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WO2008049260A2 - Procédé de préparation d'esters d'acide gras - Google Patents

Procédé de préparation d'esters d'acide gras Download PDF

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Publication number
WO2008049260A2
WO2008049260A2 PCT/CH2007/000525 CH2007000525W WO2008049260A2 WO 2008049260 A2 WO2008049260 A2 WO 2008049260A2 CH 2007000525 W CH2007000525 W CH 2007000525W WO 2008049260 A2 WO2008049260 A2 WO 2008049260A2
Authority
WO
WIPO (PCT)
Prior art keywords
acid
transesterification
fatty acid
catalyst
carried out
Prior art date
Application number
PCT/CH2007/000525
Other languages
German (de)
English (en)
Other versions
WO2008049260A3 (fr
Inventor
Falko Chrost
Lukas Dammann
Anton Hirtl
Joachim Adler
Kurt VON DÄNIKEN
Original Assignee
Mecan Ecosystems Ag
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mecan Ecosystems Ag filed Critical Mecan Ecosystems Ag
Publication of WO2008049260A2 publication Critical patent/WO2008049260A2/fr
Publication of WO2008049260A3 publication Critical patent/WO2008049260A3/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
    • 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
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • 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 and / or fatty acid ester mixtures of lower monohydric alcohols having 1 to 5 carbon atoms by transesterification of fatty acid glycerides with the lower alcohols in the presence of basic or acidic catalysts.
  • fatty acid esters with lower monohydric alcohols having 1 to 5 carbon atoms are suitable, for example, as pharmaceutical, dietetic or cosmetic raw materials, as diesel fuels, as heating oils, as shell oils, as hydraulic oils or as intermediates for the preparation of further fatty acid derivatives, such as fatty alcohols.
  • Such fatty acid esters have been known for a long time.
  • the production takes place on an industrial scale mainly by base-catalyzed transesterification of fatty acid glycerides with lower alcohols, the procedure being in principle that the fatty acid glycerides with the lower alcohol in the presence of a basic catalyst with depending on
  • the reaction conditions depend on the particular fatty acid glycerides used. For example, it is known that oils and fats of natural origin, as they are commonly used, and which may have a more or less high content of free fatty acids depending on their origin and pretreatment, in the presence of basic catalysts at temperatures around 240 0 C and pressures of about 100 bar with 7 to 8-fold molar excess of the alcohol can be transesterified (Ullmann, Enzyklopädie der ischen Chemie, 4th ed., Vol. 11, p.432, 1976).
  • transesterifications can be carried out at temperatures around the boiling point of the alcohol used and at normal or only slightly elevated pressure with lower excesses of the lower alcohols, if the oils and fats previously used by methods such as distillation, alkali extraction, acid-catalyzed pre-esterification etc. to a maximum Deacidified content of free fatty acids of 0.5% and then dried.
  • an alkaline catalyst is dissolved in the liquid glycerides of the reaction vessel.
  • triglycerides in the presence of suitable catalysts, such as.
  • suitable catalysts such as.
  • As zinc soaps preferably in direct current columns at temperatures of 200 0 C to 240 0 C and reacted at pressures up to 90 bar with alcohol in molar excess. After separation of the excess alcohol, alkyl ester-glycerol mixtures are obtained, which are separated in a separator into the lighter ester phase and into the glycerol phase. This phase separation is followed by further work-up and purification of the products. The ester phase is washed with water to remove the glycerol residues dissolved in the product. In the process, about 40% of the zinc soaps dissolved in the ester are also washed out in the form of zinc hydroxide.
  • Mixture having a maximum acid number of 1 is transesterified in a continuous manner, while the actual transesterification step takes place in a manner which involves washing the product with water requires.
  • Pressure preferably atmospheric pressure and as high as possible
  • Alcohol is supplied in a suitable manner to the fatty acid glyceride. That is, the fatty acid glyceride is added in a first stage, only a portion of the required amount of lower alcohol and catalyst for transesterification.
  • Figure 1 schematically shows a plant for carrying out the inventive method.
  • the supply of the lower alcohol and the catalyst is carried out by injection into the circulating stream (5, 8) in front of the static mixer in order to obtain the highest possible degree of separation BEZW.
  • suitable passive measures e.g. the use of venturi mixers in the reactors (21, 23) also maintains the emulsion during the reaction time.
  • the two-stage or multi-stage procedure has the advantage of further reducing the excess alcohol and increasing the transesterified product.
  • the process can be carried out in a continuous manner by using a suitable passive separation process, preferably with coalescence or membrane separators (19, 22), to separate the heavy, glycerol-containing phase (7).
  • a suitable passive separation process preferably with coalescence or membrane separators (19, 22)
  • coalescence or membrane separators (19, 22) to separate the heavy, glycerol-containing phase (7).
  • the Inventive methods are carried out continuously.
  • the method is designed such that only a minimum number of corrective interventions in the process become necessary and the method can also be carried out without intensive monitoring and therefore very cost-effectively.
  • Suitable fatty acid glycerides are triglycerides (4) as naturally occurring in vegetable and animal oils and fats, e.g. 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., and intermediates isolated or synthesized by the above-mentioned vegetable oils and fats or by interesterification etc., animal fats such as Beef tallow, or animal cadaver extraction fats, e.g. BSE risk material, but also waste oils, e.g. used frying oil.
  • vegetable oils and fats e.g. 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
  • the vegetable and animal oils and fats can be used in the process according to the invention after a minimal pretreatment to remove coarse particles, refined or unrefined, and in addition to mucilages, turbidity and other impurities free fatty acids up to 20% and above or up to an acid number (SZ ) of 14.
  • Suitable lower monohydric alcohols (1) are those having one to five carbon atoms, for example
  • Suitable catalysts are alkali metal or alkaline earth metal compounds (2) in the form of the oxides, hydroxides, hydrides, carbonates, acetates or alkoxides of the lower alcohols, preferably sodium hydroxide, potassium hydroxide, sodium and potassium alkoxides of the lower monohydric alcohols having 1 to 5 carbon atoms ,
  • strong nonvolatile mineral acids such as e.g. Sulfuric acid, phosphoric acid, alcoholic hydrochloric acid, xylene sulfonic acid, p-toluenesulfonic acid, sulfamic acid (sulfamic acid) and oxalic acid as acidic catalysts (3) are suitable.
  • the two essential characteristics of the inventive method are the amount of catalyst used, which despite high impurity level and high content of free fatty acids of Fettklareglyceride used at temperatures between 40 ° C and the boiling point of the lower alcohol used, at atmospheric pressure and only slight excess of alcohol high degrees of transesterification and a problem-free separation of the glycerol phase can be achieved; and secondly, conducting the transesterification in two or more sequential steps, thereby achieving a high degree of transesterification and easy removal of the catalyst residues from the ester phase and other impurities remaining in the ester phase, such as glycerol.
  • the inventive method does not rule out that the fatty acid esters thus prepared, if required by the intended use, be subjected to further purification (14) by known means, eg by vacuum distillation (16), removal of residual amounts of the lower alcohols by evaporation or blow-out Drying by means of silica gel (9, H), molecular sieves (10), coalescence aids (10) etc., removal of higher melting fractions of fatty acid esters by freezing, color and odor improvement or reduction of peroxide by treatment with bleaching earths etc. or by addition of additives such as pour point depressants , Viscosity improvers, corrosion inhibitors, Odixationsschutzmitteln, Cetaniereverêtern, etc. adapted in a known manner to the respective intended use become .
  • the advantages of the process according to the invention are, in particular, that, depending on the use of the preferably mentioned amounts of lower alcohol and transesterification catalyst, it is possible to achieve any desired degree of transesterification which, for many applications, results in further purification of the fatty acid ester, e.g. make redundant by distillation, for example, if the fatty acid esters are to be used as diesel fuels.
  • the catalyst residues no washing processes with water or acids together with the associated complicated drying of the fatty acid esters and no ion exchangers are required.
  • the fatty acid esters can be prepared in a technically extremely simple manner.
  • rapeseed oil with an acid number (SZ) of 1 600 kg rapeseed oil with an acid number (SZ) of 1 are pumped into the plant per hour.
  • SZ acid number
  • the first stage 66.4 kg of methanol and 18 kg of 30% strength methanolic potassium hydroxide solution are metered.
  • the mixture is emulsified at 60 ° C. for 40 minutes.
  • the reaction solution is pumped via a Koaleszenzabscheider in the second stage.
  • the heavy phase is separated and discharged.
  • another 37.5 kg of methanol and 5 kg of 30% methanolic potassium hydroxide solution are added.
  • After another 40 minute reaction time at 60 0 C is again the heavy phase carried out by coalescence and transferred the remaining reaction mixture in the third module.

Landscapes

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

Abstract

La présente invention concerne un procédé de préparation en continu d'esters d'acide gras à partir de substances de départ biogènes contenant des graisses ou de l'huile et ayant des teneurs variables en acides gras libres, par transestérification à catalyse acide ou basique de glycérides d'acide gras. Le procédé de l'invention se caractérise en ce qu'il s'effectue en continu selon un processus en plusieurs phases et que les produits de transestérification sont utilisés sans eau.
PCT/CH2007/000525 2006-10-27 2007-10-22 Procédé de préparation d'esters d'acide gras WO2008049260A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1720/06 2006-10-27
CH17202006 2006-10-27

Publications (2)

Publication Number Publication Date
WO2008049260A2 true WO2008049260A2 (fr) 2008-05-02
WO2008049260A3 WO2008049260A3 (fr) 2008-09-25

Family

ID=39201869

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CH2007/000525 WO2008049260A2 (fr) 2006-10-27 2007-10-22 Procédé de préparation d'esters d'acide gras

Country Status (1)

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WO (1) WO2008049260A2 (fr)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3932514A1 (de) * 1989-09-29 1991-04-18 Henkel Kgaa Kontinuierliches verfahren zum herstellen niederer alkylester
DE4123928A1 (de) * 1991-07-19 1993-01-21 Metallgesellschaft Ag Verfahren zum erzeugen von fettsaeure-methylester oder fettsaeure-aethylester und glycerin durch umesterung von oelen oder fetten
AT397510B (de) * 1991-11-06 1994-04-25 Wimmer Theodor Verfahren zur herstellung von fettsäureestern kurzkettiger alkohole
DE19721474C1 (de) * 1997-05-23 1998-06-04 Henkel Kgaa Verfahren zur Herstellung niederer Alkylester
AU5048700A (en) * 1999-06-09 2000-12-28 Cognis Corporation Process for the reduction of glycerin in transesterification operations
DE10043644A1 (de) * 2000-09-05 2002-03-28 Goes Ges Fuer Forschung Und Te Verfahren zur kontinuierlichen Herstellung von Biomethanol- und Bioethanoldiesel in Kleinstanlagen
US20030032826A1 (en) * 2001-07-20 2003-02-13 The Board Of Regents Of The University Of Nebraska Transesterification process for production of biodiesel

Also Published As

Publication number Publication date
WO2008049260A3 (fr) 2008-09-25

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