WO2004083350A1 - Ester alkylique d'acide gras purifie a faible teneur en soufre et son procede de production - Google Patents

Ester alkylique d'acide gras purifie a faible teneur en soufre et son procede de production Download PDF

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Publication number
WO2004083350A1
WO2004083350A1 PCT/AT2004/000105 AT2004000105W WO2004083350A1 WO 2004083350 A1 WO2004083350 A1 WO 2004083350A1 AT 2004000105 W AT2004000105 W AT 2004000105W WO 2004083350 A1 WO2004083350 A1 WO 2004083350A1
Authority
WO
WIPO (PCT)
Prior art keywords
fatty acid
acid alkyl
alkyl ester
ppm
sulfur content
Prior art date
Application number
PCT/AT2004/000105
Other languages
German (de)
English (en)
Inventor
Martin Mittelbach
Michael Koncar
Wilhelm Hammer
Helmut Gössler
Wolfgang Glasl
Original Assignee
Bdi Anlagenbau Gesellschaft M.B.H.
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 Bdi Anlagenbau Gesellschaft M.B.H. filed Critical Bdi Anlagenbau Gesellschaft M.B.H.
Publication of WO2004083350A1 publication Critical patent/WO2004083350A1/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
    • 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
    • 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 invention relates to a process for the purification of a fatty acid alkyl ester obtained by transesterification of a triglyceride containing sulfur compounds and / or by esterification of a fatty acid containing sulfur compounds with lower alcohols.
  • the invention further relates to a new fatty acid alkyl ester ("biodiesel") with a low sulfur content.
  • triglycerides are understood to be esters of higher, saturated and / or unsaturated fatty acids with glycerol. Such esters are e.g. Oils and fats of vegetable or animal origin. However, many fats of natural origin also contain free fatty acids to a greater or lesser extent. These fats are therefore a mixture of triglycerides and free fatty acids, the main constituent of this mixture usually being the triglycerides.
  • Transesterification is understood to mean the alcoholysis of triglycerides, that is to say the reaction with lower alcohols, in particular methanol and ethanol, the monoesters of fatty acids and glycerol being formed via the intermediates di- and monoglycerides.
  • Fatty acid esters are important intermediates in oleochemistry.
  • 200,000 tons of vegetable oil methyl esters are produced as raw materials, mainly for surfactants.
  • the fatty acid methyl ester is becoming increasingly important as a diesel substitute fuel.
  • Basic catalysts alkali metal hydroxides, alcoholates, oxides, carbonates, anion exchangers
  • acidic catalysts mineral acids, p-toluenesulfonic acid, boron trifluoride, cation exchangers
  • enzymes lipases
  • Catalysts which are soluble in the reaction mixture are preferably used today. These form a homogeneous mixture and ensure fast turnover rates and mild reaction conditions.
  • the most commonly used homogeneous catalysts are sodium and potassium hydroxide and sodium methylate, which are added to the vegetable oil in solution in alcohol. Such a method is known from AT-B 386 222.
  • Acid catalysis requires higher reaction temperatures and pressures and a more complex reaction procedure.
  • An acidic transesterification is known from FR-A - 85 02340.
  • the transesterification with basic catalysis is generally carried out without using a solvent.
  • the reaction begins with a two-phase system consisting of triglyceride and alcohol, but with increasing progress of the reactin and the formation of esters, a homogeneous phase is formed, which in turn becomes two-phase due to the formation and excretion of glycerol, the light phase being the crude fatty acid alkyl ester and the heavy phase being a phase rich in glycerol ,
  • Biodiesel is usually obtained from vegetable and animal oils and fats (triglycerides) by catalytic transesterification with methanol. These triglycerides contain sulfur-containing compounds that originate from the plant or animal starting material and can only be partially separated even by refining. However, it has been shown that even after the transesterification in the ester, sulfur compounds can still be detected, and that under certain circumstances. in an amount that far exceeds the above limit.
  • the present invention starts and the aim is to provide a process for the purification of a fatty acid alkyl ester obtained by transesterification of a triglyceride containing sulfur compounds and / or by esterification of a fatty acid containing sulfur compounds with lower alcohols.
  • the process according to the invention is characterized in that the fatty acid alkyl ester obtained is treated with a basic medium.
  • a suitable base medium is, for example, a solid base, in particular a basic ion exchanger, and above all an aqueous basic medium, preferably an aqueous alkali.
  • An aqueous alkali hydroxide, in particular KOH, or an aqueous alkaline earth hydroxide, in particular calcium hydroxide, is preferably used as the aqueous alkali in the process according to the invention.
  • the treatment with the basic medium is best carried out at a temperature between 15 ° C and 65 ° C, in particular between 30 ° C and 45 ° C.
  • a very preferred embodiment of the process according to the invention consists in distilling the fatty acid alkyl ester treated with the aqueous, basic medium. It has been shown that the distillation enables a drastic reduction in the sulfur content in the ester. This is completely surprising, since after conventional washes, distillation has only an unsatisfactory effect on reducing the sulfur compounds.
  • Methanol is used in particular as the lower alcohol.
  • the invention also relates to a fatty acid alkyl ester which is obtained by the process according to the invention from a triglyceride or a fatty acid which has a sulfur content of more than 10 ppm, in particular more than 30 ppm, and is characterized in that the sulfur content of the fatty acid alkyl ester is less than 10 ppm, in particular less than 5 ppm, preferably less than 2.5 ppm and particularly preferably less than 1 ppm.
  • the fatty acid alkyl ester according to the invention is preferably in the form of a methyl ester (“biodiesel”).
  • 850 g of methyl ester which was obtained from animal fat and distilled in accordance with the process described in WO 02/28811 (PCT / AT01 / 00320) and had a sulfur content of 26 ppm due to the sulfur compounds contained, became 1.0 with 25 g molar, aqueous KOH solution added and at 20 ° C for 5 min. touched.
  • the mixture was transferred to a separatory funnel from which a heavy aqueous phase was drawn off after two hours.
  • the remaining organic phase was distilled at 1 mbar over a Vigreux column. Only 2 ppm of sulfur were detectable in the distillate.
  • Example 1 was repeated, but the treatment according to the invention with aqueous KOH was not carried out. After distillation of the starting product in the same apparatus under the same process conditions, 23 ppm sulfur were measured in the distillate.
  • the sulfur content in the distillate obtained was only 2 ppm.
  • the sulfur content in the distillate obtained was less than 1 ppm.
  • the sulfur content of the ester was 97 ppm.
  • the ester was then distilled (1 mbar; 110-130 ° C). 170.3 g of residue were obtained.
  • the sulfur content of the distillate obtained was only 9 ppm.

Landscapes

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

Abstract

L'invention concerne un procédé servant à purifier un ester alkylique d'acide gras obtenu par transestérification d'un triglycéride contenant des composés soufre et/ou par estérification d'un acide gras contenant des composés soufre avec des alcools inférieurs. Le procédé selon l'invention est caractérisé en ce que l'ester alkylique d'acide gras obtenu est traité avec un milieu basique, puis est éventuellement distillé.
PCT/AT2004/000105 2003-03-20 2004-03-19 Ester alkylique d'acide gras purifie a faible teneur en soufre et son procede de production WO2004083350A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA451/2003 2003-03-20
AT0045103A AT412280B (de) 2003-03-20 2003-03-20 Gereinigter fettsäurealkylester mit niedrigem schwefelgehalt und verfahren zu seiner herstellung

Publications (1)

Publication Number Publication Date
WO2004083350A1 true WO2004083350A1 (fr) 2004-09-30

Family

ID=32234880

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AT2004/000105 WO2004083350A1 (fr) 2003-03-20 2004-03-19 Ester alkylique d'acide gras purifie a faible teneur en soufre et son procede de production

Country Status (2)

Country Link
AT (1) AT412280B (fr)
WO (1) WO2004083350A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012054946A1 (fr) * 2010-10-28 2012-05-03 Theodor Wimmer Procédé de production d'esters d'acides gras d'alcools inférieurs
WO2016091640A1 (fr) * 2014-12-11 2016-06-16 Bdi-Bioenergy International Ag Procédé de nettoyage d'esters d'alkyle d'acide gras
EP3309241A1 (fr) * 2016-10-17 2018-04-18 UBPM Umwelt-Beratung und Produkt-Management GmbH & Co. KG Procédé et utilisation d'un agent d'oxydation permettant l'oxydation du soufre élémentaire et/ou des composés du soufre en présence de dérivés d'acide gras
EP3404082A1 (fr) 2017-05-19 2018-11-21 GEA Mechanical Equipment GmbH Procédé de réduction de la teneur en monoglycérides (mg), notamment en monoglycérides saturés (gmg) dans un biodiesel brut
EP3514222A1 (fr) * 2013-06-19 2019-07-24 Argent Energy (Uk) Limited Procédé de production de biodiesel et de produits associés

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT513799B1 (de) 2012-12-18 2020-02-15 Mag Schell Klaus Verfahren zur Herstellung eines Bio-Diesel-Kraftstoffes mit einem speziell ausgelegten Reaktor und quasi katalytisch wirksamer nanoskalig strukturierter Materialoberfläche des Reaktors

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0269173A2 (fr) * 1986-11-24 1988-06-01 Unilever N.V. Adsorbant à base de métal-oxyde-silice et son utilisation dans le raffinage d'huiles
AT386222B (de) 1986-09-02 1988-07-25 Hans Dr Junek Verfahren und vorrichtung zur herstellung eines als kraft- bzw. brennstoff geeigneten fettsaeureestergemisches
SU1687597A1 (ru) * 1989-07-05 1991-10-30 Ташкентский Политехнический Институт Им.А.Р.Бируни Способ рафинации рапсового масла
US6096194A (en) * 1999-12-02 2000-08-01 Zeochem Sulfur adsorbent for use with oil hydrogenation catalysts
US6242620B1 (en) * 1998-03-05 2001-06-05 Henkel Corporation Process for making carboxylic acid esters

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2577569B1 (fr) * 1985-02-15 1987-03-20 Inst Francais Du Petrole Procede de fabrication d'une composition d'esters d'acide gras utilisables comme carburant de substitution du gazole avec de l'alcool ethylique hydrate et composition d'esters ainsi formes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT386222B (de) 1986-09-02 1988-07-25 Hans Dr Junek Verfahren und vorrichtung zur herstellung eines als kraft- bzw. brennstoff geeigneten fettsaeureestergemisches
EP0269173A2 (fr) * 1986-11-24 1988-06-01 Unilever N.V. Adsorbant à base de métal-oxyde-silice et son utilisation dans le raffinage d'huiles
SU1687597A1 (ru) * 1989-07-05 1991-10-30 Ташкентский Политехнический Институт Им.А.Р.Бируни Способ рафинации рапсового масла
US6242620B1 (en) * 1998-03-05 2001-06-05 Henkel Corporation Process for making carboxylic acid esters
US6096194A (en) * 1999-12-02 2000-08-01 Zeochem Sulfur adsorbent for use with oil hydrogenation catalysts

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199232, Derwent World Patents Index; Class D23, AN 1992-266645, XP002283488 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012054946A1 (fr) * 2010-10-28 2012-05-03 Theodor Wimmer Procédé de production d'esters d'acides gras d'alcools inférieurs
EP3514222A1 (fr) * 2013-06-19 2019-07-24 Argent Energy (Uk) Limited Procédé de production de biodiesel et de produits associés
US10501697B2 (en) 2013-06-19 2019-12-10 Argent Energy (Uk) Limited Biodiesel composition and related process and products
US10961473B2 (en) 2013-06-19 2021-03-30 Argent Energy (UK) Limited, Argent Engery Limited Process for producing biodiesel and related products
WO2016091640A1 (fr) * 2014-12-11 2016-06-16 Bdi-Bioenergy International Ag Procédé de nettoyage d'esters d'alkyle d'acide gras
CN107001232A (zh) * 2014-12-11 2017-08-01 Bdi-生物能国际股份公司 用于纯化脂肪酸烷基酯类的方法
US10150934B2 (en) 2014-12-11 2018-12-11 Bdi-Bioenergy International Ag Method for the purification of fatty acid aklyl esters
EP3230253B1 (fr) 2014-12-11 2019-12-25 BDI Holding GmbH Procédé de nettoyage d'esters alkyles d'acides gras
EP3309241A1 (fr) * 2016-10-17 2018-04-18 UBPM Umwelt-Beratung und Produkt-Management GmbH & Co. KG Procédé et utilisation d'un agent d'oxydation permettant l'oxydation du soufre élémentaire et/ou des composés du soufre en présence de dérivés d'acide gras
EP3404082A1 (fr) 2017-05-19 2018-11-21 GEA Mechanical Equipment GmbH Procédé de réduction de la teneur en monoglycérides (mg), notamment en monoglycérides saturés (gmg) dans un biodiesel brut
WO2018210573A1 (fr) 2017-05-19 2018-11-22 Gea Mechanical Equipment Gmbh Procédé pour la diminution de la teneur en monoglycérides saturés dans un biodiesel brut
US10982159B2 (en) 2017-05-19 2021-04-20 Gea Mechanical Equipment Gmbh Method for reducing the content of saturated monoglycerides in a raw biodiesel

Also Published As

Publication number Publication date
AT412280B (de) 2004-12-27
ATA4512003A (de) 2004-05-15

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