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EP1812371A1 - Procede permettant de produire desespere a partir d'huiles vegetales ou de graisses animales au moyen de catalyseurs heterogenes - Google Patents

Procede permettant de produire desespere a partir d'huiles vegetales ou de graisses animales au moyen de catalyseurs heterogenes

Info

Publication number
EP1812371A1
EP1812371A1 EP05818968A EP05818968A EP1812371A1 EP 1812371 A1 EP1812371 A1 EP 1812371A1 EP 05818968 A EP05818968 A EP 05818968A EP 05818968 A EP05818968 A EP 05818968A EP 1812371 A1 EP1812371 A1 EP 1812371A1
Authority
EP
European Patent Office
Prior art keywords
process according
catalyst
oil
reaction
monoalcohol
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Withdrawn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
EP05818968A
Other languages
German (de)
English (en)
Inventor
Dante Siano
Mario Nastasi
Elio Santacesaria
Martino Di Serio
Riccardo Tesser
Giuseppe Minutillo
Marianna Ledda
Teresa Tenore
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.)
ASER SRL
Original Assignee
ASER SRL
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 ASER SRL filed Critical ASER SRL
Publication of EP1812371A1 publication Critical patent/EP1812371A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/005—Spinels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • 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 aim of the present invention is to provide a process for producing esters from vegetable oils or animal fats which overcomes the drawbacks of the known processes mentioned above, has a lower cost and can be performed continuously, using low ratios between the quantities of alcohol and oil or fat and low ratios between the quantities of catalyst and oil or fat.
  • An object of the present invention is to provide a process which is adapted for producing esters, particularly biodiesel, from vegetable oils or animal fats and also allows to produce the glycerin co-product with high purity and therefore with a higher market price.
  • Another object of the present invention is to provide a process for preparing esters, particularly biodiesel, from vegetable oils or animal fats even in the presence of large amounts of water and/or free fatty acid.
  • Another object of the present invention is to provide a process for preparing esters, particularly biodiesel, from vegetable oils or animal fats with limited formation of surfactant species in solution which facilitate the forming of emulsions and slow the step of separation of glycerin and ester, particularly of biodiesel, avoiding the need to neutralize the products and 3 the need for an operation for separating the glycerin from the residues of homogeneous catalyst.
  • the aliphatic monoalcohol contains for example 1 to 5 carbon atoms.
  • Figures 1 and 2 are X-ray diffractograms of some catalysts given in Example 1. Ways to carrying out the Invention
  • a molar ratio of monoalcohol/oil or fat ranging from 4 to 30 is preferably used.
  • the oil or fat used in the process according to the present invention can contain free acid, even at high concentrations, particularly even higher than 1% by weight of free acid.
  • the reaction stage can also occur in the presence of water, particularly even in the presence of more than 10,000 ppm of water.
  • An example of monoalcohol which can be used in the process of the present invention is bioethanol, optionally partially rectified, containing more than 90% ethanol. 4
  • the reaction stage of the process according to the present invention can be performed continuously or discontinuously.
  • the catalyst used in the process according to the present invention can be obtained by calcination of a hydrotalcite-like compound, preferably performed at a temperature ranging from 300 to 700 0 C.
  • An example of a compound such as hydrotalcite adapted to obtain the catalyst used in the present invention is a hydrotalcite-like compound which comprises carbonate anions.
  • the catalysts used in the process according to the present invention can be obtained by calcination of the hydrotalcite-like compound, preferably performed for a time ranging from 2 to 20 hours and/or preferably performed with a heating rate ranging from 1 °C/min to 10 °C/min, and/or preferably performed in an atmosphere of air or inert gas.
  • the crystalline phase obtained after calcination is markedly different from that of the original hydrotalcite-like solids.
  • the catalyst used in the process according to the present invention can comprise for example a phase such as magnesium oxide or mixed aluminum and magnesium oxide with the characteristic positions of the 2- theta angles in X-ray diffraction spectra, as shown in Figures 1 and 2.
  • the catalyst can comprise magnesium oxide as periclase phase.
  • the catalyst can be heated to a temperature ranging from 150 to 200 0 C, for example 200 0 C, before it is used in the reaction stage.
  • the hydrotalcite-like compounds suitable to obtain the catalysts used in the process according to the present invention can be obtained for example by means of a method which comprises the stages of coprecipitation of an aqueous solution of magnesium and aluminum salts with a solution of a salt of an alkaline metal, for example potassium or sodium carbonate, rendered strongly basic for example by means of potassium or sodium hydroxide respectively. Precipitation is performed by 5 adding its solution, in drops, heated for example to 60 0 C, followed by keeping it under agitation and heated for example to 60 0 C overnight. The resulting precipitate is filtered and washed with water and then dried with hot air, for example at 100 0 C.
  • a salt of an alkaline metal for example potassium or sodium carbonate
  • Precipitation is performed by 5 adding its solution, in drops, heated for example to 60 0 C, followed by keeping it under agitation and heated for example to 60 0 C overnight.
  • the resulting precipitate is filtered and washed with water and then dried with hot air, for example
  • hydrotalcite-like compound references a double hydroxide with a layered structure, particularly a compound having the formula [M(II)i. x M(III) x (OH) 2 ] x+ (A n -)x/n.mH 2 O, in which M(II) is a cation (SI) of a divalent metal; M(III) is a cation of a trivalent metal; A is an anion with a charge n, x is the atomic ratio M(II)/(M(II)+M(III)), m is the number of water molecules present in the crystalline structure or reticular water.
  • hydrotalcite-like compounds used to prepare the catalysts used in the process according to the present invention, M(II) is Mg, M(III) is Al, and preferably A is carbonate and x is ⁇ 0.5.
  • hydrotalcite- like compound as used here also refers to synthetic compounds but also to natural hy drotalcite .
  • hydrotalcite-like compounds and “hydrotalcites” are used here interchangeably.
  • catalysts constituted by magnesium oxide or mixed oxides of magnesium and aluminum obtained by calcination of hydrotalcite-like Al-Mg compounds with a ratio of Mg/Al > 1 allow transesterif ⁇ cation of oils and esterification of fats, especially for producing biodiesel, with high conversion rates.
  • the reaction can be performed even by using oils which contain high concentrations of water and/or free fatty acid.
  • bioethanol as used here means 95% ethyl alcohol by 6 volume (with 5% water by volume), obtained from partial rectification of biomass fermentation products.
  • the process according to the invention comprises mixing the vegetable oils or animal fats with an aliphatic alcohol, preferably methanol and ethanol. The reaction mixture is then heated to the reaction temperature and placed in contact with the catalyst.
  • catalysts constituted by magnesium oxide or magnesium and aluminum oxides obtained by calcination of Al-Mg hydrotalcites with a ratio of Mg/Al > 1 are active in the reaction conditions adopted in the reaction for transesterification of oils and esterification of fats.
  • reaction conditions used are: reaction temperature ranging from 100 to 250° C, alcohol/oil molar ratio ranging from 4 to 30. These catalysts can be used in the process according to the present invention even in the presence of high concentrations of water, achieving high conversions.
  • the catalyst is separated, the excess methanol is distilled, and the glyceric phase is separated from the ester phase. If the conversion of the ester phase is o be increased, said phase can be subjected to an additional transesterification stage.
  • the transesterification reaction can be performed in batch mode or in continuous reactors, both of the agitator-equipped type and of the fixed-bed type.
  • the examples that follow are given as illustration of the invention and must not be considered as limiting its scope.
  • the catalysts were prepared by following the method described by McKenzie et al. [8].
  • A containing Mg(NO 3 )2 and A1(NO 3 )2 1.0 molar in Mg + Al and different Mg/Al atomic ratios (0, 3, 4, 10, ⁇ ); B, prepared by dissolving NaOH and Na 2 CO 3 as indicated in [8].
  • Solution A was fed at the rate of 1 cmVmin for 4 hours under vigorous agitation, while solution B was fed, when necessary, in order to keep the pH constant at 10.
  • the resulting gels were kept at 65 0 C for 24 hours and then filtered and washed to pH 7. They were dried at 85 0 C for 14 hours and the resulting solids were then calcined in air at 500 0 C for 14 hours.
  • Table 1 lists the theoretical compositions of the various prepared catalysts and the compositions determined by atomic absorption.
  • CHT3 designates the catalyst obtained for an Mg/Al atomic ratio of approximately 3;
  • CHT4 designates the catalyst obtained for an Mg/Al atomic ratio of approximately 4;
  • CHTlO designates the catalyst obtained for an Mg/Al atomic ratio of approximately 10.
  • Figures 1 and 2 illustrate X-ray diffractograms of the synthesized catalysts.
  • the crystalline phase obtained after calcination is markedly different from that of the original hydrotalcite-like solids: the signs of a crystalline phase such as periclase magnesium oxide are in fact evident.
  • the reflections have positions which are close to those of periclase magnesium oxide, and the precise position and the presence of the lower reflections depend on the composition of the catalyst.
  • Table 1 Example 1 - S nthesis of the catalysts
  • the reactor was placed in an oven with forced ventilation and subjected to the following temperature program: 14 minutes at 50 0 C, heating at 20 °C/min up to the set reaction temperature. The reactors were held at this temperature for 60 minutes. The reactor was then cooled rapidly down to ambient temperature.
  • the resulting conversion was determined by using the H-NMR technique [7]. Tests were conducted at 2 temperatures: 180 and 200 0 C.
  • a reaction test was performed by loading into a small steel reactor 1.9 g of soybean oil, 0.1 g of stearic acid (acid oil 10% by weight) and 0.9 g of methanol.
  • the reactor was placed in a forced-ventilation oven and subjected to the following temperature program: 14 minutes at 50 0 C, heating at 20 ° C/min up to 180 0 C; the reactors were kept at this temperature for 60 minutes. The reactor was then cooled rapidly down to ambient temperature.
  • the resulting conversion was determined by using the H-NMR technique [10].
  • the resulting value of the conversion equal to 25%, highlights the effect of free acidity on the transesterification reaction.
  • the final acidity was also measured and was found to be equal to 6.5% by weight.
  • reaction tests were conducted by loading into small steel reactors 2 g of soybean oil, 0.9 g of methanol, and 0.1 g of catalyst. Before use, the catalysts were kept at 200 0 C for 2 hours.
  • the reactors were placed in a forced-ventilation oven and subjected to the following temperature program: 14 minutes at 50 0 C, heating to 20 °
  • the alumina is not active, whereas there is a maximum of activity for an Mg/Al ratio ranging from 3 to 8. Pure magnesium oxide also exhibits good activity in 10 transesterification.
  • the catalyst CHT4 which gave the best performance in the tests of Example 2 was tested in the presence of large amounts of water.
  • a reaction test was conducted by loading into a small steel reactor 2 g of soybean oil, 0.9 g of methanol, 0.1 g of catalyst, and 10,000 ppm of water.
  • the reactor was placed in a forced- ventilation oven and subjected to the following temperature program: 14 minutes at 50° C, heating at 20 ° C/min up to 180 0 C; the reactor was held at this temperature for 60 minutes. The reactor was then cooled rapidly down to ambient temperature.
  • a reaction test was conducted by loading into a 1 -liter autoclave with agitator 250 g of soybean oil, 114 g of methanol, and 5 g of catalyst (MgO). The autoclave was heated to 225 0 C. After 120 minutes, a sample was taken and H-NMR [10] analysis yielded a conversion of 88.4%.
  • Table 3 shows that the resulting conversions are comparable in the two cases despite using, in the test with MgO, a lower methanol/oil ratio than in the test performed by Stern et al. with ZnO.
  • the autoclave was then cooled to ambient temperature.
  • the product unloaded from the autoclave was filtered.
  • the methanol was distilled and the glyceric phase was separated from the ester phase by means of a separation funnel.
  • the ester phase was analyzed by gas chromatography [11] and the composition shown in Table 3 was obtained.
  • a reaction test was conducted by loading into a 1 -liter autoclave, equipped with an agitator, 250 g of soybean oil, 114 g of methanol, and 2.5 g of catalyst (HT4).
  • the autoclave was then cooled to ambient temperature.
  • the product discharged from the autoclave was filtered.
  • the methanol was distilled and the glyceric phase was separated from the ester phase by means of a separation funnel.
  • the ester phase is analyzed by gas chromatography [11] and the composition listed in Table 3 is obtained.
  • the reaction tests were performed by loading small steel reactors.
  • the test with methanol was performed by loading 2 g of soybean oil, 0.9 g of alcohol and 0.1 g of catalyst; the tests with ethanol and bioethanol were instead performed by loading 2 g of oil, 2 g of alcohol and 0.1 g of catalyst.
  • the catalysts were kept at 200 0 C for 2 hours before use.
  • the reactors were placed in a forced- ventilation oven and subjected to the following temperature program: 2 minutes at 50 0 C, heating at 15°C/min up to 200 0 C; the reactors were held at this temperature for 100 minutes. The reactors were then cooled rapidly down to ambient temperature.
  • compositions of the ester phase were determined by gas chromatography [11] and are listed in Table 4.
  • the ester content obtained by using methanol was equal to 95.5%; this value is slightly higher than the value obtained in Example 2, with the same catalyst at 18O 0 C, and this clearly points out that catalytic activity is influenced by temperature.
  • the ester content obtained by using 99% ethanol by weight was equal to 95.8%; this value points out that the catalyst is not influenced by the different chain length of the two alcohols.
  • the ester content obtained by using bioethanol was equal to 95.9%; this value confirms that the catalyst is not affected by the presence of water.
  • ETS-10 are active in the transesterification reaction at temperatures below 125 0 C.
  • the activity of these catalysts is compromised by the presence of free acidity and for an acid oil containing 27% by weight of free acidity the final conversion obtained after 4 hours of reaction remains fixed at 13.7%.
  • the comparison test was performed by using the following conditions:
  • the catalyst was kept at 200 0 C for 2 hours before use.
  • the reactors were placed in a forced- ventilation oven and subjected to 15 the following temperature program: 14 minutes at 50 0 C, heating at 20 ° C/minute up to 180 0 C; the reactors were kept at this temperature for various reaction times. The reactors were then cooled rapidly down to ambient temperature. The resulting conversions were determined by using H-NMR[IO].
  • Table 5 lists the results obtained for the various tests.
  • the HT4 catalyst allows to obtain higher conversions to methyl esters than what has been reported by Suppes, is not deactivated by the high concentration of free acid, and also has a catalytic effect on the esterification reaction, since a significant decrease in the acidity of the oil is observed.

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

Abstract

L'invention concerne un procédé permettant de produire des esters d'acides gras et de la glycérine, au moyen de catalyseurs hétérogènes, en particulier un procédé permettant de produire du biodiesel. Les étapes de ce procédé consistent à faire réagir des huiles végétales ou des graisses animales avec un monoalcool aliphatique, à une température comprise entre 100 et 250 °C, en présence d'un catalyseur qui contient un oxyde de magnésium ou des oxydes mélangés de magnésium et d'aluminium, obtenu par calcination de composés de type hydrotalcite, qui contiennent de l'Al et du Mg, à raison d'un rapport atomique Mg/Al >1, de manière à former des esters d'acides gras et de la glycérine; à séparer le monoalcool qui n'a pas réagi; et à séparer les esters d'acide gras et la glycérine.
EP05818968A 2004-11-11 2005-11-09 Procede permettant de produire desespere a partir d'huiles vegetales ou de graisses animales au moyen de catalyseurs heterogenes Withdrawn EP1812371A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT002163A ITMI20042163A1 (it) 2004-11-11 2004-11-11 Processo per la produzione di esteri da oli vegetali o grassi animali con l'impiego di catalizzatori eterogenei
PCT/EP2005/011985 WO2006050925A1 (fr) 2004-11-11 2005-11-09 Procede permettant de produire desespere a partir d'huiles vegetales ou de graisses animales au moyen de catalyseurs heterogenes

Publications (1)

Publication Number Publication Date
EP1812371A1 true EP1812371A1 (fr) 2007-08-01

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EP05818968A Withdrawn EP1812371A1 (fr) 2004-11-11 2005-11-09 Procede permettant de produire desespere a partir d'huiles vegetales ou de graisses animales au moyen de catalyseurs heterogenes

Country Status (4)

Country Link
EP (1) EP1812371A1 (fr)
BR (1) BRPI0517657A (fr)
IT (1) ITMI20042163A1 (fr)
WO (1) WO2006050925A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0504759A (pt) * 2005-09-01 2007-06-12 Univ Rio De Janeiro processo catalìtico para transesterificação de óleos vegetais e gorduras utilizando-se catalisadores sólidos básicos
GB0617476D0 (en) * 2006-09-06 2006-10-18 Univ Newcastle Improved process for biodiesel production
DE102007061872A1 (de) 2007-12-19 2009-06-25 Bayer Technology Services Gmbh Verfahren zur Herstellung von Fettsäurealkylestern
PH12010501172A1 (en) * 2007-12-19 2009-06-25 Bayer Technology Services Gmbh Method for producing fatty acid alkyl esters
DE102008036295A1 (de) 2008-08-04 2010-02-11 Bayer Technology Services Gmbh Katalysatorzusammensetzung zur Umesterung
ITMI20080894A1 (it) * 2008-05-16 2009-11-17 Biocompany Srl Processo per la preparazione di biodiesel
WO2010020998A2 (fr) * 2008-07-30 2010-02-25 Indian Oil Corporation Limited Composition catalytique permettant la transestérification d'huiles et de graisses d'origine organique/naturelle pour produire des esters d'alkyle, et son procédé de préparation
CN103370405B (zh) 2011-02-14 2016-05-11 科学与工业研究委员会 使用生态友好固体碱催化剂由甘油三酯油制备脂肪酸烷基酯(生物柴油)的改进方法
BR112013031789A2 (pt) 2011-06-21 2020-10-13 W. R. Grace & Co, - Conn purificação catalítica de ésteres de alquila de ácido graxo usados em combustível
GB201119871D0 (en) 2011-11-17 2011-12-28 Davy Process Techn Ltd Process
GB201218078D0 (en) 2012-10-09 2012-11-21 Davy Process Techn Ltd Process
DE102013106382A1 (de) 2013-06-19 2014-12-24 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren zum Herstellen von Fettalkoholen aus Fettsäuremethylester
TW201602336A (zh) 2014-06-09 2016-01-16 Ｗ Ｒ 康格雷氏公司 天然油及脂之催化脫氧方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL9302126A (nl) * 1993-12-07 1995-07-03 Meern Bv Engelhard De Werkwijze voor het interesterificeren van triglycerides.
CA2336513C (fr) * 2000-02-17 2010-08-24 Tatsuo Tateno Methode de production d'esters d'acide gras et combustibles contenant un ester d'acide gras

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006050925A1 *

Also Published As

Publication number Publication date
WO2006050925A8 (fr) 2006-07-27
WO2006050925A1 (fr) 2006-05-18
BRPI0517657A (pt) 2008-10-14
ITMI20042163A1 (it) 2005-02-11

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