EP0200982B1 - Procédé d'interestérification catalytique de glycérides d'acides gras avec des alcanols inférieurs - Google Patents

Procédé d'interestérification catalytique de glycérides d'acides gras avec des alcanols inférieurs Download PDF

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Publication number
EP0200982B1
EP0200982B1 EP86105506A EP86105506A EP0200982B1 EP 0200982 B1 EP0200982 B1 EP 0200982B1 EP 86105506 A EP86105506 A EP 86105506A EP 86105506 A EP86105506 A EP 86105506A EP 0200982 B1 EP0200982 B1 EP 0200982B1
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EP
European Patent Office
Prior art keywords
fatty acid
alkanol
glycerol
phase
transesterification
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP86105506A
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German (de)
English (en)
Other versions
EP0200982A1 (fr
Inventor
Lutz Dr. Jeromin
Eberhard Peukert
Gerhard Dr. Wollmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT86105506T priority Critical patent/ATE39947T1/de
Publication of EP0200982A1 publication Critical patent/EP0200982A1/fr
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Publication of EP0200982B1 publication Critical patent/EP0200982B1/fr
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Classifications

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

Definitions

  • the invention relates to an improved process for the preparation of esters of fatty acids or fatty acid mixtures and lower monofunctional alcohols by catalytic transesterification of fatty acid glycerides with the lower monofunctional alcohols in the presence of basic catalysts.
  • the corresponding C, -4- alcohols are suitable as lower monofunctional alcohols, methanol being of decisive technical importance in practice.
  • Fatty acid glycerides in the sense of the teaching according to the invention are corresponding triglycerides or any partial esters of fatty acids or fatty acid mixtures and glycerol. Of particular importance here are the triglycerides and, above all, fats and / or oils of native origin which can be converted into fatty acid methyl esters in a simple manner by the process according to the invention.
  • Fatty acid methyl esters are of great technical importance as a starting material for the production of fatty alcohols and other oleochemical products such as ester sulfates, fatty acid alkanolamides and soaps.
  • the industrial production of the fatty acid methyl esters takes place predominantly by catalytic transesterification (alcoholysis) of fatty acid triglyceride mixtures, as are present in the fats and oils of vegetable and / or animal origin.
  • Such pre-esterification of acidic fatty acid glycerides can be carried out in several ways. For example, it is possible to work in the presence of alkaline catalysts from 240 ° C. and 20 bar (Ullmann, Encyclopedia of Industrial Chemistry, 4th edition, volume 11, 1976, page 432). However, this type of pre-esterification with methanol in turn requires the use of expensive reactors. It is also known to esterify the free fatty acids in the oil with added monofunctional lower alcohols, especially methanol, in a homogeneous phase by means of acid catalysis, for. B. using p-toluenesulfonic acid as a catalyst.
  • a transesterification process is known in which anhydrous fatty acid glycerides are treated with an alcohol at elevated temperatures and in the presence of a transesterification catalyst, then the catalyst is removed in the cold, the excess alcohol is distilled off and finally the fatty acid ester obtained from the glycerol separates.
  • the Ver used catalysts, sodium alkyl carbonates and sodium alkyl sulfites, are almost neutral and practically insoluble in the cold.
  • the teaching of the present invention is based on the fact that fatty acid glycerides are reacted with lower monofunctional alcohols, in particular with methanol, with basic catalysis without problems under mild reaction conditions, in particular at ambient pressure, low temperatures and low use of methanol to give the corresponding alkyl esters and free glycerol can and that for the preconditions set here - low contents of the feed material in free fatty acids and water - there are sufficient practical possibilities of implementation.
  • the inventors have set themselves the task of modifying this base-catalyzed transesterification of the fatty acid glycerides with monofunctional alcohols, in particular methanol, in such a way that solids which are practically insoluble in the feedstock or reaction mixture are used as catalysts - and thus with heterogeneous catalysis. It is obvious that considerable simplifications are obtained in this way, in particular when the catalyst is separated from the reaction mixture.
  • the solution to the problem according to the invention is based on the surprising finding that solid sodium carbonate Na 2 CO 3 and / or sodium hydrogen carbonate NaHCO 3 are suitable as heterogeneous solid catalysts, the desired alcoholic cleavage of fatty acid glycerides under the mild conditions known per se, in particular of low pressures and temperatures catalyze effectively.
  • the invention relates in a first embodiment to the use of solid sodium carbonate and / or sodium bicarbonate as heterogeneous solid catalysts in the transesterification of deacidified to an acid number of at most 1 and to a water content of at most 0.8% by weight of anhydrous fatty acid glycerides with im essential anhydrous monofunctional C '-4 alcohols to fatty acid alkyl esters and glycerol.
  • the invention relates to a process for the catalytic transesterification of fatty acid glycerides, in particular fats and / or oils of natural origin, with monofunctional Cl-4-alkanols by reacting the acidified to an acid number of at most 1 and to a water content of at most 0.8 %
  • anhydrous glyceride starting material with the essentially anhydrous alkanol in the presence of a catalyst which is practically insoluble in the cold, in the range from atmospheric pressure and moderately elevated temperatures above 60 ° C., preferably in the range of the boiling point of the alkanol, with subsequent separation of the glycerol released.
  • the new process is characterized in that solid sodium carbonate and / or solid sodium bicarbonate is used as a heterogeneous solid catalyst.
  • the process is carried out under energy-saving and cost-saving conditions in such a way that the fatty acid glyceride feedstock is reacted in the range of normal pressure and at only moderately elevated temperatures which do not substantially exceed the range of about 100.degree.
  • the process temperature in the transesterification is preferably in the range of the boiling point of the alkanol used. Since work is carried out at normal pressure or only slightly elevated pressures, the reaction temperature for the transesterification of the glycerides with methanol is usually in the range from about 60 to 75 ° C., preferably in the range from about 65 to 70 ° C.
  • Suitable fatty acid glycerides are in particular appropriately pretreated (deacidified) fats and / or oils of vegetable and / or animal origin. They are subjected to the transesterification with monofunctional alkanols with 1 to 4 carbon atoms. Methanol is preferably used as the lower alkanol.
  • the glyceride feed material should have an acid number of at most 1, preferably acid number of at most 0.7, it being particularly expedient to work with acid numbers in the range of about 0.5 or less.
  • the water content of the glyceride feed should be as low as possible; it is not more than about 0.8% by weight, it is preferred to work under practically anhydrous conditions. Deacidified and anhydrous glyceride feed material can easily be obtained as a reaction product of the upstream process stages described in the introduction - in particular as a product of a pre-esterification of the starting material.
  • the reaction mixture uses weight ratios of alkanol - preferably methanol - to fatty acid glyceride in the range from 0.2 to 1: 1 and particularly preferably in the range from 0.2 to 0.5: 1.
  • the heterogeneously catalyzed transesterification can be carried out batchwise or continuously.
  • the catalyst can be either a finer or coarser powder, in Form of chips or tablets or as impregnation catalyst applied to a support material.
  • the catalyst material can be arranged as a fixed bed, it is also possible to work with a moving bed of catalyst material, for example in stirred tanks, in a fluidized bed or fluidized bed in pulsation devices and the like. It is particularly expedient to carry out the heterogeneously catalyzed transesterification at normal pressure with low boiling point of the alcohol.
  • the released glycerol is preferably separated from the reaction mixture by phase separation.
  • it may be expedient to cool the reaction mixture or a partial stream branched off from the reaction mixture. It is advantageous to evaporate part of the monofunctional alcohol from the reaction mixture or from the branched-off partial stream of the reaction mixture before this cooling.
  • the solubility of the released glycerol in the fatty acid ester / alcohol / oil phase is reduced and at the same time the density of the glycerol phase is increased, so that the resulting glycerol can be easily removed by phase separation.
  • the alkanol drawn off from the reaction mixture in this way is preferably returned to the reactor in a circuit.
  • the partial removal of the glycerol from the reaction mixture is carried out in such a way that when a partial stream, in particular continuously branched out of the reactor, is freed from the methanol and then separated from free glycerol, the methyl ester / oil phase returned to the reactor is a homogeneous liquid phase is, d. H. that neither a separate methanol phase nor a phase consisting of free glycerol occurs in the recirculated liquid phase.
  • a particularly preferred embodiment of the invention consists in first passing at least a partial stream of the reactant mixture through an evaporator in which the free alkanol present is evaporated at least partially in the continuous process.
  • the liquid phase is then cooled to temperatures below 50 ° C., in particular to temperatures in the range from 30 to 40 ° C., whereupon the heavier glycerol phase is separated and discharged by phase separation, while part of the lighter ester phase is recycled into the transesterification as a recycle stream the evaporated alkanol portion and fresh reactants are fed in simultaneously.
  • the transesterification is carried out in several stages in a reactor cascade.
  • the process according to the invention is particularly suitable as an important process step in the processing of natural in particular unpurified fats and / or oils such as coconut oil, palm kernel oil, soybean oil, tallow and the like. It is not necessary to clean these raw materials from the naturally contained sludge and mucilage.
  • the natural starting material is first subjected to pre-esterification as described at the beginning.
  • the process carried out with solid cation exchange resins according to the applicant's older EP-A-192 035 is particularly suitable here.
  • the material obtained in this preliminary stage with acid numbers preferably below 0.7 contains, in addition to methanol, the excess from the pre-esterification also water components which can be partially or completely expelled as a mixture.
  • the proportion of bound glycerol in the methyl ester phase after the glycerol separation was approximately 0.5% by weight. The values were reproducible over several days without changing the catalyst.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Claims (8)

1. Utilisation de carbonate de sodium solide et/ou de bicarbonate de sodium solide comme catalyseurs solides en phase hétérogène dans la transestérification par des alcools monofonctionnels en C, à C4 essentiellement libres d'eau, en esters alkyliques d'acides gras et en glycérine, de glycérides d'acides gras, en particulier de graisses et/ou d'huiles d'origine naturelle, désacidifiés jusqu'à un indice acide de 1 au plus et libérés d'eau jusqu'à une teneur en eau de 0,8 % en poids au plus.
2. Procédé de transestérification catalytique de glycérides d'acides gras provenant en particulier de graisses et/ou d'huiles d'origine naturelle par des alcools monofonctionnels en C, à C4 par réaction du matériau de départ glycéridique désa- cidifié jusqu'à un indice acide de 1 au plus et libéré d'eau jusqu'à une teneur en eau de 0,8 % en poids au plus, au moyen d'alcool essentiellement libre d'eau, en présence d'un catalyseur pratiquement insoluble à froid, aux alentours de la pression normale et à des températures modérément élevées, supérieures à 60 °C, de préférence dans la zone de la température d'ébullition de l'alcool, avec séparation subséquente de la glycérine libérée, caractérisé en ce que l'on utilise comme catalyseur solide en phase hétérogène le carbonate de sodium et/ou le bicarbonate de sodium solides.
3. Procédé selon la revendication 2, caractérisé en ce que l'on utilise les catalyseurs solides sous forme de poudre - en particulier dans ce cas en dispersion dans le mélange de réactifs - ou sous forme d'un matériau en morceaux, et éventuellement présent sur un matériau de support - en particulier dans ce cas sous la forme de catalyseurs en lit fixe.
4. Procédé selon les revendications 2 et 3, caractérisé en ce que l'on utilise des glycérides d'acides gras désacidifiés présentant un indice acide de 0,7 au plus et pratiquement libres d'eau.
5. Procédé selon les revendications 2 à 4, caractérisé en ce que l'on travaille en début de réaction avec des proportions en poids d'alcool au glycéride d'acides gras dans la plage de 0,2 à 1 : 1, et de préférence dans la plage de 0,2 à 0,5 : 1 et que l'on utilise comme alcool de préférence le méthanol.
6. Procédé selon les revendications 2 à 5, caractérisé en ce que la glycérine libérée est séparée du mélange réactionnel par refroidissement et séparation de phases, par quoi l'alcool est tout d'abord vaporisé et une phase contenant la glycérine libre est ensuite séparée.
7. Procédé selon les revendications 2 à 6, caractérisé en ce que, dans un procédé en continu, l'on conduit au moins un courant partiel du mélange de réactifs dans un vaporiseur dans lequel l'alcool libre présent est vaporisé au moins partiellement, et qu'ensuite la phase liquide est refroidie à des températures inférieures à 50 °C, en particulier à des températures dans la plage de 30 à 40 °C, suite à quoi on sépare et retire la phase de glycérine plus lourde par séparation de phases, pendant que l'on réinjecte en transestérification dans un circuit fermé une partie de la phase ester plus légère, en même temps que l'on alimente la transestérification en la fraction alcool vaporisée et en réactifs frais.
8. Procédé selon les revendications 2 à 7, caractérisé en ce que la transestérification est effectuée en plusieurs étapes dans une cascade de réacteurs.
EP86105506A 1985-04-29 1986-04-21 Procédé d'interestérification catalytique de glycérides d'acides gras avec des alcanols inférieurs Expired EP0200982B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86105506T ATE39947T1 (de) 1985-04-29 1986-04-21 Verfahren zur katalytischen umesterung von fettsaeureglyceriden mit niederen alkanolen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853515403 DE3515403A1 (de) 1985-04-29 1985-04-29 Verfahren zur katalytischen umesterung von fettsaeureglyceriden mit niederen alkanolen
DE3515403 1985-04-29

Publications (2)

Publication Number Publication Date
EP0200982A1 EP0200982A1 (fr) 1986-11-12
EP0200982B1 true EP0200982B1 (fr) 1989-01-11

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Family Applications (1)

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EP86105506A Expired EP0200982B1 (fr) 1985-04-29 1986-04-21 Procédé d'interestérification catalytique de glycérides d'acides gras avec des alcanols inférieurs

Country Status (7)

Country Link
EP (1) EP0200982B1 (fr)
JP (1) JPS61254255A (fr)
AT (1) ATE39947T1 (fr)
BR (1) BR8601882A (fr)
DE (2) DE3515403A1 (fr)
GB (1) GB2174697B (fr)
PH (1) PH23503A (fr)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2698101B1 (fr) * 1992-11-19 1995-01-06 Arceau Huileries Procédé de transestérification catalytique de corps gras d'origine végétale ou animale et procédé de récupération des produits obtenus.
NL9302126A (nl) * 1993-12-07 1995-07-03 Meern Bv Engelhard De Werkwijze voor het interesterificeren van triglycerides.
US5844111A (en) * 1995-06-07 1998-12-01 The Procter & Gamble Company Method for purifying an inert gas while preparing lower alkyl esters
US5648483A (en) * 1995-06-07 1997-07-15 The Procter & Gamble Company Continuous transesterification method for preparing polyol polyesters
JP4752118B2 (ja) * 2000-02-17 2011-08-17 住友化学株式会社 脂肪酸エステルの製造方法および脂肪酸エステルを含む燃料
CA2336513C (fr) 2000-02-17 2010-08-24 Tatsuo Tateno Methode de production d'esters d'acide gras et combustibles contenant un ester d'acide gras
JP4936605B2 (ja) * 2001-04-12 2012-05-23 株式会社レボインターナショナル 脂肪酸アルキルエステルの製造方法
DE10154365A1 (de) * 2001-11-06 2003-05-15 Cognis Deutschland Gmbh Verfahren zur Herstellung von Fettsäureestern aus nicht entsäuerten Fetten und Ölen
FR2838433B1 (fr) * 2002-04-11 2005-08-19 Inst Francais Du Petrole Procede de production d'esters alkyliques a partir d'une huile vegetale ou animale et d'un monoalcool aliphatique
JP4204926B2 (ja) 2003-08-07 2009-01-07 花王株式会社 脂肪酸エステルの製造方法
CA2535747A1 (fr) 2003-08-29 2005-03-10 Nippon Shokubai Co., Ltd. Procede de production d'alkyl esters d'acide gras et/ou de glycerine et composition renfermant lesdits esters
US7270768B2 (en) * 2003-09-23 2007-09-18 Mli Associates, Llc Environmentally benign anti-icing or deicing fluids employing triglyceride processing by-products
JP4219349B2 (ja) 2005-09-16 2009-02-04 富士フイルム株式会社 脂肪酸アルキルエステルの製造方法及び燃料
JP5047499B2 (ja) 2005-12-28 2012-10-10 花王株式会社 脂肪酸アルキルエステルの製造方法
KR20090125248A (ko) 2007-02-06 2009-12-04 자노스 테스즈 변형된 구조의 트리글리세리드에 기반한 연료 또는 연료 첨가물의 용도 및 그 제조 방법
FR2918060B1 (fr) 2007-06-29 2009-09-18 Inst Francais Du Petrole Amelioration de la separation dans un procede de production d'esters alkyliques a partir d'huile vegetale ou animale et d'un monoalcool aliphatique
FR2918059B1 (fr) * 2007-06-29 2010-10-29 Inst Francais Du Petrole Amelioration de la decantation dans un procede de production d'esters alkyliques a partir d'huile vegetale ou animale et d'un monoalcool aliphatique.
EP2201155B1 (fr) * 2007-09-05 2015-10-21 Ceramatec, Inc. Procédé de production de biodiesel au moyen d'un catalyseur donneur d'ions alcalins
JP5306011B2 (ja) 2008-03-26 2013-10-02 花王株式会社 水硬性組成物用早強剤
EP2258668B1 (fr) 2008-03-26 2019-04-24 Kao Corporation Composition d'additif pour compositions hydrauliques

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE506421A (fr) *
US2561394A (en) * 1946-03-16 1951-07-24 Donald E Marshall Method of coating particulate materials
DE3421217A1 (de) * 1984-06-07 1985-09-05 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von fettsaeureestern kurzkettiger alkohole

Also Published As

Publication number Publication date
GB8608680D0 (en) 1986-05-14
PH23503A (en) 1989-08-16
JPS61254255A (ja) 1986-11-12
EP0200982A1 (fr) 1986-11-12
ATE39947T1 (de) 1989-01-15
GB2174697A (en) 1986-11-12
DE3661737D1 (en) 1989-02-16
DE3515403A1 (de) 1986-10-30
GB2174697B (en) 1988-12-21
BR8601882A (pt) 1986-12-30

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