EP0184740B1 - Procédé de préparation d'esters méthyl d'acides gras - Google Patents

Procédé de préparation d'esters méthyl d'acides gras Download PDF

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Publication number
EP0184740B1
EP0184740B1 EP85115217A EP85115217A EP0184740B1 EP 0184740 B1 EP0184740 B1 EP 0184740B1 EP 85115217 A EP85115217 A EP 85115217A EP 85115217 A EP85115217 A EP 85115217A EP 0184740 B1 EP0184740 B1 EP 0184740B1
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EP
European Patent Office
Prior art keywords
methanol
oil phase
glycerol
transesterification
fatty acids
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 - Lifetime
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EP85115217A
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German (de)
English (en)
Other versions
EP0184740A3 (en
EP0184740A2 (fr
Inventor
Herbert Dr. Lepper
Lothar Friesenhagen
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
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Priority to AT85115217T priority Critical patent/ATE61332T1/de
Publication of EP0184740A2 publication Critical patent/EP0184740A2/fr
Publication of EP0184740A3 publication Critical patent/EP0184740A3/de
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Publication of EP0184740B1 publication Critical patent/EP0184740B1/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 a process for the preparation of fatty acid methyl ester mixtures by catalytic transesterification from natural fats and oils which contain free fatty acids.
  • 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 sulfonates, fatty acid alkanolamides and soaps.
  • the industrial production of the fatty acid methyl esters is predominantly carried out by catalytic transesterification (alcoholysis) of fatty acid triglyceride mixtures as they are present in the fats and oils of vegetable and animal origin.
  • fats and oils can be transesterified at 25 to 100 ° C. with a 0.5 to 1.0 molar excess of alcohol under normal pressure to give the corresponding fatty acid ester mixtures.
  • a corresponding method is described as the first stage of soap production in US Pat. No. 2,360,844. This alkali-catalyzed, pressure-free transesterification can be carried out without problems, as long as fats and oils are used which are largely anhydrous and whose free fatty acid content is below 0.5% by weight (corresponding to an acid number of about 1).
  • fats and oils with a higher content of free fatty acids in the presence of alkali or zinc catalysts at 240 ° C. under a pressure of about 100 bar with a 7- to 8-molar excess of methanol can be added to the corresponding ones
  • Fatty acid methyl esters are transesterified (Ullmann, Encyclopedia of Industrial Chemistry, 4th edition, Volume 11 (1976), page 432).
  • the unpressurized transesterification is characterized by a significantly lower methanol requirement and - because of the lower reaction temperatures - by a lower energy consumption.
  • the transesterification works under normal pressure without expensive pressure reactors. Due to the fact that there are almost always larger amounts of water and fatty acids in technical fats and oils, the unpressurized transesterification requires drying and a reduction in the acid number - e.g. by
  • the pre-esterification of the acidic fats and oils can be carried out in the presence of alkaline catalysts at 240 ° C and 20 bar (Ullmann, Encyclopedia of Industrial Chemistry, 4th Edition, Volume 11 (1976), page 432). This type of pre-esterification with methanol in turn requires the use of expensive pressure reactors.
  • the invention had for its object to facilitate the production of fatty acid methyl esters from such triglyceride starting materials that contain large amounts of water and free fatty acids.
  • both process stages should be able to be carried out at comparatively low temperatures and without the use of pressure reactors.
  • the excess alcohol required for the transesterification should be kept as low as possible, taking into account the necessary processing and cleaning steps.
  • it should enable the production of fatty acid methyl esters in an energy-saving and cost-effective manner, especially with starting materials such as those obtained as fats and oils of vegetable or animal origin.
  • stage a) of the process according to the invention the proportion of free fatty acids present in the triglyceride mixtures of the starting material is esterified in the presence of acidic esterification catalysts with an excess of methanol.
  • comparatively mild reaction conditions are chosen so that a transesterification of the triglycerides with methanol does not take place or does not take place to a significant extent.
  • the ratio between triglyceride and methanol is expediently chosen so that on the one hand there is a clear excess of methanol over the free acid to be esterified, and on the other hand a clean separation into an oil and a methanol phase is ensured at the end of the reaction.
  • 20 to 50 parts by volume of methanol are normally used per 100 parts by volume of starting material.
  • stage a The pre-esterification of stage a) is usually carried out at normal pressure.
  • Working with low overpressure can be advantageous in various cases. In this case, however, only pressures up to 5 bar come into consideration, for the realization of which no special pressure reactors are required.
  • all acidic, non-volatile esterification catalysts are suitable as catalysts for stage a), for example the corresponding systems based on Lewis acids, low-volatility inorganic acids and their acidic partial esters and heteropolyacids.
  • Alkyl, aryl or alkarylsulfonic acids such as e.g. Methanesulfonic acid, naphthalenesulfonic acid and dodecylbenzenesulfonic acid.
  • Sulfuric acid and glycerol monosulfuric acid are examples of low volatile inorganic acids and their partial esters.
  • Suitable heteropolyacids are the tungstic and molybdate phosphoric acids. These catalysts are generally used in amounts of 0.5 to 5 parts by weight per 100 parts by weight of starting material.
  • the reactants together with the catalyst were heated to the intended reaction temperature with vigorous stirring and then held at this temperature until the acid number of the oil phase had dropped to the desired value.
  • the acid number of the oil phase is preferably reduced to values below 1 in stage a).
  • Process stage a) can be carried out batchwise or continuously.
  • the alcohol and oil components can be carried out in cocurrent and in countercurrent.
  • reaction mixture is left at temperatures between 40 and 60 ° C. without further stirring.
  • a separation into an oil and a methanol phase occurs.
  • the two liquid phases are separated in a known manner.
  • the methanol phase which contains most of the water of reaction and practically all of the amount of catalyst, is worked up by distillation to recover the catalyst and the methanol.
  • the catalyst remains in the distillation residue, which can be used again as a catalyst additive in stage a) of the process according to the invention without further purification steps.
  • the oil phase resulting from step a) is mixed with the intended amount of glycerol-methanol mixture and the mixture obtained is stirred vigorously for 1 to 5 minutes. The mixture is then left to stand still until phase separation and the extracted oil phase is separated off. In order to separate the water of reaction and catalyst residues still present as far as possible, it has proven to be advantageous not to carry out the entire extraction in stage b) at normal temperature, but at 40 to 60.degree.
  • Step b) can be carried out in batch mode in a simple stirred tank.
  • this sub-step of the process according to the invention can be carried out in a cascade of stirred tanks or in a column equipped with static mixing elements. It is also possible to continuously pass the oil phase and the glycerol-methanol mixture in countercurrent through an extraction column.
  • the deacidified and largely anhydrous triglycerides are subjected to the pressure-free, alkali-catalyzed, transesterification with methanol in a manner known per se.
  • the following conditions are expediently observed:
  • the transesterification is carried out with essentially anhydrous methanol.
  • the methanol is used in a 50 to 150 percent excess over the stoichiometric amount required for the transesterification.
  • Alkali metal hydroxides, in particular sodium and potassium hydroxide, and alkali metal alcoholates, in particular sodium methylate, are particularly suitable as catalysts.
  • the catalysts are used in amounts of 0.05 to 0.2 parts by weight per 100 parts by weight of triglyceride.
  • the mixture of triglyceride (oil phase), methanol and catalyst is heated to the intended reaction temperature with stirring.
  • the transesterification reaction takes place at sufficient speed even at 25 to 30 ° C. In general, however, it is preferred to carry out the transesterification reaction at temperatures from 50 to 100 ° C., especially at the reflux temperature.
  • the reaction mixture is allowed to stand without further stirring until the phases have separated.
  • the phases are then separated in a known manner.
  • the glycerol phase containing methanol is generally used as an extracting agent in stage b) of the process according to the invention before it is worked up to glycerol and methanol in a manner known per se.
  • the methyl ester phase is further processed in a manner known per se via appropriate purification and distillation steps to give the desired starting materials for organic syntheses.
  • the separated oil phase (204 kg; acid number 0.8; water content 0.34 percent by weight; methanol content 14.1 percent by weight) was 40.8 kg glycerol-methanol mixture from the alkali-catalyzed pressure-free transesterification (59.0 percent by weight) at 50 to 55 ° C. Glycerin; 28.1 weight percent methanol; 12.8 weight percent fat derivatives; 0.1 weight percent free alkali) added.
  • the two-phase mixture was stirred for 10 minutes. After the stirring process had ended, the two phases were clearly separated in a few minutes. After draining off the glycerol phase, 196 kg of oil phase remained (acid number 0.4; water content 0.08 percent by weight; methanol content 10.6 percent by weight).
  • the extracted oil phase was refluxed with 35 liters (27.7 kg) of methanol and 0.3 kg of sodium methylate as the transesterification catalyst with stirring for 30 minutes.
  • the reaction mixture was then cooled to 50 ° C.
  • the methanol-containing glycerol phase which separated out was separated off.
  • the remaining crude coconut fatty acid methyl ester (188 kg) contained 0.4 weight percent bound glycerin, 0.02 weight percent water and 8.1 weight percent methanol; its acid number was 0.04.
  • the low level of bound glycerol shows that the transesterification has taken place with a very high degree of conversion. If this value is related to the content of bound glycerin in the coconut oil used (13.2 percent by weight), it follows that 97% of the bound glycerin were released during the transesterification and only 3% are still present in the crude methyl ester.
  • Example 2 200 liters (174 kg) of coconut oil (acid number 15.1) were reacted with 60 liters (47.4 kg) of methanol in the presence of 1.6 kg of p-toluenesulfonic acid with stirring at 65 ° C.
  • the oil phase obtained (204 kg; acid number 0.8; water content 0.34 percent by weight) was fed directly to the unpressurized transesterification.
  • the oil phase was heated to reflux with 36, 51 (288 kg) methanol and 0.3 kg Na methylate with stirring for 30 minutes. After cooling to 50 ° C., the lower phase containing methanol and glycerol was separated off.
  • the raw coconut fatty acid methyl ester (186 kg) contained 2.3 weight percent bound glycerol, 0.09 weight percent water and 7.9 weight percent methanol; its acid number was 0.04.
  • This example shows that the catalyst used can be easily recovered from the methanol phase by pre-esterification by distilling off the methanol and the water of reaction. When the catalyst is reused, there is no appreciable impairment in activity.
  • Example 2 The methanol phase obtained in Example 2 was again evaporated and the residue was used for a further pre-esterification. Almost the same results as in Example 2 were obtained.
  • the following analytical values were determined for the oil phase: 0.33 percent by weight water; 15.5 weight percent methanol; Acid number 0.9.
  • the separated oil phase (204 kg) was at 50 to 55 ° C with 40.8 kg glycerol-methanol mixture from the alkali-catalyzed unpressurized transesterification (55.0 weight percent glycerol; 33.7 weight percent methanol; 11.2 weight percent fat derivatives; 0, 1 weight percent free alkali) stirred for 10 minutes. After renewed phase separation, the oil phase had an acid number of 0.5.
  • the oil phase (195 kg) was transesterified at 65 ° C. with the addition of 35 l (27.7 kg) of methanol and 0.3 kg of sodium methylate.
  • the raw coconut fatty acid methyl ester obtained (185 kg) contained 0.5 percent by weight glycerol, 0.02 percent by weight water and 7.6 percent by weight methanol; its acid number was 0.04.
  • Example 2 Analogously to Example 1, 200 liters (174 kg) of beef tallow (acid number 21) were pre-esterified with 60 liters (47.4 kg) of methanol in the presence of 1.6 kg of p-toluenesulfonic acid. The oil phase separated off from the reaction mixture was extracted with 40.8 kg of glycerol-methanol mixture from a previous alkali-catalyzed pressure-free transesterification. The pre-esterified tallow had an acid number of 0.6 after separation from the glycerol-methanol phase.
  • Example 2 Analogously to Example 1, 200 liters (174 kg) of coconut oil (acid number 15.1) were reacted with 60 liters (47.4 kg) of methanol in the presence of 0.4 kg of 98 percent by weight sulfuric acid at 65 ° C. for 15 minutes.
  • the separated oil phase (206 kg; acid number 0.7; water content 0.31 percent by weight; methanol content 11.3 percent by weight) was extracted from the alkali-catalyzed transesterification (57.1 percent by weight) with a 41.2 kg glycerol-methanol mixture at 50 - 55 ° C Glycerin; 33.0 weight percent methanol; 9.8 weight percent fat derivatives; 0.1 weight percent free alkali) stirred for 10 minutes. After the phase separation, 0.13 percent by weight of water and 11.6 percent by weight of methanol were found in the oil phase; the acid number was 0.2.
  • the oil phase (197 kg) was transesterified at 65 ° C. with the addition of 35 l (27.7 kg) of methanol and 0.3 kg of sodium methylate.
  • the resulting coconut fatty acid methyl ester (188 kg) contained 0.5 weight percent glycerol, 0.2 weight percent water and 6.1 weight percent methanol; the acid number was 0.04.
  • Example 6 was repeated with the modification that the oil phase obtained from the pre-esterification was fed directly to the alkali-catalyzed unpressurized transesterification without intermediate extraction with a glycerol-methanol mixture. With this procedure, a Obtained coconut fatty acid methyl ester containing 2 percent by weight bound glycerin.
  • Example 6 shows that the degree of conversion in the transesterification of the pre-esterified oil can be considerably improved if the pre-esterified oil is extracted with a glycerol-methanol mixture before the transesterification.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Hydrogenated Pyridines (AREA)

Claims (8)

  1. Procédé pour la préparation d'esters méthyliques d'acides gras par transestérification catalytique de graisses et d'huiles naturelles contenant des acides gras libres, dans lequel
    a) dans une pré-estérification, on estérifie les acides gras libres présents dans le produit de départ, en présence de catalyseurs d'estérification acides, à 50 - 120°C et sous des pressions dans la plage de la pression normale à 5 bars, avec du méthanol qui est présent en excès par rapport aux acides gras libres, et on sépare la phase alcoolique contenant le catalyseur et une partie de l'eau de réaction,
    b) on extrait la phase huileuse restante et,
    c) on soumet la phase huileuse traitée à la transestérification sans pression avec du méthanol, catalysée par un alcali, caractérisé en ce que, pour l'élimination de l'eau de réaction résiduelle, on extrait la phase huileuse restante a 40 - 60°C avec un mélange de méthanol et de glycérol, dans lequel le rapport pondéral du glycérol au méthanol va de 1 : 0,25 à 1 : 1,25.
  2. Procédé selon la revendication 1, caractérisé en ce que, dans l'étape a), on utilise de 20 à 50 parties en volume de méthanol pour 100 parties en volume de produit de départ.
  3. Procédé selon les revendications 1 et 2, caractérisé en ce que, dans l'étape a), on opère sous la pression normale.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que, dans l'étape a), on utilise en tant que catalyseurs des acides sulfoniques aliphatiques et/ou aromatiques.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que dans l'étape a), on abaisse l'indice d'acide de la phase huileuse à des valeurs inférieures à 1.
  6. Procédé selon la revendication 5, caractérisé en ce que le mélange de glycérol et d'alcool utilisé provient de la transestérification sans pression de la phase huileuse, catalysée par un alcali.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que, dans l'étape b), on utilise de 10 à 30 parties en volume de mélange de glycérol et de méthanol pour 100 parties en volume de phase huileuse.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que l'on effectue l'étape c) à 50 - 100°C.
EP85115217A 1984-12-08 1985-11-30 Procédé de préparation d'esters méthyl d'acides gras Expired - Lifetime EP0184740B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85115217T ATE61332T1 (de) 1984-12-08 1985-11-30 Verfahren zur herstellung von fettsaeuremethylestern.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843444893 DE3444893A1 (de) 1984-12-08 1984-12-08 Verfahren zur herstellung von fettsaeuremethylestern
DE3444893 1984-12-08

Publications (3)

Publication Number Publication Date
EP0184740A2 EP0184740A2 (fr) 1986-06-18
EP0184740A3 EP0184740A3 (en) 1987-09-09
EP0184740B1 true EP0184740B1 (fr) 1991-03-06

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EP85115217A Expired - Lifetime EP0184740B1 (fr) 1984-12-08 1985-11-30 Procédé de préparation d'esters méthyl d'acides gras

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US (1) US4652406A (fr)
EP (1) EP0184740B1 (fr)
JP (1) JPH0662502B2 (fr)
AT (1) ATE61332T1 (fr)
BR (1) BR8506119A (fr)
CA (1) CA1261870A (fr)
DE (2) DE3444893A1 (fr)
ES (1) ES8606242A1 (fr)
GB (1) GB2168701B (fr)
MX (1) MX162267A (fr)
MY (1) MY101291A (fr)
TR (1) TR25060A (fr)
ZA (1) ZA859371B (fr)

Cited By (5)

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US7828978B2 (en) 2006-01-11 2010-11-09 Doug Geier Simultaneous synthesis and purification of a fatty acid monoester biodiesel fuel
US7951967B2 (en) 2006-04-28 2011-05-31 Sk Chemicals Co., Ltd. Method and apparatus for preparing fatty acid alkyl ester using fatty acid
US8530684B2 (en) 2008-04-01 2013-09-10 Sk Chemicals Co., Ltd. Method for preparing fatty acid alkyl ester using fatty acid
US8895765B2 (en) 2008-11-07 2014-11-25 Sk Chemicals Co., Ltd. Method and apparatus for preparing alkyl ester fatty acid using fatty acid
EP1322588B1 (fr) 2000-10-05 2016-06-29 Bdi-Bioenergy International Ag Procede de production d'esters alkyliques d'acides gras

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WO1987007632A1 (fr) * 1986-06-11 1987-12-17 Bio-Energy Technology Ltd. Production de carburant biologique
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SE9001245L (sv) * 1990-04-05 1991-10-06 Carl Johan Lindquist Foerestringsprocess
US6262022B1 (en) 1992-06-25 2001-07-17 Novartis Ag Pharmaceutical compositions containing cyclosporin as the active agent
GB9113872D0 (en) * 1991-06-27 1991-08-14 Sandoz Ag Improvements in or relating to organic compounds
CA2083346A1 (fr) * 1991-12-13 1993-06-14 Eric G. Lundquist Procede d'esterification par catalyse
DE4209779C1 (fr) * 1992-03-26 1993-07-15 Oelmuehle Leer Connemann Gmbh & Co., 2950 Leer, De
HK1004520A1 (en) 1992-05-13 1998-11-27 Novartis Ag Ophthalmic compositions containing a cyclosporin
PT589843E (pt) 1992-09-25 2002-04-29 Novartis Ag Composicoes farmaceuticas contendo ciclosporinas
AT399336B (de) * 1993-07-14 1995-04-25 Martin Mag Dr Mittelbach Verfahren zur herstellung von fettsäurealkylestern
SK285019B6 (sk) * 1997-01-30 2006-04-06 Novartis Ag Tvrdá želatínová tobolka
DE19732578C2 (de) * 1997-07-29 2000-08-24 Aventis Res & Tech Gmbh & Co Verwendung von sulfonierten aromatischen Polyetherketon-Kationenaustauschern und sulfonierten Polyphenylensulfid-Kationenaustauschern als Katalysatoren
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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
DE10154365A1 (de) * 2001-11-06 2003-05-15 Cognis Deutschland Gmbh Verfahren zur Herstellung von Fettsäureestern aus nicht entsäuerten Fetten und Ölen
AT504727A1 (de) * 2002-04-12 2008-07-15 Energea Umwelttechnologie Gmbh Verfahren und anlage zur veresterung von fettsäuren
US20060042158A1 (en) * 2004-08-26 2006-03-02 Lee John H Fuel products from plant or animal lipids
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JPWO2007000913A1 (ja) * 2005-06-27 2009-01-22 国立大学法人東京工業大学 高級脂肪酸エステルの製造方法
US7622600B1 (en) * 2006-01-06 2009-11-24 Redland Industries, Inc. System and method for the continuous production of bio-diesel
WO2008016330A2 (fr) * 2006-08-01 2008-02-07 Sie Hendery @ Hendery Bioformule pour remplacer le carburant diesel
WO2008070756A2 (fr) * 2006-12-06 2008-06-12 Southern Illinois University Carbondale Procédés de production d'esters d'alkyle d'acide gras
US20080289248A1 (en) * 2007-05-23 2008-11-27 Southern Illinois University Carbondale Immobilized esterification catalysts for producing fatty acid alkyl esters
WO2008071040A1 (fr) 2006-12-15 2008-06-19 China Petroleum & Chemical Corporation Procédé de préparation de biodiesel
WO2008071041A1 (fr) 2006-12-15 2008-06-19 China Petroleum & Chemical Corporation Procédé de préparation de biodiesel
JP2008260819A (ja) * 2007-04-11 2008-10-30 National Institute Of Advanced Industrial & Technology バイオディーゼル燃料の製造方法
US20080282606A1 (en) * 2007-04-16 2008-11-20 Plaza John P System and process for producing biodiesel
US20100242346A1 (en) * 2007-09-19 2010-09-30 Best Energies, Inc Processes for the esterification of free fatty acids and the production of biodiesel
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CN102066539B (zh) * 2008-05-14 2017-02-08 科学与工业研究委员会 蓖麻油脂肪酸基长链酯酯和它们作为潜在润滑油基础油料的衍生物
US20090285876A1 (en) * 2008-05-14 2009-11-19 Hein Arthur J Natural butters reconstituted by transesterification with glycerin and its use in cosmetics applications
BRPI0921034B1 (pt) † 2008-11-17 2019-11-19 Basf Se processo para preparar ésteres de ácido graxo e/ou misturas de éster de ácido graxo de alcoóis monovalentes de cadeia curta, e, uso de ácido metanossulfônico
WO2010077685A1 (fr) 2008-12-08 2010-07-08 Onestep Llc Transestérification en une étape de matière première utilisant un catalyseur gazeux
BRPI1012681B1 (pt) 2009-06-26 2019-03-26 China Petroleum & Chemical Corporation Composição de diesel e método de aumentar a estabilidade de oxidação de biodiesel
ES2713526T3 (es) 2009-07-17 2019-05-22 Korea Advanced Inst Sci & Tech Procedimiento de producción de ésteres alquílicos de ácidos grasos usando microorganismos que tienen capacidad de producir aceite
MY151440A (en) * 2009-10-29 2014-05-30 Malaysian Palm Oil Board Mpob A method of converting free fatty acid (ffa) from oil to methyl ester
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CN102851122A (zh) * 2011-06-30 2013-01-02 中国石油化工股份有限公司 一种制备脂肪酸酯的方法
CN103013678B (zh) * 2011-09-20 2014-12-31 中国石油化工股份有限公司 降低生物柴油粗产品酸值的方法以及生物柴油的制备方法
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US9328054B1 (en) 2013-09-27 2016-05-03 Travis Danner Method of alcoholisis of fatty acids and fatty acid gyicerides
US20170066995A1 (en) * 2014-03-04 2017-03-09 Basf Se Method for Degumming And Esterification Of An Oil
ES2585706B1 (es) * 2016-04-21 2017-08-14 Soluciones Industriales Extremeñas Sll Procedimiento mejorado para el refino y esterificación continua de cualquier material graso de origen vegetal o animal, especialmente diseñado para subproductos animales de categoría 1 y 2
ES2660207B8 (es) * 2016-09-21 2019-01-10 Bio Oils Huelva S L Procedimiento de alta eficacia para la producción de alquil-ésteres de ácidos grasos mediante catálisis ácida y procedimiento de tratamiento
FR3059328B1 (fr) * 2016-11-25 2018-11-16 Arkema France Composition acide pour le traitement d'acides gras
CN109982776A (zh) * 2016-11-25 2019-07-05 阿肯马法国公司 用于加工脂肪酸的酸组合物
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CN112823200A (zh) * 2018-10-10 2021-05-18 巴斯夫欧洲公司 制备生物柴油的方法
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US7828978B2 (en) 2006-01-11 2010-11-09 Doug Geier Simultaneous synthesis and purification of a fatty acid monoester biodiesel fuel
US7951967B2 (en) 2006-04-28 2011-05-31 Sk Chemicals Co., Ltd. Method and apparatus for preparing fatty acid alkyl ester using fatty acid
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ES8606242A1 (es) 1986-04-16
ES549666A0 (es) 1986-04-16
MY101291A (en) 1991-09-05
US4652406A (en) 1987-03-24
EP0184740A3 (en) 1987-09-09
GB8528953D0 (en) 1986-01-02
BR8506119A (pt) 1986-08-26
MX162267A (es) 1991-04-19
EP0184740A2 (fr) 1986-06-18
DE3444893A1 (de) 1986-06-12
ATE61332T1 (de) 1991-03-15
TR25060A (tr) 1992-09-22
JPS61140544A (ja) 1986-06-27
GB2168701A (en) 1986-06-25
GB2168701B (en) 1988-11-30
ZA859371B (en) 1986-07-30
DE3582022D1 (de) 1991-04-11
JPH0662502B2 (ja) 1994-08-17
CA1261870A (fr) 1989-09-26

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