EP1565424A1 - Procede de fabrication d'esters d'alkyle - Google Patents

Procede de fabrication d'esters d'alkyle

Info

Publication number
EP1565424A1
EP1565424A1 EP02779013A EP02779013A EP1565424A1 EP 1565424 A1 EP1565424 A1 EP 1565424A1 EP 02779013 A EP02779013 A EP 02779013A EP 02779013 A EP02779013 A EP 02779013A EP 1565424 A1 EP1565424 A1 EP 1565424A1
Authority
EP
European Patent Office
Prior art keywords
solution
acid
alcohol
mixture
glycerides
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.)
Withdrawn
Application number
EP02779013A
Other languages
German (de)
English (en)
Other versions
EP1565424A4 (fr
Inventor
Raymond Muskett
Colin Arthur Anderson
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.)
Biodiesel Australia Ltd
Original Assignee
Biodiesel Australia Ltd
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 Biodiesel Australia Ltd filed Critical Biodiesel Australia Ltd
Publication of EP1565424A1 publication Critical patent/EP1565424A1/fr
Publication of EP1565424A4 publication Critical patent/EP1565424A4/fr
Withdrawn legal-status Critical Current

Links

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
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C11C3/10—Ester interchange
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • 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 present invention relates to a method for production of alkyl esters from mixtures of glycerides and free fatty acids, in particular mixtures of glycerides and free fatty acids from grease trap waste, tallows, animal fats, vegetable lipids and other high fatty acid content lipids.
  • mixtures of glycerides and free fatty acids from grease trap waste, tallows, animal fats, vegetable lipids and other high fatty acid content lipids.
  • it has been found to be very effective in efficiently producing alkyl esters from lower fatty acid, higher glyceride content lipids.
  • Biodiesel Alkyl esters of fatty acids found in natural lipids, commonly known as biodiesel, are becoming increasingly recognised as viable fuel alternatives for diesel engines. They are known to reduce the output of particulate, hydrocarbon pollutants and improve the lubrication of diesel engines. Biodiesel may also be successfully used as a lubricant, a hydraulic fluid and as a multi-purpose solvent.
  • biodiesel is attractive from a commercial and environmental viewpoint because the raw materials applicable to this invention may be sourced from renewable oilseed feedstocks, used vegetable oils, palm oil, coconut oil, soapstock materials as a lipid-rich byproduct of vegetable oil refining, tallows, animal fats, or from grease trap waste which would normally be disposed of in land fill and other waste disposal facilities.
  • the Haas et al method for synthesis of fatty acid methyl esters from soapstock involves another two-step process wherein the soapstock is first saponified and then esterified in an acidic alcohol solution.
  • Haas et al reports that a 60% recovery of fatty acid methyl ester is achieved with this method.
  • the method is characterised, however, by high consumption of the reagents.
  • the present invention attempts to overcome at least in part some of the aforementioned disadvantages and to provide new advantages including low or nil glycerol production and the method is amenable to low capital plant costs and plant mobility.
  • a method for production of alkyl esters from a mixture of glycerides and free fatty acids comprising: a) addition of an acid to an alcoholic solution of the mixture to decrease the pH of the solution to about 1 to 2 to effect acid-catalysed alkyl esterification; b) treatment of the solution from step a) with a concentrated alkoxide solution to raise the pH of the solution to about 12 to effect base-catalysed transesterification of glycerides contained in the mixture; c) treatment of the solution from step b) with acid to decrease the pH of the solution to about 2 to effect acid-catalysed esterification of residual saponified by-products from step b); d) removal of alcohol from the solution from step c); and e) separation of resulting alkyl esters.
  • the present invention describes a method for reacting a mixture of free fatty acids and glycerides, commonly found in grease trap waste, tallows, animal fats, palm oil, coconut oil, and other naturally occurring lipids, including waste or fresh unused vegetable oils and tallows with short-chain alcohols such as methanol, ethanol, propanol, or butanol to produce corresponding alkyl esters.
  • grease trap waste encompasses a highly variable mixture of organic fats, greases and vegetable oils, comprising a high free fatty acid and mono-, di-, and triglyceride content, contaminated by detergents, water, soaps, inorganic and particulate matter.
  • free fatty acid (FFA) and glycerides will be taken to mean the total content of free fatty acids and mono-, di-, and triglycerides comprised in grease trap waste, tallows, animal fats, and other naturally occurring lipids, and available for alkyl esterification.
  • the grease trap waste is between 80 to 100% free fatty acid and glycerides.
  • the alcohol includes low-boiling point alcohols, preferably methanol, ethanol, propanol, and butanol in their single-chain and isomerised forms.
  • low-boiling point alcohols preferably methanol, ethanol, propanol, and butanol in their single-chain and isomerised forms.
  • longer-chain alcohols can be utilised in a similar fashion in accordance with the present invention.
  • a mixture of free fatty acids and glycerides, in the form of grease extracted from grease trap waste, tallows, animal fats, and other naturally occurring animal or vegetable lipids, is mixed and agitated in the alcohol to form a miscible single-phase alcoholic solution of the mixture.
  • an immiscible suspension of lipids may form in the alcohol.
  • the suspension is continually agitated to prevent separation of the lipid and alcohol into two distinct phases.
  • the agitated suspension is to be regarded and treated as an alcoholic solution of the mixture of lipids and glycerides.
  • Neither type of mixture is dependent on, or requires a co-solvent in the process.
  • use of such co-solvents will not impair the reaction or its final alkyl ester product.
  • Co-solvent usage may marginally increase the reaction rate but the reaction is quite rapid and goes to completion in the absence of co-solvent.
  • the mixture of free fatty acids and glycerides is dissolved in a similar volume of alcohol to afford about 50% v/v alcoholic solution of the mixture. In this way, the alcohol is in molar excess of the total free fatty acid content, preferably in a range of 1:10 to 1:25.
  • the reaction proceeds satisfactorily with a lesser or greater proportion of alcohol to lipids, however the reaction proceeds optimally at about 50% v/v.
  • vigorous agitation of the two-phase homogeneous solution throughout the reaction procedure effects similar results with regard to alkyl ester production.
  • the alcoholic solution of the mixture is first treated with an acid catalyst to effect acid-catalysed alkyl esterification, then treated with a base catalyst to effect base- catalysed transesterification of glycerides contained in the mixture.
  • the resulting reaction mixture is finally treated with an acid catalyst to effect acid-catalysed alkyl esterification of residual saponified by-products resulting from the previous treatment steps.
  • the acid-catalysed esterification and base-catalysed transesterification steps are performed under reflux conditions, although said steps may also be performed at ambient temperatures, albeit with longer reaction times unless high pressures are used.
  • the method of the present invention is preferably performed at ambient atmospheric pressure. However, it is envisaged that said method can be successfully performed under higher pressures with use of a pressure Vessel, or under autoclave conditions.
  • Acid catalysts include, but are not limited to, concentrated strong inorganic acids such as sulphuric acid, hydrochloric acid, phosphoric acid, and perchloric acid.
  • the ratio of added acid-catalyst to total fatty acid content is about 1 :20 in the first acid-catalysed alkyl esterification reaction step, and about 1:5 in the second acid- catalysed esterification reaction step.
  • Base catalysts include, but are not limited to, alcoholic solutions of sodium hydroxide and/or potassium hydroxide, or sodium or potassium dissolved in the short-chain alcohol of choice.
  • alcoholic solutions of sodium hydroxide and/or potassium hydroxide, or sodium or potassium dissolved in the short-chain alcohol of choice Preferably, a 10% w/w alkali metal alkoxide solution is used as the base catalyst, such that the ratio of added base-catalyst to total fatty acid content is about 1:5.
  • the alcohol is removed from the resulting reaction mixture by distillation or by separation with microfiltration membranes, with or without vacuum assistance, leaving a two-phase heterogeneous mixture of alkyl esters and a solid phase.
  • the alkyl esters are separated from the solid phase by decantation, and further purified by filtration or separated by filtration alone.
  • the alkyl ester can be treated with a weak base to effectively neutralise residual acid remaining in the alky ester phase, or alternatively by ion exchange or microfiltration. It is envisaged that the pH of the alkyl ester phase will be neutralised to about pH 6-7.
  • the neutralisation step is achieved by addition of small amounts of sodium bicarbonate or calcium carbonate or magnesium carbonate to the alkyl ester phase. It is envisaged that other well known means for neutralising pH such as elution of the liquid phase through an ion exchange resin or membrane separation, can be successfully employed to effect neutralisation of residual acid within the alkyl ester phase.
  • Residual water can then be removed by conventional means such as passing the alkyl ester phase over a hygrosopic dessicant or by heating the alkyl ester sufficiently to remove steam at atmospheric pressures or under vacuum or by microfiltration. Depending on the final intended use of the alkyl ester, a small amount of entrained water may be acceptable and its removal may not be necessary.
  • the inventors have found that the alkyl esters produced by the method of the present invention remain uncontaminated by glycerol byproducts from the acid- catalysed esterification and base-catalysed transesterification reactions of this invention. An exception was found from the treatment of fresh unused vegetable oil whereby a small quantity of good quality glycerol was readily separated.
  • the amount of glycerol byproduct was at less than 8% of the starting oil and noticeably less than the amount generated by other esterification methods. No noticeable glycerol production occurred when treating other lipids such as palm oil, coconut oil, animal tallow or grease trap waste. The residual product after alkyl ester separation showed no signs of glycerol by gas chromatography testing.
  • Example A single phase 1:1 v/v methanolic solution of grease trap waste (800 ml) in methanol (800 ml) was prepared.
  • a GC/MS analysis of the grease trap waste indicated that the major components of the grease trap waste were octadecanoic acid and n- hexadecanoic acid.
  • the pH of the methanolic solution of grease trap waste was 4, reflecting a high fatty acid content.
  • Concentrated sulphuric acid (98%) (8.5 g) was added with stirring to the methanolic solution resulting in a solution pH of between 1 and 2.
  • the methanolic solution was refluxed for 30 minutes.
  • a sodium methoxide solution of 10% w/w NaOH in methanol (160 ml) was then added dropwise to the stirred refluxing methanolic solution resulting in a final pH of 12.
  • the residual sediment formed from the reaction mixture using ethanol and potassium hydroxide was less crustiform than the sediment described in the Example, it was readily separated from the ethyl esters by filtration.
  • the crustiform residue was found to comprise mostly sodium sulphate with minor entrained methyl ester that combined with the sodium sulphate totalled 9% by weight of the starting grease trap waste.
  • the conversion of grease trap waste to methyl ester therefore exceeded 91%.
  • the entire processing time to final product alkyl ester is less than 1 hour. Furthermore, by increasing the amount of acid in the first step it was found that the reaction time was accelerated thereby reducing the overall reactions processing time.
  • the process is not sensitive to or damaged by residual water contaminating the starting lipid. It is a rapid and efficient process and method that can be made even faster by increasing reaction kinetics by increasing the catalytic dosage amounts and/or many well known methods including increased heat, pressure and agitation.
  • the final product alkyl ester does not require water washing thereby eliminating a major processing step common to other methods that is both time consuming and polluting. Glycerol byproduction is eliminated in most lipid feedstocks tested.
  • the method and process permits design of commercial plants that should be low in capital cost, small in size, with high production rates and be portable as truck mounted, trailer-coupled units, or as a static plant.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (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)
  • Fats And Perfumes (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de fabrication d'esters d'alkyle à partir d'un mélange de glycerides et d'acides gras libres provenant principalement des déchets de boîtes à graisse. Le mélange est d'abord solvaté dans un alcool à point d'ébullition bas, après quoi le pH de la solution est porté à environ 1 à 2 par l'addition d'un acide afin d'effectuer l'estérification d'alkyle catalysé par acide. On traite ensuite la solution acide avec une solution concentrée d'alcoxyde pour porter le pH de la solution jusqu'à environ pH12 et effectuer la transestérification catalysée par des bases des glycerides contenus dans le mélange. On traite ensuite la solution qui en résulte avec un acide pour réduire le pH de la solution jusqu'à environ 2 et effectuer l'estérification catalysée par acides des sous-produits saponifiés résiduels. Le solvant à base d'alcool est évacué par distillation ou par toute autre technique appropriée, et les esters d'alkyle ainsi obtenus sont séparés de n'importe quels résidus restants et neutralisés des acides résiduels.
EP02779013A 2002-11-27 2002-11-27 Procede de fabrication d'esters d'alkyle Withdrawn EP1565424A4 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/AU2002/001594 WO2004048311A1 (fr) 2002-11-27 2002-11-27 Procede de fabrication d'esters d'alkyle

Publications (2)

Publication Number Publication Date
EP1565424A1 true EP1565424A1 (fr) 2005-08-24
EP1565424A4 EP1565424A4 (fr) 2006-05-31

Family

ID=32330490

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02779013A Withdrawn EP1565424A4 (fr) 2002-11-27 2002-11-27 Procede de fabrication d'esters d'alkyle

Country Status (6)

Country Link
EP (1) EP1565424A4 (fr)
JP (1) JP2006508148A (fr)
CN (1) CN1720214A (fr)
AU (1) AU2002342410A1 (fr)
CA (1) CA2507329A1 (fr)
WO (1) WO2004048311A1 (fr)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI114280B (fi) 2001-01-11 2004-09-30 Eriksson Capital Ab Polyamidiin ja polyamidilohkoja ja polyeetterilohkoja sisältäviin polymeereihin perustuva makkarankuori, joka on savustettavissa
FR2872812B1 (fr) * 2004-07-12 2006-09-08 Inst Francais Du Petrole Procede de production d'esters alkyliques d'acides gras et de glycerine de haute purete
JP4515840B2 (ja) * 2004-07-13 2010-08-04 株式会社レボインターナショナル 脂肪酸アルキルエステルの製造方法
KR20070116613A (ko) 2005-02-28 2007-12-10 유니버시티 오브 오타와 바이오-연료 생산을 위한 장치 및 방법
US7619104B2 (en) 2005-04-04 2009-11-17 Renewable Products Development Laboratories, Inc. Process for producing biodiesel or fatty acid esters from multiple triglyceride feedstocks
AU2006254851A1 (en) * 2005-06-09 2006-12-14 Biosphere Environmental Energy Llc Systems and methods for esterification and transesterification of fats and oils
US7842653B2 (en) 2005-06-16 2010-11-30 Council Of Scientific & Industrial Research Process for the preparation of lubricants
WO2007027669A1 (fr) * 2005-08-29 2007-03-08 Cps Biofuels, Inc. Carburant biodiesel ameliore, additifs, et lubrifiants
US7754643B2 (en) 2005-10-07 2010-07-13 Council Of Scientific & Industrial Research Transesterification catalyst and a process for the preparation thereof
US7482480B2 (en) 2005-10-10 2009-01-27 Council Of Scientific & Industrial Research Process for the preparation of hydrocarbon fuel
ES2332284T3 (es) 2005-10-10 2010-02-01 Council Of Scientific And Industrial Research Proceso para la preparacion de carbonato de dialquilo.
ES2721427T3 (es) 2006-04-28 2019-07-31 Sk Chemicals Co Ltd Procedimiento para preparar éster alquílico de ácido graso usando destilado de ácido graso
CN100434164C (zh) * 2006-07-10 2008-11-19 张冰青 一种催化剂体系及采用该催化剂体系生产生物柴油的方法
US8084655B2 (en) 2007-06-15 2011-12-27 E. I. Du Pont De Nemours And Company Catalytic process for converting renewable resources into paraffins for use as diesel blending stocks
US8124801B2 (en) 2008-06-24 2012-02-28 Benefuel Inc. Process of manufacturing of fatty acid alkyl esters
EP2303827B1 (fr) 2008-06-25 2019-10-16 Benefuel Inc. Procédé de fabrication d' alkylesters d' acides gras
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
CN102465058A (zh) * 2010-11-04 2012-05-23 朱建军 一种制备生物柴油的生产工艺
MY163273A (en) 2011-03-09 2017-08-30 Benefuel Inc Systems and methods for making bioproducts
CN102311883B (zh) * 2011-08-10 2013-04-24 北京清研利华石油化学技术有限公司 一种制备高纯度生物柴油的方法
CN102951934A (zh) * 2011-08-24 2013-03-06 江苏洁净环境科技有限公司 一种餐厨垃圾处理工艺

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0127104A1 (fr) * 1983-05-30 1984-12-05 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation d'esters d'acides gras et d'alcools aliphatiques à courte chaîne à partir de graisses et/ou d'huiles contenant des acides gras libres

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WO1987007632A1 (fr) * 1986-06-11 1987-12-17 Bio-Energy Technology Ltd. Production de carburant biologique
AT394374B (de) * 1990-06-29 1992-03-25 Wimmer Theodor Verfahren zur herstellung von fettsaeureestern niederer alkohole
AU778808B2 (en) * 2001-05-31 2004-12-23 Biodiesel Australia Ltd Method for production of alkyl esters

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0127104A1 (fr) * 1983-05-30 1984-12-05 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation d'esters d'acides gras et d'alcools aliphatiques à courte chaîne à partir de graisses et/ou d'huiles contenant des acides gras libres

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2004048311A1 *

Also Published As

Publication number Publication date
EP1565424A4 (fr) 2006-05-31
WO2004048311A1 (fr) 2004-06-10
CA2507329A1 (fr) 2004-06-10
JP2006508148A (ja) 2006-03-09
CN1720214A (zh) 2006-01-11
AU2002342410A1 (en) 2004-06-18

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