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WO2002038529A1 - Method for the production of fatty acid esters of lower alcohols - Google Patents

Method for the production of fatty acid esters of lower alcohols Download PDF

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Publication number
WO2002038529A1
WO2002038529A1 PCT/AT2001/000348 AT0100348W WO0238529A1 WO 2002038529 A1 WO2002038529 A1 WO 2002038529A1 AT 0100348 W AT0100348 W AT 0100348W WO 0238529 A1 WO0238529 A1 WO 0238529A1
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Prior art keywords
fatty acid
methanol
lower alcohols
phase
mixture
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PCT/AT2001/000348
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German (de)
French (fr)
Inventor
Theodor Wimmer
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Energea Umwelttechnologie GmbH
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Energea Umwelttechnologie GmbH
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Priority to AU2002213634A priority Critical patent/AU2002213634A1/en
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the present invention relates to a process for the preparation of fatty acid esters of lower alcohols with 1 to 4 carbon atoms, in particular methanol, suitable for use as diesel substitute fuels (biodiesel) by neutralizing the alkali-catalyzed transesterification of fatty acid glycerides with lower alcohols, in particular with methanol, as By-product of the heavy phase, the so-called glycerol phase, and by sulfuric acid-catalyzed esterification of the mixture of free fatty acids and fatty acid esters of lower alcohols, in particular methanol, obtained with the neutralization of the glycerol phase, with lower alcohols with 1-4 C atoms, preferably with methanol.
  • biodiesel Such methods are described for example in AT 397 510 B and EP 708 813 A.
  • These and most other processes use alkali metal hydrox.de or alcoholates as catalysts for the transesterification of fatty acid glycerides such as e.g. Rapeseed oil, sunflower oil or used edible fats with lower alcohols, especially with methanol, resulting in a by-product called glycerol phase, which contains, besides glycerol, a considerable proportion of alkali salts of fatty acids and fatty acid esters of the alcohol used for the transesterification.
  • the glycerol phase is economically worthless and represents a disposal product.
  • the fatty acids and fatty acid esters contained in it deteriorate the yield of biodiesel and thus the economy of a biodiesel plant.
  • carboxylic acid or Fatty acid esters can be esterified by esterifying the free acids with lower alcohols, preferably at the boiling point of the alcohols, in the presence of strong acids, such as hydrogen chloride, sulfuric acid or sulfonic acids.
  • a process for the esterification of a fatty acid / fatty acid ester mixture isolated from the glycerol phase is described in EP 708 813 A, the free fatty acids obtained from the neutralization of the glycerol phase being heated to 85 ° C. for two hours with methanol and concentrated sulfuric acid as catalyst, the content of free fatty acids decreases from approx. 50% to 12.5% and the entire mixture is fed to an alkali-catalyzed transesterification without further treatment and the catalyst acid is discharged via the transesterification process.
  • Concentrated sulfuric acid, benzene, p-toluene or methanesulfonic acid are mostly used as esterification catalysts.
  • One problem with the use of these acids is the recycling or disposal of the catalyst acid.
  • the acids either have to be regenerated, that is to say dewatered, in order to be able to be used again as catalysts, or they undergo, for example, an alkali-catalyzed transesterification process supplied or neutralized and get into the wastewater as non-biodegradable salts or accumulate as worthless by-products.
  • the object of the present invention is to provide an improved method for obtaining diesel substitute fuels
  • fatty acid esters of lower alcohols preferably methanol
  • glycerol phase obtained in the alkali-catalyzed transesterification of fatty acid glycerides with lower alcohols, which avoids the disadvantages mentioned and provides a fatty acid ester suitable as diesel fuel, and furthermore the lower alcohols contained in the glycerol phase are recovered and you get a raw glycerol with 60 to 90% glycerol.
  • phase containing the fatty acid esters of the lower alcohols in a manner known per se by treatment with alkali metal hydroxides, preferably potassium hydroxide solution, by washing with water and / or acids and evaporation of the excess lower alcohol, and that
  • the phase consisting of the excess lower alcohol, preferably methanol, sulfuric acid and water of reaction Neutralization of a further glycerol phase is used, the neutralized mixture being divided into a light phase consisting of free fatty acids, fatty acid esters of lower alcohols, preferably of methanol, and free lower alcohols, preferably methanol, and a heavier phase consisting of glycerol, the excess lower alcohol, preferably methanol, and Separates alkali sulfate.
  • the esterification of the mixture of free fatty acids and fatty acid esters of lower alcohols obtained from the neutralization of the glycerol phase is carried out at temperatures not above 50 ° C., preferably not above 40 ° C. and particularly preferably not above 35 ° C. This ensures an optimal manufacturing process, which is advantageously still energy-saving.
  • the concentrated sulfuric acid serving as catalyst is used in a concentration of 0.5-17% by mass, based on the mass of the fatty acid / fatty acid ester mixture.
  • the amount of sulfuric acid used is at most equal to or less than the amount required to neutralize the amount of alkali soaps contained in the glycerol phase. In the event that the amount of sulfuric acid used for the esterification is smaller than would be necessary to neutralize the glycerol phase, neutralization is carried out with additional sulfuric acid.
  • the lower alcohols with 1 to 4 carbon atoms are used in an amount of 15 to 200% by mass, based on the amount of the fatty acid / fatty acid ester mixture.
  • Ethanol, 1- and 2-propanol, 1-butanol, 2-butanol and isobutanol are also suitable as lower alcohols with 1 to 4 carbon atoms.
  • the esterification of the fatty acid / Fettklareestergemisches with 'the lower alcohols and which is concentrated sulfuric acid with vigorous stirring to generate the greatest possible turbulence in a period of 0.5 to 3 hours is thus accelerated by vigorous stirring, with the greatest possible turbulence, the degree of esterification being more than 95 percent after 0.5 to 3 hours.
  • methanol is used as the lower alcohol.
  • the phase consisting of the fatty acid esters of the lower alcohols, preferably of methanol, which still contains small amounts of free fatty acids is treated in a manner known per se with alkali metal hydroxides, preferably potassium hydroxide solution, and by washing with water and / or diluted acids and evaporation of the excess lower alcohol are cleaned or can be introduced into the washing process of a biodiesel plant.
  • alkali metal hydroxides preferably potassium hydroxide solution
  • the glycerol phases used are preferably those obtained in the transesterification of fatty acid glycerides with lower alcohols catalyzed by potassium hydroxide or potassium alcoholate.
  • the heavy phase resulting from the neutralization of the glycerol phase consisting of glycerol, excess lower alcohol and alkali sulfate, can be distilled to give lower alcohol which is returned to the esterification and a crude glycerol with 60-90 percent glycerol and in solid alkali sulfate, which in the case of potassium sulfate as Fertilizers used in agriculture can be refurbished.
  • a particular advantage of the process according to the invention can be seen in the fact that the sulfuric acid is used both as a catalyst for the esterification and subsequently for the neutralization of the glycerol phase, so that only one auxiliary substance is required for both processes, which is converted into an alkali metal sulfate, preferably potassium sulfate that can be used as a fertilizer in agriculture and that no biodegradable products such as sulfonic acids or their salts as waste products and that the esterification takes place in an energy-saving manner at moderate temperatures with high degrees of esterification of over 95%.
  • the process also meets the requirements.
  • Another advantage of the process according to the invention is that the amount of sulfuric acid required to neutralize the alkali metal salts of the fatty acids in the glycerol phase far exceeds the amount required to esterify the same amount of fatty acid, so that relatively high sulfuric acid concentrations can be used for the esterification, which at the low temperatures and times of 0.5-3 hours cause a high degree of esterification.
  • ester phase (108 grams) is mixed with 0.35 grams of a 50 percent potassium hydroxide solution and stirred for 2 minutes. After the stirrer has been switched off, the mixture separates into a phase which is 5 grams heavier and consists of the potassium salts of rapeseed fatty acids, methanol and water and in 103 grams of a lighter ester phase.
  • the ester phase is then washed first with water and then with dilute sulfuric acid and the excess methanol is removed in a rotary evaporator.
  • the rapeseed fatty acid methyl ester thus obtained contains less than 0.2% free fatty acids and meets all other requirements for usability as diesel fuel.
  • the phase (73.3 grams) consisting of 11.0 grams of sulfuric acid, 58.3 grams of methanol and 4 grams of water of reaction is separated off and allowed to flow into 300 grams of a glycerol phase which stems from a transesterification of rapeseed oil with methanol catalyzed by potassium hydroxide and has the following composition: 73 grams of potassium salts of rapeseed fatty acids 26 grams of rapeseed methyl ester 100 grams of glycerol 56 grams of methanol 45 grams of water
  • the neutralized mixture is filtered or centrifuged to separate solid potassium sulfate, after which the filtrate is dissolved in 100 grams of a lighter phase consisting of 65 grams of rapeseed fatty acids, 26 grams of rapeseed methyl ester and 9 grams of methanol and 246 grams of a heavier phase which contains glycerol, methanol and water , and which after evaporation of the methanol gives a crude glycerol with at least 60% glycerol.
  • a lighter phase consisting of 65 grams of rapeseed fatty acids, 26 grams of rapeseed methyl ester and 9 grams of methanol and 246 grams of a heavier phase which contains glycerol, methanol and water , and which after evaporation of the methanol gives a crude glycerol with at least 60% glycerol.
  • a lighter phase consisting of 65 grams of rapeseed fatty acids, 26 grams of rapeseed methyl este
  • reaction mixture 100 grams of a mixture consisting of 40% fatty acids, 52% fatty acid hylester and 8% methanol are stirred intensively with 120 grams of methanol and 2.8 grams of concentrated sulfuric acid for 2 hours at a temperature of 50 ° C with a magnetic stirrer. After switching off the stirrer, the reaction mixture separates into 102 grams of an ester phase consisting of 93.6 grams of fatty acid methyl ester, 0.4 grams of free fatty acids and 8 grams of methanol, and into 120.8 grams of a phase consisting of 2.7 grams of sulfuric acid, 2. 5 grams of water of reaction and 115 grams of methanol.
  • ester phase (102 grams) is mixed with 0.30 grams of a 30 percent solution of potassium hydroxide in methanol, stirred for 2 minutes, and proceed as in Example 1).
  • the fatty acid methyl ester thus obtained contains 0.08% free fatty acids.
  • Deep-frying oil with methanol comes from and has the following composition:
  • the neutralized mixture is filtered or centrifuged to separate solid potassium sulfate, after which the filtrate is in 100 grams of a lighter phase consisting of 40 grams of fatty acids, 52 grams of fatty acid methyl ester and 8 grams of methanol and 350 grams of a heavy phase containing glycerin methanol and water.
  • the lighter phase is fed to a further esterification as described at the beginning in this example.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a method for the production of fatty acid esters of lower alcohols, in particular of methanol, from the glycerine phase accumulated during the base-catalysed transesterification of fatty acid glycerides, in particular with methanol. The fatty acids formed from the neutralisation of the glycerine phase are esterified with lower alcohols, preferably with methanol and concentrated sulphuric acid. The phase, comprising sulphuric acid, methanol and water, obtained after the phase separation of the esterification mixture is used for neutralisation of the glycerine phase.

Description

Verfahren zur Herstellung von Fettsäureestern niederer Alkohole Process for the preparation of fatty acid esters of lower alcohols

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von zur Verwendung als Dieselersatzkraftstoffe (Biodiesel) geeigneten Fettsäureestern niederer Alkohole mit 1 - 4 C-Atomen, insbesondere des Methanols, durch Neutralisation der bei der alkalikatalysierten Umesterung von Fettsäureglyceriden mit niederen Alkoholen, insbesondere mit Methanol, als Nebenprodukt anfallenden schweren Phase, der sogenannten Glycerinphase, und durch schwefelsäurekatalysierte Veresterung des bei der Neutralisation der Glycerinphase erhaltenen Gemisches von freien Fettsäuren und Fettsäureestern niederer Alkohole, insbesondere des Methanols, mit niederen Alkoholen mit 1 - 4 C-Atomen, vorzugsweise mit Methanol.The present invention relates to a process for the preparation of fatty acid esters of lower alcohols with 1 to 4 carbon atoms, in particular methanol, suitable for use as diesel substitute fuels (biodiesel) by neutralizing the alkali-catalyzed transesterification of fatty acid glycerides with lower alcohols, in particular with methanol, as By-product of the heavy phase, the so-called glycerol phase, and by sulfuric acid-catalyzed esterification of the mixture of free fatty acids and fatty acid esters of lower alcohols, in particular methanol, obtained with the neutralization of the glycerol phase, with lower alcohols with 1-4 C atoms, preferably with methanol.

Fettsäureester niederer Alkohole insbesondere des Methanols haben in letzter Zeit große Bedeutung als Dieselersatzkraftstoffe (Biodiesel) erlangt. Solche Verfahren werden beispielsweise in der AT 397 510 B und der EP 708 813 A beschrieben. Diese und die meisten anderen Verfahren verwenden Alkalimetallhydrox.de- oder -alkoholate als Katalysatoren für die Umesterung von Fettsäureglyceriden wie z.B. Rapsöl, Sonnenblumenöl oder gebrauchten Speisefetten mit niederen Alkoholen, insbesondere mit Methanol, wobei ein als Glycerinphase bezeichnetes Nebenprodukt anfällt, welches neben Glycerin einen erheblichen Anteil an Alkalisalzen von Fettsäuren und an Fettsäureestern des zur Umesterung verwendeten Alkohols enthält. Die Glycerinphase ist in dieser Form ökonomisch wertlos und stellt ein Entsorgungsprodukt dar. Die darin enthaltenen Fettsäuren und Fettsäureester verschlechtem die Ausbeute an Biodiesel und damit die Wirtschaftlichkeit einer Biodieselanlage.Fatty acid esters of lower alcohols, especially of methanol, have recently become very important as diesel substitute fuels (biodiesel). Such methods are described for example in AT 397 510 B and EP 708 813 A. These and most other processes use alkali metal hydrox.de or alcoholates as catalysts for the transesterification of fatty acid glycerides such as e.g. Rapeseed oil, sunflower oil or used edible fats with lower alcohols, especially with methanol, resulting in a by-product called glycerol phase, which contains, besides glycerol, a considerable proportion of alkali salts of fatty acids and fatty acid esters of the alcohol used for the transesterification. In this form, the glycerol phase is economically worthless and represents a disposal product. The fatty acids and fatty acid esters contained in it deteriorate the yield of biodiesel and thus the economy of a biodiesel plant.

Es ist bekannt, dass die in der Glycerinphase als Alkalisalze enthaltenen Fettsäuren und die Fettsäureester durch Neutralisation mit einer Säure isoliert werden können. Ein solches Verfahren wird in der AT 392 977 B beschrieben. Das erhaltene Gemisch aus freien Fettsäuren und Fettsäureestern ist aber infolge des hohen Gehaltes an freien Fettsäuren nicht als Dieselkraftstoff verwendbar und besitzt ebenfalls keinen wirtschaftlichen Wert.It is known that the fatty acids contained in the glycerol phase as alkali salts and the fatty acid esters can be isolated by neutralization with an acid. Such a method is described in AT 392 977 B. However, the mixture of free fatty acids and fatty acid esters obtained is due to the high content of free fatty acids, it cannot be used as diesel fuel and also has no economic value.

Aus den Lehrbüchern der organisch-präparativen Chemie, beispielsweise „Organikum" 13. Aufl. 1974, S 441 ff oder'Weygand/Hilgetag, „Organisch- Chemische Experimentierkunst, 4. Aufl. 1970, S 377ff, ist bekannt, dass Carbonsäure- bzw. Fettsäureester durch Veresterung der freien Säuren mit niederen Alkoholen vorzugsweise bei Siedetemperatur der Alkohole in Gegenwart von starken Säuren, wie Chlorwasserstoff, Schwefelsäure oder Sulfonsäuren verestert werden können.From the textbooks of organic-preparative chemistry, for example "Organikum" 13th ed. 1974, p 441 ff or ' Weygand / Hilgetag, "Organisch-Chemische Experimentierkunst, 4th ed. 1970, p 377ff, it is known that carboxylic acid or Fatty acid esters can be esterified by esterifying the free acids with lower alcohols, preferably at the boiling point of the alcohols, in the presence of strong acids, such as hydrogen chloride, sulfuric acid or sulfonic acids.

Ein Verfahren zur Veresterung eines aus der Glycerinphase isolierten Fettsäure/Fettsäureestergemisches wird in der EP 708 813 A beschrieben, wobei die aus der Neutralisation der Glycerinphase erhaltenen freien Fettsäuren mit Methanol und konzentrierter Schwefelsäure als Katalysator zwei Stunden auf 85 °C erhitzt werden, wobei der Gehalt an freien Fettsäuren von ca. 50 % auf 12,5 % zurückgeht und das ganze Gemisch ohne weitere Behandlung einer alkalikatalysierten Umesterung zugeführt wird und die Katalysatorsäure über den Umesterungsprozess ausgeschleust wird.A process for the esterification of a fatty acid / fatty acid ester mixture isolated from the glycerol phase is described in EP 708 813 A, the free fatty acids obtained from the neutralization of the glycerol phase being heated to 85 ° C. for two hours with methanol and concentrated sulfuric acid as catalyst, the content of free fatty acids decreases from approx. 50% to 12.5% and the entire mixture is fed to an alkali-catalyzed transesterification without further treatment and the catalyst acid is discharged via the transesterification process.

Weitere Verfahren zur Veresterung von freien Fettsäuren werden in den EP 127104 A und EP 184 740 A beschrieben, wobei die freien Fettsäuren in einem Gemisch mit Fettsäuretriglyceriden vorliegen und die Veresterung durch Erhitzen mit Methanol bei 65 °C mit Schwefelsäure oder einer Sulfonsäure als Katalysator durchgeführt wird.Further processes for the esterification of free fatty acids are described in EP 127104 A and EP 184 740 A, the free fatty acids being present in a mixture with fatty acid triglycerides and the esterification being carried out by heating with methanol at 65 ° C. using sulfuric acid or a sulfonic acid as catalyst ,

Als Veresterungskatalysatoren werden meistens konzentrierte Schwefelsäure, Benzol-, p-Toluol-, oder Methansulfonsäure eingesetzt. Ein Problem bei der Anwendung dieser Säuren stellt die Verwertung bzw. Entsorgung der Katalysatorsäure dar. Die Säuren müssen entweder regeneriert, das heißt entwässert werden, um als Katalysatoren wieder verwendet werden zu können oder sie werden beispielsweise einem alkalikatalysierten Umesterungsprozess zugeführt oder neutralisiert und gelangen als biologisch nicht abbaubare Salze in das Abwasser oder fallen als wertlose Nebenprodukte an.Concentrated sulfuric acid, benzene, p-toluene or methanesulfonic acid are mostly used as esterification catalysts. One problem with the use of these acids is the recycling or disposal of the catalyst acid. The acids either have to be regenerated, that is to say dewatered, in order to be able to be used again as catalysts, or they undergo, for example, an alkali-catalyzed transesterification process supplied or neutralized and get into the wastewater as non-biodegradable salts or accumulate as worthless by-products.

Die Aufgabe der vorliegenden Erfindung besteht darin, ein verbessertes Verfahren zur Gewinnung von als Dieselersatzkraftstoffe geeignetenThe object of the present invention is to provide an improved method for obtaining diesel substitute fuels

Fettsäureestern niederer Alkohole, vorzugsweise des Methanols, aus der bei der alkalikatalysierten Umesterung von Fettsäureglyceriden mit niederen Alkoholen anfallenden Glycerinphase zur Verfügung zu stellen, welches die genannten Nachteile vermeidet und einen als Dieselkraftstoff geeigneten Fettsäureester liefert und man weiters die in der Glycerinphase enthaltenen niederen Alkohole zurückgewinnt und man ein Rohglycerin mit 60 bis 90 % Glycerinanteil erhält.To provide fatty acid esters of lower alcohols, preferably methanol, from the glycerol phase obtained in the alkali-catalyzed transesterification of fatty acid glycerides with lower alcohols, which avoids the disadvantages mentioned and provides a fatty acid ester suitable as diesel fuel, and furthermore the lower alcohols contained in the glycerol phase are recovered and you get a raw glycerol with 60 to 90% glycerol.

Das erfindungsgemäße Verfahren ist dadurch gekennzeichnet, dass manThe process according to the invention is characterized in that

a) die Veresterung des aus der Neutralisation der Glycerinphase erhaltenen Gemisches aus freien Fettsäuren und Fettsäureestern niederer Alkohole, insbesondere des Methanols, mit einem Überschuss eines niederen Alkohols mit 1 - 4 C-Atomen, vorzugsweise Methanol, in Gegenwart von konzentrierter Schwefelsäure durchführt, wobei sich das Reaktionsgemisch nach erfolgter Veresterung in eine Phase bestehend aus dem Fettsäureester des niederen Alkohols, vorzugsweise des Methanols, und in eine Phase bestehend aus dem überschüssigen niederen Alkohol vorzugsweise Methanol, Schwefelsäure und Reaktionswasser trennt, und dass man .a) the esterification of the mixture of free fatty acids and fatty acid esters of lower alcohols, in particular methanol, obtained from the neutralization of the glycerol phase with an excess of a lower alcohol having 1-4 C atoms, preferably methanol, in the presence of concentrated sulfuric acid, whereby after the esterification has taken place, the reaction mixture is separated into a phase consisting of the fatty acid ester of the lower alcohol, preferably methanol, and into a phase consisting of the excess lower alcohol, preferably methanol, sulfuric acid and water of reaction, and that.

b) die die Fettsäureester der niederen Alkohole enthaltende Phase in an sich bekannter Weise durch Behandeln mit Alkalihydroxiden, vorzugsweise Kalilauge, durch Waschen mit Wasser und/oder Säuren und Abdampfen des überschüssigen niederen Alkohols reinigt, und dass manb) the phase containing the fatty acid esters of the lower alcohols in a manner known per se by treatment with alkali metal hydroxides, preferably potassium hydroxide solution, by washing with water and / or acids and evaporation of the excess lower alcohol, and that

c) die Phase bestehend aus dem überschüssigen niederen Alkohol vorzugsweise Methanol, Schwefelsäure und Reaktionswasser zur Neutralisation einer weiteren Glycerinphase verwendet, wobei sich das neutralisierte Gemisch in eine leichte Phase bestehend aus freien Fettsäuren, Fettsäureestern niederer Alkohole vorzugsweise des Methanols und freien niederen Alkoholen vorzugsweise Methanol und in eine schwerere Phase bestehend aus Glycerin, dem überschüssigen niederen Alkohol, vorzugsweise Methanol, und Alkalisulfat trennt.c) the phase consisting of the excess lower alcohol, preferably methanol, sulfuric acid and water of reaction Neutralization of a further glycerol phase is used, the neutralized mixture being divided into a light phase consisting of free fatty acids, fatty acid esters of lower alcohols, preferably of methanol, and free lower alcohols, preferably methanol, and a heavier phase consisting of glycerol, the excess lower alcohol, preferably methanol, and Separates alkali sulfate.

Gemäß einem weiteren Merkmal der Erfindung wird die Veresterung des aus der Neutralisation der Glycerinphase erhaltenen Gemisches aus freien Fettsäuren und Fettsäureestern niederer Alkohole bei Temperaturen nicht über 50 °C, vorzugsweise nicht über 40 °C und besonders vorzugsweise nicht über 35 °C durchgeführt. Dadurch wird ein optimaler Herstellprozess, der vorteilhafterweise noch energiesparend ist, gewährleistet.According to a further feature of the invention, the esterification of the mixture of free fatty acids and fatty acid esters of lower alcohols obtained from the neutralization of the glycerol phase is carried out at temperatures not above 50 ° C., preferably not above 40 ° C. and particularly preferably not above 35 ° C. This ensures an optimal manufacturing process, which is advantageously still energy-saving.

Nach einer weiteren Ausgestaltung der Erfindung wird die als Katalysator dienende konzentrierte Schwefelsäure in einer Konzentration von 0,5 - 17 Masse% bezogen auf die Masse des Fettsäure-/ Fettsäureestergemisches eingesetzt. Die eingesetzte Menge Schwefelsäure ist dabei höchstens gleich groß oder kleiner als die zur Neutralisation der in der Glycerinphase enthaltenen Menge an Alkaliseifen erforderlichen Menge. Für den Fall, dass die zur Veresterung eingesetzte Menge Schwefelsäure kleiner ist, als zur Neutralisation der Glycerinphase nötig wäre, wird mit zusätzlicher Schwefelsäure neutralisiert.According to a further embodiment of the invention, the concentrated sulfuric acid serving as catalyst is used in a concentration of 0.5-17% by mass, based on the mass of the fatty acid / fatty acid ester mixture. The amount of sulfuric acid used is at most equal to or less than the amount required to neutralize the amount of alkali soaps contained in the glycerol phase. In the event that the amount of sulfuric acid used for the esterification is smaller than would be necessary to neutralize the glycerol phase, neutralization is carried out with additional sulfuric acid.

Gemäß einem weiteren Merkmal der Erfindung werden die niederen Alkohole mit 1 - 4 C-Atomen in einer Menge von 15 bis 200 Masse% bezogen auf die Menge des Fettsäure-/ Fettsäureestergemisches eingesetzt. Als niedere Alkohole mit 1 - 4 C-Atomen kommen außerdem Ethanol, 1- und 2-Propanol, 1-Butanol, 2-ButanoI und Isobutanol in Frage.According to a further feature of the invention, the lower alcohols with 1 to 4 carbon atoms are used in an amount of 15 to 200% by mass, based on the amount of the fatty acid / fatty acid ester mixture. Ethanol, 1- and 2-propanol, 1-butanol, 2-butanol and isobutanol are also suitable as lower alcohols with 1 to 4 carbon atoms.

Nach einer weiteren Ausgestaltung der Erfindung wird die Veresterung des Fettsäure-/ Fettsäureestergemisches mit'den niederen Alkoholen und der konzentrierten Schwefelsäure unter intensivem Rühren bei Erzeugung möglichst großer Turbulenzen in einem Zeitraum von 0,5 bis 3 Stunden durchgeführt. Die Veresterungsreaktion wird also durch intensives Rühren unter Bildung möglichst großer Turbulenzen beschleunigt, wobei der Veresterungsgrad nach 0,5 bis 3 Stunden mehr als 95 Prozent beträgt.According to a further embodiment of the invention, the esterification of the fatty acid / Fettsäureestergemisches with 'the lower alcohols and which is concentrated sulfuric acid with vigorous stirring to generate the greatest possible turbulence in a period of 0.5 to 3 hours. The esterification reaction is thus accelerated by vigorous stirring, with the greatest possible turbulence, the degree of esterification being more than 95 percent after 0.5 to 3 hours.

Gemäß einer Weiterbildung der Erfindung wird als niederer Alkohol Methanol verwendet. Nach einer weiteren Ausgestaltung der Erfindung wird die Phase bestehend aus den Fettsäureestern der niederen Alkohole, vorzugsweise des Methanols, welche noch geringe Anteile an freien Fettsäuren enthält, in an sich bekannter Weise mit Alkalihydroxiden, vorzugsweise Kalilauge, behandelt und durch Waschen mit Wasser und/oder verdünnten Säuren und Abdampfen des überschüssigen niederen Alkohols gereinigt oder kann in den Waschprozess einer Biodieselanlage eingeschleust werden.According to a development of the invention, methanol is used as the lower alcohol. According to a further embodiment of the invention, the phase consisting of the fatty acid esters of the lower alcohols, preferably of methanol, which still contains small amounts of free fatty acids, is treated in a manner known per se with alkali metal hydroxides, preferably potassium hydroxide solution, and by washing with water and / or diluted acids and evaporation of the excess lower alcohol are cleaned or can be introduced into the washing process of a biodiesel plant.

Als Glycerinphasen werden vorzugsweise solche eingesetzt, die bei der Kaliumhydroxid- oder Kaliumalkoholat- katalysierten Umesterung von Fettsäureglyceriden mit niederen Alkoholen erhalten werden.The glycerol phases used are preferably those obtained in the transesterification of fatty acid glycerides with lower alcohols catalyzed by potassium hydroxide or potassium alcoholate.

Die bei der Neutralisation der Glycerinphase anfallende schwere Phase bestehend aus Glycerin, überschüssigem niederem Alkohol und Alkalisulfat kann destillativ zu niederem Alkohol, der in die Veresterung zurückgeführt wird und ein Rohglycerin mit 60 - 90 prozentigem Glycerinanteil und in festes Alkalisulfat, welches im Falle von Kaliumsulfat als Düngemittel in der Landwirtschaft Verwendung finden kann, aufgearbeitet werden.The heavy phase resulting from the neutralization of the glycerol phase, consisting of glycerol, excess lower alcohol and alkali sulfate, can be distilled to give lower alcohol which is returned to the esterification and a crude glycerol with 60-90 percent glycerol and in solid alkali sulfate, which in the case of potassium sulfate as Fertilizers used in agriculture can be refurbished.

Ein besonderer Vorteil des erfindungsgemäßen Verfahrens ist darin zu sehen, dass die Schwefelsäure sowohl als Katalysator zur Veresterung als auch nachfolgend zur Neutralisation der Glycerinphase verwendet wird, sodass für beide Prozesse nur ein einziger Hilfsstoff benötigt wird, der in ein Alkalisulfat, vorzugsweise Kaliumsulfat, umgewandelt wird, das als Düngemittel in der Landwirtschaft Anwendung finden kann und dass keine biologisch nicht abbaubaren Produkte wie Sulfonsäuren bzw. deren Salze als Abfallprodukte anfallen, und dass die Veresterung energiesparend bei mäßigen Temperaturen mit hohen Veresterungsgraden von über 95 % erfolgt. Das Verfahren kommt damit neben den wirtschaftlichen auch den ökologischen Erfordernissen der Biodieselerzeugung entgegen.A particular advantage of the process according to the invention can be seen in the fact that the sulfuric acid is used both as a catalyst for the esterification and subsequently for the neutralization of the glycerol phase, so that only one auxiliary substance is required for both processes, which is converted into an alkali metal sulfate, preferably potassium sulfate that can be used as a fertilizer in agriculture and that no biodegradable products such as sulfonic acids or their salts as waste products and that the esterification takes place in an energy-saving manner at moderate temperatures with high degrees of esterification of over 95%. In addition to the economic and ecological requirements of biodiesel production, the process also meets the requirements.

Ein weiterer Vorteil des erfindungsgemäßen Verfahrens besteht darin, dass die zur Neutralisation der Alkalisalze der Fettsäuren in der Glycerinphase erforderliche Menge Schwefelsäure die zur Veresterung derselben Menge Fettsäure erforderliche Menge bei weitem überschreitet, sodass zur Veresterung relativ hohe Schwefelsäurekonzentrationen eingesetzt werden können, die bei den niedrigen Temperaturen und Zeiten von 0,5 - 3 Stunden einen hohen Veresterungsgrad bewirken.Another advantage of the process according to the invention is that the amount of sulfuric acid required to neutralize the alkali metal salts of the fatty acids in the glycerol phase far exceeds the amount required to esterify the same amount of fatty acid, so that relatively high sulfuric acid concentrations can be used for the esterification, which at the low temperatures and times of 0.5-3 hours cause a high degree of esterification.

Ein weiterer Vorteil ist in der Tatsache zu sehen, dass die in der Glycerinphase enthaltenen, aus der Umesterung stammenden niederen Alkohole zurückgewonnen werden, und ein Rohglycerin mit einem Glycerinanteil von 60 bis 90 % gewonnen wird.Another advantage can be seen in the fact that the lower alcohols contained in the glycerol phase and originating from the transesterification are recovered, and a crude glycerol with a glycerol content of 60 to 90% is obtained.

Die Erfindung wird durch die folgenden Beispiele näher erläutert:The invention is illustrated by the following examples:

Beispiel 1)Example 1)

100 Gramm eines Gemisches bestehend aus 65 % Rapsfettsäuren, 26 % Rapsmethylester und 9 % Methanol werden mit 70 Gramm Methanol und 11 ,3 Gramm konzentrierter Schwefelsäure 2 Stunden bei einer Temperatur von 30 °C mit einem Flügelrührer intensiv gerührt. Nach Abstellen des Rührers trennt sich das Gemisch in 108 Gramm einer Esterphase bestehend aus 99,3 Gramm Rapsmethylester, 0,7 Gramm Rapsfettsäuren und 8 Gramm Methanol und 73,3 Gramm einer Phase bestehend aus 11 ,0 Gramm Schwefelsäure, 58,3 Gramm Methanol und 4 Gramm Reaktionswasser. Die Esterphase (108 Gramm) wird zur weiteren Reinigung mit 0,35 Gramm einer 50 prozentigen Kalilauge versetzt und 2 Minuten gerührt. Das Gemisch trennt sich nach Abstellen des Rührers irr 5 Gramm schwerere Phase bestehend aus den Kaliumsalzen von Rapsfettsäuren, Methanol und Wasser und in 103 Gramm leichtere Esterphase.100 grams of a mixture consisting of 65% rapeseed fatty acids, 26% rapeseed methyl ester and 9% methanol are vigorously stirred with 70 g of methanol and 11.3 g of concentrated sulfuric acid for 2 hours at a temperature of 30 ° C. using a paddle stirrer. After the stirrer has been switched off, the mixture separates into 108 grams of an ester phase consisting of 99.3 grams of rapeseed methyl ester, 0.7 grams of rapeseed fatty acids and 8 grams of methanol and 73.3 grams of a phase consisting of 11.0 grams of sulfuric acid and 58.3 grams of methanol and 4 grams of water of reaction. For further purification, the ester phase (108 grams) is mixed with 0.35 grams of a 50 percent potassium hydroxide solution and stirred for 2 minutes. After the stirrer has been switched off, the mixture separates into a phase which is 5 grams heavier and consists of the potassium salts of rapeseed fatty acids, methanol and water and in 103 grams of a lighter ester phase.

Die Esterphase wird nun zuerst mit Wasser und anschließend mit verdünnter Schwefelsäure gewaschen und das überschüssige Methanol in einem Rotationsverdampfer entfernt.The ester phase is then washed first with water and then with dilute sulfuric acid and the excess methanol is removed in a rotary evaporator.

Der so erhaltene Rapsfettsäuremethylester enthält weniger als 0,2 % freie Fettsäuren und erfüllt alle übrigen Anforderungen an die Verwendbarkeit als Dieselkraftstoff.The rapeseed fatty acid methyl ester thus obtained contains less than 0.2% free fatty acids and meets all other requirements for usability as diesel fuel.

Die Phase (73,3 Gramm) bestehend aus 11 ,0 Gramm Schwefelsäure, 58,3 Gramm Methanol und 4 Gramm Reaktionswasser wird abgetrennt und unter Rühren zu 300 Gramm einer Glycerinphase zufließen gelassen, welche aus einer mit Kaliumhydroxid katalysierten Umesterung von Rapsöl mit Methanol stammt und folgende Zusammensetzung hat: 73 Gramm Kaliumsalze von Rapsfettsäuren 26 Gramm Rapsmethylester 100 Gramm Glycerin 56 Gramm Methanol 45 Gramm WasserThe phase (73.3 grams) consisting of 11.0 grams of sulfuric acid, 58.3 grams of methanol and 4 grams of water of reaction is separated off and allowed to flow into 300 grams of a glycerol phase which stems from a transesterification of rapeseed oil with methanol catalyzed by potassium hydroxide and has the following composition: 73 grams of potassium salts of rapeseed fatty acids 26 grams of rapeseed methyl ester 100 grams of glycerol 56 grams of methanol 45 grams of water

Das neutralisierte Gemisch wird zur Abtrennung von festem Kaliumsulfat filtriert oder zentrifugiert, wonach sich das Filtrat in 100 Gramm einer leichteren Phase bestehend aus 65 Gramm Rapsfettsäuren, 26 Gramm Rapsmethylester und 9 Gramm Methanol und 246 Gramm einer schwereren Phase, welche Glycerin, Methanol und Wasser enthält, und die nach Abdampfen des Methanols ein Rohglycerin mit mindestens 60 % Glycerinanteil ergibt. Beispiel 2)The neutralized mixture is filtered or centrifuged to separate solid potassium sulfate, after which the filtrate is dissolved in 100 grams of a lighter phase consisting of 65 grams of rapeseed fatty acids, 26 grams of rapeseed methyl ester and 9 grams of methanol and 246 grams of a heavier phase which contains glycerol, methanol and water , and which after evaporation of the methanol gives a crude glycerol with at least 60% glycerol. Example 2)

100 Gramm eines Gemisches bestehend aus 40% Fettsäuren, 52% Fettsäure hylester und 8% Methanol werden mit 120 Gramm Methanol und 2.8 Gramm konzentrierter Schwefelsäure 2 Stunden bei einer Temperatur von 50°C mit einem Magnetrührer intensiv gerührt. Nach Abstellen des Rührers trennt sich das Reaktionsgemisch in 102 Gramm einer Esterphase bestehend aus 93,6 Gramm Fettsäuremethylester, 0,4 Gramm freie Fettsäuren und 8 Gramm Methanol, und in 120,8 Gramm einer Phase bestehend aus 2,7 Gramm Schwefelsäure, 2,5 Gramm Reaktionswasser und 115 Gramm Methanol.100 grams of a mixture consisting of 40% fatty acids, 52% fatty acid hylester and 8% methanol are stirred intensively with 120 grams of methanol and 2.8 grams of concentrated sulfuric acid for 2 hours at a temperature of 50 ° C with a magnetic stirrer. After switching off the stirrer, the reaction mixture separates into 102 grams of an ester phase consisting of 93.6 grams of fatty acid methyl ester, 0.4 grams of free fatty acids and 8 grams of methanol, and into 120.8 grams of a phase consisting of 2.7 grams of sulfuric acid, 2. 5 grams of water of reaction and 115 grams of methanol.

Die Esterphase (102 Gramm) wird zur weitren Reinigung mit 0,30 Gramm einer 30-prozentigen Lösung von Kaliumhydroxid in Methanol versetzt, 2 Minuten gerührt, und wie in Beispiel 1) weiterverfahren. Der so erhaltene Fettsäuremethylester enthält 0,08% freie Fettsäuren.For further purification, the ester phase (102 grams) is mixed with 0.30 grams of a 30 percent solution of potassium hydroxide in methanol, stirred for 2 minutes, and proceed as in Example 1). The fatty acid methyl ester thus obtained contains 0.08% free fatty acids.

Die Phase (120,8 Gramm) bestehend aus 2,7 Gramm Schwefelsäure,The phase (120.8 grams) consisting of 2.7 grams of sulfuric acid,

2,5 Gramm Wasser und 115 Gramm Methanol wird abgetrennt und unter2.5 grams of water and 115 grams of methanol are separated and under

Rühren zu 323 Gramm einer Glycerinphase zufließen gelassen, welche aus einer mit Kaliumhydroxid katalysierten Umesterung eines gebrauchtenStirring flowed in to 323 grams of a glycerol phase, which from a transesterification catalyzed with potassium hydroxide used a

Fritieröles mit Methanol stammt und folgende Zusammensetzung hat:Deep-frying oil with methanol comes from and has the following composition:

46 Gramm Kaliumsalze von Fettsäuren46 grams of potassium salts of fatty acids

52 Gramm Fettsäuremethylester52 grams of fatty acid methyl ester

100 Gramm Glycerin 65 Gramm Methanol100 grams of glycerin 65 grams of methanol

60 Gramm Wasser60 grams of water

Zu weiteren Neutralisation werden noch 9,6 Gramm 50-prozentigeFor further neutralization, 9.6 grams are 50 percent

Schwefelsäure zugegeben.Sulfuric acid added.

Das neutalisierte Gemisch wird zur Abtrennung von festem Kaluimsulfat filtriert oder zentrifugiert, wonach sich das Filtrat in 100 Gramm einer leichteren Phase bestehend aus 40 Gramm Fettsäuren, 52 Gramm Fettsäuremethylester und 8 Gramm Methanol und 350 Gramm einer schweren Phase, welche Glycerin Methanol und Wasser enthält.The neutralized mixture is filtered or centrifuged to separate solid potassium sulfate, after which the filtrate is in 100 grams of a lighter phase consisting of 40 grams of fatty acids, 52 grams of fatty acid methyl ester and 8 grams of methanol and 350 grams of a heavy phase containing glycerin methanol and water.

Die leichtere Phase wird einer weiteren Veresterung wie in diesem Beispiel eingangs beschrieben, zugeführt. The lighter phase is fed to a further esterification as described at the beginning in this example.

Claims

Patentansprüche claims 1. Verfahren zur Herstellung von zur Verwendung als Dieselersatzkraftstoffe (Biodiesel) geeigneten Fettsäureestern niederer Alkohole mit 1 - 4 C- Atomen, insbesondere des Methanols, durch Neutralisation der bei der alkalikatalysierten Umesterung von Fettsäureglyceriden mit niederen Alkoholen, insbesondere mit Methanol, als Nebenprodukt anfallenden schweren Phase, der sogenannten Glycerinphase und durch schwefelsäurekatalysierte Veresterung des bei der Neutralisation der Glycerinphase erhaltenen Gemisches von freien Fettsäuren und1. A process for the preparation of fatty acid esters of lower alcohols with 1 to 4 carbon atoms, in particular methanol, suitable for use as diesel substitute fuels (biodiesel), by neutralizing the heavy by-products which occur in the alkali-catalyzed transesterification of fatty acid glycerides with lower alcohols, in particular with methanol Phase, the so-called glycerol phase and by sulfuric acid-catalyzed esterification of the mixture of free fatty acids and obtained in the neutralization of the glycerol phase Fettsäureestern niederer Alkohole, insbesondere des Methanols, mit niederen Alkoholen mit 1 - 4 C-Atomen, vorzugsweise mit Methanol, dadurch gekennzeichnet, dass manFatty acid esters of lower alcohols, especially of methanol, with lower alcohols with 1-4 C atoms, preferably with methanol, characterized in that a) die Veresterung des aus der Neutralisation der Glycerinphase erhaltenen Gemisches aus freien Fettsäuren und Fettsäureestern niederer Alkohole insbesondere des Methanols mit einem Überschuss eines niederen Alkohols mit 1 - 4 C-Atomen vorzugsweise Methanol in Gegenwart von konzentrierter Schwefelsäure durchführt, wobei sich das Reaktionsgemisch nach erfolgter Veresterung in eine Phase bestehend aus dem Fettsäureester des niederen Alkohols, vorzugsweise des Methanols und in eine Phase bestehend aus dem überschüssigen niederen Alkohol, vorzugsweise Methanol, Schwefelsäure und Reaktionswasser trennt, und dass mana) the esterification of the mixture of free fatty acids and fatty acid esters of lower alcohols obtained from the neutralization of the glycerol phase, in particular of methanol, with an excess of a lower alcohol having 1 to 4 carbon atoms, preferably methanol, in the presence of concentrated sulfuric acid, the reaction mixture taking place after the Esterification into a phase consisting of the fatty acid ester of the lower alcohol, preferably methanol and into a phase consisting of the excess lower alcohol, preferably methanol, sulfuric acid and water of reaction, and that one b) die die Fettsäureester der niederen Alkohole enthaltende Phase in an sich bekannte Weise durch Behandeln mit Alkalihydroxiden, vorzugsweise Kalilauge, durch Waschen mit Wasser und/oder Säuren und Abdampfen des überschüssigen niederen Alkohols reinigt, und dass manb) the phase containing the fatty acid esters of the lower alcohols in a manner known per se by treatment with alkali metal hydroxides, preferably potassium hydroxide solution, by washing with water and / or acids and evaporation of the excess lower alcohol, and in that c) die Phase bestehend aus dem überschüssigen niederen Alkohol vorzugsweise Methanol, Schwefelsäure und Reaktionswasser zur Neutralisation einer weiteren Glycerinphase verwendet, wobei sich das neutralisierte Gemisch in eine leichte Phase bestehend aus freien Fettsäuren, Fettsäureestern niederer Alkohole insbesondere des Methanols und freien niederen Alkoholen vorzugsweise Methanol und in eine schwerere Phase bestehend aus Glycerin, dem überschüssigen niederen Alkohol, vorzugsweise Methanol, und Alkalisulfat trennt.c) the phase consisting of the excess lower alcohol, preferably methanol, sulfuric acid and water of reaction Neutralization of a further glycerol phase is used, the neutralized mixture being divided into a light phase consisting of free fatty acids, fatty acid esters of lower alcohols, especially of methanol and free lower alcohols, preferably methanol, and a heavier phase consisting of glycerol, the excess lower alcohol, preferably methanol, and Separates alkali sulfate. 2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass die Veresterung des aus der Neutralisation der Glycerinphase erhaltenen Gemisches aus freien Fettsäuren und Fettsäureestern niederer Alkohole bei Temperaturen nicht über 50 °C, vorzugsweise nicht über 40 °C und besonders vorzugsweise nicht über 35 °C durchgeführt wird.2. The method according to claim 1, characterized in that the esterification of the mixture of free fatty acids and fatty acid esters of lower alcohols obtained from the neutralization of the glycerol phase at temperatures not above 50 ° C, preferably not above 40 ° C and particularly preferably not above 35 ° C is carried out. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die als Katalysator dienende konzentrierte Schwefelsäure in einer Menge von 0,5 bis 17 Masse% bezogen auf die Masse des Fettsäure-/ Fettsäureestergemisches eingesetzt wird.3. The method according to claim 1 or 2, characterized in that the concentrated sulfuric acid serving as a catalyst is used in an amount of 0.5 to 17 mass% based on the mass of the fatty acid / fatty acid ester mixture. 4. Verfahren nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die niederen Alkohole mit 1 - 4 C-Atomen in einer4. The method according to at least one of claims 1 to 3, characterized in that the lower alcohols with 1 - 4 carbon atoms in one Menge von 15 bis 200 Prozent bezogen auf die Menge des Fettsäure-/ Fettsäureestergemisches eingesetzt werden.Amount of 15 to 200 percent based on the amount of the fatty acid / fatty acid ester mixture can be used. 5. Verfahren nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Veresterung des Fettsäure-/5. The method according to at least one of claims 1 to 4, characterized in that the esterification of the fatty acid / Fettsäureestergemisches mit den niederen Alkoholen und der konzentrierten Schwefelsäure unter intensivem Rühren bei Erzeugung möglichst großer Turbulenzen in einem Zeitraum von 0,5 bis 3 Stunden durchgeführt wird.Fatty acid ester mixture with the lower alcohols and the concentrated sulfuric acid is carried out with vigorous stirring and the greatest possible turbulence in a period of 0.5 to 3 hours. 6. Verfahren nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass als niederer Alkohol Methanol verwendet wird. Verfahren nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass man die Fettsäureester der niederen Alkohole, vorzugsweise des Methanols, nach der Behandlung mit Alkalihydroxiden, vorzugsweise Kalilauge, in den Waschprozess einer Biodieselanlage einschleust. 6. The method according to at least one of claims 1 to 5, characterized in that methanol is used as the lower alcohol. Process according to at least one of Claims 1 to 6, characterized in that the fatty acid esters of the lower alcohols, preferably methanol, are introduced into the washing process of a biodiesel plant after treatment with alkali metal hydroxides, preferably potassium hydroxide solution.
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