WO2006081644A2 - Procede catalytique d'esterification d'acides gras - Google Patents

Procede catalytique d'esterification d'acides gras Download PDF

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Publication number
WO2006081644A2
WO2006081644A2 PCT/BR2006/000013 BR2006000013W WO2006081644A2 WO 2006081644 A2 WO2006081644 A2 WO 2006081644A2 BR 2006000013 W BR2006000013 W BR 2006000013W WO 2006081644 A2 WO2006081644 A2 WO 2006081644A2
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WO
WIPO (PCT)
Prior art keywords
acid
fact
accordance
alcohol
catalyser
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Application number
PCT/BR2006/000013
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English (en)
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WO2006081644A3 (fr
Inventor
Octavio Augusto Ceva Antunes
Original Assignee
Universidade Federal Do Rio De Janeiro-Ufrj
Aranda, Donato, Alexandre, Gomes
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Application filed by Universidade Federal Do Rio De Janeiro-Ufrj, Aranda, Donato, Alexandre, Gomes filed Critical Universidade Federal Do Rio De Janeiro-Ufrj
Publication of WO2006081644A2 publication Critical patent/WO2006081644A2/fr
Publication of WO2006081644A3 publication Critical patent/WO2006081644A3/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
    • 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 is related to the esterification process of fatty acids that were previously extracted from oils or fats, that is, generally compounded and containing more than 50% of carboxylic acids, preferentially from 12 to 20 carbon atoms derived from the process of refinement of vegetable oils and animal fats .
  • these fatty acids are esterified with alcohols of 1 to 4 carbon atoms by the use of homogeneous or heterogeneous acid catalysers .
  • the esters produced are vacuum distilled thus reaching a high level of purity.
  • oils and fats In order for the oils and fats to be used in human feeding, several properties must be achieved, thus reaching a specified product .
  • One of the mandatory tests for this condition is the acidity rate .
  • These fatty acids are removed by physical processes such as vacuum distillation or distillation by means of carrier steam or chemical processes, such as the neutralization by alkaline solutions . These physical processes generate "acid sediments", that is, mixtures of fatty acids of different molecular weight, while there may even be low concentration of glycerol , traces of monoglycerides, diglycerides, triglycerides and unsaponifiable matter.
  • Biodiesel comprised by esters in fatty acids, is an alternative combustible obtained from renewable biological sources, such as vegetable oils and animal fats .
  • renewable biological sources such as vegetable oils and animal fats .
  • biodiesel is an environmentally clean combustible because it reduces the emissions of atmospheric pollutants and particulate matter, in addition to being biodegradable and non-toxic . Because it presents physical chemical properties similar to the petrol-diesel, biodiesel can be used directly in the engine with no major mechanical alterations or maintenance expenses .
  • Biodiesel can be produced from a number of oleaginous plants, such as soy, sunflower, canola, cole, castor oil, peanuts, dendS oil and cotton .
  • oleaginous plants such as soy, sunflower, canola, cole, castor oil, peanuts, dendS oil and cotton .
  • There are four classic ways to obtain biodiesel from triglycerides F. Ma and M.A. Hanna, Bioresource Technology 70 ( 1999 ) 1-15 ) : direct use of vegetable oils, microemulsions, thermal cracking (pirolysis ) and transesterification .
  • the most used process for the obtention of biodiesel is the transesterification of the triglycerides with one alcohol, forming esters that constitute the fuel, and glycerol :
  • the acidity in the ester phase is reduced up to 2% by esterification in the presence of a dissecting agent for alcohol, such as a molecular sieve .
  • the last stage is the transesterification of this ester phase with basic catalysers (NaOH, KOH, comprised of lithium or ion exchange resins, at a temperature between 20 and 100 0 C.
  • the ester thus obtained contains only traces of alkaline salts , glycerol and alcohol, with purity above 97% .
  • the oil so refined is then submitted to a conventional transesterification, with basic catalysis .
  • the pre- esterification reduces the amount of the basic catalyser to be used and limits the saponification, increasing the yield of esters .
  • Bas ⁇ et al . US patent 5, 525, 126)
  • the pre-esterification stage can be eliminated, even for loads with high content of free fatty acids, using as catalyser a mixture of barium acetate and calcium acetate, which does not cause the formation of soaps .
  • the transesterification must be conducted preferentially with anhydride methanol, at a temperature between 200 and 250 0 C for around 3 h, followed by cooling until up to around 63 0 C.
  • the mixture of esters obtained presented acidity content below 0.8% in weight, even with loads with 50% of free fatty acids .
  • the pre-esterification of the free fatty acids with homogeneous acid catalysis presents the disadvantage of the difficulty in removing the residue of catalyser from the pre-esterified material .
  • the removal of the catalyser is generally made through the washing of the mixture with methanol, which is separated from the oil phase by extraction with immiscible solvent with the oil, normally glycerin. That way, part of the esterified fatty acids is lost, reducing the yield of the process . So as to bypass this problem, one may use biocatalysers (enzymes ) or solid acid catalysers . Foglia et al .
  • Heterogeneous acid catalysers were used by Bradin (US patent 5, 578 , 090 ) for the esterification of free fatty acids with alcohols or olefins .
  • water is formed as subproduct , which can dilute or destroy the acid catalyser.
  • olefins there is no water formation, but there must be a strict temperature control (below 70°C) in order to avoid excessive polymerization of the olefin .
  • catalysers Lewis acids were used, among them, aluminum chloride and iron chloride, being the latter preferable for esterification with olefins because it minimizes the parallel reactions of dimerization and polymerization .
  • alcohols are used, specifically methanol or ethanol .
  • Methanol is the most used one due to its low cost and high polarity. Normally, alcohol is used excessively so as to dislodge the balance to a maximum yield of ester .
  • the reaction can be catalyzed by bases (NaOH, KOH, carbonates or alcohol oxides) , acids
  • the products are a mixture of esters, glycerol, alcohol, catalyser and tri ⁇ , di- and monoglycerides .
  • the excess alcohol is recovered by distillation and glycerol is separated by decantation .
  • the ester is purified by washing .
  • the ester obtained results in a significant reduction of viscosity, fitting into the specification of the diesel oil and improving the atomatization of the fuel .
  • An object of the present invention is a process for the production in high purity of ester of fatty acids, the use of catalysers, especially acids (homogeneous or heterogeneous ) and the vacuum distillation of the products obtained.
  • An additional object of the present invention refers to the catalytic process, presenting the reaction ranges of optimal conditions regarding temperature, pressure, spatial time and concentration of the reagents, for the efficient transformation of fatty acids, especially the ones present in the sediment of the palm, in esters, particularly the methylic or ethylic esters .
  • Figures 1 through 4 present the conversion graphs ( % ) versus reaction time (min) for the reaction of esterification of different fatty acids .
  • Figure 5 presents, as an example, a chromatogram of the methylic esters of fatty acids of the palm obtained in esterification with heterogeneous catalysis (Table 1 ) .
  • the objectives of the present invention include a process for the production, in high purity, of fatty acids esters, the use of acid catalysers (homogeneous or heterogeneous ) and the vacuum distillation of the products .
  • Example 1 The examples of the achievement of the invention must not be faced so as to limit the invention, but under an illustrative point of view.
  • Example 1 The examples of the achievement of the invention must not be faced so as to limit the invention, but under an illustrative point of view.
  • acid catalysers are used for the esterification of mixtures of fatty acids, defined as carboxylic acids with chains containing between 12 and 20 carbon atoms, with or without double bonds among carbons .
  • These fatty acids may be esterified with alcohols with 1 to 4 carbon atoms .
  • the present invention shows that the addition of alcohol in stoichiometrical excess is essential .
  • methanol and ethanol are the major alcohols employed.
  • other products may be used both for the formation of biodiesel and for the formation of additives for the increase in lubricity, rate of ketene or even as tensoactives or surfactants .
  • esters thus formed may be also employed as solvents or intermediaries of tensoactives or detergents .
  • molar ratios of alcohol/fatty acid between 1.5 and 15, being preferentially employed ratios between 2 and 5.
  • the high pressure favors the reaction; however, it is not indispensable .
  • the range of reaction temperature described above makes the pressure of the process compulsorily well above the atmospheric pressure .
  • the reactions involve components in the liquid phase and active sites located inside the particles of solid catalysers, being, therefore, subject to limitation by mass transference .
  • catalysers having thermal stability and acidity of Br ⁇ nsted and/or Lewis under the reaction conditions may be employed.
  • the following catalysers are employed:
  • Sulfated zircon sulfur content of 3% to 6% , with superficial area between 30 and 200 m 2 /g, pre-calcinated between 300 and 800 0 C;
  • Zircon doped with tungsten (tungsten content between 5% to 15% ) , with superficial area between 70 and 200 mVg, pre-calcinated between 300 and 800 0 C;
  • Zeolites having hydrogen as compensation cation with a molar ratio silica/aluminum between 4 and 160 and superficial area between 20 and 800 m 2 /g;
  • Polynaphthalensulphonic acid defined as product of calcinations in the range of 200 to 350 0 C, with atmosphere containing oxygen at the concentration of 0.01 to 1% and a mixture of naphthalene/concentrated sulphuric acid with a massive ratio of 0.5 to 10, respectively .
  • the time of calcination varies from 1 to 8 hours .
  • the esterification process of fatty acids can be operated in batches, in continuous reactor of the perfect mixture type, as well as in fixed bed reactors .
  • the spatial time in relation with the fatty acid is of 10 to 90 min, being preferentially from 15 to 60 min .
  • new reaction steps may be necessary aiming at an overall higher yield.
  • the catalysers are kept isolated through a fixed bed or removed after the reaction by simple filtration .
  • Tables 1 through 4 describe the reaction conditions employed in Example 1 in detail .
  • Table 5 presents, as an Example, a few physical chemical properties of the methylic ester obtained in accordance with the procedure described in Table 1. The tests were performed by using ASTM standards described in the table itself.

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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)

Abstract

La présente invention concerne un procédé destiné à l'estérification d'acides gras issus d'huiles végétales ou de graisses animales. Ce procédé permet d'obtenir des esters avec un degré de pureté élevé et peut être utilisé dans la production de biodiesel à forte valeur ajoutée.
PCT/BR2006/000013 2005-02-02 2006-02-02 Procede catalytique d'esterification d'acides gras WO2006081644A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRPI0500333-4 2005-02-02
BRPI0500333-4A BRPI0500333A (pt) 2005-02-02 2005-02-02 processo catalìtico para esterificação de ácidos graxos

Publications (2)

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WO2006081644A2 true WO2006081644A2 (fr) 2006-08-10
WO2006081644A3 WO2006081644A3 (fr) 2007-10-18

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2451580A (en) * 2007-08-01 2009-02-04 Smet Ballestra Engineering S A Esterification process
FR2929621A1 (fr) * 2008-04-08 2009-10-09 Arkema France Utilisation d'acide methane sulfonique pour l'esterification d'acides gras
WO2010055158A1 (fr) * 2008-11-17 2010-05-20 Basf Se Utilisation de l'acide méthanesulfonique pour la fabrication d'esters d'acide gras
DE102008060902A1 (de) 2008-12-09 2010-06-10 Grace Gmbh & Co. Kg Verfahren zur Herstellung von Biodiesel
WO2011085461A1 (fr) * 2010-01-18 2011-07-21 Marcos Vinicios Marques Fagundes Procédé pour désémulsification et estérification intégrée d'acides gras et de leurs dérivés au moyen de réactifs résiduels et récupération simultanée d'alcool et élimination d'eau
CN102965201A (zh) * 2012-12-12 2013-03-13 中国科学院长春应用化学研究所 一种柴油抗磨剂的制备方法
CN106365988A (zh) * 2016-08-27 2017-02-01 广州嘉德乐生化科技有限公司 一种聚甘油酯的制备方法
WO2018096248A1 (fr) 2016-11-25 2018-05-31 Arkema France Composition acide pour le traitement d'acides gras
WO2018096249A1 (fr) 2016-11-25 2018-05-31 Arkema France Composition acide pour le traitement d'acides gras
US10239812B2 (en) 2017-04-27 2019-03-26 Sartec Corporation Systems and methods for synthesis of phenolics and ketones
US10544381B2 (en) 2018-02-07 2020-01-28 Sartec Corporation Methods and apparatus for producing alkyl esters from a reaction mixture containing acidified soap stock, alcohol feedstock, and acid
US10696923B2 (en) 2018-02-07 2020-06-30 Sartec Corporation Methods and apparatus for producing alkyl esters from lipid feed stocks, alcohol feedstocks, and acids

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9102877B2 (en) 2008-11-12 2015-08-11 Sartec Corporation Systems and methods for producing fuels from biomass

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004096962A1 (fr) * 2003-04-29 2004-11-11 Escola De Química/Ufrj Procede catalytique pour l'esterification d'acides gras presents dans les grignons acides de palmier a l'aide de catalyseurs solides acides
WO2004103934A2 (fr) * 2003-05-16 2004-12-02 Stepan Company Procede de fabrication d'esters d'alkyle par pression

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004096962A1 (fr) * 2003-04-29 2004-11-11 Escola De Química/Ufrj Procede catalytique pour l'esterification d'acides gras presents dans les grignons acides de palmier a l'aide de catalyseurs solides acides
WO2004103934A2 (fr) * 2003-05-16 2004-12-02 Stepan Company Procede de fabrication d'esters d'alkyle par pression

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2451580A (en) * 2007-08-01 2009-02-04 Smet Ballestra Engineering S A Esterification process
FR2929621A1 (fr) * 2008-04-08 2009-10-09 Arkema France Utilisation d'acide methane sulfonique pour l'esterification d'acides gras
WO2010055158A1 (fr) * 2008-11-17 2010-05-20 Basf Se Utilisation de l'acide méthanesulfonique pour la fabrication d'esters d'acide gras
US8692008B2 (en) 2008-11-17 2014-04-08 Basf Se Use of methanesulfonic acid for preparing fatty acid esters
DE102008060902A1 (de) 2008-12-09 2010-06-10 Grace Gmbh & Co. Kg Verfahren zur Herstellung von Biodiesel
WO2011085461A1 (fr) * 2010-01-18 2011-07-21 Marcos Vinicios Marques Fagundes Procédé pour désémulsification et estérification intégrée d'acides gras et de leurs dérivés au moyen de réactifs résiduels et récupération simultanée d'alcool et élimination d'eau
CN102965201A (zh) * 2012-12-12 2013-03-13 中国科学院长春应用化学研究所 一种柴油抗磨剂的制备方法
CN106365988B (zh) * 2016-08-27 2019-04-26 广州嘉德乐生化科技有限公司 一种聚甘油酯的制备方法
CN106365988A (zh) * 2016-08-27 2017-02-01 广州嘉德乐生化科技有限公司 一种聚甘油酯的制备方法
WO2018096248A1 (fr) 2016-11-25 2018-05-31 Arkema France Composition acide pour le traitement d'acides gras
WO2018096249A1 (fr) 2016-11-25 2018-05-31 Arkema France Composition acide pour le traitement d'acides gras
CN109963832A (zh) * 2016-11-25 2019-07-02 阿肯马法国公司 用于加工脂肪酸的酸组合物
US10780433B2 (en) 2016-11-25 2020-09-22 Arkema France Acid composition for processing fatty acids
US11534743B2 (en) 2016-11-25 2022-12-27 Arkema France Acid composition for processing fatty acids
US10239812B2 (en) 2017-04-27 2019-03-26 Sartec Corporation Systems and methods for synthesis of phenolics and ketones
US10544381B2 (en) 2018-02-07 2020-01-28 Sartec Corporation Methods and apparatus for producing alkyl esters from a reaction mixture containing acidified soap stock, alcohol feedstock, and acid
US10696923B2 (en) 2018-02-07 2020-06-30 Sartec Corporation Methods and apparatus for producing alkyl esters from lipid feed stocks, alcohol feedstocks, and acids

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Publication number Publication date
BRPI0500333A (pt) 2006-09-12
WO2006081644A3 (fr) 2007-10-18

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