WO2016079671A1 - Process for obtaining vegetable oil rich in 1,3- diacylglycerols - Google Patents

Process for obtaining vegetable oil rich in 1,3- diacylglycerols Download PDF

Info

Publication number
WO2016079671A1
WO2016079671A1 PCT/IB2015/058883 IB2015058883W WO2016079671A1 WO 2016079671 A1 WO2016079671 A1 WO 2016079671A1 IB 2015058883 W IB2015058883 W IB 2015058883W WO 2016079671 A1 WO2016079671 A1 WO 2016079671A1
Authority
WO
WIPO (PCT)
Prior art keywords
diacylglycerols
process according
oil
dag
vegetable oil
Prior art date
Application number
PCT/IB2015/058883
Other languages
French (fr)
Inventor
Juana Isabel DI COSIMO
Veronica Karina DIEZ
Cristian Alejandro FERRETI
Pablo Antonio TORRESI
Original Assignee
Consejo Nacional De Investigaciones Cientificas Y Tecnicas (Conicet)
Universidad Nacional Del Litoral
Inis Biotech Llc
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 Consejo Nacional De Investigaciones Cientificas Y Tecnicas (Conicet), Universidad Nacional Del Litoral, Inis Biotech Llc filed Critical Consejo Nacional De Investigaciones Cientificas Y Tecnicas (Conicet)
Publication of WO2016079671A1 publication Critical patent/WO2016079671A1/en

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
    • C11C3/02—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with glycerol
    • C11C3/025—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with glycerol with a stoechiometric excess of glycerol
    • 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
    • C11C3/06—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils with glycerol
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6436—Fatty acid esters
    • C12P7/6445—Glycerides
    • C12P7/6458—Glycerides by transesterification, e.g. interesterification, ester interchange, alcoholysis or acidolysis

Definitions

  • the present invention falls within the technical field of functional foods, particularly edible oils formulations with high concentrations of 1,3- diacylglycerols .
  • TAG triacylglycerols
  • a diet rich in lipids containing TAG is manifested in the accumulation of TAG in adipose tissue and an increase in plasma TAG. Both parameters are directly related to obesity, atherosclerosis, and other diseases related to high consumption of fats or oils.
  • DAG diacylglycerols
  • the oil's TAG can become DAG catalytically by enzymatic processes, or by homogeneous or heterogeneous catalysis.
  • DAG derived from a fatty acid in particular there are two isomers: 1,2-DAG and 1,3-DAG.
  • alkali metal alkoxides sodium methoxide, sodium ethoxide, potassium isopropoxide
  • metal glycerates alkali metal hydrides (LiH) and other hydroxides and oxides of alkaline earth and alkali metals such as LiOH, RbOH, CsOH, Ca(OH) 2 , SrO or KOH .
  • the advantage of the heterogeneous catalytic processes using solid catalysts for glycerolysis or transesterification reactions is that the catalyst is not dissolved in the reaction medium so that subsequent separation is much simpler, much less expensive and the catalyst is fully recycled for a new cycle of operation.
  • a supported alkali metal hydroxide may cause leaching of said hydroxide to the reaction medium, resulting in a homogeneous catalytic process. If this was the case, the dissolved potassium should be removed from the final product. This has not been discussed by the authors in their studies.
  • the present invention provides a process for obtaining an oil rich in diacylglycerols from triacylglycerols .
  • the process comprises a transesterification reaction between a triacylglycerol (TAG) and glycerol (Gly) , according to the stoichiometry: 2 TAG + Gly -4 ⁇ 3 DAG.
  • TAG triacylglycerol
  • Gly glycerol
  • the oil of the present invention is rich in 1 , 3-diacylglycerols , as this is the isomer of interest.
  • This process seeks to transform the TAG of the edible soybean oil, sunflower or other vegetable oils in an oil containing between 20 and 40% by weight of the 1 , 3-diacylglycerol isomer.
  • the process of the present invention solves the problems the prior art could not save, by obtaining an oil rich in food grade 1,3-DAG in less time than 10 hours, in the absence of liquid catalysts, in the absence of hydroxides, in the absence of the need for solvent stripping operations, with low load of catalyst in a simple and economical way.
  • the present invention describes a process for obtaining vegetable oil rich in 1 , 3-diacylglycerols with at least 10% by weight of 1 , 3-diacylglycerols characterized in that it comprises the following steps: a. mixing vegetable oil with glycerol in a glycerol/oil molar ratio between 0.5 and 2;
  • step b reacting, for a time of between 4 and 8 hours, the mixture of step a) , at a temperature of between 180 and 240 °C in an inert atmosphere, in the presence of a solid catalyst of MgO in a ratio of between 0.1% and 3% by weight relative to the mass of oil;
  • the glycerol/oil molar ratio is between 0.6 and 1.6, preferably between 0.6 and 1.0, more preferably is between 0.8 and 1.0, most preferably it is 0.8.
  • the ratio of the catalyst is 2% by weight based on the mass of oil.
  • reaction time is 8 hours .
  • step c) it is cooled to 150 °C for a time of 2 hours.
  • it is cooled to 150 °C for a time of 2 hours and subsequently cooled to 25 °C for a time of 12 hours.
  • it is performed in the absence of said step c) .
  • a vegetable oil rich in 1,3- diacylglycerols is obtained, which comprises between 12 and 39% of monoacylglycerols, between 20 and 40% of 1 , 3-diacylglycerols, between 4 and 17% of 1 , 2-diacylglycerols, and between 19 and 37% of triacylglycerols .
  • the process of the present invention is conducted in the absence of soluble catalysts such as hydroxides or liquids, where the reaction time is less than 10 hours.
  • Another object of the present invention is a vegetable oil rich in 1 , 3-diacylglycerols, comprising between 12 and 39% of monoacylglycerols, between 20 and 40% of 1, 3-diacylglycerols, between 4 and 17% 1,2- diacylglycerols, between 19 and 37% triacylglycerols; preferably 27.4% of monoacylglycerols, 34.9% of 1,3- diacylglycerols, 16.5% of 1 , 2-diacylglycerols, 21.2% of triacylglycerols; more preferably a vegetable oil comprising between 25 and 35% of 1, 3-diacylglycerols .
  • the present invention describes a vegetable oil rich in 1 , 3-diacylglycerols , with at least 10% by weight of 1,3-DAG and the process for obtaining the oil.
  • the present invention provides a fast, economical and simple process of transesterification of TAG with glycerol, to form DAG, resulting in an edible oil with low-TAG, rich in 1,3-DAG.
  • the process of the present invention enables obtaining DAG from vegetable oil, by transforming the TAG present therein by transesterification with glycerin.
  • the vegetable oil should be mixed with glycerin, its ratio is essential to get adequate yields of the DAG of interest.
  • the molar ratio of Gly/TAG must be between 0.5 and 2, to obtain good yields as explained in Examples 1-4.
  • the second step is conducting the transesterification reaction, preferably in a 7-necked agitated glass reactor, provided with connections for the inlet and outlet of a gas stream of inert gas, preferably nitrogen and the remaining ones, for charging reagents and catalyst for sampling, for the temperature sensor and the stirrer shaft.
  • Said reactor is heated by a furnace which should take the reaction mixture to a temperature of preferably between 200 and 240 °C, as described in Examples 1 and 5.
  • the agitation system should preferably provide a stirring rate of at least 700rpm, so as to ensure that the reactor operates under a perfect mix.
  • the reactor pressure should preferably be maintained at 1 atm, this being achieved by continuous passage through the reactor in a nitrogen gas stream of 20 to 100 cm 3 /min.
  • MgO the most suitable catalyst for this reaction.
  • the amount of MgO is a very important variable that influences outright in the amount of DAG produced. Through the examples 1 and 6 it is concluded that the optimum amount of catalyst is between 0.1 and 3% by weight based on the mass of TAG.
  • the reaction should proceed for a period of time between 4 and 8 h, as shown in Examples 1 to 4 of Table 2.
  • the reaction mixture is cooled to temperatures between 25 and 150 °C, holding it for an additional period of time between 2 and 12 h at that temperature, since it has been shown that said step influences the performance of the reaction, as shown in Examples 7, 8 and 9.
  • Example 1 Analysis of the crude oil phase containing all acylglycerols was by liquid chromatography (HPLC) and was confirmed by gas chromatography. The results make up Example 1 and they are presented in Table 1. % by weight content of glycerides was 15.3% of monoacylglycerols, 49.3% of diacylglycerols (33.4% of 1 , 3-diacylglycerols isomers; 15.9% of 1 , 2-diacylglycerols isomers) and 35.4% of triacylglycerols .
  • Example 1 The assay of Example 1 was repeated, but lowering the reaction temperature to 200 °C and keeping the rest of the conditions equal to Example 1. The results obtained at 200 °C make up Example 5 and they are presented in Table 3. The operation at 200 °C decreases the final concentration of 1 , 3-diacylglycerols (1,3-DAG) to 10.7%.
  • Example 1 The assay of Example 1 was repeated, but using soybean oil instead of sunflower oil, that is, changing the type of triacylglycerol used. The remaining experimental conditions were kept equal to Example 1. The results make up Example 7 and they are presented in Table 5. The use of soybean oil yields a final concentration of 1, 3-diacylglycerols (1,3-DAG) of 30.8%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Health & Medical Sciences (AREA)
  • Biotechnology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

A process for obtaining vegetable oil rich in 1,3- diacylglycerols with at least 10% by weight of 1,3- diacylglycerols comprising a transesterification reaction of triacylglycerol and glycerin in the presence of a solid catalyst is provided. A vegetable oil rich in 1,3- diacylglycerols containing 20 to 40% by weight of 1,3- diacylglycerols is also provided.

Description

Title
PROCESS FOR OBTAINING VEGETABLE OIL RICH IN 1,3- DIACYLGLYCEROLS
Technological Field of the Invention
The present invention falls within the technical field of functional foods, particularly edible oils formulations with high concentrations of 1,3- diacylglycerols .
Prior Art
Nowadays, worldwide, there is great interest in the design of food which tends to human health care. In the case of food industry, it is intended that the food possess low levels of cholesterol, Na+, trans fats or oils with low content of triacylglycerols (TAG) of saturated fatty acids, etc. Vegetable oils contain TAG primarily derived from the following fatty acids: oleic, linoleic, linolenic, palmitic and stearic fatty acids being oleic, linoleic and linolenic the most beneficial to health because they have one, two three unsaturations, respectively .
A diet rich in lipids containing TAG is manifested in the accumulation of TAG in adipose tissue and an increase in plasma TAG. Both parameters are directly related to obesity, atherosclerosis, and other diseases related to high consumption of fats or oils.
Great emphasis has been placed on the development of oils beneficial for health and is known in the prior art that 1 , 3-diacylglycerols (1,3-DAG) are hydrolyzed in the duodenum to 1-monoacylglycerols (1-MAG) . Thus, TAG resynthesis is avoided, stooping plasma TAG levels and their accumulation in tissues. This phenomenon does not occur with 1, 2-diacylglycerols (1,2-DAG) as hydrolysis in the duodenum results in mainly 2-monoacylglycerols (2- MAG) (as TAG'S hydrolysis) thereby permitting TAG resynthesis way, with the subsequent increase in plasma TAG and its deposits in tissues.
It is also known in the prior art the process used to obtain diacylglycerols (DAG) , which is based on reacting oil with glycerin or glycerol by a glycerolysis reaction, also called transesterification .
The oil's TAG can become DAG catalytically by enzymatic processes, or by homogeneous or heterogeneous catalysis. For each DAG derived from a fatty acid in particular there are two isomers: 1,2-DAG and 1,3-DAG.
Glycerolysis or transesterification reactions catalyzed by enzymes are known in the prior art in processes for obtaining DAG as described in patents EP0836805 (Al) and US6261812 (Bl) among others. The drawback that this type of enzymatic processes has is that the use of enzymes is expensive, thus the final product price will be high for the consumer. Another drawback is that the process should proceed at relatively low temperatures, since the catalyst, being an enzyme, is susceptible to temperature changes, which affects the process' performance. In addition, it should be noted that at low temperatures, the reaction tends to form TAG and change the ratio of the isomers.
Other processes use catalysts in homogeneous phase for glycerolysis or transesterification reactions using catalysts dissolved in the reaction medium, such as NaOH or sodium acetate, as described in the patent WO03029392 (Al) . Also, alkali metal alkoxides (sodium methoxide, sodium ethoxide, potassium isopropoxide ) , metal glycerates, alkali metal hydrides (LiH) and other hydroxides and oxides of alkaline earth and alkali metals such as LiOH, RbOH, CsOH, Ca(OH)2, SrO or KOH .
This type of transesterifications in homogeneous phase is also used in the production of monoacylglycerols, but they have the disadvantage that the catalyst dissolves in the reaction medium. Therefore, a step of removing the catalyst by neutralization or other methods must be included, with the resulting increase in process costs. The catalyst must be removed from the reaction medium to prevent further degradation of the product in alkaline medium with formation of soaps or other undesirable products. In addition, the catalyst must be completely removed to make it suitable for human consumption, as is done routinely in the industry with processes using NaOH. All homogeneous patented processes require many steps of synthesis and the use of vacuum in some cases.
The advantage of the heterogeneous catalytic processes using solid catalysts for glycerolysis or transesterification reactions is that the catalyst is not dissolved in the reaction medium so that subsequent separation is much simpler, much less expensive and the catalyst is fully recycled for a new cycle of operation.
There are many scientific publications using solid catalysts for the production of monoacylglycerols, as mentioned by Corma in the document "Production of Food Emulsifiers, Monoglycerides, by Glycerolysis of Fats With Solid Base Catalysts" published in 1998.
The document "Low-temperature chemical glycerolysis to produce diacylglycerols by heterogeneous base catalyst", developed by Zhong et al, published in 2014, describes a process for obtaining diacylglycerols, through a process of transesterification of TAG glycerol by heterogeneous catalysis, wherein the reaction is carried out at low temperature, 80 - 90 °C, the reaction medium is acetone and the catalyst is KOH supported on MgO. The authors mention that the obtained yields are 40% of DAG, but not specifying what percentage corresponds to the isomer of interest, 1,3-DAG. This process has the disadvantage that when using low temperatures, the reaction time extends to 12 - 24 h, with the consequent increase in production costs. But the main disadvantage is that the use of acetone allows working with a single liquid phase where there are both the TAG, the glycerol, the reaction products and the solvent, various stages must be added to separate the products of the reagents reacted and a step of distillation to remove the solvent process. With respect to the catalyst being supported, its preparation is elaborate and expensive. Furthermore, due to the fact of working at low temperature, high catalyst loadings of from 2.5 to 6.5% by weight of the TAG must be used. Furthermore, the use of a supported alkali metal hydroxide may cause leaching of said hydroxide to the reaction medium, resulting in a homogeneous catalytic process. If this was the case, the dissolved potassium should be removed from the final product. This has not been discussed by the authors in their studies.
The present invention provides a process for obtaining an oil rich in diacylglycerols from triacylglycerols . The process comprises a transesterification reaction between a triacylglycerol (TAG) and glycerol (Gly) , according to the stoichiometry: 2 TAG + Gly -4 ► 3 DAG.
Preferably, the oil of the present invention is rich in 1 , 3-diacylglycerols , as this is the isomer of interest. This process seeks to transform the TAG of the edible soybean oil, sunflower or other vegetable oils in an oil containing between 20 and 40% by weight of the 1 , 3-diacylglycerol isomer.
The process of the present invention solves the problems the prior art could not save, by obtaining an oil rich in food grade 1,3-DAG in less time than 10 hours, in the absence of liquid catalysts, in the absence of hydroxides, in the absence of the need for solvent stripping operations, with low load of catalyst in a simple and economical way.
Brief description of the invention
The present invention describes a process for obtaining vegetable oil rich in 1 , 3-diacylglycerols with at least 10% by weight of 1 , 3-diacylglycerols characterized in that it comprises the following steps: a. mixing vegetable oil with glycerol in a glycerol/oil molar ratio between 0.5 and 2;
b. reacting, for a time of between 4 and 8 hours, the mixture of step a) , at a temperature of between 180 and 240 °C in an inert atmosphere, in the presence of a solid catalyst of MgO in a ratio of between 0.1% and 3% by weight relative to the mass of oil;
c. cooling for a time between 2 and 14 hours in constant agitation;
d. filtering the means for removing the catalyst; e. separating the remaining glycerin to obtain vegetable oil rich in 1 , 3-diacylglycerols with at least 10% by weight of 1 , 3-diacylglycerols in the oil phase.
Wherein in said step a) the glycerol/oil molar ratio is between 0.6 and 1.6, preferably between 0.6 and 1.0, more preferably is between 0.8 and 1.0, most preferably it is 0.8.
Wherein in said step b) the ratio of the catalyst is 2% by weight based on the mass of oil.
Wherein in said step b) the reaction time is 8 hours .
Wherein in said step c) it is cooled to 150 °C for a time of 2 hours. Alternatively it is cooled to 150 °C for a time of 2 hours and subsequently cooled to 25 °C for a time of 12 hours. Further, in another form of carrying out the invention, it is performed in the absence of said step c) .
Through the process of the present invention, a vegetable oil rich in 1,3- diacylglycerols is obtained, which comprises between 12 and 39% of monoacylglycerols, between 20 and 40% of 1 , 3-diacylglycerols, between 4 and 17% of 1 , 2-diacylglycerols, and between 19 and 37% of triacylglycerols .
In addition, the process of the present invention is conducted in the absence of soluble catalysts such as hydroxides or liquids, where the reaction time is less than 10 hours.
Another object of the present invention is a vegetable oil rich in 1 , 3-diacylglycerols, comprising between 12 and 39% of monoacylglycerols, between 20 and 40% of 1, 3-diacylglycerols, between 4 and 17% 1,2- diacylglycerols, between 19 and 37% triacylglycerols; preferably 27.4% of monoacylglycerols, 34.9% of 1,3- diacylglycerols, 16.5% of 1 , 2-diacylglycerols, 21.2% of triacylglycerols; more preferably a vegetable oil comprising between 25 and 35% of 1, 3-diacylglycerols .
Detailed description of the invention
The present invention describes a vegetable oil rich in 1 , 3-diacylglycerols , with at least 10% by weight of 1,3-DAG and the process for obtaining the oil.
The present invention provides a fast, economical and simple process of transesterification of TAG with glycerol, to form DAG, resulting in an edible oil with low-TAG, rich in 1,3-DAG.
The process of the present invention enables obtaining DAG from vegetable oil, by transforming the TAG present therein by transesterification with glycerin. In a first step, the vegetable oil should be mixed with glycerin, its ratio is essential to get adequate yields of the DAG of interest. The molar ratio of Gly/TAG must be between 0.5 and 2, to obtain good yields as explained in Examples 1-4. The second step is conducting the transesterification reaction, preferably in a 7-necked agitated glass reactor, provided with connections for the inlet and outlet of a gas stream of inert gas, preferably nitrogen and the remaining ones, for charging reagents and catalyst for sampling, for the temperature sensor and the stirrer shaft. Said reactor is heated by a furnace which should take the reaction mixture to a temperature of preferably between 200 and 240 °C, as described in Examples 1 and 5. The agitation system should preferably provide a stirring rate of at least 700rpm, so as to ensure that the reactor operates under a perfect mix. The reactor pressure should preferably be maintained at 1 atm, this being achieved by continuous passage through the reactor in a nitrogen gas stream of 20 to 100 cm3/min. For the reaction to occur, it is necessary to add the solid catalyst, where the most suitable catalyst for this reaction is MgO . The amount of MgO is a very important variable that influences outright in the amount of DAG produced. Through the examples 1 and 6 it is concluded that the optimum amount of catalyst is between 0.1 and 3% by weight based on the mass of TAG. The reaction should proceed for a period of time between 4 and 8 h, as shown in Examples 1 to 4 of Table 2.
Alternatively, after the transesterification, the reaction mixture is cooled to temperatures between 25 and 150 °C, holding it for an additional period of time between 2 and 12 h at that temperature, since it has been shown that said step influences the performance of the reaction, as shown in Examples 7, 8 and 9.
Once that time period has elapsed, it is separated from the catalyst by centrifugation and decanting the remaining heavier glycerin and located on the bottom of the decanter, which thereby allows obtaining the DAG in the upper oil phase. The content of the various acylglycerols is analyzed in the oil phase by high performance liquid chromatography (HPLC) .
Example 1
In a 7-necked glass batch reactor provided with condenser and mechanical stirring system, 4.4 g of glycerol and 70.0 g of commercial sunflower oil were added so as to achieve a molar ratio Gly/TAG = 0.6 . The system was heated under stirring (700 rpm) at atmospheric pressure at a temperature of 220 °C and then 0.70 g of MgO (catalyst) was added, so as to obtain a percentage mass ratio r = Catalyst/Triacylglycerol (TAG) of 1%. After 8 hours of reaction, the catalyst was filtered and the separation of the remaining glycerin was conducted by decantation and centrifugation. Analysis of the crude oil phase containing all acylglycerols was by liquid chromatography (HPLC) and was confirmed by gas chromatography. The results make up Example 1 and they are presented in Table 1. % by weight content of glycerides was 15.3% of monoacylglycerols, 49.3% of diacylglycerols (33.4% of 1 , 3-diacylglycerols isomers; 15.9% of 1 , 2-diacylglycerols isomers) and 35.4% of triacylglycerols .
Table 1
Obtained results in the glycerolysis of sunflower oil employing different molar ratios R = Glycerol
(Gly) /Triacylglycerol (TAG)
Ex. R = Catalytic results
Gly/TAG TAG MAG DAG 1,3-DAG 1 , 2-DAG 1,3- DAG/
(molar) (g %) (g %) (g %) (g %) (g %) 1,2- -DAG
1 0.6 35.4 15.3 49.3 33.4 15.9 2. .1
2 0.8 23.2 24.0 52.9 35.9 17.0 2. .1
3 1.0 21.2 27.4 51.4 34.9 16.5 2. .1
4 1.6 19.5 38.4 42.1 28.5 13.6 2. .1
Concentrations at t = 8 h; Experimental conditions : T :
220 °C; r = Cat/TAG = 1.0 (g %) )
Examples 2, 3 and 4
The assays of Example 1 were repeated, but varying the mass of glycerin, so as to vary the molar ratio of reactants (R) between 0.8 and 1.6 and keeping all other conditions equal to Example 1. They were added 11.8g; 7,3g and 6.1g of glycerin to achieve molar ratios R = Gly/TAG pf 1.6; 1.0 and 0.8, respectively. The results of these assays make up Examples 4, 3 and 2, respectively and are shown in Table 1. The best result was achieved with Example 2, using a molar ratio R = 0.8 which produces 35.9% of 1, 3-diacylglycerols .
using the assays from Examples 1 to 4, the effect of varying the total reaction time between 4 and 8 hours on the total content of DAG and the isomer distribution was studied. The results are presented in Table 2. The
results in Table 2 show a significant increase in the total content of DAG by increasing the reaction time from 4 to 6 hours . Extending the reaction for a further 2 hours (8 hours of total reaction time) produces a slight additional increase in the total content of DAG and concentration of 1,3-DAG isomers.
Table 2
Obtained results in the glycerolysis of sunflower oil employing different molar ratios R = Glycerol (Gly) /Triacylglycerol (TAG) with different reaction times
Ex. R = Catalytic results (g %)
Gly/TAG DAG 1,3- DAG 1, 2-DAG DAG 1,3-DAG 1 , 2-DAG DAG 1,3- -DAG 1,2- -DAG (molar) 4h 6h 8h
1 0.6 25.1 17 .1 8.0 44.2 30.4 13.8 49.3 33 .4 15 .9
2 0.8 43.3 30 .8 12.5 50.7 35.0 15.7 52.9 35 .9 17 .0
3 1.0 30.5 21 .0 9.5 47.3 32.1 15.2 51.4 34 .9 16 .5
4 1.6 19.1 13 .4 5.7 30.6 21.7 8.9 42.1 28 .5 13 .6
Experimental conditions : T = 220 °C; r= Cat/TAG = 1.0 (g
Example 5
The assay of Example 1 was repeated, but lowering the reaction temperature to 200 °C and keeping the rest of the conditions equal to Example 1. The results obtained at 200 °C make up Example 5 and they are presented in Table 3. The operation at 200 °C decreases the final concentration of 1 , 3-diacylglycerols (1,3-DAG) to 10.7%.
Table 3
Obtained results in the glycerolysis of sunflower oil employing different reaction temperatures, T Ex. T Catalytic results
(°C) TAG MAG DAG 1, 3-DAG 1,2-DAG 1,3-DAG/
(g %) (g %) (g %) (g %) (g %) 1,2-DAG
1 220 35.4 15.3 49.3 33.4 15.9 2.1
5 200 71.5 12.9 15.6 10.7 4.9 2.2
Concentrations at t = 8 h; Experimental conditions: R =
Gly/TAG = 0.6 (molar); r = Cat/TAG = 1.0% by weight
Example 6
The assay of Example 1 was repeated, but increasing the percentage mass ratio r = Catalyst/Triacylglycerol (TAG) at 2% and keeping the rest of the conditions equal to Example 1. To this end, a mass of 1.4 g of catalyst and 70.0 g of triacylglycerol were used. The results make up Example 6 and they are presented in Table 4. The use of a mass ratio catalyst/Triacylglycerol of 2% produces a final concentration of 1 , 3-diacylglycerols (1,3-DAG) of 35.8% and a significant improvement in the ratio 1,3- DAG/ 1.2-DAG compared to Example 1.
Table 4
Obtained results in the glycerolysis of sunflower oil employing different molar ratios r =
Catalyst/Triacylglycerol (TAG)
Ex. r Catalytic results
TAG MAG DAG 1, 3-DAG 1,2-DAG 1,3-DAG/
(g %) (g %) (g %) (g %) (g %) 1,2-DAG
1 1.0 35.4 15.3 49.3 33.4 15.9 2.1
6 2.0 36.1 14.1 49.8 35.8 14.0 2.5
Concentrations at t = 8 h; Experimental conditions: T =
220 °C; R = Gly/TAG = 0.6 (molar) Example 7
The assay of Example 1 was repeated, but using soybean oil instead of sunflower oil, that is, changing the type of triacylglycerol used. The remaining experimental conditions were kept equal to Example 1. The results make up Example 7 and they are presented in Table 5. The use of soybean oil yields a final concentration of 1, 3-diacylglycerols (1,3-DAG) of 30.8%.
Table 5
Obtained results for glycerolysis of different oils
Ex. Employed TAG Catalytic results
TAG MAG DAG 1, 3-DAG 1,2-DAG 1,3-DAG/
(g %) (g %) (g %) (g %) (g %) 1,2-DAG
1 Sunflower 35.4 15.3 49.3 33.4 15.9 2.1
7 soybean 36.4 16.1 47.5 30.8 16.7 1.9
Concentrations at t = 8 h; Experimental conditions: T =
Gly/TAG = 0.6 (molar); r = Cat/TAG
Examples 8 and 9
At the end of the assay of Example 7, the reaction mixture was cooled under stirring to 150 °C and was kept 2 hours reacting at that temperature. A sample of the oil phase was then taken and the results obtained make up Example 8 presented in Table 6. Then, without stopping the stirring, the reaction mixture was further cooled to room temperature and kept for 12 hours at that temperature, at the end of which the catalyst was removed and the concentration of acylglycerols was measured. The results make up Example 9 presented in Table 6. The results of Table 6 show an isomer ratio of 1,3-DAG/1,2- DAG = 2.3 after reacting for 2 hours at 150 °C after the assay of Example 7 (Example 8) . The subsequent treatment of 12 hours at 25 °C after the assay of Example 8 (Example 9) did not produce a significant improvement in the total concentration of DAG nor in the 1, 3-DAG/l, 2-DAG ratio .
Table 6
Effect of treatment under stirring performed to the oil mixture after the glycerolysis of soybean oil of example
7
Ex. Treatment Catalytic results
after example TAG MAG DAG 1,3- -DAG 1,2- -DAG 1,3- -DAG/
7 (g %) (g %) (g %) (g %) (g %) 1,2 -DAG
7 36.4a 16. la 47.5a 30. .6a 17. 0a 1. .8a
8 2h at 150 °C 35.9 16.6 47.5 32 .9 14 .6 2 .3
9 2h at 150 °C + 34.3 16.7 49.0 34 .0 15 .0 2 .3
12h at 25 °C
a Concentrations at t = 8 h; Experimental conditions: T = 220 °C; R = Gly/TAG = 0.6 (molar); r = Cat/TAG = 1.0% by weight

Claims

Claims It being particularly well described and determined the nature of the invention and how to carry it out, it is stated to claim of ownership and exclusive right:
1. A process for obtaining vegetable oil rich in 1, 3-diacylglycerols with at least 10% by weight of 1,3- diacylglycerols characterized in that it comprises the following steps:
a. mixing vegetable oil with glycerol in a glycerol/oil molar ratio between 0.5 and 2;
b. reacting, for a time of between 4 and 8 hours, the mixture of step a) , at a temperature of between 180 and 240 °C in an inert atmosphere, in the presence of a solid catalyst of MgO in a ratio of between 0.1% and 3% by weight relative to the mass of oil;
c. cooling for a time between 2 and 14 hours under constant agitation;
d. filtering the means for removing the catalyst; e. separating the remaining glycerin to obtain vegetable oil rich in 1 , 3-diacylglycerols with at least 10% by weight of 1 , 3-diacylglycerols in the oil phase.
2. The process according to claim 1, characterized in that in said step a) the glycerol/oil molar ratio is between 0.6 and 1.6.
3. The process according to claim 1, characterized in that in said step a) the glycerol/oil molar ratio is between 0.6 and 1.0.
4. The process according to claim 1, characterized in that in said step a) the glycerol/oil molar ratio is between 0.8 and 1.0.
5. The process according to claim 1, characterized in that in said step a) the glycerol/oil molar ratio is 0.8.
6. The process according to claim 1, characterized in that said step b) is carried out under stirring at 700 rpm, at atmospheric pressure, wherein said inert atmosphere is a nitrogen stream of 20 to 100 cm3/min.
7. The process according to claim 1, characterized in that in said step b) the ratio of the catalyst is 2% by weight based on the mass of oil.
8. The process according to claim 1, characterized in that in said step b) the reaction time is 8 hours.
9. The process according to claim 1, characterized in that in said step c) it is cooled to 150 °C for a time of 2 hours.
10. The process according to claim 1, characterized in that in said step c) it is cooled to 150 °C for a time of up to 2 hours and subsequently cooled to 25 °C and maintained at said temperature for a time up to 12 hours.
11. The process according to claim 1, characterized in that it is carried out in the absence of step c) .
12. The process according to claim 1, characterized in that it is carried out in the absence of liquid catalysts.
13. The process according to claim 1, characterized in that it is performed in the absence of hydroxides as catalysts .
14. The process according to claim 1, characterized in that said vegetable oil rich in 1 , 3-diacylglycerols comprises between 20 and 40% by weight of 1,3- diacylglycerols .
15. The process according to claim 1, characterized in that said vegetable oil rich in 1 , 3-diacylglycerols comprises between 12 and 39% of monoacylglycerols , between 20 and 40% of 1 , 3-diacylglycerols, between 4 and 17% of 1 , 2-diacylglycerols, and between 19 and 37% of triacylglycerols .
16. A vegetable oil rich in 1 , 3-diacylglycerols , characterized in that it is prepared by the process according to claim 1 and it comprises between 20 and 40% by weight of 1 , 3-diacylglycerols .
17. A vegetable oil rich in 1 , 3-diacylglycerols as in claim 16, characterized in that said oil comprises between 12 and 39% of monoacylglycerols, between 20 and 40% of 1 , 3-diacylglycerols , between 4 and 17% of 1 2- diacylglycerols, and between 19 and 37% triacylglycerols.
18. The oil according to claim 16, characterized in that it comprises 27.4% of monoacylglycerols, 34.9% of 1, 3-diacylglycerols, 16.5% of 1 , 2-diacylglycerols , and 21.2% triacylglycerols.
19. The oil according to claim 16, characterized in that it comprises between 25 and 35% of 1,3- diacylglycerols .
PCT/IB2015/058883 2014-11-18 2015-11-17 Process for obtaining vegetable oil rich in 1,3- diacylglycerols WO2016079671A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ARP20140104313 2014-11-18
ARP140104313A AR098443A1 (en) 2014-11-18 2014-11-18 PROCESS OF OBTAINING RICH VEGETABLE OIL IN 1,3-DIACILGLICEROLES

Publications (1)

Publication Number Publication Date
WO2016079671A1 true WO2016079671A1 (en) 2016-05-26

Family

ID=55069916

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2015/058883 WO2016079671A1 (en) 2014-11-18 2015-11-17 Process for obtaining vegetable oil rich in 1,3- diacylglycerols

Country Status (2)

Country Link
AR (1) AR098443A1 (en)
WO (1) WO2016079671A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0010333A1 (en) * 1978-10-20 1980-04-30 THE PROCTER & GAMBLE COMPANY Diglyceride manufacture and use in making confectioner's butter
EP0679712A1 (en) * 1994-03-31 1995-11-02 Loders Croklaan B.V. Low safa oils
EP0836805A1 (en) 1996-10-18 1998-04-22 Kao Corporation General-purpose oils composition
US6261812B1 (en) 1997-08-18 2001-07-17 Kao Corporation Process for producing diglycerides
WO2003029392A1 (en) 2001-10-03 2003-04-10 Archer-Daniels-Midland Company Chemical process for the production of 1,3-diglyceride oils

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0010333A1 (en) * 1978-10-20 1980-04-30 THE PROCTER & GAMBLE COMPANY Diglyceride manufacture and use in making confectioner's butter
EP0679712A1 (en) * 1994-03-31 1995-11-02 Loders Croklaan B.V. Low safa oils
EP0836805A1 (en) 1996-10-18 1998-04-22 Kao Corporation General-purpose oils composition
US6261812B1 (en) 1997-08-18 2001-07-17 Kao Corporation Process for producing diglycerides
WO2003029392A1 (en) 2001-10-03 2003-04-10 Archer-Daniels-Midland Company Chemical process for the production of 1,3-diglyceride oils

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
NANJING ZHONG ET AL: "Low-temperature chemical glycerolysis to produce diacylglycerols by heterogeneous base catalyst", EUROPEAN JOURNAL OF LIPID SCIENCE AND TECHNOLOGY., vol. 116, no. 4, 20 February 2014 (2014-02-20), DE, pages 470 - 476, XP055262945, ISSN: 1438-7697, DOI: 10.1002/ejlt.201300438 *
PRODUCTION OF FOOD EMULSIFIERS, MONOGLYCERIDES, BY GLYCEROLYSIS OF FATS WITH SOLID BASE CATALYSTS, 1998
ZHONG ET AL., LOW-TEMPERATURE CHEMICAL GLYCEROLYSIS TO PRODUCE DIACYLGLYCEROLS BY HETEROGENEOUS BASE CATALYST, 2014

Also Published As

Publication number Publication date
AR098443A1 (en) 2016-05-26

Similar Documents

Publication Publication Date Title
Wang et al. From microalgae oil to produce novel structured triacylglycerols enriched with unsaturated fatty acids
US7420072B2 (en) Apparatus and method for producing biodiesel fuel
JP4297267B2 (en) Method for producing high-purity fatty acid alkyl ester by single-stage continuous process
CN101421215B (en) A process for the decarboxylation of fatty acids
May Transesterification of palm oil: effect of reaction parameters
JP5944303B2 (en) A method for producing a fatty acid monoglyceride-containing mixture.
CN101818176B (en) Method for transforming fatty acid ethyl ester into glyceride
JPWO2007088702A1 (en) Fatty acid alkyl ester production method and fatty acid alkyl ester production apparatus
CN102965404B (en) Preparation method of high-purity diglyceride
Shahla et al. The evaluation of various kinetic models for base-catalyzed ethanolysis of palm oil
Lakshmi et al. Mixing characteristics of the oil–methanol system in the production of biodiesel using edible and non-edible oils
CN105821089A (en) Method for enzymatically synthesizing medium-long chain structure triglyceride
CA2393403C (en) Method for commercial preparation of linoleic acid
CN104046662B (en) Transesterification preparation method for 1,3-dioleic acid-2-triglyceride palmitate
WO2016058284A1 (en) Method for preparing glyceride type polyunsaturated fatty acids
CN102257108B (en) Use of methanesulfonic acid for producing fatty acid esters
CA2524492A1 (en) Method for the production of fatty acids having a low trans-fatty acid content
WO2016079671A1 (en) Process for obtaining vegetable oil rich in 1,3- diacylglycerols
JP5397876B2 (en) Method for producing biodiesel fuel
CN106148439A (en) A kind of method that power ultrasonic pretreatment enzyme law catalysis Adeps Sus domestica glycerol rhizolomy prepares diglyceride
Brucato et al. High temperature solid-catalized transesterification for biodiesel production
CN109082447B (en) Preparation method of mixed ester rich in OPO structure ester
US6414171B1 (en) Method for commercial preparation of conjugated linoleic acid from by-products of vegetable oil refining
CN111892992A (en) Method for preparing diglyceride by chemical catalysis
CN102206554B (en) Method for preparing biodiesel

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15820260

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15820260

Country of ref document: EP

Kind code of ref document: A1