EP0127104A1 - Process for the preparation of fatty-acid esters of short chain aliphatic alcohols from free fatty-acid-containing fats and/or oils - Google Patents

Process for the preparation of fatty-acid esters of short chain aliphatic alcohols from free fatty-acid-containing fats and/or oils Download PDF

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EP0127104A1
EP0127104A1 EP84105794A EP84105794A EP0127104A1 EP 0127104 A1 EP0127104 A1 EP 0127104A1 EP 84105794 A EP84105794 A EP 84105794A EP 84105794 A EP84105794 A EP 84105794A EP 0127104 A1 EP0127104 A1 EP 0127104A1
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Prior art keywords
esterification
oil phase
phase
entrainer
acid
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EP0127104B1 (en
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Herbert Dr. Lepper
Lothar Friesenhagen
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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

Definitions

  • Fatty acid esters of short-chain aliphatic alcohols are of great technical importance. They are important starting materials for the production of fatty alcohols, for example, but are also used to obtain other oleochemical products such as soaps, surfactants, alkanolamides, etc.
  • fatty acid esters of lower alcohols takes place predominantly by alcoholysis of the corresponding fats and / or oils of natural origin, which are known to be fatty acid triglycerides. Vegetable and / or animal fats or oils, however, almost always contain considerable amounts of free fatty acids, and this free acid content can vary within a wide range depending on the origin of the material and its history. The free fatty acid content is almost always above 3 percent by weight.
  • the acid number of the commercially available raw coconut oil is normally not more than 10 to 20. For other vegetable oils, the acid number, especially of good qualities, is less than 10, for lower qualities it is, for example, in the range of 20 to 25.
  • Technical tallow based on its acid number evaluated and traded, the content of free fatty acids - depending on the quality - between 1 and 15 to 20 percent by weight - corresponding to an acid number of about 30 to 40 - in some cases even higher.
  • the acid number of the triglyceride to be used in the transesterification influences the possibilities or process conditions of the transesterification reaction to a considerable extent.
  • the BRADSHAW process used in technology uses e.g. B. the alkali-catalyzed transesterification of fats, the SZ of which should not exceed 1.5, with methyl alcohol as the 1st stage of a continuous soap production - see, for example, Ullmann, Encyclopedia of Industrial Chemistry, 3rd edition, volume 7, page 525 ff .; 4th edition, volume 11, page 490 ff.
  • the pressure-free transesterification - which is energetically advantageous due to the lower temperatures and the significantly lower methanol requirement and does not require pressure reactors - reduces the SZ - e.g. B. by preceding conversion of the free fatty acids into the corresponding alkyl or glycerol esters - in advance.
  • this pre-esterification can be carried out alkali-catalyzed at 240 ° C. and 20 bar. In this case too, expensive pressure reactors must be used for the pre-esterification with methanol and other short-chain alcohols.
  • the invention has for its object to facilitate the production of fatty acid esters of lower monoalcohols when using such triglyceride starting materials that contain not inconsiderable amounts of free fatty acids. Based on the combination of a pre-esterification of the free acids with subsequent transesterification, both process stages should be able to be carried out at comparatively low temperatures and without using reactors designed for higher pressures. In addition, it should be possible to reduce the high excess of alcohol required, for example, in pressure transesterification, which is a cost factor that should not be underestimated due to the necessary reprocessing and cleaning steps. Overall, the invention thus aims to realize the production of fatty acid esters of lower alcohols in an energy-saving and cost-effective manner, especially with starting materials such as those obtained in the context of natural, in particular vegetable and / or animal fats and / or oils.
  • the invention proposes a process for the preparation of fatty acid esters of short-chain aliphatic alcohols by catalytic transesterification of fats and / or oils containing free fatty acids (oil phase) with the corresponding monoalcohols, which is characterized in that the oil phase in the presence of acidic esterification catalysts Temperatures not exceeding 120 ° C and pressures not exceeding 5 bar and in the presence of a liquid entraining agent which is essentially immiscible with the oil phase are subjected to a pre-esterification with the monoalcohols, then phase separation into an entraining agent phase containing the acidic catalyst and water of reaction and the treated oil phase separates, and this oil phase of the transesterification, while the catalyst-containing entrainer phase is returned to the pre-esterification stage after at least partial drying.
  • the acid number of natural, vegetable and / or animal fats and / or oils can vary within a wide range.
  • the SZ of commercially available raw coconut oil is normally not more than 10 to 20.
  • the SZ is below 10 for good qualities, for example in the range of 20 to 25 for lower qualities, which are evaluated and treated according to the SZ , are in the content of free fatty acids, depending on the quality, between 1 and 15 to 20 weight percent - d. H. with acid numbers up to, for example, 30 to 40 - but sometimes even higher.
  • Starting materials with SZ up to 60 or even above can be used in the process according to the invention.
  • the first step of the process according to the invention consists in an esterification of the free fatty acids contained in the triglyceride, accelerated by acid catalysts, with the short-chain monoalcohol.
  • Preferred monoalcohols are C1 to C4 - mono-alcohols and in particular methanol.
  • the monoalcohol, which is also to be used in the subsequent transesterification stage, is expediently already used in this stage of the pre-esterification.
  • This pre-esterification stage takes place according to the invention in the presence of the method described conditions liquid entrainer instead, which is essentially immiscible with the oil phase.
  • esterification conditions are chosen such that transesterification of the triglycerides with the monoalcohol does not take place or does not occur to any significant extent.
  • the pre-esterification can be carried out, for example, at temperatures from 40 to 120.degree. C., preferably at 50 to 100.degree. C., working without pressure or at best with slightly elevated pressures, which are generally not above 5 bar. The use of pressure reactors is therefore not necessary here.
  • Suitable entraining agents are in particular sufficiently high-boiling polyfunctional alcohols and / or their ethers or partial ethers which are liquid at 50 ° C. and preferably already at room temperature. Accordingly, suitable liquid entraining agents are, for example, ethylene glycol, propylene glycol, polyethylene glycols, glycol ethers, for example propyl glycol, or diglycol ethers such as methyl diglycol.
  • suitable liquid entraining agents are, for example, ethylene glycol, propylene glycol, polyethylene glycols, glycol ethers, for example propyl glycol, or diglycol ethers such as methyl diglycol.
  • glycerin is particularly suitable as a liquid entrainer. Glycerin is released anyway in the subsequent stage of the transesterification. The choice of glycerin as an entrainer in the first stage of the process thus brings understandable further process simplifications.
  • the entrainer serves in particular as a liquid carrier for the acid catalyst in the first stage (pre-esterification).
  • All acidic, non-volatile esterification catalysts are basically suitable, for example So corresponding systems based on Lewis acids, low volatile inorganic acids and / or their acidic partial esters, heteropolyacids and the like.
  • a particularly suitable class of acidic catalysts are organic sulfonic acids, which can be described, for example, by the general formula RSO3H, where R represents an alkyl, aryl or alkaryl radical.
  • suitable sulfonic acids are methanesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid or alkylbenzenesulfonic acid.
  • sulfuric acid or its half-ester can be used as the non-volatile inorganic acid.
  • Suitable heteropolyacids are, for example, the tungstic or the molybdate phosphoric acids.
  • the reaction of the free fatty acids with the monoalcohols takes place as the fastest reaction under the conditions of the pre-esterification stage chosen according to the invention, so that not only the transesterification of the triglycerides with the monoalcohol but also the reaction of the free fatty acids with the glycerol used as entrainer does not or not to any appreciable extent entry.
  • glycerol is only very slightly soluble in triglycerides under the chosen reaction conditions.
  • the acidic esterification catalysts and the reaction formed during the esterification dissolve onswasser much better in glycerin than in triglycerides.
  • the result of this is that after the esterification, virtually the entire amount of the esterification catalyst used and the water of reaction formed are in the glycerol phase. Accordingly, the oil phase is practically free of acid catalyst and water of reaction, both of which would interfere with the further reaction in the subsequent alkali-catalyzed reaction.
  • the catalyst-containing glycerol phase can be freed from water of reaction and, if desired, from excess alcohol after it has been discharged from the first process stage, so that the catalyst-containing glycerol phase can be recycled to the pre-esterification stage.
  • the glycerin - or rather the entrainer which is not miscible with the oil phase - thus serves practically as a liquid carrier substance for the catalyst used and discharges the water of reaction formed in the first process stage from the oil phase.
  • the amount of acid catalyst used in the pre-esterification influences the speed of this pre-esterification within certain limits. Because fiction according to which the catalyst can be recovered and recycled practically quantitatively in a simple manner, a restriction of the amount of catalyst is not necessary for reasons of cost. In general, amounts of catalyst in the range from 0.5 to 5.0 percent by weight, based on the oil phase used, will be used. However, the use of smaller or larger quantities is not excluded.
  • the amount of entrainer is also hardly influenced by cost considerations, since the entrainer is recovered and recycled practically quantitatively. However, the following point of view is important:
  • the amount of entrainer - e.g. glycerin - must be coordinated with the amount of monofunctional alcohol used in the pre-esterification so that after the pre-esterification there is a sufficient difference in density between the oil phase and the entrainer phase for a satisfactory phase separation is present.
  • a characteristic density value for the oil phase is, for example, 0.88.
  • the density of methanol is 0.79 and that of glycerin is 1.25. Methanol and glycerin are homogeneously miscible, water of reaction and acid catalyst additionally complicate this phase.
  • the two-phase reaction product from the pre-esterification will have the oil phase as the upper phase and the entrainer phase as the lower phase.
  • simple preliminary tests can be used to determine which mixing ratios of monoalcohol and entrainer, in particular glycerol, are particularly useful to facilitate the phase separation after completion of the pre-esterification.
  • the following mixing ratios are preferably used: for 100 parts by volume of oil phase, 5 to 50 parts by volume, in particular 5 to 25 parts by volume of the liquid entraining agent are usually used, while 10 to 50 parts by volume, preferably 15 to 30 parts by volume, of the monoalcohol are used at the same time.
  • the amount of monoalcohol used has a positive influence on the speed and completeness of the esterification of the free fatty acids in the first stage of the process, although the solubility of the monoalcohol in the triglyceride is limited and is given as constant for a given reaction temperature. Nevertheless, it has been shown that an increase in the amount of monoalcohol results in a faster and more complete esterification of the free fatty acids. For cost reasons, however, it is advisable to limit the amount of monoalcohol in the pre-esterification, as stated, since the reprocessing of the excess alcohol is a not inconsiderable cost factor.
  • the pre-esterification can be carried out batchwise or continuously.
  • the starting materials - for example methanol, glycerol and oil phase - can be carried out in cocurrent, but also in countercurrent. If work is carried out in countercurrent, the mixture of monoalcohol and liquid entrainer is expediently counteracted to the oil phase.
  • the subsequent phase separation of the reaction product from the pre-esterification is easy to carry out due to the difference in density between the two phases. Normally, a simple settling tank can be used for this.
  • the separated oil phase (195 kg) contained 10.2 percent by weight of methanol and had an acid number of 0.8. From the sulfur content of the oil phase (26 ppm) it can be calculated - taking into account the sulfur content of the coconut oil used (12 ppm) - that more than 99% by weight of the p-toluenesulfonic acid used remained in the glycerol phase.
  • the separated glycerol phase (45 kg) contained 45 weight percent methanol, 1.3 weight percent water (0.58 kg). The latter corresponds to 92 percent by weight of the water of reaction formed in the reduction of the acid number from 12 to 0.8 by esterification.
  • the G lycerinphase was distilled to remove methanol and water. 20 kg of a 2.8 percent by weight water-containing methanol were obtained as the distillate.
  • the distillation residue of the glycerol phase (25 kg) had an acid number of 20.6. This corresponds to 99 percent by weight of the p-toluenesulfonic acid used.
  • the transesterification of the oil phase to the corresponding methyl esters was carried out with the addition of 0.35 kg sodium methylate (as a 30% solution in methanol) and 2 0 1 methanol at 60-65 ° C. It imagined two-phase reaction mixture (methyl ester phase and glycerol phase). The upper phase (methyl ester phase) was then washed with water. In the raw methyl ester thus freed from methanol and glycerol residues, the degree of conversion was determined via the content of bound glycerol. The degree of conversion of the raw methyl ester was 97%.
  • the oil phase obtained in this way had an acid number of 0.7 and a sulfur content of 28 ppm.
  • the G lycerinphase was worked up as in Example. 1
  • the activity of the recycled p-toluenesulfonic acid in the pre-esterification was still good.
  • the p-toluenesulfonic acid was recovered practically quantitatively with the glycerol phase.
  • the oil phase obtained in this pre-esterification had an acid number of 0.5. As the acid analysis showed, more than 99 percent by weight of the methanesulfonic acid used was in the glycerol phase obtained.
  • Palm oil with an acid number of 14.5 was pre-esterified analogously to Example 1, 40 1 methanol, 2 0 1 glycerol and 1.6 kg of p-toluenesulfonic acid being used per 200 liters of oil.
  • the resulting oil phase (acid number 0.7) was transesterified after separation of the glycerol phase with the addition of 0.35 kg of sodium methylate and 15.8 kg of methanol at 65 ° C.
  • the crude methyl ester worked up analogously to Example 1 contained 0.4 percent by weight of bound glycerol. The degree of conversion of the triglyceride used was 96%.
  • coconut oil with an acid number of 14 was pre-esterified with ethanol analogously to Example 1, using 200 liters of oil, 40 liters of ethanol, 1.6 kg of p-toluenesulfonic acid and instead of glycerol 20 liters of polyethylene glycol with an average molecular weight of 600.
  • the mixture was heated to 80 ° C. with stirring for about 30 minutes.
  • the acid number of the coconut oil obtained after separation of the glycerol phase was 0.9.
  • the coconut oil was then transesterified with ethanol with the addition of 0.2% by weight of KOH, based on the amount of oil used, to give coconut fatty acid ethyl ester at a temperature of 80.degree.
  • the content of the crude ethyl ester in bound glycerol was 0.7 percent by weight.
  • the conversion of coconut oil to butyl coconut fatty acid was carried out by first reacting 20 liters of coconut oil with 4 liters of butanol and 2 liters of glycerol in the presence of 0.2 kg of p-toluenesulfonic acid with stirring at 120 ° C. After cooling to 80-90 ° C., the glycerol phase was separated off. The oil phase had an acid number of 0.8 and was then transesterified with butanol in the presence of potassium hydroxide as a catalyst to give the corresponding coconut fatty acid ester with an approximately 95% degree of conversion.
  • coconut oil with an acid number of 16 was pre-esterified with methanol in such a way that 20 l of coconut oil, 4 l of methanol and 1.8 kg of polyethylene glycol of average molecular weight 3000 in the presence of 160 g of p-toluenesulfonic acid in a closed stirred tank at 100 ° C. and slightly overpressure ( approx. 2 bar) was implemented. After a reaction time of 15 minutes, the acid number of the coconut oil was 0.5. After cooling to 60 ° C, the polyethylene glycol phase was drained. The deacidified coconut oil was transesterified in the presence of 0.2 percent by weight sodium methylate with methanol at 65 ° C. with a 97% degree of conversion.

Abstract

Zur Herstellung von Fettsäureestern kurzkettiger, aliphatischer Alkohole durch katalytische Umesterung freie Fettsäuren enthaltender natürlicher Fette und/oder Öle (Ölphase) mit den entsprechenden Monoalkoholen unterwirft man die Ölphase in Gegenwart saurer Veresterungskatalysatoren bei Temperaturen nicht über 120°C und Drucken nicht über bar und in Gegenwart eines mit der Ölphase im wesentlichen nicht mischbaren flüssigen Schleppmittels einer Vorveresterung mit den Monoalkoholeri, trennt anschließend das Reaktionsprodukt in eine den sauren Katalysator und Reaktionswasser enthaltende Schleppmittelphase und die behandelte Ölphase, und führt diese Ölphase der Umesterung zu, während die katalysatorhaltige Schleppmittelphase nach wenigstens anteiliger Trocknung in die Stufe der Vorveresterung zurückgeführt wird.To produce fatty acid esters of short-chain, aliphatic alcohols by catalytic transesterification, natural fats and / or oils (oil phase) containing free fatty acids with the corresponding monoalcohols are subjected to the oil phase in the presence of acidic esterification catalysts at temperatures not above 120 ° C and pressures not above bar and in the presence a liquid entrainer, which is essentially immiscible with the oil phase, of a pre-esterification with the monoalcohols, then separates the reaction product into an entrainer phase containing the acidic catalyst and water of reaction and the treated oil phase, and leads this oil phase to the transesterification, while the catalyst-containing entrainer phase after at least partial drying is returned to the pre-esterification stage.

Description

Fettsäureester kurzkettiger aliphatischer Alkohole, insbesondere solcher mit bis zu 4 C-Atomen und insbesondere Fettsäuremethylester besitzen große technische Bedeutung. Sie sind beispielsweise wichtige Ausgangsmaterialien für die Herstellung von Fettalkoholen, werden aber auch zur Gewinnung anderer fettchemischer Produkte, beispielsweise von Seifen, Tensiden, Alkanolamiden usw. eingesetzt.Fatty acid esters of short-chain aliphatic alcohols, in particular those with up to 4 carbon atoms and in particular fatty acid methyl esters, are of great technical importance. They are important starting materials for the production of fatty alcohols, for example, but are also used to obtain other oleochemical products such as soaps, surfactants, alkanolamides, etc.

Die technische Herstellung von Fettsäureestern niederer Alkohole erfolgt überwiegend durch Alkoholyse der entsprechenden Fette und/oder Öle natürlichen Ursprungs, die bekanntlich Fettsäuretriglyceride sind. Pflanzliche und/oder tierische Fette bzw. Öle enthalten allerdings fast immer beträchtliche Mengen an freien Fettsäuren, wobei dieser Gehalt an freien Säuren je nach Ursprung des Materials und seiner Vorgeschichte in einem weiten Bereich schwanken kann. Fast immer liegt der Gehalt an freien Fettsäuren oberhalb von 3 Gewichtsprozent. Die Säurezahl des handelsüblichen rohen Kokosöls liegt normalerweise nicht über 10 bis 20. Bei anderen pflanzlichen Ölen liegt die Säurezahl, insbesondere bei guten Qualitäten, unter 10, bei minderen Qualitäten liegt sie beispielsweise im Bereich von 20 bis 25. Technische Talge, die nach ihrer Säurezahl bewertet und gehandelt werden, liegen im Gehalt an freien Fettsäuren - je nach Qualität - zwischen 1 und 15 bis 20 Gewichtsprozent- entsprechend einer Säurezahl von etwa 30 bis 40 - teilweise auch noch höher.The technical production of fatty acid esters of lower alcohols takes place predominantly by alcoholysis of the corresponding fats and / or oils of natural origin, which are known to be fatty acid triglycerides. Vegetable and / or animal fats or oils, however, almost always contain considerable amounts of free fatty acids, and this free acid content can vary within a wide range depending on the origin of the material and its history. The free fatty acid content is almost always above 3 percent by weight. The acid number of the commercially available raw coconut oil is normally not more than 10 to 20. For other vegetable oils, the acid number, especially of good qualities, is less than 10, for lower qualities it is, for example, in the range of 20 to 25. Technical tallow, based on its acid number evaluated and traded, the content of free fatty acids - depending on the quality - between 1 and 15 to 20 percent by weight - corresponding to an acid number of about 30 to 40 - in some cases even higher.

Die Säurezahl des in die Umesterung einzusetzenden Triglycerids beeinflußt die Möglichkeiten bzw. Verfahrensbedingungen der Umesterungsreaktion in beträchtlichem Ausmaß.The acid number of the triglyceride to be used in the transesterification influences the possibilities or process conditions of the transesterification reaction to a considerable extent.

Die Herstellung von Fettsäureestern durch Alkoholyse von Fetten und/oder Ölen kann dementsprechend technisch nach verschiedenen Verfahren durchgeführt werden:

  • In Gegenwart von Alkalikatalysatoren können Neutralfette schon bei Temperaturen von 30 bis 70 °C mit einem 50 bis 100 prozentigen Überschuß über die stöchiometrisch erforderliche Menge Alkohol glatt in die entsprechenden Alkylester umgewandelt werden. Hierbei sind allerdings nur solche Fette und Öle problemlos umzusetzen, deren Gehalt an freien Fettsäuren möglichst-unter 0,5 Gewichtsprozent liegt, entsprechend einer Säurezahl (SZ) der Triglyceride von etwa 1 und weniger.
Accordingly, the production of fatty acid esters by alcoholysis of fats and / or oils can be carried out industrially using various processes:
  • In the presence of alkali catalysts, neutral fats can be converted smoothly into the corresponding alkyl esters at temperatures of 30 to 70 ° C. with a 50 to 100 percent excess over the stoichiometrically required amount of alcohol. However, only fats and oils with a free fatty acid content of less than 0.5 percent by weight, corresponding to an acid number (SZ) of the triglycerides of about 1 or less, can be easily converted.

Das in der Technik angewandte BRADSHAW-Verfahren benutzt z. B. die alkalikatalysierte Umesterung von Fetten, deren SZ nicht über 1,5 liegen soll, mit Methylalkohol als 1. Stufe einer kontinuierlichen Seifenherstellung - vergl. beispielsweise Ullmann, Enzyklopädie der technischen Chemie, 3. Auflage, Band 7, Seite 525 ff.; 4. Auflage, Band 11, Seite 490 ff.The BRADSHAW process used in technology uses e.g. B. the alkali-catalyzed transesterification of fats, the SZ of which should not exceed 1.5, with methyl alcohol as the 1st stage of a continuous soap production - see, for example, Ullmann, Encyclopedia of Industrial Chemistry, 3rd edition, volume 7, page 525 ff .; 4th edition, volume 11, page 490 ff.

Nach einem anderen technischen Verfahren - siehe Ullmann aa0. 4. Auflage, Band 11, Seite 432 - können auch Fette und Öle mit höheren Säurezahlen umgeestert werden. Bei diesem Verfahren wird jedoch die Herstellung von Fettsäuremethylestern in Gegenwart von Alkli- oder Zink-Katalysatoren bei 240 °C unter erhöhtem Druck (ca. 100 bar) mit deutlichem Methanolüberschuß (7 bis 8facher molarer Überschuß) durchgeführt.According to another technical process - see Ullmann aa0. 4th edition, volume 11, page 432 - fats and oils with higher acid numbers can also be transesterified. However, this process involves the production of fat Acid methyl esters in the presence of alkali or zinc catalysts at 240 ° C under increased pressure (about 100 bar) with a clear excess of methanol (7 to 8 times molar excess).

Wegen des fast immer vorliegenden beträchtlichen Gehaltes an freien Fettsäuren in technischen Fetten und Ölen natürlichen Ursprungs, setzt die drucklose Umesterung - die wegen der niedrigeren Temperaturen und des deutlich geringeren Methanolbedarfs energetisch vorteilhaft ist und ohne Druckreaktoren auskommt - eine Verringerung der SZ - z. B. durch vorhergehende Umwandlung der freien Fettsäuren in die entsprechenden Alkyl- oder Glycerinester - voraus.Because of the almost always present considerable amount of free fatty acids in technical fats and oils of natural origin, the pressure-free transesterification - which is energetically advantageous due to the lower temperatures and the significantly lower methanol requirement and does not require pressure reactors - reduces the SZ - e.g. B. by preceding conversion of the free fatty acids into the corresponding alkyl or glycerol esters - in advance.

Diese Vorveresterung kann gemäß Ullmann aa0, 4. Auflage, Band 11, Seite 432 alkalikatalysiert bei 240 °C und 20 bar durchgeführt werden. Auch in diesem Fall müssen bei der Vorveresterung mit Methanol und anderen kurzkettigen Alkoholen teure Druckreaktoren verwendet werden.According to Ullmann aa0, 4th edition, volume 11, page 432, this pre-esterification can be carried out alkali-catalyzed at 240 ° C. and 20 bar. In this case too, expensive pressure reactors must be used for the pre-esterification with methanol and other short-chain alcohols.

Der Erfindung liegt die Aufgabe zugrunde, die Herstellung von Fettsäureestern niederer Monoalkohole beim Einsatz solcher Triglycerid-Ausgangsmaterialien zu erleichtern, die nicht unbeträchtliche Mengen an freien Fettsäuren enthalten. Ausgehend von der Kombination einer Vorveresterung der freien Säuren mit anschließender Umesterung, sollen beide Verfahrensstufen bei vergleichsweise niedrigen Temperaturen und ohne Verwendung von für höhere Drucke ausgelegten Reaktoren durchgeführt werden können. Darüber hinaus soll der beispielsweise in der Druckumesterung erforderliche hohe Alkoholüberschuß reduziert werden können, der über die notwendigen Aufarbeitungs-und-Reinigungssehritte einen nicht zu unterschätzenden Kostenfaktor darstellt. Insgesamt will die Erfindung damit die Herstellung von Fettsäureestern niederer Alkohole energiesparend und kostengünstig, gerade auch mit solchen Ausgangsmaterialien, verwirklichen, wie sie im Rahmen natürlicher, insbesondere pflanzlicher und/oder tierischer Fette und/oder Öle anfallen.The invention has for its object to facilitate the production of fatty acid esters of lower monoalcohols when using such triglyceride starting materials that contain not inconsiderable amounts of free fatty acids. Based on the combination of a pre-esterification of the free acids with subsequent transesterification, both process stages should be able to be carried out at comparatively low temperatures and without using reactors designed for higher pressures. In addition, it should be possible to reduce the high excess of alcohol required, for example, in pressure transesterification, which is a cost factor that should not be underestimated due to the necessary reprocessing and cleaning steps. Overall, the invention thus aims to realize the production of fatty acid esters of lower alcohols in an energy-saving and cost-effective manner, especially with starting materials such as those obtained in the context of natural, in particular vegetable and / or animal fats and / or oils.

Zur Lösung dieser Aufgabe schlägt die Erfindung ein Verfahren zur Herstellung von Fettsäureestern kurzkettiger aliphatischer Alkohole durch katalytische Umesterung freie Fettsäuren enthaltender Fette und/oder Öle (Olphase) mit den entsprechenden Monoalkoholen vor, das dadurch gekennzeichnet ist, daß man die Ölphase in Gegenwart saurer Veresterungskatalysatoren bei Temperaturen nicht über 120 °C und Drucken nicht über 5 bar und in Gegenwart eines mit der Ölphase im wesentlichen nicht mischbaren flüssigen Schleppmittels einer Vorveresterung mit den Monoalkoholen unterwirft, anschließend das Reaktionsprodukt durch Phasentrennung in eine den sauren Katalysator und Reaktionswasser enthaltende Schleppmittelphase und die behandelte Ölphase trennt, und diese Ölphase der Umesterung zuführt, während die katalysatorhaltige Schleppmittelphase nach wenigstens anteiliger Trocknung in die Stufe der Vorveresterung zurückgeführt wird.To achieve this object, the invention proposes a process for the preparation of fatty acid esters of short-chain aliphatic alcohols by catalytic transesterification of fats and / or oils containing free fatty acids (oil phase) with the corresponding monoalcohols, which is characterized in that the oil phase in the presence of acidic esterification catalysts Temperatures not exceeding 120 ° C and pressures not exceeding 5 bar and in the presence of a liquid entraining agent which is essentially immiscible with the oil phase are subjected to a pre-esterification with the monoalcohols, then phase separation into an entraining agent phase containing the acidic catalyst and water of reaction and the treated oil phase separates, and this oil phase of the transesterification, while the catalyst-containing entrainer phase is returned to the pre-esterification stage after at least partial drying.

Das erfindungsgemäße Verfahren läßt sich demgemäß durch die folgenden vier Schritte darstellen:

  • 1. Umsetzung des freie Fettsäuren enthaltenden Triglycerids mit dem kurzkettigen Monoalkohol in Gegenwart eines sauren Katalysators, jedoch unter solchen Verfahrensbedingungen, daß weitgehend selektiv die freien Fettsäuren des Einsatzmaterials in die entsprechenden Alkylester umgewandelt werden. Dabei wird in Gegenwart eines mit dem Triglycerid-Einsatzmaterial im wesentlichen nicht mischbaren unter Verfahrensbedingungen flüssigen Schleppmittels gearbeitet. In dieser Verfahrensstufe der Vorveresterung gelingt es ohne Schwierigkeiten, unter den nachstehend noch im einzelnen geschilderten, milden Bedingungen, die SZ des Triglycerids auf Werte im Bereich von 1 oder darunter herabzusetzen.
  • 2. Abtrennung der Schleppmittelphase, die praktisch die gesamte Menge des eingesetzten Katalysators und des bei der Veresterung gebildeten Reaktionswassers sowie den im Reaktionsgemisch noch vorliegenden freien Anteil des Monoalkohols enthält, aus dem zweiphasigen Reaktionsgemisch.
  • 3. Entfernung von Reaktionswasser und vorzugsweise auch dem Alkohol aus der Schleppmittelphase - bevorzugt durch Destillation - und Recyclisierung des den Katalysator enthaltenden Schleppmittels in die Stufe der Vorveresterung gemäß Ziffer 1.
  • 4. Nachfolgende Umesterung des Triglycerids mit nur noch geringem Gehalt an freier Fettsäure mit dem monofunktionellen Alkohol unter energie- und kostengünstigen Bedingungen in an sich bekannter Weise, wobei insbesondere unter Verwendung eines basischen Katalysators gearbeitet werden kann.
The method according to the invention can accordingly be represented by the following four steps:
  • 1. Implementation of the free fatty acid-containing triglyceride with the short-chain monoalcohol in the presence of an acid catalyst, but under such process conditions that the free fatty acids of the feedstock are converted largely selectively into the corresponding alkyl esters. The process is carried out in the presence of an entraining agent which is essentially immiscible with the triglyceride feedstock under process conditions. In this stage of the pre-esterification process, it is possible without difficulty to reduce the SC of the triglyceride to values in the range of 1 or less under the mild conditions described in detail below.
  • 2. Separation of the entrainer phase, which contains practically the entire amount of the catalyst used and the water of reaction formed during the esterification, and the free portion of the monoalcohol still present in the reaction mixture, from the two-phase reaction mixture.
  • 3. Removal of water of reaction and preferably also the alcohol from the entrainer phase - preferably by distillation - and recycling of the entrainer containing the catalyst in the stage of pre-esterification according to number 1.
  • 4. Subsequent transesterification of the triglyceride with only a low content of free fatty acid with the monofunctional alcohol under energy and inexpensive conditions in a manner known per se, it being possible in particular to use a basic catalyst.

Die Säurezahl natürlicher, pflanzlicher und/oder tierischer Fette und/oder Öle kann in einem weiten Bereich schwanken. So liegt die SZ des handelsüblichen rohen Kokosöls normalerweise nicht über 10 bis 20. Bei anderen pflanzlichen Ölen ist die SZ bei guten Qualitäten unterhalb 10, bei minderen Qualitäten beispielsweise im Bereich von 20 bis 25. Technische Talge, die nach der SZ bewertet und behandelt werden, liegen im Gehalt an freien Fettsäuren, je nach Qualität, zwischen 1 und 15 bis 20 Gewichtsprozent - d. h. bei Säurezahlen bis zu beispielsweise 30 bis 40 - zum Teil aber auch noch höher. So können im erfindungsgemäßen Verfahren Ausgangsmaterialien mit SZ bis 60 oder auch darüber eingesetzt werden.The acid number of natural, vegetable and / or animal fats and / or oils can vary within a wide range. The SZ of commercially available raw coconut oil is normally not more than 10 to 20. For other vegetable oils, the SZ is below 10 for good qualities, for example in the range of 20 to 25 for lower qualities, which are evaluated and treated according to the SZ , are in the content of free fatty acids, depending on the quality, between 1 and 15 to 20 weight percent - d. H. with acid numbers up to, for example, 30 to 40 - but sometimes even higher. Starting materials with SZ up to 60 or even above can be used in the process according to the invention.

Der erste Schritt des erfindungsgemäßen Verfahrens besteht in einer durch saure Katalysatoren beschleunigten Veresterung der im Triglycerid enthaltenen freien Fettsäuren mit dem kurzkettigen Monoalkohol. Bevorzugte Monoalkohole sind C1 bis C4 - Monoalkohole und insbesondere Methanol. Zweckmäßigerweise wird in dieser Stufe der Vorveresterung bereits der Monoalkohol eingesetzt, der auch in der nachfolgenden Umesterungsstufe Verwendung finden soll. Diese Vorveresterungsstufe findet erfindungsgemäß in Gegenwart des unter Verfahrensbedingungen flüssigen Schleppmittels statt, das mit der Ölphase im wesentlichen nicht mischbar ist. Dabei werden so vergleichsweise milde Veresterungsbedingungen gewählt, daß-eine Umesterung der Triglyceride mit dem Monoalkohol nicht oder in nicht wesentlichen Ausmaße stattfindet. Die Vorveresterung kann beispielsweise bei Temperaturen von 40 bis 120 °C, vorzugsweise bei 50 bis 100 °C durchgeführt werden, wobei drucklos oder mit bestenfalls schwach erhöhten Drucken gearbeitet wird, die im allgemeinen nicht oberhalb 5 bar liegen. Ein Einsatz von Druckreaktoren ist hier also nicht erforderlich.The first step of the process according to the invention consists in an esterification of the free fatty acids contained in the triglyceride, accelerated by acid catalysts, with the short-chain monoalcohol. Preferred monoalcohols are C1 to C4 - mono-alcohols and in particular methanol. The monoalcohol, which is also to be used in the subsequent transesterification stage, is expediently already used in this stage of the pre-esterification. This pre-esterification stage takes place according to the invention in the presence of the method described conditions liquid entrainer instead, which is essentially immiscible with the oil phase. In this case, comparatively mild esterification conditions are chosen such that transesterification of the triglycerides with the monoalcohol does not take place or does not occur to any significant extent. The pre-esterification can be carried out, for example, at temperatures from 40 to 120.degree. C., preferably at 50 to 100.degree. C., working without pressure or at best with slightly elevated pressures, which are generally not above 5 bar. The use of pressure reactors is therefore not necessary here.

Als Schleppmittel eignen sich insbesondere hinreichend hochsiedende, bei 50 °C und vorzugsweise auch schon bei Raumtemperatur flüssige polyfunktionelle Alkohole und/oder ihre Ether bzw. Partialether. Geeignete flüssige Schleppmittel sind dementsprechend beispielsweise Ethylenglykol, Propylenglykol, Polyethylenglykole, Glykolether, beispielsweise Propylglykol, oder Diglykolether wie Methyldiglykol. Ganz besonders eignet sich allerdings als flüssiges Schleppmittel Glycerin. Glycerin wird in der nachfolgenden Stufe der Umesterung ohnehin freigesetzt. Die Auswahl des Glycerins als Schleppmittel schon in der ersten Verfahrensstufe bringt damit verständliche weitere Verfahrensvereinfachungen.Suitable entraining agents are in particular sufficiently high-boiling polyfunctional alcohols and / or their ethers or partial ethers which are liquid at 50 ° C. and preferably already at room temperature. Accordingly, suitable liquid entraining agents are, for example, ethylene glycol, propylene glycol, polyethylene glycols, glycol ethers, for example propyl glycol, or diglycol ethers such as methyl diglycol. However, glycerin is particularly suitable as a liquid entrainer. Glycerin is released anyway in the subsequent stage of the transesterification. The choice of glycerin as an entrainer in the first stage of the process thus brings understandable further process simplifications.

Das Schleppmittel dient insbesondere als flüssiger Träger für den sauren Katalysator in der ersten Stufe (Vorveresterung). Alle sauren, nicht flüchtigen Veresterungskatalysatoren sind grundsätzlich geeignet, beispielsweise also entsprechende Systeme auf Basis von Lewis-Säuren, schwerflüchtige anorganische Säuren und/oder ihre sauren Partialester, Heteropolysäuren und dergleichen. Eine besonders geeignete Klasse der sauren Katalysatoren sind organische Sulfonsäuren, die beispielsweise durch die allgemeine Formel RSO3H beschrieben werden können, wobei R einen Alkyl-, Aryl- oder Alkarylrest darstellt. Beispiel geeigneter Sulfonsäuren sind Methansulfonsäure, Toluolsulfonsäure, Naphthalinsulfonsäure oder Alkylbenzolsulfonsäure. Als schwerflüchtige anorganische Säure kann beispielsweise Schwefelsäure oder ihr Halbester Verwendung finden. Geeignete Heteropolysäuren sind etwa die Wolframato- oder die Molybdato-Phosphorsäuren.The entrainer serves in particular as a liquid carrier for the acid catalyst in the first stage (pre-esterification). All acidic, non-volatile esterification catalysts are basically suitable, for example So corresponding systems based on Lewis acids, low volatile inorganic acids and / or their acidic partial esters, heteropolyacids and the like. A particularly suitable class of acidic catalysts are organic sulfonic acids, which can be described, for example, by the general formula RSO3H, where R represents an alkyl, aryl or alkaryl radical. Examples of suitable sulfonic acids are methanesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid or alkylbenzenesulfonic acid. For example, sulfuric acid or its half-ester can be used as the non-volatile inorganic acid. Suitable heteropolyacids are, for example, the tungstic or the molybdate phosphoric acids.

Die Reaktion der freien Fettsäuren mit den Monoalkoholen verläuft unter den erfindungsgemäß gewählten Bedingungen der Vorveresterungsstufe als schnellste Reaktion, so daß nicht nur die Umesterung der Triglyceride mit dem Monoalkohol sondern auch die Reaktion der freien Fettsäuren mit dem als Schleppmittel eingesetzten Glycerin nicht oder nicht in nennenswertem Umfang eintritt.The reaction of the free fatty acids with the monoalcohols takes place as the fastest reaction under the conditions of the pre-esterification stage chosen according to the invention, so that not only the transesterification of the triglycerides with the monoalcohol but also the reaction of the free fatty acids with the glycerol used as entrainer does not or not to any appreciable extent entry.

Dem bei der Vorveresterung zugesetzten Glycerin - oder den anderen genannten Schleppmitteln - kommt im erfindungsgemäßen Verfahren eine sehr wichtige Funktion zu: Glycerin ist unter den gewählten Umsetzungsbedingungen nur in sehr geringem Ausmaß in Triglyceriden löslich. Andererseits lösen sich die sauren Veresterungskatalysatoren sowie das bei der Veresterung gebildete Reaktionswasser sehr viel besser im Glycerin als in den Triglyceriden. Das hat zur Folge, daß nach der Veresterung praktisch die gesamte Menge des eingesetzten Veresterungskatalysators und das gebildete Reaktionswasser sich in der Glycerinphase befinden. Die Ölphase ist dementsprechend praktisch von saurem Katalysator und von Reaktionswasser frei, die beide die weitere Umsetzung in der nachfolgenden alkalikatalysierten Umsetzung stören würden.The glycerol added during the pre-esterification - or the other entraining agents mentioned - has a very important function in the process according to the invention: glycerol is only very slightly soluble in triglycerides under the chosen reaction conditions. On the other hand, the acidic esterification catalysts and the reaction formed during the esterification dissolve onswasser much better in glycerin than in triglycerides. The result of this is that after the esterification, virtually the entire amount of the esterification catalyst used and the water of reaction formed are in the glycerol phase. Accordingly, the oil phase is practically free of acid catalyst and water of reaction, both of which would interfere with the further reaction in the subsequent alkali-catalyzed reaction.

Durch einfache Destillation läßt sich die katalysatorhaltige Glycerinphase nach ihrer Ausschleusung aus der ersten Verfahrensstufe von Reaktionswasser und gewünschtenfalls von Alkoholüberschüssen befreien, so daß die katalysatorhaltige Glycerinphase im Kreislauf in die Stufe der Vorveresterung zurückgeführt werden kann. Das Glycerin - oder besser gesagt das mit der Ölphase nicht mischbare Schleppmittel - dient somit praktisch als flüssige Trägersubstanz für den eingesetzten Katalysator und schleust das in der ersten Verfahrensstufe gebildete Reaktionswasser aus der Ölphase aus.By simple distillation, the catalyst-containing glycerol phase can be freed from water of reaction and, if desired, from excess alcohol after it has been discharged from the first process stage, so that the catalyst-containing glycerol phase can be recycled to the pre-esterification stage. The glycerin - or rather the entrainer which is not miscible with the oil phase - thus serves practically as a liquid carrier substance for the catalyst used and discharges the water of reaction formed in the first process stage from the oil phase.

Unter den geschilderten milden Bedingungen der ersten Verfahrensstufe bleibt die Menge des eingesetzten und recyclisierten Schleppmittels, insbesondere Glycerins, praktisch konstant, da seine Reaktion mit den freien Fettsäuren noch nicht stattfindet.Under the mild conditions of the first process stage described, the amount of entrainer used and recycled, in particular glycerol, remains practically constant since its reaction with the free fatty acids does not yet take place.

Die in der Vorveresterung eingesetzte Menge an saurem Katalysator beeinflußt in bestimmten Grenzen die Geschwindigkeit dieser Vorveresterung. Da erfindungsgemäß der Katalysator auf einfache Weise praktisch quantitativ wiedergewonnen und zurückgeführt werden kann, Ist eine Beschränkung der Katalysatormenge aus Kostengründen nicht erforderlich. Im allgemeinen werden Katalysatormengen im Bereich von 0,5 bis 5,0 Gewichtsprozent - bezogen auf eingesetzte Olphase - verwendet werden. Die Verwendung kleinerer oder größerer Mengen ist jedoch nicht ausgeschlossen.The amount of acid catalyst used in the pre-esterification influences the speed of this pre-esterification within certain limits. Because fiction according to which the catalyst can be recovered and recycled practically quantitatively in a simple manner, a restriction of the amount of catalyst is not necessary for reasons of cost. In general, amounts of catalyst in the range from 0.5 to 5.0 percent by weight, based on the oil phase used, will be used. However, the use of smaller or larger quantities is not excluded.

Die Menge des Schleppmittels wird ebenfalls durch Kostengesichtspunkte kaum beeinflußt, da das Schleppmittel praktisch quantitativ wiedergewonnen und zurückgeführt wird. Wichtig ist allerdings der folgende Gesichtspunkt: Die Menge des Schleppmittels - also beispielsweise des Glycerins - ist mit der in der Vorveresterung eingesetzten Menge des monofunktionellen Alkohols so abzustimmen, daß im Anschluß an die Vorveresterung ein für eine zufriedenstellende Phasentrennung ausreichender Dichteunterschied zwischen der Olphase und der Schleppmittelphase vorliegt. Ein charakteristischer Dichtewert für die Ölphase ist beispielsweise 0,88. Die Dichte von Methanol beträgt 0,79 und die von Glycerin 1,25. Methanol und Glycerin sind homogen mischbar, Reaktionswasser und saurer Katalysator beschweren zusätzlich diese Phase. In der Regel wird also das zweiphasige Reaktionsprodukt aus der Vorveresterung die Olphase als obere und die Schleppmittelphase als untere Phase aufweisen. Soweit erforderlich, kann durch einfache Vorversuche festgestellt werden, welche Mischungsverhältnisse von Monoalkohol und Schleppmittel, insbesondere Glycerin, besonders zweckmäßig sind, um die Phasentrennung nach Abschluß der Vorveresterung zu erleichtern. Bevorzugt wird dabei mit den folgenden Mischungsverhältnissen gearbeitet: Auf 100 Volumenteile Ölphase kommen üblicherweise 5 bis 50 Volumenteile, insbesondere 5 bis 25 Volumenteile des flüssigen Schleppmittels zum Einsatz, während gleichzeitig 10 bis 50 Volumenteile, vorzugsweise 15 bis 30 Volumenteile des Monoalkohols eingesetzt werden.The amount of entrainer is also hardly influenced by cost considerations, since the entrainer is recovered and recycled practically quantitatively. However, the following point of view is important: The amount of entrainer - e.g. glycerin - must be coordinated with the amount of monofunctional alcohol used in the pre-esterification so that after the pre-esterification there is a sufficient difference in density between the oil phase and the entrainer phase for a satisfactory phase separation is present. A characteristic density value for the oil phase is, for example, 0.88. The density of methanol is 0.79 and that of glycerin is 1.25. Methanol and glycerin are homogeneously miscible, water of reaction and acid catalyst additionally complicate this phase. As a rule, the two-phase reaction product from the pre-esterification will have the oil phase as the upper phase and the entrainer phase as the lower phase. If necessary, simple preliminary tests can be used to determine which mixing ratios of monoalcohol and entrainer, in particular glycerol, are particularly useful to facilitate the phase separation after completion of the pre-esterification. The following mixing ratios are preferably used: for 100 parts by volume of oil phase, 5 to 50 parts by volume, in particular 5 to 25 parts by volume of the liquid entraining agent are usually used, while 10 to 50 parts by volume, preferably 15 to 30 parts by volume, of the monoalcohol are used at the same time.

Die Einsatzmenge des Monoalkohols hat dabei einen positiven Einfluß auf die Geschwindigkeit und Vollständigkeit der Veresterung der freien Fettsäuren in der ersten Verfahrensstufe, obwohl die Löslichkeit des Monoalkohols im Triglycerid begrenzt und für eine gegebene Umsetzungstemperatur als konstant vorgegeben ist. Gleichwohl hat sich gezeigt, daß durch eine Erhöhung der Menge des Monoalkohols eine schnellere und vollständigere Veresterung der freien Fettsäuren bewirkt wird. Aus Kostengründen empfiehlt es sich allerdings in der Vorveresterung die Menge des Monoalkohols - wie angegeben - nach obenhin zu begrenzen, da die Wiederaufarbeitung des überschüssigen Alkohols einen nicht unbeträchtlichen Kostenfaktor darstellt.The amount of monoalcohol used has a positive influence on the speed and completeness of the esterification of the free fatty acids in the first stage of the process, although the solubility of the monoalcohol in the triglyceride is limited and is given as constant for a given reaction temperature. Nevertheless, it has been shown that an increase in the amount of monoalcohol results in a faster and more complete esterification of the free fatty acids. For cost reasons, however, it is advisable to limit the amount of monoalcohol in the pre-esterification, as stated, since the reprocessing of the excess alcohol is a not inconsiderable cost factor.

Die Vorveresterung kann diskontinuierlich oder auch kontinuierlich durchgeführt werden. Bei der kontinuierlichen Vorveresterung können die Einsatzstoffe - beispielsweise also Methanol, Glycerin und Ölphase - im Gleichstrom, aber auch im Gegenstrom, geführt werden. Wird im Gegenstrom gearbeitet, so wird zweckmäßigerweise die Mischung von Monoalkohol und flüssigem Schleppmittel der Olphase entgegengeführt.The pre-esterification can be carried out batchwise or continuously. In the case of continuous pre-esterification, the starting materials - for example methanol, glycerol and oil phase - can be carried out in cocurrent, but also in countercurrent. If work is carried out in countercurrent, the mixture of monoalcohol and liquid entrainer is expediently counteracted to the oil phase.

Die nachfolgende Phasentrennung des Reaktionsproduktes aus der Vorveresterung ist aufgrund des Dichteunterschiedes zwischen den beiden Phasen einfach durchzuführen. Im Normalfall kann hierfür ein einfacher Absetzbehälter zur Verwendung kommen.The subsequent phase separation of the reaction product from the pre-esterification is easy to carry out due to the difference in density between the two phases. Normally, a simple settling tank can be used for this.

Die Abtrennung vom Reaktionswasser und gewünschtenfalls Alkoholüberschuß aus der Schleppmittelphase durch Destillation erfolgt in an sich bekannterWeise. Schließlich wird dann auch die Umesterung des entsäuerten vorveresterten Öls in Gegenwart eines alkalischen Katalysators nach an sich bekannter Weise vorgenommen, vergleiche hierzu den eingangs zitierten Stand der Technik.The water of reaction and, if desired, excess alcohol from the entrainer phase are separated off by distillation in a manner known per se. Finally, the transesterification of the deacidified pre-esterified oil is then carried out in the presence of an alkaline catalyst in a manner known per se, see the prior art cited at the beginning.

Die nachfolgenden Beispiele schildern einzelne bestimmte Ausführungsformen des neuen Verfahrens.The following examples describe certain specific embodiments of the new method.

Beispiel 1example 1

In einem 400 1 Rührbehälter wurden 200 1 (174kg)Kokosöl der Säurezahl 12 mit 50 1 Methanol, . 20 1 Glycerin und 1,6 kg p-Toluolsulfonsäure unter Rühren 30 Minuten lang zum Rückflußkochen erhitzt. Anschliessend wurde das Reaktionsgemisch längere Zeit bei 50 - 60°C belassen, wobei eine saubere Trennung in eine öl- und eine Glycerinphase eintrat.200 l (174 kg) of coconut oil of acid number 12 with 5 l of 1 . 2 0 1 glycerol and 1.6 kg of p-toluenesulfonic acid heated to reflux with stirring for 30 minutes. The reaction mixture was then left at 50-60 ° C. for a long time, a clean separation into an oil and a glycerol phase occurring.

Die abgetrennte ölphase (195 kg) enthielt 10,2 Gewichtsprozent Methanol und besaß eine Säurezahl von 0,8. Aus dem Schwefelgehalt der ölphase (26 ppm) läßt sich - unter Berücksichtigung des Schwefelgehaltes des eingesetzten Kokosöls (12 ppm) - errechnen, daß mehr als 99 % Gewichtsprozent der eingesetzten p-Toluolsulfonsäure in der Glycerinphase verblieben sind.The separated oil phase (195 kg) contained 10.2 percent by weight of methanol and had an acid number of 0.8. From the sulfur content of the oil phase (26 ppm) it can be calculated - taking into account the sulfur content of the coconut oil used (12 ppm) - that more than 99% by weight of the p-toluenesulfonic acid used remained in the glycerol phase.

Die abgetrennte Glycerinphase (45 kg) enthielt neben 45 Gewichtsprozent Methanol 1,3 Gewichtsprozent Wasser (0,58 kg). Letzteres entspricht 92 Gewichtsprozent des in der Reduzierung der Säurezahl von 12 auf 0,8 durch Veresterung gebildeten Reaktionswassers. Die Glycerinphase wurde destillativ von Methanol und Wasser befreit. Hierbei fielen 20 kg eines 2,8 Gewichtsprozent Wasser enthaltenden Methanols als Destillat an. Der Destillationsrückstand der Glycerinphase (25 kg) besaß eine Säurezahl von 20,6. Dies entspricht 99 Gewichtsprozent der eingesetzten p-Toluolsulfonsäure.The separated glycerol phase (45 kg) contained 45 weight percent methanol, 1.3 weight percent water (0.58 kg). The latter corresponds to 92 percent by weight of the water of reaction formed in the reduction of the acid number from 12 to 0.8 by esterification. The G lycerinphase was distilled to remove methanol and water. 20 kg of a 2.8 percent by weight water-containing methanol were obtained as the distillate. The distillation residue of the glycerol phase (25 kg) had an acid number of 20.6. This corresponds to 99 percent by weight of the p-toluenesulfonic acid used.

Die Umesterung der Ölphase zu den entsprechenden Methylestern erfolgte unter Zusatz von 0,35 kg Natriummethylat (als 30 %ige Lösung im Methanol) und von 20 1 Methanol bei 60 - 65°C. Es bildete sich ein zweiphasiges Reaktionsgemisch (Methylesterphase und Glycerinphase). Die obere Phase (Methylesterphase) wurde anschließend mit Wasser gewaschen. In dem so von Methanol- und Glycerinresten befreiten Rohmethylester wurde der Umsetzungsgrad über den Gehalt an gebundenem Glycerin bestimmt. Der Umsetzungsgrad des Rohmethylesters lag bei 97 %.The transesterification of the oil phase to the corresponding methyl esters was carried out with the addition of 0.35 kg sodium methylate (as a 30% solution in methanol) and 2 0 1 methanol at 60-65 ° C. It imagined two-phase reaction mixture (methyl ester phase and glycerol phase). The upper phase (methyl ester phase) was then washed with water. In the raw methyl ester thus freed from methanol and glycerol residues, the degree of conversion was determined via the content of bound glycerol. The degree of conversion of the raw methyl ester was 97%.

Beispiel 2Example 2

Der Destillationsrückstand der Glycerinphase, der im Beispiel 1 bei der Vorveresterung erhalten worden war, wurde zusammen mit 200 1 Kokosöl (Säurezahl = 12) und 40 1 Methanol unter Rühren und Rückfluß - ohne Zugabe von frischem Glycerin und frischem Katalysator - umgesetzt. Die so gewonnene Ölphase hatte eine Säurezahl von 0,7 und einen Schwefelgehalt von 28 ppm.The distillation residue of the glycerol phase, which had been obtained in the pre-esterification in Example 1, was reacted with 2 0 0 1 coconut oil (acid number = 12) and 4 0 1 methanol with stirring and reflux - without the addition of fresh glycerol and fresh catalyst. The oil phase obtained in this way had an acid number of 0.7 and a sulfur content of 28 ppm.

Die Glycerinphase wurde wie in Beispiel 1 aufgearbeitet. Der Rückstand der Glycerinphase (Säurezahl = 20,2) wurde in 9 folgenden Ansätzen immer wieder eingesetzt ohne weitere Zugabe von Glycerin oder Katalysator. Die Aktivität der zurückgeführten p-Toluolsulfonsäure in der Vorveresterung war unverändert gut. Die p-Toluolsulfonsäure wurde praktisch quantitativ mit der Glycerinphase zurückgewonnen.The G lycerinphase was worked up as in Example. 1 The residue of the glycerol phase (acid number = 20.2) was used again and again in 9 subsequent batches without further addition of glycerol or catalyst. The activity of the recycled p-toluenesulfonic acid in the pre-esterification was still good. The p-toluenesulfonic acid was recovered practically quantitatively with the glycerol phase.

Beispiel 3Example 3

Analog Beispiel 1 wurden im Verlauf von 30 Minuten 200 1 Kokosöl der Säurezahl 14 mit 50 1 Methanol und 20 1 Glycerin in Gegenwart von 0,8 kg Methansulfonsäure umgesetzt.Analogously to Example 1 , 200 l of coconut oil of acid number 14 were reacted with 50 l of methanol and 20 l of glycerol in the presence of 0.8 kg of methanesulfonic acid in the course of 30 minutes.

Die bei dieser Vorveresterung erhaltene ölphase besaß eine Säurezahl von 0,5. Die eingesetzte Methansulfonsäure befand sich, wie die Säureanalyse zeigte, zu mehr als 99 Gewichtsprozent in der erhaltenen Glycerinphase.The oil phase obtained in this pre-esterification had an acid number of 0.5. As the acid analysis showed, more than 99 percent by weight of the methanesulfonic acid used was in the glycerol phase obtained.

Beispiel 4Example 4

  • a) Der Einsatz von C10-C12-Alkylbenzolsulfonsäuren anstelle von p-Toluolsulfonsäure (siehe Beispiel 1) erbrachte hinsichtlich der Säurezahl der erhaltenen ölphase, der Wiedergewinnung des Katalysators, der Abtrennung des Reaktionswassers und des Umsetzungsgrades praktisch die gleichen Ergebnisse wie die mit p-Toluolsulfonsäure durchgeführten Versuche.a) The use of C 10 -C 12 alkylbenzenesulfonic acids instead of p-toluenesulfonic acid (see Example 1) gave practically the same results as those with p with regard to the acid number of the oil phase obtained, the recovery of the catalyst, the removal of the water of reaction and the degree of conversion -Toluenesulfonic acid performed experiments.
  • b) Durchaus vergleichbare Ergebnisse wurden auch erzielt, wenn als Ausgangsmaterial Rindertalg eingesetzt und im übrigen wie in Beispiel 1 gearbeitet wurde.b) Quite comparable results were also achieved if beef tallow was used as the starting material and the rest of the procedure was as in Example 1.
Beispiel 5Example 5

Palmöl der Säurezahl 14,5 wurde analog Beispiel 1 vorverestert, wobei auf 200 1 öl 40 1 Methanol, 20 1 Glycerin und 1,6 kg p-Toluolsulfonsäure eingesetzt wurden. Die hierbei erhaltene ölphase (Säurezahl 0,7) wurde nach Abtrennung der Glycerinphase unter Zusatz von 0,35kg Natriummethylat und 15,8 kg Methanol bei 65°C umgeestert. Der analog Beispiel 1 aufgearbeitete Rohmethylester enthielt 0,4 Gewichtsprozent an gebundenem Glycerin. Der Umsetzungsgrad des eingesetzten Triglycerids lag bei 96 %.Palm oil with an acid number of 14.5 was pre-esterified analogously to Example 1, 40 1 methanol, 2 0 1 glycerol and 1.6 kg of p-toluenesulfonic acid being used per 200 liters of oil. The resulting oil phase (acid number 0.7) was transesterified after separation of the glycerol phase with the addition of 0.35 kg of sodium methylate and 15.8 kg of methanol at 65 ° C. The crude methyl ester worked up analogously to Example 1 contained 0.4 percent by weight of bound glycerol. The degree of conversion of the triglyceride used was 96%.

Beispiel 6Example 6

Kokosöl der Säurezahl 14 wurde analog dem Beispiel 1 vorverestert, wobei auf 200 1 Öl 50 1 Methanol, 1,6 kg p-Toluolsulfonsäure und anstelle von Glycerin 25 1 Ethylenglykol eingesetzt wurden. Hierbei wie bei der anschließenden Umesterung unter Zusatz von Natriummethylat als Katalysator wurden praktisch gleich gute Umsetzungsgrade wie in Beispiel 1 erhalten.Coconut oil with the acid number 14 was pre-esterified analogously to Example 1, with 50 liters of methanol, 1.6 kg of p-toluenesulfonic acid and 25 liters of ethylene glycol being used instead of glycerol for 200 liters of oil. In this case, as in the subsequent transesterification with the addition of sodium methylate as a catalyst, practically the same degrees of conversion were obtained as in Example 1.

Beispiel 7Example 7

Kokosöl der Säurezahl 14 wurde mit Ethanol analog Beispiel 1 vorverestert, wobei auf 200 1 Öl 40 1 Ethanol, 1,6 kg p-Toluolsulfonsäure und anstelle von Glycerin 20 1 Polyethylenglykol der mittleren Molmasse 600 eingesetzt wurden. Das Gemisch wurde ca. 30 Min. unter Rühren auf 80°C erhitzt. Die Säurezahl des nach Abtrennung der Glycerinphase erhaltenen Kokosöls lag bei 0,9. Das Kokosöl wurde anschließend mit Ethanol unter Zusatz von 0,2 Gewichtsprozent KOH, bezogen auf die öleinsatzmenge, zu Kokosfettsäureethylester bei einer Temperatur von 80°C umgeestert. Der Gehalt des rohen Ethylesters an gebundenem Glycerin lag bei 0,7 Gewichtsprozent.Coconut oil with an acid number of 14 was pre-esterified with ethanol analogously to Example 1, using 200 liters of oil, 40 liters of ethanol, 1.6 kg of p-toluenesulfonic acid and instead of glycerol 20 liters of polyethylene glycol with an average molecular weight of 600. The mixture was heated to 80 ° C. with stirring for about 30 minutes. The acid number of the coconut oil obtained after separation of the glycerol phase was 0.9. The coconut oil was then transesterified with ethanol with the addition of 0.2% by weight of KOH, based on the amount of oil used, to give coconut fatty acid ethyl ester at a temperature of 80.degree. The content of the crude ethyl ester in bound glycerol was 0.7 percent by weight.

Beispiel 8Example 8

Die Umwandlung von Kokosöl in Kokosfettsäurebutylester wurde in der Weise durchgeführt, daß zunächst 20 1 Kokosöl mit 4 1 Butanol und 2 1 Glycerin in Gegenwart von 0,2 kg p-Toluolsulfonsäure unter Rühren bei 120°C umgesetzt wurde. Nach Abkühlen auf 80 - 90°C wurde die Glycerinphase abgetrennt. Die ölphase besaß eine Säurezahl von 0,8 und wurde anschließend mit Butanol in Gegenwart von Kaliumhydroxid als Katalysator zu dem entsprechenden Kokosfettsäureester mit einem etwa 95 %igen Umsetzungsgrad umgeestert.The conversion of coconut oil to butyl coconut fatty acid was carried out by first reacting 20 liters of coconut oil with 4 liters of butanol and 2 liters of glycerol in the presence of 0.2 kg of p-toluenesulfonic acid with stirring at 120 ° C. After cooling to 80-90 ° C., the glycerol phase was separated off. The oil phase had an acid number of 0.8 and was then transesterified with butanol in the presence of potassium hydroxide as a catalyst to give the corresponding coconut fatty acid ester with an approximately 95% degree of conversion.

Beispiel 9Example 9

Kokosöl der Säurezahl 16 wurde mit Methanol in der Weise vorverestert, daß 20 1 Kokosöl, 4 1 Methanol und 1,8 kg Polyethylenglykol der mittleren Molmasse 3000 in Gegenwart von 160 g p-Toluolsulfonsäure in einem geschlossenen Rührbehälter bei 100°C und leichtem Überdruck (ca. 2 bar) umgesetzt wurde. Nach einer Reaktionszeit von 15 Minuten lag die Säurezahl des Kokosöls bei 0,5. Nach Abkühlen auf 60°C wurde die Polyethylenglykolphase abgelassen. Das entsäuerte Kokosöl wurde in Gegenwart von 0,2 Gewichtsprozent Natriummethylat mit Methanol bei 65°C mit einem 97 %igen Umsetzungsgrad umgeestert.Coconut oil with an acid number of 16 was pre-esterified with methanol in such a way that 20 l of coconut oil, 4 l of methanol and 1.8 kg of polyethylene glycol of average molecular weight 3000 in the presence of 160 g of p-toluenesulfonic acid in a closed stirred tank at 100 ° C. and slightly overpressure ( approx. 2 bar) was implemented. After a reaction time of 15 minutes, the acid number of the coconut oil was 0.5. After cooling to 60 ° C, the polyethylene glycol phase was drained. The deacidified coconut oil was transesterified in the presence of 0.2 percent by weight sodium methylate with methanol at 65 ° C. with a 97% degree of conversion.

Beispiel 10Example 10

Die Umwandlung von Kokosöl (Säurezahl = 16) zu Kokosfettsäuremethylester wurde analog Beispiel 1 durchgeführt, wobei jedoch in der Vorveresterungsstufe Butylglykol anstelle von Glycerin eingesetzt wurde. Die hierbei und bei der nachfolgenden Umesterung erzielten Ergebnisse waren den in Beispiel 1 erhaltenen praktisch gleich.The conversion of coconut oil (acid number = 16) to coconut fatty acid methyl ester was carried out analogously to Example 1, but using butyl glycol instead of glycerol in the pre-esterification stage. The results obtained here and in the subsequent transesterification were practically the same as those obtained in Example 1.

Beispiel 11Example 11

  • a) Anstelle des in Beispiel 1 verwendeten Glycerins wurde Propylenglykol mit ebenfalls gnten Ergebnissen eingesetzt.a) Instead of the glycerol used in Example 1, propylene glycol was used with similar results.
  • b) Anstelle der in Beispiel 1 eingesetzten p-Toluolsulfonsäure wurde 98 gewichtsprozentige Schwefelsäure in einer Menge von 0,25 Gewichtsprozent, bezogen auf eingesetztes Kokosöl, als Katalysator bei der Vorveresterung eingesetzt, wobei gleich gute Ergebnisse wie in Beispiel 1 erhalten wurden. b ) Instead of the p-toluenesulfonic acid used in Example 1, 98% by weight sulfuric acid in an amount of 0.25% by weight, based on the coconut oil used, was used as the catalyst in the pre-esterification, the same results as in Example 1 being obtained.
  • c) Als saurer Katalysator für die Vorveresterung wurde anstelle von p-Toluolsulfonsäure (Beispiel 1) 12-Phosphormolybdänsäure in einer Menge von 1 Gewichtsprozent, bezogen auf eingesetztes Kokosöl, eingesetzt, wobei ebenfalls eine ausreichend gute Vorveresterung der in dem Kokosöl (Säurezahl = 16) enthaltenen freien Fettsäuren durchgeführt werden konnte.c) Instead of p-toluenesulfonic acid (Example 1), 12-phosphomolybdic acid was used as the acidic catalyst for the pre-esterification in an amount of 1 percent by weight, based on coconut oil used, with a sufficiently good pre-esterification of the coconut oil (acid number = 16) contained free fatty acids could be performed.

Claims (11)

1. Verfahren zur Herstellung von Fettsäureestern kurzkettiger, aliphatischer Alkohole durch katalytische Umesterung freie Fettsäuren enthaltender natürlicher Fette und/oder öle (ölphase) mit den entsprechenden Monoalkoholen, dadurch gekennzeichnet, daß man die ölphase in Gegenwart saurer Veresterungskatalysatoren bei Temperaturen nicht über 120°C und Drucken nicht über 5 bar und in Gegenwart eines mit der ölphase im wesentlichen nicht mischbaren flüssigen Schleppmittels einer Vorveresterung mit den Monoalkoholen unterwirft, anschließend das Reaktionsprodukt durch Phasentrennung in eine den sauren Katalysator und Reaktionswasser enthaltende Schleppmittelphase und die behandelte ölphase trennt, und diese ölphase der Umesterung zuführt, während die katalysatorhaltige Schleppmittelphase nach wenigstens anteiliger Trocknung in die Stufe der Vorveresterung zurückgeführt wird.1. Process for the preparation of fatty acid esters of short-chain, aliphatic alcohols by catalytic transesterification of natural fatty acids and / or oils (oil phase) containing free fatty acids with the corresponding monoalcohols, characterized in that the oil phase in the presence of acidic esterification catalysts at temperatures not exceeding 120 ° C. and Pressure does not exceed 5 bar and in the presence of a liquid entrainer, which is essentially immiscible with the oil phase, is subjected to a pre-esterification with the monoalcohols, then separates the reaction product by phase separation into an entrainer phase containing the acidic catalyst and water of reaction and the treated oil phase, and this oil phase to the transesterification feeds, while the catalyst-containing entrainer phase after at least partial drying is returned to the pre-esterification stage. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man in der Stufe der Vorveresterung die Säurezahl der behandelten ölphase auf Werte unterhalb 1 senkt.2. The method according to claim 1, characterized in that the acid number of the treated oil phase is reduced to values below 1 in the pre-esterification stage. 3. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, daß man als Schleppmittel hochsiedende., bei 50°C und vorzugsweise auch schon bei Raumtemperatur flüssige polyfunktionelle Alkohole und/oder ihre Ether bzw. Partialether einsetzt.3. The method according to claim 1 and 2, characterized in that one uses high-boiling,. At 50 ° C and preferably already at room temperature liquid polyfunctional alcohols and / or their ethers or partial ethers. 4. Verfahren nach Ansprüchen 1 - 3, dadurch gekennzeichnet, daß man als Schleppmittel Glycerin einsetzt.4. Process according to Claims 1-3, characterized in that glycerol is used as entrainer. 5. Verfahren nach Ansprüchen 1 - 4, dadurch gekennzeichnet, daß die Vorveresterung bei Temperaturen von 40 - 120°C, vorzugsweise bei 50 - 100°C, und vorzugsweise unter Normaldruck durchgeführt wird.5. Process according to claims 1-4, characterized in that the pre-esterification is carried out at temperatures of 40-120 ° C, preferably at 50-100 ° C, and preferably under normal pressure. 6. Verfahren nach Ansprüchen 1 - 5, dadurch gekennzeichnet, daß als saurer Katalysator der Vorveresterungsstufe schwerflüchtige Säuren, insbesondere aliphatische und/oder aromatische Sulfonsäuren, eingesetzt werden.6. Process according to Claims 1-5, characterized in that non-volatile acids, in particular aliphatic and / or aromatic sulfonic acids, are used as the acid catalyst of the pre-esterification stage. 7. Verfahren nach Ansprüchen 1 - 6, dadurch gekennzeichnet, daß das Schleppmittel und insbesondere das Mischungsverhältnis Schleppmittel/Monoalkohol derart gewählt werden, daß ein zur zügigen Phasentrennung hinreichender Dichteunterschied zwischen ölphase und Monoalkohol enthaltender Schleppmittelphase besteht.7. The method according to claims 1-6, characterized in that the entrainer and in particular the mixture ratio of entrainer / monoalcohol are chosen such that there is a sufficient difference in density between the oil phase and monoalcohol-containing entrainer phase for rapid phase separation. 8. Verfahren nach Ansprüchen 1 - 7, dadurch gekennzeichnet, daß auf 100 Volumenteile ölphase 5 - 50 Volumenteile, vorzugsweise 5 - 25 Volumenteile, des flüssigen Schleppmittels und 10 - 50 Volumenteile, vorzugsweise 15 - 30 Volumenteile, des Monoalkohols eingesetzt werden.8. The method according to claims 1-7, characterized in that 5 to 50 parts by volume, preferably 5 to 25 parts by volume, of the liquid entrainer and 10 to 50 parts by volume, preferably 15 to 30 parts by volume, of the monoalcohol are used per 100 parts by volume of the oil phase. 9. Verfahren nach Ansprüchen 1 - 8, dadurch gekennzeichnet, daß auch die nachfolgende Umesterung der Glyceride mit den Monoalkoholen bei Temperaturen unterhalb 120 C - vorzugsweise bei Temperaturen von 50 - 100°C - und Drucken unterhalb 5 bar - vorzugsweise bei Normaldruck - durchgeführt wird, wobei zweckmäßigerweise unter basischer Katalyse gearbeitet wird.9. The method according to claims 1-8, characterized in that the subsequent transesterification of the glycerides with the monoalcohols at temperatures below half 120 C - preferably at temperatures of 50 - 100 ° C - and pressures below 5 bar - preferably at normal pressure - is carried out, expediently under basic catalysis. 10. Verfahren nach Ansprüchen 1 - 9, dadurch gekennzeichnet, daß C1 - C4-Monoalkohole und insbesondere Methanol eingesetzt werden.10. The method according to claims 1-9, characterized in that C 1 - C 4 monoalcohols and in particular methanol are used. 11. Verfahren nach Ansprüchen 1 - 10, dadurch gekennzeichnet, daß als ölphase technische Fette und/oder öle, insbesondere natürlichen Ursprungs, mit Säurezahlen bis 60 oder auch darüber eingesetzt werden, wobei in der Stufe der Vorveresterung eine praktisch selektive Umsetzung des freien Fettsäureanteils zu entsprechenden Estern niederer aliphatischer Alkohole bewirkt wird.11. The method according to claims 1-10, characterized in that technical fats and / or oils, in particular of natural origin, with acid numbers up to 60 or above are used as the oil phase, with a practically selective conversion of the free fatty acid portion to in the stage of pre-esterification corresponding esters of lower aliphatic alcohols is effected.
EP84105794A 1983-05-30 1984-05-21 Process for the preparation of fatty-acid esters of short chain aliphatic alcohols from free fatty-acid-containing fats and/or oils Expired EP0127104B1 (en)

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0184740A2 (en) * 1984-12-08 1986-06-18 Henkel Kommanditgesellschaft auf Aktien Process for the preparation of methyl esters of fatty acids
FR2577569A1 (en) * 1985-02-15 1986-08-22 Inst Francais Du Petrole PROCESS FOR THE PRODUCTION OF A COMPOSITION OF FATTY ACID ESTERS AS FUEL FOR SUBSTITUTING GASOLINE WITH HYDRATED ETHYL ALCOHOL AND COMPOSITION OF ESTERS THUS FORMED
WO1993001263A1 (en) * 1991-07-08 1993-01-21 Henkel Kommanditgesellschaft Auf Aktien Method of preparing lower-alkyl esters of fatty acids
EP0535290A1 (en) * 1991-09-02 1993-04-07 Primavesi, Markus Process and apparatus for continuous production of fatty acid esters
WO1993009212A1 (en) * 1991-11-06 1993-05-13 Theodor Wimmer Process for preparing fatty acid esters of short-chain monohydric alcohols
WO1995002662A1 (en) * 1993-07-14 1995-01-26 Idaho Research Foundation, Inc. Method for purifying alcohol esters
WO1995013343A1 (en) * 1993-11-08 1995-05-18 Henkel Kommanditgesellschaft Auf Aktien Method of producing lower-alkyl esters of fatty acids
EP1308498A1 (en) * 2001-11-06 2003-05-07 Cognis Deutschland GmbH & Co. KG Method for the production of fatty acid esters from non-deacidified fats and oils
WO2004029016A1 (en) * 2002-09-20 2004-04-08 Oelmühle Leer Connemann Gmbh & Co. Method and device for producing biodiesel
WO2004085585A1 (en) * 2003-03-28 2004-10-07 Korea Institute Of Energy Research Manufacturing method of bio-diesel oil
EP1565424A1 (en) * 2002-11-27 2005-08-24 Biodiesel Australia Ltd Method for production of alkyl esters
US6960673B2 (en) 2000-12-04 2005-11-01 Westfalia Separator Ag Method for pretreating crude oils and raw fats for the production of fatty acid esters
US7256301B2 (en) 2002-04-12 2007-08-14 Energea Umwelttechnologie Gmbh Method and system for the esterification of fatty acids
EP2000522A1 (en) 2007-05-30 2008-12-10 Petroleo Brasileiro S.A. Petrobras Method for the production of biodiesel from vegetable oils and fats, using heterogeneous catalysts
US7540952B2 (en) 2005-07-07 2009-06-02 Petroleo Brasileiro S.A. - Petrobras Catalytic cracking process for the production of diesel from vegetable oils
WO2009123369A1 (en) 2008-04-01 2009-10-08 Sk Chemicals Co., Ltd. Method for preparing fatty acid alkyl ester using fatty acid
WO2010053258A2 (en) 2008-11-07 2010-05-14 에스케이케미칼 주식회사 Method and apparatus for preparing alkyl ester fatty acid using fatty acid
WO2011008058A2 (en) 2009-07-17 2011-01-20 한국과학기술원 Method for producing fatty acid alkyl esters using microorganisms having oil-producing ability
WO2012054946A1 (en) 2010-10-28 2012-05-03 Theodor Wimmer Method for producing fatty acid esters of lower alcohols
WO2015012538A1 (en) 2013-07-22 2015-01-29 에스케이케미칼 주식회사 Method for preparing fatty acid alkyl ester using fat
US9085746B2 (en) 2011-05-13 2015-07-21 Cognis Ip Management Gmbh Process for obtaining oleochemicals with reduced content of by-products
EP2358851B2 (en) † 2008-11-17 2018-01-10 Basf Se Use of methanesulfonic acid for producing fatty acid esters
WO2018015191A1 (en) 2016-07-18 2018-01-25 Basf Se Low corrosion alkane sulfonic acids for condensation reactions

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3501761A1 (en) * 1985-01-21 1986-07-24 Henkel KGaA, 4000 Düsseldorf METHOD FOR PRE-Esterification OF FREE FATTY ACIDS IN RAW FATS AND / OR OILS
WO1987007632A1 (en) * 1986-06-11 1987-12-17 Bio-Energy Technology Ltd. Bio-fuel production
US4834908A (en) * 1987-10-05 1989-05-30 Basf Corporation Antagonism defeating crop oil concentrates
US4946230A (en) * 1988-04-27 1990-08-07 Mazda Motor Corporation Method and an apparatus for charging an anti-lock brake system with brake liquid
ES2062293T3 (en) * 1989-04-05 1994-12-16 Unilever Nv PROCEDURE FOR THE PRODUCTION OF LOWER ALKYL MONOSTERS OF FATTY ACIDS.
FR2748490B1 (en) * 1996-05-07 1998-06-19 Inst Francais Du Petrole PROCESS FOR THE MANUFACTURE OF ETHYL ESTERS
DE19956599C2 (en) * 1999-11-25 2003-11-13 Cognis Deutschland Gmbh Process for the production of deacidified triglycerides
ATA16992000A (en) 2000-10-05 2001-12-15 Michael Dr Koncar METHOD FOR PRODUCING FATTY ACID ALKYL ESTERS
US6965044B1 (en) * 2001-07-06 2005-11-15 Iowa State University Research Foundation Method of converting free fatty acids to fatty acid methyl esters with small excess of methanol
BR0301103A (en) * 2003-04-29 2005-10-04 Escola De Quimica Ufrj Catalytic process for esterification of fatty acids present in palm acid sludge using solid acid catalysts
US7619104B2 (en) * 2005-04-04 2009-11-17 Renewable Products Development Laboratories, Inc. Process for producing biodiesel or fatty acid esters from multiple triglyceride feedstocks
US20080113067A1 (en) * 2005-10-17 2008-05-15 Monoj Sarma Protein-Containing Food Product and Coating for a Food Product and Method of Making Same
US20070087085A1 (en) * 2005-10-17 2007-04-19 Bunge Oils, Inc. Protein-containing food product and coating for a food product and method of making same
KR100782126B1 (en) * 2006-01-10 2007-12-05 한국에너지기술연구원 Tungsten oxide zirconia catalyst for removing free fatty acid in used soybean oil and application thereof
ES2721427T3 (en) * 2006-04-28 2019-07-31 Sk Chemicals Co Ltd Procedure for preparing fatty acid alkyl ester using fatty acid distillate
JP2008260819A (en) * 2007-04-11 2008-10-30 National Institute Of Advanced Industrial & Technology Method for producing bio-diesel fuel
US20080282606A1 (en) * 2007-04-16 2008-11-20 Plaza John P System and process for producing biodiesel
WO2008149661A1 (en) * 2007-05-31 2008-12-11 National University Corporation Kyoto Institute Of Technology Method for production of fatty acid ester
US20090038692A1 (en) * 2007-08-09 2009-02-12 21St Century R & D, Llc Modification of vegetable oils for fuel applications
US20110139106A1 (en) 2007-08-09 2011-06-16 21St Century R & D, Llc Modification of fats and oils for fuel and lubricating applications
FR2929621A1 (en) * 2008-04-08 2009-10-09 Arkema France Esterifying free fatty acid, useful to prepare bio-diesel, comprises providing a fatty substance comprising free fatty acid, adding alcohol and methane sulfonic acid, conducting esterification reaction, and recovering the fatty substance
CA2752562A1 (en) 2008-12-08 2010-07-08 Initio Fuels Llc Single step transesterification of feedstock using a gaseous catalyst
FR2957075B1 (en) 2010-03-04 2012-06-22 Centre Nat Rech Scient METHOD FOR OBTAINING BIOSOLVANT COMPOSITIONS BY ESTERIFICATION AND OBTAINED BIOSOLVANT COMPOSITIONS
EP2522711B1 (en) 2011-05-13 2018-12-05 Cognis IP Management GmbH Process for obtaining oleochemicals with reduced content of by-products
JP2014040527A (en) * 2012-08-22 2014-03-06 Osaka Prefecture Univ Method for purifying fatty acid alkyl esters
US9328054B1 (en) 2013-09-27 2016-05-03 Travis Danner Method of alcoholisis of fatty acids and fatty acid gyicerides
WO2020074435A1 (en) * 2018-10-10 2020-04-16 Basf Se Method of producing biodiesel
US10933111B2 (en) * 2019-01-08 2021-03-02 Boston Biotechnology US CORP Treating dry eye disorders
WO2023159293A1 (en) * 2022-02-24 2023-08-31 Brasil Bio Fuels S.A Composition, process for the production of low-acidity triglycerides and partial glycerides and product thus obtained

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4164506A (en) * 1977-03-17 1979-08-14 Kao Soap Co., Ltd. Process for producing lower alcohol esters of fatty acids

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1421605A (en) * 1921-04-05 1922-07-04 Us Ind Alcohol Co Process for manufacturing esters
US1651666A (en) * 1922-12-22 1927-12-06 Standard Dev Co Process of making esters
US2383632A (en) * 1942-10-17 1945-08-28 Colgate Palmolive Peet Co Process of treating fatty glycerides
US2469371A (en) * 1946-08-14 1949-05-10 Baker Castor Oil Co Process of reacting glyceride oils
US4076948A (en) * 1968-10-10 1978-02-28 El Paso Products Company Process for treatment of adipic acid mother liquor
US3692822A (en) * 1970-04-20 1972-09-19 Gulf Research Development Co Process for preparing esters
JPS5221485A (en) * 1975-08-08 1977-02-18 Mitsubishi Rayon Co Method of dyeing aromatic polyamide fiber with solvent

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4164506A (en) * 1977-03-17 1979-08-14 Kao Soap Co., Ltd. Process for producing lower alcohol esters of fatty acids

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0184740A3 (en) * 1984-12-08 1987-09-09 Henkel Kommanditgesellschaft Auf Aktien Process for the preparation of methyl esters of fatty acids
EP0184740A2 (en) * 1984-12-08 1986-06-18 Henkel Kommanditgesellschaft auf Aktien Process for the preparation of methyl esters of fatty acids
FR2577569A1 (en) * 1985-02-15 1986-08-22 Inst Francais Du Petrole PROCESS FOR THE PRODUCTION OF A COMPOSITION OF FATTY ACID ESTERS AS FUEL FOR SUBSTITUTING GASOLINE WITH HYDRATED ETHYL ALCOHOL AND COMPOSITION OF ESTERS THUS FORMED
EP0194165A1 (en) * 1985-02-15 1986-09-10 Institut Français du Pétrole Process for manufacturing a fatty-acid ester composition for use as a diesel oil fuel substitute with hydrated ethyl alcohol, and ester composition so formed
US5455370A (en) * 1991-07-08 1995-10-03 Henkel Kommanditgesellschaft Auf Aktien Process for the production of fatty acid lower alkyl esters
WO1993001263A1 (en) * 1991-07-08 1993-01-21 Henkel Kommanditgesellschaft Auf Aktien Method of preparing lower-alkyl esters of fatty acids
EP0535290A1 (en) * 1991-09-02 1993-04-07 Primavesi, Markus Process and apparatus for continuous production of fatty acid esters
WO1993009212A1 (en) * 1991-11-06 1993-05-13 Theodor Wimmer Process for preparing fatty acid esters of short-chain monohydric alcohols
US5434279A (en) * 1991-11-06 1995-07-18 Wimmer; Theodor Process for preparing fatty acid esters of short-chain monohydric alcohols
WO1995002662A1 (en) * 1993-07-14 1995-01-26 Idaho Research Foundation, Inc. Method for purifying alcohol esters
US5424467A (en) * 1993-07-14 1995-06-13 Idaho Research Foundation Method for purifying alcohol esters
WO1995013343A1 (en) * 1993-11-08 1995-05-18 Henkel Kommanditgesellschaft Auf Aktien Method of producing lower-alkyl esters of fatty acids
US5773636A (en) * 1993-11-08 1998-06-30 Henkel Kommanditgesellschaft Auf Aktien Process for the production of fatty acid lower alkyl esters
US7109363B2 (en) 2000-12-04 2006-09-19 Westfalia Separator Ag Method for the production of fatty acid esters
US6960673B2 (en) 2000-12-04 2005-11-01 Westfalia Separator Ag Method for pretreating crude oils and raw fats for the production of fatty acid esters
EP1308498A1 (en) * 2001-11-06 2003-05-07 Cognis Deutschland GmbH & Co. KG Method for the production of fatty acid esters from non-deacidified fats and oils
US7256301B2 (en) 2002-04-12 2007-08-14 Energea Umwelttechnologie Gmbh Method and system for the esterification of fatty acids
WO2004029016A1 (en) * 2002-09-20 2004-04-08 Oelmühle Leer Connemann Gmbh & Co. Method and device for producing biodiesel
EP1565424A1 (en) * 2002-11-27 2005-08-24 Biodiesel Australia Ltd Method for production of alkyl esters
EP1565424A4 (en) * 2002-11-27 2006-05-31 Biodiesel Australia Ltd Method for production of alkyl esters
WO2004085585A1 (en) * 2003-03-28 2004-10-07 Korea Institute Of Energy Research Manufacturing method of bio-diesel oil
US7834203B2 (en) 2003-03-28 2010-11-16 Korea Institute Of Energy Research Manufacturing method of bio-diesel oil
US7540952B2 (en) 2005-07-07 2009-06-02 Petroleo Brasileiro S.A. - Petrobras Catalytic cracking process for the production of diesel from vegetable oils
EP2000522A1 (en) 2007-05-30 2008-12-10 Petroleo Brasileiro S.A. Petrobras Method for the production of biodiesel from vegetable oils and fats, using heterogeneous catalysts
US8530684B2 (en) 2008-04-01 2013-09-10 Sk Chemicals Co., Ltd. Method for preparing fatty acid alkyl ester using fatty acid
WO2009123369A1 (en) 2008-04-01 2009-10-08 Sk Chemicals Co., Ltd. Method for preparing fatty acid alkyl ester using fatty acid
WO2010053258A2 (en) 2008-11-07 2010-05-14 에스케이케미칼 주식회사 Method and apparatus for preparing alkyl ester fatty acid using fatty acid
EP2358851B2 (en) † 2008-11-17 2018-01-10 Basf Se Use of methanesulfonic acid for producing fatty acid esters
US9322004B2 (en) 2009-07-17 2016-04-26 Korea Advanced Institute Of Science And Technology Method of producing fatty acid alkyl ester using microorganisms having ability to produce oil
WO2011008058A2 (en) 2009-07-17 2011-01-20 한국과학기술원 Method for producing fatty acid alkyl esters using microorganisms having oil-producing ability
WO2012054946A1 (en) 2010-10-28 2012-05-03 Theodor Wimmer Method for producing fatty acid esters of lower alcohols
US9085746B2 (en) 2011-05-13 2015-07-21 Cognis Ip Management Gmbh Process for obtaining oleochemicals with reduced content of by-products
WO2015012538A1 (en) 2013-07-22 2015-01-29 에스케이케미칼 주식회사 Method for preparing fatty acid alkyl ester using fat
US9938487B2 (en) 2013-07-22 2018-04-10 Sk Chemicals Co., Ltd. Method for preparing fatty acid alkyl ester using fat
WO2018015191A1 (en) 2016-07-18 2018-01-25 Basf Se Low corrosion alkane sulfonic acids for condensation reactions

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MY8700278A (en) 1987-12-31
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GB2140817A (en) 1984-12-05
PH19123A (en) 1986-01-08
DE3319590A1 (en) 1984-12-06
DE3462698D1 (en) 1987-04-23
GB8413115D0 (en) 1984-06-27
EP0127104B1 (en) 1987-03-18

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