WO2009110854A2 - Procédé pour la désacidification d'huiles végétales à forte acidité et d'huiles de friture utilisées en tant que charge d'alimentation de biodiesel - Google Patents

Procédé pour la désacidification d'huiles végétales à forte acidité et d'huiles de friture utilisées en tant que charge d'alimentation de biodiesel Download PDF

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Publication number
WO2009110854A2
WO2009110854A2 PCT/TR2009/000026 TR2009000026W WO2009110854A2 WO 2009110854 A2 WO2009110854 A2 WO 2009110854A2 TR 2009000026 W TR2009000026 W TR 2009000026W WO 2009110854 A2 WO2009110854 A2 WO 2009110854A2
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WO
WIPO (PCT)
Prior art keywords
methanol
extraction
phase
lime
oils
Prior art date
Application number
PCT/TR2009/000026
Other languages
English (en)
Other versions
WO2009110854A3 (fr
Inventor
Zeynep Selma Turkay
Hale Gurbuz
Original Assignee
Zeynep Selma Turkay
Hale Gurbuz
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 Zeynep Selma Turkay, Hale Gurbuz filed Critical Zeynep Selma Turkay
Priority to EP09717468A priority Critical patent/EP2262880A2/fr
Publication of WO2009110854A2 publication Critical patent/WO2009110854A2/fr
Publication of WO2009110854A3 publication Critical patent/WO2009110854A3/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
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/006—Refining fats or fatty oils by extraction
    • 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
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/007—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids using organic solvents
    • 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

  • Present invention relates to the removal of the free fatty acids from high acidity oils or used frying oils which is going to be used for the production of biodiesel.
  • Biodiesel which contains fatty acid methyl ester in a minimum amount of 96.5 % by weight, is produced mainly from homogeneous alkali catalyzed transesterification reaction of animal and vegetable fats and oils with methanol.
  • the feedstocks should meet some requirements for the high reaction efficiency. The most important requirement is that the free fatty acid (FFA) content of fats and oils should be less than 0.5 %. Otherwise, the free fatty acids react with the alkali catalyst to produce soap, which causes either loss of catalyst or difficulties for the separation of the ester and glycerine phases after the reaction. Water formation through the soap reaction causes serious problems such as loss of the catalyst activity or hydrolysis of both triglycerides and methyl esters. For this reason a pretreatment step is required for deacidification of feedstock before transesterification reaction (Mittelbach and Remschmidt, 2004).
  • the process of neutralization of free fatty acids with aqueous sodium hydroxide solution is widely used for the deacidification of crude oils and fats for edible and technical purposes. This process can be applied to oils and fats containing FFA up to 8-10 %. For oils and fats containing more FFA, deacidification process can be performed only with the high neutral oil losses due the formation of high amount of soap or it could not be possible to separate the soap phase from the oil.
  • numerous of processes can be used such as distilation (physical refining), miscella refining, re-esterification with glycerol or liquid-liquid extraction (solvent extraction) processes (Bhosle and Subramanian, 2005).
  • Deacidification by liquid-liquid extraction for the removal of free fatty acids from oils and fats is based on the different solubility of triglycerides and fatty acids in organic solvents, such as methanol, ethanol or aceton.
  • Operation conditions of a deacidification process such as the kind and the amount of solvent, temperature and the number of stages of the countercurrent or crosscurrent extraction systems for the removal of the desired amount of free fatty acids can be calculated using phase diagrams of three components systems, namely neutral oil (triglycerid)-fatty acid-solvent (Rius and Martinez-Moreno, 1948; Rigamonti et a/., 1951; Batista et a/., 1999; Gongalves et a/., 2004; Rodrigues et al.,2007).
  • Methanol in the extract phase consisting the essential part of the solvent fed in the column is also evaporated and is recycled to the extraction column together with the methanol recovered from the raffinate phase.
  • the flow diagram of this conventional deacidification process using methanol extraction is shown in Figure !
  • One object of the present invention is to apply a liquid-liquid extraction process to the high acidity vegetable oils and used frying oils with methanol to obtain a deacidified oil which can be used as biodiesel feedstock.
  • Another object of the present invention is to react the extract phase with lime (calcium oxide), slaked lime (calcium hydroxide), or dolomitic lime to precipitate the free fatty acids as calcium soaps,
  • Yet another object of the present invention is to feed back the regenerated methanol phase to the extraction process after the filtration of solid soaps.
  • the process of the invention consists of the following steps:
  • Figure 1 the flow diagram of the conventional deacidification process of oils and fats with methanol extraction is shown.
  • the recovery of methanol from the extract phases obtained after crosscurrent or countercurrent extraction is performed by the precipitation of free fatty acids dissolved in this phase with lime as calcium soap and by separating them through filtration.
  • Extraction In this operation, feedstock is extracted with methanol, preferably 100% methanol, at ambient temperature in batch or continuous, crosscurrent or countercurrent extraction apparatus wherein the number of stage and the amount of solvent is used according to the desired degree of deacidification. If the feedstock contains solid impurities, a pre-filtration is performed. 2. Feeding of the raffinate phase to biodiesel production: After the extraction, the raffinate phase which contains 8-10% methanol is sent to the transesterification reaction after completing the amount of methanol required for transesterification and adding the required kind and amount of catalyst.
  • methanol preferably 100% methanol
  • the extract phase which has a composition depending on the feedstock and the amount of solvent, and usually contains 90-95% methanol, is reacted with preferably powder calcium hydroxide in a reactor, preferably mixing under reflux at the temperature approximetly 55-60 0 C, according the following equation.
  • the reactor comprises a reflux condenser and a stirrer.
  • composition of the extract phase (E3) has been determined. Additionally, the qualitative analysis of compositions of three extract phases and also of the used frying oil has been performed by using thin layer chromatography as shown in Figure 3, where MG: monoglyceride, DG: diglyceride, FFA: free fatty acid, TG: triglyceride.
  • anhydrous methanol as solvent in liquid-liquid extraction.
  • aqueous methanol with water content up to 10% can be used in the extraction.
  • the water content of the raffinate phase after extraction is higher than the water content required in transesterification reaction (500 ppm), it can be used in biodiesel production after removing its solvent hence the water.
  • water is formed in the regenerated extract phase after the reaction with calcium hydroxide. Based on the reaction stoichiometry, the amount of water can be calculated as follows:

Landscapes

  • 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)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fats And Perfumes (AREA)

Abstract

Cette invention concerne un procédé devant être utilisé pour la désacidification d'huiles végétales à haute teneur en acide gras libre ou d'huiles de friture utilisées, pour les utiliser en tant que charge d'alimentation dans la production de biodiesel.
PCT/TR2009/000026 2008-03-07 2009-02-17 Procédé pour la désacidification d'huiles végétales à forte acidité et d'huiles de friture utilisées en tant que charge d'alimentation de biodiesel WO2009110854A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09717468A EP2262880A2 (fr) 2008-03-07 2009-02-17 Procédé pour la désacidification d'huiles végétales à forte acidité et d'huiles de friture utilisées en tant que charge d'alimentation de biodiesel

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2008/01480A TR200801480A2 (tr) 2008-03-07 2008-03-07 Biyodizel üretiminde kullanılmak üzere yüksek asitli bitkisel yağlardan ve kızartma yağlarından asit gidermek için bir proses.
TR2008/01480 2008-03-07

Publications (2)

Publication Number Publication Date
WO2009110854A2 true WO2009110854A2 (fr) 2009-09-11
WO2009110854A3 WO2009110854A3 (fr) 2009-12-30

Family

ID=40933109

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/TR2009/000026 WO2009110854A2 (fr) 2008-03-07 2009-02-17 Procédé pour la désacidification d'huiles végétales à forte acidité et d'huiles de friture utilisées en tant que charge d'alimentation de biodiesel

Country Status (3)

Country Link
EP (1) EP2262880A2 (fr)
TR (1) TR200801480A2 (fr)
WO (1) WO2009110854A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2395964A1 (es) * 2011-07-27 2013-02-18 Consejo Superior De Investigaciones Cientificas (Csic) METODO DE ELIMINACION DE JABONES CALCICOS Y PROCEDIMIENTO DE SINTESIS DE BIODIESEL LIBRE DE JABONES UTILIZANDO CaO COMO CATALIZADOR
CN103981026A (zh) * 2014-06-12 2014-08-13 深圳市新宝环保能源科技有限公司 一种降低生物柴油酸值的方法
US10059905B2 (en) 2012-11-13 2018-08-28 Rrip, Llc Method to recover free fatty acids from fats and oils

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1862037A (en) * 1929-12-04 1932-06-07 Schlenker Ernst Process for the separation of liquid and solid fatty acids
GB578751A (en) * 1942-10-17 1946-07-10 Colgate Palmolive Peet Co Process for the production of alkyl esters from fats and fatty oils
US3558679A (en) * 1967-09-22 1971-01-26 Laroche Navarron Lab Process for the extraction of the unsaponifiable fraction of vegetable oils
WO1997007186A1 (fr) * 1995-08-11 1997-02-27 Hyam Myers Consulting Pty. Limited Procede pour le raffinage d'huiles et de graisses
DE10164274A1 (de) * 2001-12-27 2003-07-17 Energietechnik Leipzig Gmbh Verfahren und Vorrichtung zur kontinuierlichen Extraktion freier Fettsäuren und spezieller Inhaltsstoffe aus nativen Ölen und zur Umesterung nativer Öle
WO2007093326A1 (fr) * 2006-02-15 2007-08-23 Aser S.R.L. Procédé de désacidification d'huiles et/ou de graisses

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10243700A1 (de) * 2002-09-20 2004-04-01 Oelmühle Leer Connemann Gmbh & Co. Verfahren und Vorrichtung zur Herstellung von Biodiesel

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1862037A (en) * 1929-12-04 1932-06-07 Schlenker Ernst Process for the separation of liquid and solid fatty acids
GB578751A (en) * 1942-10-17 1946-07-10 Colgate Palmolive Peet Co Process for the production of alkyl esters from fats and fatty oils
US3558679A (en) * 1967-09-22 1971-01-26 Laroche Navarron Lab Process for the extraction of the unsaponifiable fraction of vegetable oils
WO1997007186A1 (fr) * 1995-08-11 1997-02-27 Hyam Myers Consulting Pty. Limited Procede pour le raffinage d'huiles et de graisses
DE10164274A1 (de) * 2001-12-27 2003-07-17 Energietechnik Leipzig Gmbh Verfahren und Vorrichtung zur kontinuierlichen Extraktion freier Fettsäuren und spezieller Inhaltsstoffe aus nativen Ölen und zur Umesterung nativer Öle
WO2007093326A1 (fr) * 2006-02-15 2007-08-23 Aser S.R.L. Procédé de désacidification d'huiles et/ou de graisses

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BHOSLE B M ET AL: "New approaches in deacidification of edible oils--a review" JOURNAL OF FOOD ENGINEERING, BARKING, ESSEX, GB, vol. 69, no. 4, 1 August 2005 (2005-08-01), pages 481-494, XP004798844 ISSN: 0260-8774 *
See also references of EP2262880A2 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2395964A1 (es) * 2011-07-27 2013-02-18 Consejo Superior De Investigaciones Cientificas (Csic) METODO DE ELIMINACION DE JABONES CALCICOS Y PROCEDIMIENTO DE SINTESIS DE BIODIESEL LIBRE DE JABONES UTILIZANDO CaO COMO CATALIZADOR
US10059905B2 (en) 2012-11-13 2018-08-28 Rrip, Llc Method to recover free fatty acids from fats and oils
CN103981026A (zh) * 2014-06-12 2014-08-13 深圳市新宝环保能源科技有限公司 一种降低生物柴油酸值的方法

Also Published As

Publication number Publication date
EP2262880A2 (fr) 2010-12-22
TR200801480A2 (tr) 2009-09-23
WO2009110854A3 (fr) 2009-12-30

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