WO2003042343A1 - Esterification d'acides gras dans des huiles - Google Patents

Esterification d'acides gras dans des huiles Download PDF

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Publication number
WO2003042343A1
WO2003042343A1 PCT/AT2002/000319 AT0200319W WO03042343A1 WO 2003042343 A1 WO2003042343 A1 WO 2003042343A1 AT 0200319 W AT0200319 W AT 0200319W WO 03042343 A1 WO03042343 A1 WO 03042343A1
Authority
WO
WIPO (PCT)
Prior art keywords
alcohol
fatty acids
catalyst
esterification
reaction
Prior art date
Application number
PCT/AT2002/000319
Other languages
German (de)
English (en)
Inventor
Richard J. Gapes
Hans Baumgartner
Dragan Nimcevic
Original Assignee
Gapes Richard J
Hans Baumgartner
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 Gapes Richard J, Hans Baumgartner filed Critical Gapes Richard J
Publication of WO2003042343A1 publication Critical patent/WO2003042343A1/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

Definitions

  • the invention relates to a process for the esterification of fatty acids in oils and fats by introducing methyl alcohol or other lower alcohols into the liquid starting product.
  • oils and fats contain a certain percentage (from approx. 1 to over 40%) of free fatty acids (FFA).
  • FFA free fatty acids
  • FFA-containing material When refining fats / oils in oil refineries, FFA-containing material is usually treated with lye (mostly NaOH or KOH), whereby the FFA is saponified. This procedure is unsuitable in a biodiesel plant for various reasons.
  • the FFA react with the basic transesterification catalysts, producing the soaps (saponification).
  • the effects of this reaction are very unfavorable: high alkali consumption, increased neutralization effort, emulsion formation, lower yield.
  • the FFA When using FFA-containing oils and fats for the production of biodiesel, the FFA are usually esterified in a stirred tank. This reaction is usually before the transesterification reaction of the subsequently purified oil, using acidic catalysts (eg sulfuric acid). Since the esterification reaction is an equilibrium reaction, an almost complete esterification only takes place if one of the reaction products (for example water) is drawn off continuously or if one of the reactants (for example methanol) is present in excess.
  • acidic catalysts eg sulfuric acid
  • the reaction of the esterification differs fundamentally from the transesterification reaction.
  • 1 mol of acid organic or inorganic
  • 1 mol of alcohol reacts with 1 mol of alcohol, producing 1 mol of ester and 1 mol of water.
  • This reaction is an equilibrium reaction, whereby the equilibrium is usually only slightly shifted towards products.
  • the basis of the method according to the invention lies in the fact that the base-catalyzed transesterification reaction or the acid-catalyzed esterification reaction proceed much faster and more completely when the transesterification / esterification agent (methanol) is added to the fat / oil / FFA in a vaporous state. It is possible to catalyze acidic, basic and in some cases not at all, as will be explained below.
  • An embodiment of the process according to the invention for the esterification of the FFA with vaporous methanol can proceed as follows:
  • the fat / oil to be treated is extracted in e.g. 80 ° C preheated column filled. At the bottom of the column
  • the process can also be carried out continuously, e.g. constantly add the fat / oil and the catalyst to the top of the column and e.g. the fully reacted mixture is continuously removed at the bottom of the column.
  • the fully reacted mixture consists essentially of fat / oil, fatty methyl ester, methanol and catalyst (sulfuric acid). Since the fat / oil is immiscible with the methanol, the mixture is divided into a fat phase that also contains the fatty methyl ester and a methanol phase that contains the catalyst. The fat / oil now freed from the free fatty acids can then be easily transesterified to biodiesel.
  • a column without internals (thus a kind of simple tubular reactor) can be used, in which the flow through is not hindered. This promotes the discharge of the water formed during the esterification, which in turn shifts the equilibrium towards a reaction that is as complete as possible.
  • the process according to the invention thus consists in the presence in the presence of the fats or oils which are present in liquid form and which are optionally contaminated with free fatty acids with gaseous, for example technically pure methyl alcohol which has a temperature above its boiling point at the pressure prevailing in the reactor an acidic catalyst.
  • a preferred variant of the invention which relates to a continuous process, provides for e.g. at least substantially vertically arranged tubular reactor to supply the oil and the catalyst from above, while gaseous methyl alcohol is introduced from below and rises in the tubular reactor, the liquid reaction mixture which has reacted at the bottom and the excess methyl alcohol and water formed during the reaction at the top of the tubular reactor are withdrawn continuously in appropriate collecting sections. After condensing, the excess methyl alcohol, optionally cleaned and brought to the appropriate temperature and pressure, can be fed back to the tube reactor in the foot region thereof.
  • the fully reacted reaction mixture is fed to a settling tank or a continuously operating separator, in which it essentially separates into an oil phase lying on the bottom and a floating methanol phase.
  • settling tanks there are preferably so many available that the process in the tubular reactor can be operated continuously throughout.
  • Sulfuric acid is preferably used as the catalyst; sulfonic acids or any other acid which can be used as an esterification catalyst can also be used.
  • the catalyst itself is not the subject of the patent, therefore any suitable catalyst can be used, including basic and neutral catalysts.
  • the reaction is preferably carried out at ambient pressure, the methyl alcohol to be blown in having a temperature of about 65 ° C. (boiling point of the methyl alcohol under normal conditions) or above.
  • the reaction mixture heats up with cooling and partial condensation of the methyl alcohol.
  • the essence of the invention is essentially the gaseous nature of the alcohol, it is immaterial whether the alcohol is vaporized outside or inside the reactor. It is therefore also possible to bring the alcohol as a liquid into the reactor, where the alcohol is then e.g. the temperature of the oil / fat / FFA / etc. verdämpft. This can be particularly advantageous for designs that operate at ambient pressure (i.e. unpressurized) but at temperatures of the oil / grease / FFA / etc. work above the boiling point of the alcohol.
  • the invention is not restricted to the examples described.
  • different catalysts can be used, because of the gaseous alcohol and the temperatures used, "slower ones", which only become fully effective at higher temperatures. At particularly high temperatures, it is possible to dispense with the catalyst entirely or in large part Mixtures of alcohols and mixtures of alcohol with inert gas can be used, in particular azeotropic ones, in which the transition to the gas phase is energetically favorable and the preparation is simple.
  • the question of pressure is not critical, but it can have an impact on the profitability of the process, the yield and the course of the reaction: the volumes become smaller, the reactivity increases, the stripping effect decreases.
  • the reactor can have internals, fixed or movable (stirrer), tubular, standing or lying, if the appropriate flow is ensured.

Landscapes

  • 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)

Abstract

L'invention concerne un procédé d'estérification à catalyse acide d'acides gras dans des huiles et des graisses, c.-à-d. des esters de la glycérine avec des acides gras, par introduction d'alcools inférieurs, notamment d'alcool méthylique, dans le produit liquide initial. Le procédé selon l'invention est caractérisé en ce que l'alcool méthylique ou un autre alcool est alimenté sous forme gazeuse au mélange de réaction. L'invention concerne également d'autres modes de réalisation dudit procédé.
PCT/AT2002/000319 2001-11-16 2002-11-15 Esterification d'acides gras dans des huiles WO2003042343A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA1805/2001 2001-11-16
AT18052001 2001-11-16

Publications (1)

Publication Number Publication Date
WO2003042343A1 true WO2003042343A1 (fr) 2003-05-22

Family

ID=3689000

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AT2002/000319 WO2003042343A1 (fr) 2001-11-16 2002-11-15 Esterification d'acides gras dans des huiles

Country Status (1)

Country Link
WO (1) WO2003042343A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1328353C (zh) * 2005-02-03 2007-07-25 云南师范大学 一种动、植物油制备生物柴油的工艺
GB2451580A (en) * 2007-08-01 2009-02-04 Smet Ballestra Engineering S A Esterification process
CN113563976A (zh) * 2021-07-21 2021-10-29 湖北天基生物能源科技发展有限公司 一种废弃油脂的气相酯化系统及其处理废弃油脂的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3421217A1 (de) * 1984-06-07 1985-09-05 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von fettsaeureestern kurzkettiger alkohole
PL148080B1 (en) * 1986-05-14 1989-09-30 Procedure for the processing of tall oil and its derivatives by means of fractional destillation
WO1996040415A1 (fr) * 1995-06-07 1996-12-19 The Procter & Gamble Company Procede de purification d'un gaz inerte tout en preparant des esters alkyliques inferieurs

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3421217A1 (de) * 1984-06-07 1985-09-05 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung von fettsaeureestern kurzkettiger alkohole
PL148080B1 (en) * 1986-05-14 1989-09-30 Procedure for the processing of tall oil and its derivatives by means of fractional destillation
WO1996040415A1 (fr) * 1995-06-07 1996-12-19 The Procter & Gamble Company Procede de purification d'un gaz inerte tout en preparant des esters alkyliques inferieurs

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 113, no. 26, 24 December 1990, Columbus, Ohio, US; abstract no. 233705, GLOWACKI, JANUSZ ET AL: "Procedure for processing of tall oil and its derivatives by fractional destillation" XP002176093 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1328353C (zh) * 2005-02-03 2007-07-25 云南师范大学 一种动、植物油制备生物柴油的工艺
GB2451580A (en) * 2007-08-01 2009-02-04 Smet Ballestra Engineering S A Esterification process
CN113563976A (zh) * 2021-07-21 2021-10-29 湖北天基生物能源科技发展有限公司 一种废弃油脂的气相酯化系统及其处理废弃油脂的方法

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