WO1998056747A1 - Procede et catalyseurs pour l'obtention selective d'esters d'acides gras - Google Patents

Procede et catalyseurs pour l'obtention selective d'esters d'acides gras Download PDF

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Publication number
WO1998056747A1
WO1998056747A1 PCT/ES1997/000126 ES9700126W WO9856747A1 WO 1998056747 A1 WO1998056747 A1 WO 1998056747A1 ES 9700126 W ES9700126 W ES 9700126W WO 9856747 A1 WO9856747 A1 WO 9856747A1
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WO
WIPO (PCT)
Prior art keywords
impregnated
alkaline
fatty acid
reaction
alkaline earth
Prior art date
Application number
PCT/ES1997/000126
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English (en)
Spanish (es)
Inventor
Avelino Corma Canos
Sara Iborra Chornet
Sophie Miquel
Jaime Primo Millo
Original Assignee
Universidad Politecnica De Valencia
Consejo Superior De Investigaciones Cientificas
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 Universidad Politecnica De Valencia, Consejo Superior De Investigaciones Cientificas filed Critical Universidad Politecnica De Valencia
Priority to PCT/ES1997/000126 priority Critical patent/WO1998056747A1/fr
Publication of WO1998056747A1 publication Critical patent/WO1998056747A1/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
    • 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

Definitions

  • Transesterification is a chemical reaction that takes place, as indicated in the scheme, between an ester (1) and an alcohol (2) giving rise to a new ester (3) and another alcohol (4).
  • transesterifications can be catalyzed by both bases and acids.
  • basic catalysts is preferable, since the acids can cause, depending on the structure of the alcohols involved in the process, side reactions such as isomerization or dehydration.
  • Our invention has focused specifically on the process of transesterification between fatty esters, preferably triglycerides, and alcohols, to obtain mainly two types of esters: mono and diesters of polyhydric alcohols and esters of light monoalcohols, metallic or ethyl, of fatty acids using heterogeneous basic catalysts.
  • esters of polyhydric alcohols and oleic, palmitic, stearic, etc. fatty acids have a surfactant character and are widely used as lubricants and emulsifiers in the cosmetic and food industry. Specifically, both the monoesters and diesters of glycerin have commercial utility.
  • the present invention describes a process for obtaining monoesters of fatty acids by transesterification of triglycerides of saturated and unsaturated fatty acids, rapeseed oil, palm, coconut, sunflower, etc., with mono alcohols and polyhydroxy, preferably with methanol, ethanol and glycerin, in which heterogeneous basic catalysts are alkaline earth metal oxides, preferably MgO, mixed hydroxides of a divalent metal and another trivalent typically of magnesium and aluminum respectively, of variable composition with structure Laminate type Hydrotalcite, mixed oxides of a divalent and another trivalent metal derived from Hydrotalcites, zeolites, zeotypes and sepiolites exchanged with alkaline cations, or impregnated with alkaline or alkaline earth carbonates and finally, silicas, zeolites, zeotypes and sepiolites impregnated with organic salts of alkali metals or alc alinoterreos that after
  • the present invention relates to the use of a series of heterogeneous basic high surface catalysts to direct transesterification between a triglyceride and an alcohol to achieve a selectivity greater than 85% ester with a conversion of the order of 100 %.
  • the transesterification reaction takes place according to conventional procedures in a continuous or discontinuous reactor of the stirred tank type, or in a continuous fixed or fluidized bed reactor, in which the catalyst is located.
  • the reaction is carried out in a temperature range between 25 and 260 ° C preferably between 65 and 260 ° C and with a weight ratio of alcohol / triglyceride between 0.2 and 20, the amount of catalyst used being between 0.05 and 10% with respect to the total reagent weight.
  • the reaction is carried out at atmospheric pressure in the presence of air or in an inert atmosphere or in a pressure reactor between 2-100 atm.
  • Triglycerides can be of animal and vegetable origin, fish oil, coconut oil, rapeseed, soybeans, palm, olive, corn, etc.
  • the alcohols can be both monohydroxylic: methanol, ethanol, propanol, etc. as polyhydroxy: glycerin, xylitol, etc.
  • the catalysts referred to in the present invention are: Alkaline earth metal oxides: High surface alkaline earth metal oxides are preferably used MgO is prepared by decomposition of magnesium salts or magnesium hydroxide, as described by Matsuda et al. (React. Kinet. Catal. Lett. 4, 69 (1991).
  • Hydrotalcites and oxides derived from hydrotalcites are hydroxides of tri and divalent cations such as aluminum and magnesium. They have a laminar structure that for the specific example its formula is: Mg 6 AI 2 (OH) 16 (CO 3 ) 4H 2 0 that can be prepared with different M " l / M" ratios.
  • the calcination of the hydrotalcite structure at temperatures above 200 ° C leads to a mixed oxide of di and trivalent cation such as aluminum and magnesium, Mg 6 AI 2 O 9 , which shows application as a basic catalyst (WT Reichle, J. Catal., 94, 547 (1985); Y. Ono, Bull. Chem. Soc. Japan, 61, 1008 (1900); A. Corma et al., J. Catal. 151, 60 (1995).
  • the hydrotalcites are prepared from gels prepared from the solutions of salts of the di and trivalent metals, for example and without being limiting, Mg (NO 3 ), AI (NO 3 ) 3, Na 2 CO 3 and NAOH of with perfectly determined concentrations as described by Corma et al. in J. Catal. 148, 205 (1994).
  • Sepiolites and zeolitic catalysts with basic character are prepared by introducing alkaline cations as charge compensation cations, by ionic exchange in liquid or solid phase as described by Corma et al. in Appl. Catal. 59 237 (1990) and J. Catal. 130, 130 (1991) respectively.
  • the catalysts obtained according to this ion exchange technique with alkali cations have the following order of activity according to the cation: Cs>K>Na> Li
  • SAM mesoporous amorphous silicas
  • Sepiolites and zeolitic materials are carried out by impregnating the solid with organic salts of alkaline or alkaline earth metals followed by drying at 100 ° C and calcination at 400 ° C, which results in the formation of the corresponding oxide which is partially transformed or completely carbonate in contact with carbon dioxide.
  • Hydrotalcite Mg-AI ratio A the / (Mg + A the) 0.25 was obtained by mixing two solutions A and B at a rate of 60 ml h 1 for 4 hours.
  • Solution A was prepared by dissolving Mg (NO 3 ) 2 and AI (No 3 ) 3 in distilled water until the solution was 1.5 M in Mg + Al.
  • the gel The resulting was heated in an autoclave at 200 ° C for 18 hours.
  • Example II Impregnation of SAM silica with potassium acetate
  • SAM mesoporous amorphous silica (synthesized according to the patent: US Pat. No. 5 049 536 (1991) by G. Bellussi are added to a 5 molar solution of potassium acetate. , MG Clerici, A.Carati and F. Cavani) keeping the mixture under magnetic stirring at room temperature for 2 hours.
  • the solid is filtered and the sample is calcined at 500 ° C for three hours.
  • the percentage of impregnated potassium is 20% by weight.
  • the exchange is carried out twice under the same conditions by filtering and washing the catalyst with deionized water until no chlorides are present after each exchange. Finally, the solid is dried at 100 ° C for 90 minutes.
  • the elementary analysis gives a molar relationship.
  • Example IV Transesterification of rapeseed oil with glycerin in the presence of MgO
  • glycerin and rapeseed oil are added in a glycerin / oil weight ratio of 1.2.
  • the system is heated, at atmospheric pressure, at the temperature of
  • Example V Influence of the glycerin / rapeseed oil ratio
  • the reaction is carried out under the same conditions as in the previous example with a magnesium oxide (area: 278 m2 / g) and varying the glycerin / rapeseed oil ratio in Weight from 0.3 to 1.8.
  • the results are included in table 2.

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  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de transestérification catalytique de graisses d'origine végétale ou animale avec des alcools mono ou polyhydroxyliques en présence d'un catalyseur solide hétérogène du type: oxydes de métaux alcalino-terreux, hydrotalcites avec cations tri et divalents, comme par exemple Al, Cr, Mg, Zn, Ca, Cu, Mn et les oxydes mixtes correspondants dérivés de celles-ci, zéolithes, zéotypes et sépiolites échangées avec des cations alcalins, ou imprégnées de carbonates alcalins ou alcalino-terreux, silices, zéolithes, zéotypes et sépiolotes imprégnés de sels organiques de métaux alcalins ou alcalino-terreux qui, après calcination, produisent un oxyde correspondant supporté sur de tels matériaux, à un température comprise entre une température ambiante et 260 °C et sous une pression allant de 1 à 100 atmosphères, afin d'obtenir des monoesters d'acides gras à sélectivités et rendements élevés.
PCT/ES1997/000126 1997-06-10 1997-06-10 Procede et catalyseurs pour l'obtention selective d'esters d'acides gras WO1998056747A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/ES1997/000126 WO1998056747A1 (fr) 1997-06-10 1997-06-10 Procede et catalyseurs pour l'obtention selective d'esters d'acides gras

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/ES1997/000126 WO1998056747A1 (fr) 1997-06-10 1997-06-10 Procede et catalyseurs pour l'obtention selective d'esters d'acides gras

Publications (1)

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WO1998056747A1 true WO1998056747A1 (fr) 1998-12-17

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100397794B1 (ko) * 2000-10-07 2003-09-13 최재경 지방산 알킬에스테르와 지방산 에스테르 글리세린카보네이트의 동시 제조방법
WO2007025360A2 (fr) * 2005-09-01 2007-03-08 Universidade Federal Do Rio De Janeiro Procede catalytique destine a la transesterification d'huiles vegetales et de graisses au moyen de catalyseurs solides de base
US7312355B2 (en) * 2003-10-14 2007-12-25 Consejo Superior De Investigaciones Cientificas Method of preparing fatty acid monoesters
EP2038379A2 (fr) * 2006-05-30 2009-03-25 The Pennsylvania State Research Foundation Biodiesel vert
WO2009066539A1 (fr) 2007-11-22 2009-05-28 Nippon Shokubai Co., Ltd. Procédé de fabrication d'esters alkyliques d'acides gras et/ou de glycérol à l'aide de graisse ou d'huile
DE102007061872A1 (de) 2007-12-19 2009-06-25 Bayer Technology Services Gmbh Verfahren zur Herstellung von Fettsäurealkylestern
DE102008036295A1 (de) 2008-08-04 2010-02-11 Bayer Technology Services Gmbh Katalysatorzusammensetzung zur Umesterung

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5350879A (en) * 1993-11-17 1994-09-27 Uop Transesterification using metal oxide solid solutions as the basic catalyst
EP0623581A2 (fr) * 1993-05-04 1994-11-09 Engelhard De Meern B.V. Procédé d'estérification
WO1995016014A1 (fr) * 1993-12-07 1995-06-15 Engelhard De Meern B.V. Procede d'interesterification de triglycerides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0623581A2 (fr) * 1993-05-04 1994-11-09 Engelhard De Meern B.V. Procédé d'estérification
US5350879A (en) * 1993-11-17 1994-09-27 Uop Transesterification using metal oxide solid solutions as the basic catalyst
WO1995016014A1 (fr) * 1993-12-07 1995-06-15 Engelhard De Meern B.V. Procede d'interesterification de triglycerides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PETERSON G.R. ET AL.: "Rapeseed transesterification by heterogeneous calalysis", JOURNAL OF THE AMERICAN OIL CHEMIST SOCIETY,, vol. 61, no. 10, 1984, pages 1593 - 1597 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100397794B1 (ko) * 2000-10-07 2003-09-13 최재경 지방산 알킬에스테르와 지방산 에스테르 글리세린카보네이트의 동시 제조방법
US7312355B2 (en) * 2003-10-14 2007-12-25 Consejo Superior De Investigaciones Cientificas Method of preparing fatty acid monoesters
WO2007025360A2 (fr) * 2005-09-01 2007-03-08 Universidade Federal Do Rio De Janeiro Procede catalytique destine a la transesterification d'huiles vegetales et de graisses au moyen de catalyseurs solides de base
WO2007025360A3 (fr) * 2005-09-01 2007-05-18 Univ Rio De Janeiro Procede catalytique destine a la transesterification d'huiles vegetales et de graisses au moyen de catalyseurs solides de base
EP2038379A2 (fr) * 2006-05-30 2009-03-25 The Pennsylvania State Research Foundation Biodiesel vert
EP2038379A4 (fr) * 2006-05-30 2011-06-08 Pennsylvania State Res Foundation Biodiesel vert
WO2009066539A1 (fr) 2007-11-22 2009-05-28 Nippon Shokubai Co., Ltd. Procédé de fabrication d'esters alkyliques d'acides gras et/ou de glycérol à l'aide de graisse ou d'huile
US8093416B2 (en) 2007-11-22 2012-01-10 Nippon Shokubai Co., Ltd. Method for producing fatty acid alkyl esters and/or glycerin using fat or oil
DE102007061872A1 (de) 2007-12-19 2009-06-25 Bayer Technology Services Gmbh Verfahren zur Herstellung von Fettsäurealkylestern
DE102008036295A1 (de) 2008-08-04 2010-02-11 Bayer Technology Services Gmbh Katalysatorzusammensetzung zur Umesterung

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