EP2358851B1 - Utilisation de l'acide méthanesulfonique pour la fabrication d'esters d'acide gras - Google Patents

Utilisation de l'acide méthanesulfonique pour la fabrication d'esters d'acide gras Download PDF

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Publication number
EP2358851B1
EP2358851B1 EP09756298.7A EP09756298A EP2358851B1 EP 2358851 B1 EP2358851 B1 EP 2358851B1 EP 09756298 A EP09756298 A EP 09756298A EP 2358851 B1 EP2358851 B1 EP 2358851B1
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Prior art keywords
fatty acid
process according
oil
transesterification
methanesulfonic acid
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German (de)
English (en)
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EP2358851B2 (fr
EP2358851A1 (fr
Inventor
Stefan Fassbender
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BASF SE
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BASF SE
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Priority to PL09756298T priority Critical patent/PL2358851T5/pl
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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
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols

Definitions

  • the invention relates to a process for the preparation of fatty acid esters and / or fatty acid ester mixtures of monohydric alcohols having 1 to 5 carbon atoms by transesterification of fatty acid glycerides with short-chain monohydric alcohols having 1 to 5 carbon atoms in the presence of a basic catalyst, in which methanesulfonic acid is used. Furthermore, the invention relates to the use of methanesulfonic acid for the preparation of these fatty acid esters.
  • the fatty acid esters prepared according to the invention are suitable as pharmaceutical, dietary or cosmetic raw materials, as intermediates for further fatty acid derivatives, such as fatty alcohols, fatty amines or surfactants.
  • Fatty acid esters are also particularly suitable as lubricants, plasticizers, hydraulic oils, fuels or fuels for the operation of diesel engines.
  • fatty acid esters has long been known.
  • biodiesel is nowadays obtained on an industrial scale by means of a catalytic transesterification of vegetable oil.
  • This is usually dehydrated, deacidified and degummed oil with a molar excess of alcohol (usually methanol) of 6: 1 using 1 wt .-% catalyst based on the amount of the oil used (usually KOH) above the boiling point of the alcohol reacted.
  • the fatty acids contained in the fat molecules of the oil are split off catalytically and react with the present alcohol to the fatty acid ester.
  • Fats and oils are usually triglycerides, which means that one fat molecule contains three fatty acids bound to one glycerol molecule.
  • a complete transesterification reaction as it is carried out in the production of biodiesel, per molecule of fat or oil, three "molecules of biodiesel" and one molecule of glycerol.
  • Intermediates of this reaction are mono- and diglycerides.
  • Mono- and diglycerides consist of a glycerol backbone, hereinafter also referred to as glycerol backbone, to which one (monoglyceride) or two (diglyceride) fatty acids are bound. Since both polar hydroxide groups and apolar hydrocarbon chains are present in mono- and diglycerides, these have amphiphilic properties and almost always change the polarity of this solvent in organic solvents.
  • the transesterification requires a reaction time of about 8 h, with currently a conversion of about 98% is achieved.
  • the glycerol which is insoluble in the fatty acid alkyl ester (FASE), is removed from the biodiesel by means of a phase separator and used as a technical or pharmaceutical raw material after chemical and distillative purification.
  • the excess alcohol contained in the fatty acid alkyl esters is separated by distillation and returned to the process.
  • a dilute organic or inorganic acid is added to neutralize the remaining alkaline catalysts (eg KOH) and, after phase separation, the fatty acid ester phase is stripped off.
  • alkaline catalysts eg KOH
  • organic or inorganic acids are phosphoric, sulfuric, hydrochloric, nitric, boron.
  • Sulfuric acid is currently preferably used in the neutralization of the alkaline catalysts.
  • the object of the present invention is to provide a process for the preparation of fatty acid esters with improved yields.
  • the process for the preparation of fatty acid esters should be able to be integrated into known production processes without great expenditure on equipment.
  • step (b) The treatment of the fatty acid ester and / or fatty acid ester mixture with the methanesulfonic acid in step (b) can be carried out directly after the transesterification in order to at least substantially neutralize the basic catalyst used in the transesterification.
  • the residence time of the reaction products before carrying out step (b) can be selected so that a phase separation into a fatty acid ester phase and a glycerol phase takes place.
  • the heavy glycerol phase can then be removed, and the catalyst residues remaining in the ester phase can be neutralized by adding the methanesulfonic acid.
  • the transesterification in step (a) can generally be carried out in one or two or more stages, i. the fatty acid glyceride is either transesterified with the entire amount of lower alcohol and catalyst or in a first stage, only a portion of the required amount of short-chain monohydric alcohol and catalyst is used for transesterification and after the deposition and separation of a glycerol phase in a second stage or in further stages, the remaining amount (s) of short-chain, monohydric alcohol and catalyst for transesterification used in the same way, the two- and multi-stage operations bring the advantage of further reduction of excess alcohol and also increased yields of fatty acid ester with it.
  • the transesterification is carried out according to an embodiment of the invention according to the two-stage procedure, in the first stage preferably 60% to 90% of the total required amount of short-chain alcohol and catalyst and used in the second stage 10% to 40% of the total required amount of short-chain alcohol and catalyst.
  • the treatment with the methanesulfonic acid can take place immediately after the second or the last transesterification stage, i. if appropriate, without previously separating off the glycerol fraction formed in the second or last stage.
  • the transesterification by the process according to the invention is usually carried out at ambient temperatures of about +5 to + 40 ° C and atmospheric pressure and can in principle in any open or closed container of any size, which is advantageously equipped with a discharge device on the ground, are running.
  • the method according to the invention can be carried out using agitators or mechanical intensive mixers.
  • the corresponding apparatus and designs are known to those skilled in the field of apparatus engineering, for this reason will not be discussed in more detail here.
  • the inventive method can also be carried out continuously.
  • Suitable fatty acid glycerides which can be transesterified in the process according to the invention are naturally occurring vegetable and animal fats and oils, such as soybean oil, palm oil and palm fat, coconut oil and coconut fat, sunflower oil, rapeseed oil, cottonseed oil, linseed oil, castor oil, peanut oil, olive oil, safflower oil, Evening primrose oil, borage oil, carob seed oil, etc., as well as mono-, di- and triglycerides, such as triolein, tripalmitin, tristearin, glycerol monooleate and glycerol monostearate, isolated from the aforementioned vegetable oils and fats or obtained by interesterification or synthetically prepared.
  • waste oils such as used frying oil can also be used in the context of the process according to the invention.
  • Sunflower oil and rapeseed oil are preferably used in the process according to the invention.
  • the vegetable oils and fats can be used in a refined or unrefined manner and can contain, in addition to mucilages, turbid substances and other impurities, free fatty acids up to a proportion of 20% by weight and beyond.
  • dehydrated, deacidified and degummed fatty acid glycerides are used as starting materials for the process according to the invention used. The use of these leads to a simplified control of the process and also brings increased yields with it.
  • monohydric alcohols those having 1 to 5 carbon atoms are used. These are preferably selected from methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 3-methyl-1-butanol and neopentyl alcohol, and mixtures thereof. Especially preferred are methanol and ethanol, most preferred is methanol.
  • alkali metal or alkaline earth metal compounds in the form of the oxides, hydroxides, hydrides, carbonates, acetates or alcoholates of the short-chain alcohols having 1 to 5 carbon atoms, preferably sodium hydroxide, potassium hydroxide, sodium and potassium alkoxides of the short-chain monohydric compounds, are used as basic catalysts for transesterification Alcohols having 1 to 5 carbon atoms in question.
  • the basic catalysts are particularly preferably selected from KOH, NaOH, sodium and potassium methylate. Particularly preferred are potassium and sodium methylate.
  • the basic catalyst in the transesterification of fatty acid glycerides in an amount of 0.1 to 5 wt .-%, preferably in an amount of 0.5 to 1.5 wt .-%, based on the mass of the fatty acid glyceride used.
  • the lower, monohydric alcohol is added in an excess of 0.1 mol to 2.0 mol, based on 1 mol of glycerol-bound fatty acid.
  • water is used in an amount of from 0.5 to 20% by weight, based on the reaction mixture, of the transesterification of the fatty acid glycerides.
  • the basic catalyst in the form of an aqueous or alcoholic solution is added to the fatty acid glyceride.
  • the reaction mixture formed thereby can be added with a certain amount of water, which is in the range from 0.5 to 20% by weight, based on the total mass.
  • the addition of the water can be isolated or carried out in conjunction with the methanesulfonic acid.
  • the methanesulfonic acid is in the form of a 50 to 99%, preferably in the form of a 60 to 80%, particularly preferably in the form of a 70% aqueous solution added.
  • FIG. 1 shows a block diagram of the process for the production of rapeseed oil methyl ester (RME).
  • rapeseed oil As fatty acid glyceride, rapeseed oil (Vollraffinat) was used from retail.
  • the catalysts NaOH, KOH, sodium methylate and potassium methylate, the solvent methanol and the sulfuric acid for the neutralization were purchased from the laboratory retailer.

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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)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Fats And Perfumes (AREA)

Claims (15)

  1. Procédé pour la préparation d'esters d'acides gras et/ou de mélanges d'esters d'acides gras d'alcools monovalents à courte chaîne comprenant 1 à 5 atomes de carbone, comprenant
    (a) la transestérification de glycérides d'acides gras avec des alcools monovalents à courte chaîne comprenant 1 à 5 atomes de carbone en présence d'au moins un catalyseur basique pour former un mélange réactionnel qui contient les esters d'acides gras et/ou le mélange d'esters d'acides gras, et
    (b) le traitement d'au moins une partie du mélange réactionnel formé lors de la transestérification dans l'étape (a) avec de l'acide méthanesulfonique.
  2. Procédé selon la revendication 1, où, dans l'étape (a), après la fin de la transestérification et avant la réalisation de l'étape (b), le temps de séjour du mélange réactionnel est choisi de manière telle qu'il se produit une séparation des phases en une phase d'esters d'acides gras et une phase de glycérol.
  3. Procédé selon la revendication 1 ou 2, la transestérification dans l'étape (a) étant réalisée en plusieurs étapes.
  4. Procédé selon la revendication 3, la transestérification dans l'étape (a) étant réalisée en deux étapes.
  5. Procédé selon la revendication 4, où on utilise, dans la première étape, 60% à 90% de la quantité totale utilisée d'alcool et de catalyseur et, dans la deuxième étape, 10% à 40% de la quantité totale utilisée d'alcool et de catalyseur.
  6. Procédé selon l'une quelconque des revendications 1 à 5, où on utilise, comme glycérides d'acides gras, des graisses et des huiles végétales et animales naturelles, choisies parmi l'huile de soja, de palme, de palmiste, de coco, de tournesol, de colza, de lin, de ricin, d'arachide, d'olive, d'onagre et de caroube ainsi que leurs mélanges.
  7. Procédé selon l'une quelconque des revendications 1 à 6, où on utilise, comme alcool monovalent à courte chaîne du méthanol ou de l'éthanol.
  8. Procédé selon l'une quelconque des revendications 1 à 7, où on utilise comme catalyseurs basiques des composés basiques de métal alcalin ou alcalino-terreux, choisis parmi l'hydroxyde de sodium, l'hydroxyde de potassium, les alcoolates de sodium et de potassium des alcools monovalents à courte chaîne comprenant 1 à 5 atomes de carbone ou leurs mélanges.
  9. Procédé selon l'une quelconque des revendications 1 à 8, où le catalyseur basique est utilisé en une quantité de 0,5 à 5% en poids, par rapport à la masse du glycéride d'acides gras utilisé.
  10. Procédé selon l'une quelconque des revendications 1 à 9, où la quantité d'acide méthanesulfonique dans l'étape (b) est calculée de manière telle qu'elle est au moins équivalente aux quantités de catalyseur basique utilisées dans l'étape (a).
  11. Procédé selon l'une quelconque des revendications 2 à 10, où, après la fin de la transestérification dans l'étape (a), la phase d'esters d'acides gras est formée, séparée et traitée dans l'étape (b) avec de l'acide méthanesulfonique.
  12. Procédé selon l'une quelconque des revendications 1 à 11, où l'acide méthanesulfonique est utilisé sous forme d'un acide aqueux à 50 jusqu'à 99% pour le traitement dans l'étape (b).
  13. Procédé selon l'une quelconque des revendications 1 à 12, où avant la réalisation de l'étape de procédé (b) l'alcool en excès est séparé de l'étape (a).
  14. Procédé selon l'une quelconque des revendications 1 à 13, qui est réalisé sous forme de procédé continu.
  15. Utilisation d'acide méthanesulfonique lors de la préparation d'esters alkyliques d'acides gras ou de leurs mélanges en utilisant des catalyseurs basiques lors de la transestérification de glycérides d'acides gras.
EP09756298.7A 2008-11-17 2009-11-16 Utilisation de l'acide méthanesulfonique pour la fabrication d'esters d'acide gras Active EP2358851B2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL09756298T PL2358851T5 (pl) 2008-11-17 2009-11-16 Zastosowanie kwasu metanosulfonowego do wytwarzania estrów kwasów tłuszczowych
EP09756298.7A EP2358851B2 (fr) 2008-11-17 2009-11-16 Utilisation de l'acide méthanesulfonique pour la fabrication d'esters d'acide gras

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP08169225 2008-11-17
PCT/EP2009/065230 WO2010055158A1 (fr) 2008-11-17 2009-11-16 Utilisation de l'acide méthanesulfonique pour la fabrication d'esters d'acide gras
EP09756298.7A EP2358851B2 (fr) 2008-11-17 2009-11-16 Utilisation de l'acide méthanesulfonique pour la fabrication d'esters d'acide gras

Publications (3)

Publication Number Publication Date
EP2358851A1 EP2358851A1 (fr) 2011-08-24
EP2358851B1 true EP2358851B1 (fr) 2014-03-12
EP2358851B2 EP2358851B2 (fr) 2018-01-10

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EP09756298.7A Active EP2358851B2 (fr) 2008-11-17 2009-11-16 Utilisation de l'acide méthanesulfonique pour la fabrication d'esters d'acide gras

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US (1) US8692008B2 (fr)
EP (1) EP2358851B2 (fr)
CN (1) CN102257108B (fr)
BR (1) BRPI0921034B1 (fr)
ES (1) ES2457097T5 (fr)
MY (1) MY161118A (fr)
PL (1) PL2358851T5 (fr)
PT (1) PT2358851E (fr)
WO (1) WO2010055158A1 (fr)

Families Citing this family (7)

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Publication number Priority date Publication date Assignee Title
DE102010055969A1 (de) * 2010-12-23 2012-06-28 Süd-Chemie AG Verfahren zur Aufreinigung von organischen Flüssigkeiten
FR3002936B1 (fr) 2013-03-06 2015-03-06 Arkema France Utilisation d'acide sulfonique pour la recuperation de glycerol issu de la reaction de trans-esterification de triglycerides
US20170066995A1 (en) 2014-03-04 2017-03-09 Basf Se Method for Degumming And Esterification Of An Oil
WO2016028845A1 (fr) * 2014-08-19 2016-02-25 Archer Daniels Midland Company Synthèse de tensioactifs non-ioniques à partir de 5-hydroxyméthyl-2-furfurale, de 2,5-diméthanol-furane et de bis-2,5-dihydroxymethyltétrahydrofuranes
US20190301027A1 (en) 2016-07-18 2019-10-03 Basf Se Low corrosion alkane sulfonic acids for condensation reactions
GB201619827D0 (en) * 2016-11-23 2017-01-04 Lucite Int Uk Ltd Process for the production of methyl methacrylate
BR112021006249A2 (pt) 2018-10-10 2021-07-06 Basf Se método para produzir éster alquílico de ácido graxo

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US2360844A (en) † 1941-11-26 1944-10-24 Du Pont Preparation of detergents
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
US5276204A (en) * 1988-11-09 1994-01-04 Henkel Kommanditgesellschaft Auf Aktien Fatty alcohol mixtures and ethoxylates thereof showing improved low-temperature behavior
AT397510B (de) 1991-11-06 1994-04-25 Wimmer Theodor Verfahren zur herstellung von fettsäureestern kurzkettiger alkohole
FI95367C (fi) * 1994-09-07 1996-01-25 Raision Tehtaat Oy Ab Menetelmä synteettisen esterin valmistamiseksi kasviöljystä
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ITMI20032129A1 (it) * 2003-11-05 2005-05-06 Acs Dobfar Spa Procedimento per la frammentazione del dna di cellule fungine, batteriche o di lieviti per la inattivazione di antibiotici residui in biomasse da fermentazione
ITMI20040579A1 (it) * 2004-03-25 2004-06-25 Zambon Spa Processo di preparazione di gabapentina
WO2005123890A1 (fr) * 2004-06-22 2005-12-29 Akzo Nobel N.V. Biodiesels ramifies
BRPI0500333A (pt) 2005-02-02 2006-09-12 Univ Rio De Janeiro processo catalìtico para esterificação de ácidos graxos
BRPI0503631B1 (pt) 2005-08-19 2015-07-21 Petróleo Brasileiro S A Petrobras Processo para a produção de biodiesel
US7872149B2 (en) † 2006-09-19 2011-01-18 Best Energies, Inc. Biodiesel processes in the presence of free fatty acids and biodiesel producer compositions

Also Published As

Publication number Publication date
PL2358851T3 (pl) 2014-08-29
BRPI0921034B1 (pt) 2019-11-19
CN102257108B (zh) 2014-04-09
EP2358851B2 (fr) 2018-01-10
ES2457097T3 (es) 2014-04-24
US20110245521A1 (en) 2011-10-06
WO2010055158A1 (fr) 2010-05-20
BRPI0921034A2 (pt) 2015-12-29
PT2358851E (pt) 2014-04-02
EP2358851A1 (fr) 2011-08-24
PL2358851T5 (pl) 2018-09-28
MY161118A (en) 2017-04-14
US8692008B2 (en) 2014-04-08
ES2457097T5 (es) 2018-04-16
CN102257108A (zh) 2011-11-23

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