insbesondere während der Desodorisierung entfernt. Sie fallen im wäßrigen Teil des Kondensates an und müssen entsorgt werden. Da normalerweise ein Rest an Seife im Öl vorhanden ist, wird das Gemisch gewaschen und das Waschwasser durch Zentrifugieren vom Öl getrennt. Das Öl wird dann in üblicher Weise getrocknet, gebleicht und desodorisiert.Equivalent amounts of fatty acid monoesters or alkali soaps are formed from the alkali alcoholates and the alkali metals. These are removed in the course of the subsequent refining process, especially during deodorization. They fall in the aqueous part of the condensate and must be disposed of. Since there is normally a residue of soap in the oil, the mixture is washed and the wash water is separated from the oil by centrifugation. The oil is then dried, bleached and deodorized in the usual way.
Für die ungelenkte Umesterung wird ein Reaktor, der in der Gestaltung dem der Hydrogenierung ähnlich ist, verwendet. Die Umesterung mit Fettsäureestern kann sowohl im Chargenbetrieb, üblicherweise in einem geschlossenen Entsäuerungs- und Bleichapparat, als auch kontinuierlich durchgeführt werden. Bei kontinuierlichem Arbeiten werden Katalysator und Fett in geeigneten Durchlaufapparaten miteinander in Kontakt gebracht.A reactor which is similar in design to that of hydrogenation is used for the unguided transesterification. The transesterification with fatty acid esters can be carried out either in batch operation, usually in a closed deacidifying and bleaching apparatus, or continuously. In continuous work, the catalyst and grease are brought into contact with one another in suitable flow-through apparatus.
Bei der gelenkten Umesterung wird das Fett vor der Umesterung z. B. in einem Kratzkühler gekühlt. Anschließend ist eine genügend lange Verweilzeit notwendig, um die höherschmelzenden Glyceride, dem Gleichgewicht entsprechend, kristallisieren zu lassen. Animpfen erleichtert dabei die Kristallisation. Bei physikalisch raffiniertem Öl treten häufig Schwierigkeiten in Bezug auf die Wirksamkeit der Umesterung auf, da für eine erfolgreiche Reaktion ein niedriges Niveau an freien Fettsäuren vorhanden sein muß.In the controlled transesterification, the fat is z. B. cooled in a scratch cooler. A sufficiently long dwell time is then necessary to allow the higher-melting glycerides to crystallize, in accordance with the equilibrium. Inoculation facilitates crystallization. With physically refined oil, difficulties often arise with regard to the effectiveness of the transesterification, since a low level of free fatty acids must be present for a successful reaction.
Eine alternative Methode von zunehmendem Interesse stellt die Umesterung mit Hilfe von Enzymen als Katalysatoren dar. Dieser Prozeß wird im allgemeinen bei Palmölbasierten Materialien wie Kakaobutterersatz und Kokosnußöl angewendet.An alternative method of increasing interest is the transesterification using enzymes as catalysts. This process is generally used for palm oil-based materials such as cocoa butter substitute and coconut oil.
Bei der Umesterung von Fetten und Ölen mit Alkalimetallen oder Alkalialkoholaten tritt ein schwerwiegendes Problem auf. So entstehen während der Umesterung äquivalente Mengen an Fettsäuremonoester bzw. Alkaliseifen, die nach dem anschließendem Raffinationsprozeß in der wässrigen Phase anfallen und entsorgt werden müssen.A serious problem arises when transesterifying fats and oils with alkali metals or alkali alcoholates. Equivalent amounts of fatty acid monoesters or alkali soaps are formed during the transesterification, which accumulate in the aqueous phase after the subsequent refining process and must be disposed of.
Der vorliegenden Erfindung liegt daher die Aufgabe zugrunde, ein einfaches und effizientes Verfahren zur Herstellung von Fetten und/oder Ölen biologischen Ursprungs mit geänderter Fettsäureverteilung in den Glyceriden bereitzustellen. Insbesondere sollen bei dem neuen Verfahren möglichst keine Abwässer anfallen, die entsorgt werden müssen. Diese Aufgabe ist erfindungsgemäß mit einem Verfahren gemäß Anspruch 1 gelöst. Demnach eigenen sich überraschenderweise Metallsalze von basischen Aminosäuren oder Aminosäurederivaten als Katalysatoren für die Herstellung von Fetten und/oder Ölen mit geänderter Fettsäureverteilung in den Glyceriden durch Umesterung. Nach dem erfindungsgemäßen Verfahren können somit Fette und/oder Öle biologischen Ursprungs in Gegenwart dieser Salze umgesetzt werden, wobei Fette und/oder Öle entstehen, die sich in ihrer Fettsäureverteilung in den Glyceriden von den entsprechenden Ausgangsmaterialien unterscheiden. Im Rahmen dieser Erfindung wird unter Änderung der Fettsäureverteilung in den Glyceriden sowohl eine Änderung in Rich- tung einer einheitlichen Anordnung der Fettsäuren wie auch eine Änderung hin zu einer statistischen Verteilung der Fettsäuren verstanden. Die Verwendung dieser in der Reaktionsmischung unlöslichen Salze erlaubt die Durchführung heterogen katalysierter Umesterungsreaktionen, die sich insbesondere dadurch auszeichnen, daß keine zu entsorgenden Abwässer anfallen.The present invention is therefore based on the object of providing a simple and efficient method for producing fats and / or oils of biological origin with a modified fatty acid distribution in the glycerides. In particular, the new process should avoid any waste water that has to be disposed of. This object is achieved with a method according to claim 1. Accordingly, metal salts of basic amino acids or amino acid derivatives are surprisingly suitable as catalysts for the production of fats and / or oils with changed fatty acid distribution in the glycerides by transesterification. According to the process of the invention, fats and / or oils of biological origin can thus be reacted in the presence of these salts, fats and / or oils being formed which differ in their fatty acid distribution in the glycerides from the corresponding starting materials. In the context of this invention, changing the fatty acid distribution in the glycerides means both a change in the direction of a uniform arrangement of the fatty acids and a change to a statistical distribution of the fatty acids. The use of these salts, which are insoluble in the reaction mixture, allows heterogeneously catalyzed transesterification reactions to be carried out, which are distinguished in particular by the fact that no waste water to be disposed of is obtained.
Die im erfindungsgemäßen Verfahren eingesetzten Fette und Öle müssen vor der Umesterung entsäuert (Gehalt an freien Fettsäuren < 0,1 Gew.-%) und entwässert werden, damit gute Ergebnisse hinsichtlich der Geschwindigkeit der Umesterungsreaktion mit den Katalysatoren gemäß der Erfindung erzielt werden können.The fats and oils used in the process according to the invention have to be deacidified (content of free fatty acids <0.1% by weight) and dewatered before the transesterification, so that good results can be achieved with regard to the speed of the transesterification reaction with the catalysts according to the invention.
Gemäß einer bevorzugten Ausführungsform werden solche Katalysatoren verwendet, deren Aminosäurekomponente einen quaternären Stickstoff oder eine Guanidi- nogruppe aufweisen. Besonders bevorzugt sind Metallsalze von Arginin oder Camitin.According to a preferred embodiment, catalysts are used whose amino acid components have a quaternary nitrogen or a guanidino group. Metal salts of arginine or camitin are particularly preferred.
Die nach dem erfindungsgemäßen Verfahren bevorzugt verwendeten Metallionen sind Erdalkalimetallionen, insbesondere Calcium-, Strontium- oder Bariumionen, Schwermetallionen, insbesondere Silber-, Kupfer-, Zink-, Mangan-, Eisen-, Nickeloder Cobaltionen oder Seltenerdmetallionen, insbesondere Lanthanionen. Besonders bevorzugt sind Zink- oder Lanthanionen.The metal ions preferably used in the process according to the invention are alkaline earth metal ions, in particular calcium, strontium or barium ions, heavy metal ions, in particular silver, copper, zinc, manganese, iron, nickel or cobalt ions or rare earth metal ions, in particular lanthanum ions. Zinc or lanthanum ions are particularly preferred.
Im Rahmen der Erfindung ganz besonders bevorzugt verwendete Katalysatoren sind die Zink- oder Lanthansalze von Arginin oder Carnitin.Catalysts used with very particular preference in the context of the invention are the zinc or lanthanum salts of arginine or carnitine.
Auch Mischungen der erfindungsgemäßen Katalysatoren können in dem erfindungs- gemäßen Verfahren zum Einsatz kommen. Bei dem erfindungsgemäßen Verfahren werden die Katalysatoren in einer Menge von 5-25 Gew.-% eingesetzt, bevorzugt 10-20 Gew.-%. Das Verfahren kann aufgrund der thermischen Stabilität der Katalysatoren bei Temperaturen von etwa 60 bis 200°C durchgeführt werden, bevorzugt wird es bei Temperaturen von 100 bis 150°C durchgeführt, besonders bevorzugt bei etwa 125°C.Mixtures of the catalysts according to the invention can also be used in the process according to the invention. In the process according to the invention, the catalysts are used in an amount of 5-25% by weight, preferably 10-20% by weight. Due to the thermal stability of the catalysts, the process can be carried out at temperatures of about 60 to 200 ° C, preferably it is carried out at temperatures of 100 to 150 ° C, particularly preferably at about 125 ° C.
Das erfindungsgemäße, heterogen katalysierte Verfahren kann in diskontinuierlicher, halb- oder vollkontinuierlicher Arbeitsweise betrieben werden.The heterogeneously catalyzed process according to the invention can be operated in a batch, semi or fully continuous mode.
Die nach dem erfindungsgemäßen Verfahren vorzugsweise verwendeten Arginate, z.B. das Zinkarginat, können beispielsweise zu Pillen gepreßt und in einen Rohrreaktor eingefüllt werden. Gemäß einer anderen Verfahrensweise wird das pulverförmige, feinkristalline Metallarginat im Fett oder Öl suspendiert. Nach Durchlaufen einer Rührkesselkaskade wird der Katalysator abfiltriert oder mit einer Zentrifuge abge- trennt und rezirkuliert.The arginates preferably used in the process according to the invention, e.g. the zinc arginate, for example, can be pressed into pills and filled into a tubular reactor. According to another procedure, the powdery, finely crystalline metal arginate is suspended in the fat or oil. After passing through a stirred tank cascade, the catalyst is filtered off or separated off with a centrifuge and recirculated.
Der erfindungsgemäße Katalysator kann auch auf einen geeigneten Träger aufgetragen werden, um die hydrodynamischen Bedingungen in einem kontinuierlich arbeitenden Reaktor zu verbessern. Auf diese Weise erübrigt sich eine Abtrennung des pulverförmigen Katalysators aus den Produkten durch Filtration. Der Träger kann dabei zylinderförmig ausgebildet sein oder jede andere für den kontinuierlichen Ablauf der Reaktion günstige Form haben. Eine hohe Porosität ist von Nutzen, sofern die Formstabilität des Kontaktes darunter nicht zu sehr leidet.The catalyst according to the invention can also be applied to a suitable support in order to improve the hydrodynamic conditions in a continuously operating reactor. In this way, there is no need to separate the powdery catalyst from the products by filtration. The carrier can be cylindrical or any other shape that is favorable for the continuous course of the reaction. A high porosity is useful if the shape stability of the contact does not suffer too much.
Zudem betrifft die Erfindung auch Fett und/oder Öl biologischen Ursprungs, das nach dem vorstehend erläuterten Verfahren hergestellt wird. Dieses erfindungsgemäße Fett und/oder Öl weist eine andere Fettsäureverteilung als das entsprechende Ausgangsmaterial auf, und wird sich in der Regel auch durch neue Materialeigenschaften wie z.B. Schmelzpunkt oder Viskosität vom Ausgangsmaterial unterscheiden. Die beigefügte, einzige Figur zeigt graphisch die Änderung der Fettsäureverteilung nach der Umesterung.In addition, the invention also relates to fat and / or oil of biological origin, which is produced by the method explained above. This fat and / or oil according to the invention has a different fatty acid distribution than the corresponding starting material, and is usually also characterized by new material properties such as Distinguish melting point or viscosity from the starting material. The attached single figure shows graphically the change in the fatty acid distribution after the transesterification.
Nachfolgend wird das erfindungsgemäße Verfahren anhand von Bespielen näher erläutert. Beispiel 1The method according to the invention is explained in more detail below on the basis of examples. example 1
In Figur 1 ist am Beispiel einer Mischung aus Sonnenblumenöl und Kokosnußöl im Verhältnis 1:1 gezeigt, daß in Anwesenheit von Zinkarginat in Pulverform (5 Gew.-%) als Katalysator bei 125°C im Verlauf von 8 Stunden eine merkliche Verschiebung im Triglyceridspektrum entstanden ist. Dabei ist die Änderung einer Peakfläche inIn FIG. 1 using the example of a mixture of sunflower oil and coconut oil in a ratio of 1: 1, it is shown that in the presence of zinc arginate in powder form (5% by weight) as a catalyst, a noticeable shift in the triglyceride spectrum occurred at 125 ° C. in the course of 8 hours is. The change of a peak area is in
Prozent in Abhängigkeit von der Retentionszeit aufgetragen. Die Retentionszeit von 32 Minuten entspricht Tripalmitin, die von 34,3 Minuten entspricht Tristearin und Triolein. Die Peaks von Tristearin und Triolein überlappen stark.Percent plotted depending on the retention time. The retention time of 32 minutes corresponds to tripalmitin, that of 34.3 minutes corresponds to tristearin and triolein. The peaks of tristearin and triolein strongly overlap.
Beispiel 2Example 2
100 g Schweineschmalz wurden bei 125°C mit 0,5 g pulverförmigem Zinkarginat vermischt und etwa 3 Stunden lang gerührt. Danach wurde der Katalysator abfiltriert. Die Zusammensetzung des Fettes wurde gaschromatographisch untersucht. In der Tabelle 1 ist die Zusammensetzung des Fettes vor und nach der katalytischen Umesterung als Funktion der Retentionszeit wiedergegeben.100 g of pork lard were mixed with 0.5 g of powdered zinc arginate at 125 ° C. and stirred for about 3 hours. The catalyst was then filtered off. The composition of the fat was examined by gas chromatography. Table 1 shows the composition of the fat before and after the catalytic transesterification as a function of the retention time.
Tabelle 1Table 1
Zusammensetzung der Fette vor und nach der Umesterung in Abhängigkeit von der Retentionszeit in % der PeakflächeComposition of the fats before and after the transesterification depending on the retention time in% of the peak area
Die Retentionszeit von 32,0 Minuten entspricht der Komponente Tripalmitin, die von 34,1 Minuten der Komponente Tristearin. Die Erweichungstemperatur des Schmalzes hatte sich geringfügig um etwa 1°C erhöht. The retention time of 32.0 minutes corresponds to the tripalmitin component, that of 34.1 minutes to the tristearin component. The softening temperature of the lard had increased slightly by about 1 ° C.

Claims

Patentansprüche claims
1. Verfahren zur Herstellung von Fett und/oder Öl mit geänderter Fettsäureverteilung in den Glyceriden durch heterogen katalysierte Umesterung, wobei das Verfahren aus der Umsetzung des umzuesternden Fetts und/oder Öls biologischen Ursprungs in Gegenwart eines Katalysators besteht, der ein Metallsalz einer basischen Aminosäure oder eines Aminosäurederivates enthält.1. A process for the preparation of fat and / or oil with a modified fatty acid distribution in the glycerides by heterogeneously catalyzed transesterification, the process consisting of reacting the fat and / or oil of biological origin to be transesterified in the presence of a catalyst which is a metal salt of a basic amino acid or contains an amino acid derivative.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Metallkomponente des Katalysators Calcium, Strontium, Barium, ein anderes Erdalkalimetall, oder ein Schwermetall ist, insbesondere Silber, Kupfer, Zink, Mangan, Eisen, Nickel, Cobalt, Lanthan oder ein anderes Seltenerdmetall.2. The method according to claim 1, characterized in that the metal component of the catalyst calcium, strontium, barium, another alkaline earth metal, or a heavy metal, in particular silver, copper, zinc, manganese, iron, nickel, cobalt, lanthanum or another rare earth metal ,
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß als Aminosäurekomponente des Katalysators quaternä- rer Stickstoff oder eine Guanidingruppe verwendet wird.3. The method according to claim 1 or 2, characterized in that quaternary nitrogen or a guanidine group is used as the amino acid component of the catalyst.
4. Verfahren nach einem einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß als Katalysator das Zink- oder Lanthansalz des Arginins verwendet wird.4. The method according to any one of claims 1 to 3, characterized in that the zinc or lanthanum salt of arginine is used as a catalyst.
5. Verfahren nach einem einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß als Katalysator das Zink- oder Lanthansalz des Carni- tins verwendet wird.5. The method according to any one of claims 1 to 3, characterized in that the zinc or lanthanum salt of carnitine is used as a catalyst.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der Katalysator auf einen Träger aufgebracht ist.6. The method according to any one of claims 1 to 5, characterized in that the catalyst is applied to a support.
7. Verfahren nach einem einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Umesterung bei Temperaturen im Bereich von 60 bis 200°C durchgeführt wird, insbesondere im Bereich von 100 bis 150°C. 7. The method according to any one of claims 1 to 6, characterized in that the transesterification is carried out at temperatures in the range from 60 to 200 ° C, in particular in the range from 100 to 150 ° C.
8. Verfahren nach einem einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Menge an Katalysator 5 bis 25 Gew.-% beträgt, insbesondere 10 bis 20 Gew.-%.8. The method according to any one of claims 1 to 7, characterized in that the amount of catalyst is 5 to 25 wt .-%, in particular 10 to 20 wt .-%.
9. Fett und/oder Öl, hergestellt nach einem Verfahren gemäß einem der vorhergehenden Ansprüche. 9. fat and / or oil, produced by a method according to any one of the preceding claims.
EP02792891A 2002-01-09 2002-12-04 Method for transesterifying fat and/or oil by heterogeneous catalysis Withdrawn EP1465969A1 (en)

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