EP1308498B1 - Procédé de production d'esters d'acides gras à partir de graisses et d'huiles non désacidifiées - Google Patents

Procédé de production d'esters d'acides gras à partir de graisses et d'huiles non désacidifiées Download PDF

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Publication number
EP1308498B1
EP1308498B1 EP02023941A EP02023941A EP1308498B1 EP 1308498 B1 EP1308498 B1 EP 1308498B1 EP 02023941 A EP02023941 A EP 02023941A EP 02023941 A EP02023941 A EP 02023941A EP 1308498 B1 EP1308498 B1 EP 1308498B1
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EP
European Patent Office
Prior art keywords
transesterification
carried out
stage
fatty acid
range
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02023941A
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German (de)
English (en)
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EP1308498A1 (fr
Inventor
Lothar Friesenhagen
Bernhard Dr. Gutsche
Bernard Schleper
Christian Dr. Pelzer
Nicole Schöffler
Sabine Dr. Both
Claudius Lott
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Cognis IP Management GmbH
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Cognis IP Management GmbH
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Classifications

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

Definitions

  • the invention is in the field of basic oleochemicals and relates to an improved one Process for the production of fatty acid esters from unrefined natural raw materials.
  • Transesterifications are usually carried out with base catalysis. Are triglycerides with high acid numbers used, it comes to the partial neutralization of the catalyst. This doesn't just have that Disadvantage that valuable catalyst is lost, the soaps that are created also stand for the Transesterification is no longer available and remains in the residue. This way you can neither Achieve high sales yet minimize the amount of residue.
  • One tries to solve the problem by using heavy metal catalysts, such as zinc soaps, instead of alkali hydroxides begins, which increases the reaction rate and reduces the formation of soaps can. Heavy metals are, however, rather undesirable as catalysts for ecotoxicological reasons.
  • the object of the invention was therefore to find a new process for the transesterification of fats and oils using non-heavy metal catalysts to provide the above reliably avoids the disadvantages described.
  • the use of non-deacidified, non-degummed fats and oils with acid numbers up to approx. 50 are possible without catalyst losses and soaps are formed.
  • acid numbers can be reached below 1 and the amount of residue reduced.
  • fatty acid alkyl esters of the formula (I) are lauric, myristic, palmitic and stearic acid ethyl, propyl or butyl ester and technical mixtures thereof; however, be preferred Fatty acid methyl ester produced.
  • synthetic materials are also used as starting materials Triglycerides are in question, since they usually do not have any particular acid numbers Problem described at the beginning not or only in a subordinate way. In the case of natural triglycerides, So the vegetable or animal fats or oils, the selection is not critical.
  • suitable ingredients are palm oil, palm kernel oil, coconut oil, beef tallow, sunflower oil or Rapeseed oil as well as their mixtures.
  • the first step in the process takes advantage of the fact that esterification is only acid-catalyzed run and thereby faster than transesterification reactions, which in turn both through Acids as can be catalyzed by bases. So while in usual procedures the humiliation the acid number through neutralization with the basic transesterification catalyst and soap formation takes place, takes place within the meaning of the invention, an esterification of the free fatty acids with the formation of alkyl esters instead, which are preferably directly identical to the target product.
  • catalysts for this first Lewis acids come into question, which are selected from the stage of the process Group formed by alkali salts of organic carboxylic acids with 1 to 4 carbon atoms, Alkali carbonates, alkali hydrogen carbonates and solutions of the catalysts in fatty acids or Partial glycerides.
  • Typical examples are alkali acetates, alkali propionates, alkali butyrates, sodium carbonate, Sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate.
  • Particularly preferred are potassium salts, especially potassium acetate, which is optionally in fatty acids or monoglycerides solved.
  • the amount of catalyst is generally 0.1 to 2, preferably 0.5 to 1% by weight based on the starting materials.
  • the reaction is usually carried out at temperatures in the range of 100 to 300, preferably 150 to 240 ° C carried out.
  • the pressure range can be between 5 and 100 bar and is preferably 60 to 90 bar.
  • the amount of methanol is calculated according to the Acid number, i.e. based on the amount of available fatty acids.
  • alcohol preferably methanol and triglyceride in a weight ratio of 1: 2 to 2: 1.
  • the amount of catalyst is in usually 0.1 to 2, preferably 0.5 to 1 wt .-% based on the starting materials.
  • the water formed in the second stage together with the methanol and the Glycerol released from transesterification can also be water-sensitive in the third stage Catalysts are used.
  • Sodium alcoholates are particularly suitable for this purpose, such as sodium or potassium methoxide, ethoxide or butoxide. These have the advantage to be particularly active so that it is now possible to work in milder conditions and thus saving manufacturing costs.
  • the amount of catalyst is generally from 0.1 to 2, preferably 0.5 to 1% by weight based on the starting materials.
  • the second stage of transesterification typically at milder temperatures in the range of 20 to 200, preferably 70 to 150 ° C and lower pressures in the range from 1 to 10, preferably 1 to 5 bar.
  • the third stage is optional. However, their introduction can result in a significant increase in sales be achieved.
  • Example 2 60 g of raw coconut oil, 31 g of methanol and 0.6 g of potassium soap were placed in the autoclave and heated to 230.degree. A pressure of 48 bar was established. Once the temperature was reached, the mixture was stirred for 30 minutes. Thereafter, the reaction was cooled and terminated. A sample was taken from the cooled, homogenized mixture for GC analysis. Then 0.32 g of methanolic KOH were added. The mixture was heated to 230 ° C. with stirring. A pressure of 33 bar was established. Once the temperature was reached, stirring was continued for 30 minutes. The reaction mixture was then cooled.
  • Example 3 As in Example 3, 722 g of crude coconut oil, 373 g of methanol and 7.3 g of potassium soap were added to the autoclave and heated to 230.degree. A maximum pressure of 43 bar was established. Once the temperature was reached, the mixture was stirred for 30 minutes. Thereafter, the reaction was cooled and terminated. A sample was taken from the cooled, homogenized mixture for GC analysis. 3.9 g of methanolic KOH were then added. The mixture was heated to 230 ° C. with stirring. A pressure of 33 bar was established. Once the temperature was reached, stirring was continued for 30 minutes. The reaction mixture was then cooled.
  • the methanol / water was removed from 1057 g of the reaction mixture obtained in this way in a rotary evaporator between 90 ° C.-135 ° C. and a water jet vacuum. At 135 ° C., no more distillate was obtained. A total of 242.5 g of a methanol / water mixture (1.5% water content) and 808 g of organic phase could be obtained. A phase separation then took place in a separating funnel at 110 ° C. It was possible to obtain 73.5 g of the lower phase (glycerol phase) and 734.1 g of the upper phase (methyl ester phase).
  • Example 4 734 g of methyl ester mixture were mixed with 51 g of methanol and 4 g of sodium methylate in an autoclave. The mixture was heated to 130 ° C. with stirring. This created a pressure of about 4 bar. Once the temperature was reached, the mixture was stirred for 10 minutes. The reaction mixture was then cooled and the mixture was sampled for GC analysis. A list of the reaction components in percent by weight without the proportion of methanol is given in Table 4: Composition (data as percentage of area) composition TG DG MG Methyl ester fatty acid Glycerin Final rehearsal --- 0.5 1.0 93.4 1.1 4th
  • Example 5 60 g of crude coconut oil, 31 g of methanol and 0.6 g of potassium soaps were placed in an autoclave and heated to 200 ° C., a pressure of 20 bar being established. The reaction mixture was stirred for 1 hour and the course of the reaction was followed by taking samples. A list of the reaction components in percentages by weight without the proportion of methanol is given in Table 5: Composition (data as percentage of area) composition TG DG MG Methyl ester fatty acid Glycerin Sample after 30 min 17.5 15.7 15.6 45.6 1.2 4.4 Sample after 1 h - 2.1 10.2 76.2 1.0 10.5

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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)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (13)

  1. Procédé de préparation d'esters alkyliques inférieurs d'acides gras à partir de matières grasses et d'huiles non désacidifiées, selon lequel
    a) on estérifie des triglycérides industriels ayant des indices d'acide allant de 1 à 50 en présence d'acides de Lewis avec des alcools inférieurs et on abaisse ainsi l'indice d'acide à des valeurs inférieures à 2,
    b) on soumet à une transestérification le mélange désacidifié obtenu de cette manière en présence d'hydroxydes alcalins et d'alcools inférieurs et on sépare ainsi l'eau et la glycérine libérée, et le cas échéant
    c) on soumet à une transestérification supplémentaire le mélange de transestérification obtenu de cette manière en présence d'alcoolates alcalins et on sépare également ainsi la glycérine libérée,
    étant précise que dans la première étape (étape a) on utilise des acides de Lewis choisis dans le groupe des sels alcalins d'acides carboxyliques organiques comportant de 1 à 4 atomes de carbone, des carbonates alcalins, des hydrognèno carbonates alcalins ainsi que des solutions des catalyseurs dans des acides gras ou des glycérides partiels,
    et étant en outre précisé que les esters alkyliques inférieurs d'acides gras répondent à la formule (I) : R1CO-OR2 dans laquelle R1CO représente un radical acyle linéaire ou ramifié, saturé ou insaturé comportant de 6 à 22 atomes de carbone et R2 représente un radical alkyle linéaire ou ramifié comportant de 1 à 4 atomes de carbone.
  2. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on prépare des esters méthyliques d'acides gras.
  3. Procédé selon la revendication 1 ou 2,
    caractérisé en ce qu'
    on utilise des matières grasses et/ou des huiles naturelles choisies dans le groupe formé par l'huile de palme, l'huile de palmiste, l'huile de coprah, le suif de boeuf, l'huile de tournesol ou l'huile de colza ainsi que leurs mélanges.
  4. Procédé selon au moins une des revendications 1 à 3,
    caractérisé en ce que
    dans la première étape, on utilise comme acides de Lewis de l'acétate de potassium ou des solutions d'acétate de potassium dans des acides gras.
  5. Procédé selon l'une des revendications 1 à 4,
    caractérisé en ce qu'
    on utilise des sels de potassium comme acides de Lewis.
  6. Procédé selon au moins une des revendications 1 à 5,
    caractérisé en ce que
    dans la première étape on effectue l'estérification à des températures allant de 100 à 300°C.
  7. Procédé selon au moins une des revendications 1 à 6,
    caractérisé en ce que
    dans la première étape on effectue l'estérification sous des pressions allant de 5 à 100 bars.
  8. Procédé selon au moins une des revendications 1 à 7,
    caractérisé en ce que
    dans la seconde étape on effectue la transestérification en présence de solutions anhydres, éventuellement alcooliques, d'hydroxyde de sodium ou de potassium.
  9. Procédé selon au moins une des revendications 1 à 8,
    caractérisé en ce que
    dans la seconde étape on effectue la transestérification à des températures allant de 100 à 250°C.
  10. Procédé selon au moins une des revendications 1 à 9,
    caractérisé en ce que
    dans la seconde étape on effectue la transestérification sous des pressions allant de 5 à 100 bars.
  11. Procédé selon au moins une des revendications 1 à 10,
    caractérisé en ce que
    dans le troisième étape on effectue la transestérification en présence d'alcoolates alcalins.
  12. Procédé selon au moins une des revendications 1 à 11,
    caractérisé en ce que
    dans la troisième étape on effectue la transestérification à des températures allant de 20 à 200°C.
  13. Procédé selon au moins une des revendications 1 à 12,
    caractérisé en ce que
    dans la troisième étape on effectue la transestérification sous des pressions allant de 1 à 10 bars.
EP02023941A 2001-11-06 2002-10-25 Procédé de production d'esters d'acides gras à partir de graisses et d'huiles non désacidifiées Expired - Lifetime EP1308498B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10154365 2001-11-06
DE10154365A DE10154365A1 (de) 2001-11-06 2001-11-06 Verfahren zur Herstellung von Fettsäureestern aus nicht entsäuerten Fetten und Ölen

Publications (2)

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EP1308498A1 EP1308498A1 (fr) 2003-05-07
EP1308498B1 true EP1308498B1 (fr) 2005-07-20

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EP02023941A Expired - Lifetime EP1308498B1 (fr) 2001-11-06 2002-10-25 Procédé de production d'esters d'acides gras à partir de graisses et d'huiles non désacidifiées

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EP (1) EP1308498B1 (fr)
AT (1) ATE299925T1 (fr)
DE (2) DE10154365A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT502218B1 (de) 2005-07-25 2010-09-15 Bdi Biodiesel Internat Ag Verfahren zur herstellung von carbonsäurealkylestern

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2383601A (en) * 1943-04-28 1945-08-28 Colgate Palmolive Peet Co Treating fats and fatty oils
JPS6025478B2 (ja) * 1977-03-17 1985-06-18 花王株式会社 脂肪酸低級アルコ−ルエステルの製造法
DE3319590A1 (de) * 1983-05-30 1984-12-06 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung von fettsaeureestern kurzkettiger aliphatischer alkohole aus freie fettsaeuren enthaltenden fetten und/oder oelen
DE3444893A1 (de) * 1984-12-08 1986-06-12 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung von fettsaeuremethylestern
DE3515403A1 (de) * 1985-04-29 1986-10-30 Henkel KGaA, 4000 Düsseldorf Verfahren zur katalytischen umesterung von fettsaeureglyceriden mit niederen alkanolen
WO1987007632A1 (fr) * 1986-06-11 1987-12-17 Bio-Energy Technology Ltd. Production de carburant biologique
JPH04182451A (ja) * 1990-11-17 1992-06-30 Daisan Kasei Kk 高級脂肪酸モノグリセリドの製造方法
US5525126A (en) * 1994-10-31 1996-06-11 Agricultural Utilization Research Institute Process for production of esters for use as a diesel fuel substitute using a non-alkaline catalyst
JP2000144172A (ja) * 1998-11-13 2000-05-26 Sumitomo Chem Co Ltd 脂肪酸エステル類の製造方法および脂肪酸エステル類の用途

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Publication number Publication date
ATE299925T1 (de) 2005-08-15
EP1308498A1 (fr) 2003-05-07
DE50203669D1 (de) 2005-08-25
DE10154365A1 (de) 2003-05-15

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