JP2006083390A - Monoglyceride-containing composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a monoglyceride-containing composition having a high monoglyceride content. <P>SOLUTION: This monoglyceride-containing composition is obtained by a method including a process in which glycerol is reacted with at least one acyl-containing compound selected from a group consisting of a fatty acid and a glycerol ester and a catalyst containing at least one metal selected from a group consisting of iron, cobalt, and manganese is used in an amount of 0.1-60 ppm as a mass ratio of the metal to a total mass of the glycerol and the acyl-containing compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a monoglyceride-containing composition having a high monoglyceride content.

Monoglycerides widely used as cosmetics, foods, industrial emulsifiers or lubricating oils are produced by esterification reaction of glycerin and fatty acid or transesterification reaction of glycerin and fat. These reactions are carried out without a catalyst or in the presence of a catalyst, but generally a mixture of glycerin, monoglyceride, diglyceride and triglyceride is produced. The reaction system is usually a heterogeneous system, and the amount of monoglyceride produced is affected by the solubility of glycerin in the fatty acid phase or the produced ester phase, so it is not possible to increase the monoglyceride content simply by increasing the amount of glycerin charged. Can not. For this reason, when it is desired to obtain a monoglyceride having higher performance, that is, high purity, purification by molecular distillation is performed.
US-A2474740 and US-A2478354 disclose a method of using 5 to 15% hydrous glycerin to promote transesterification with fats and oils without using a catalyst.
US-A2206167 discloses a method for producing monoglyceride from glycerin oil and fat by transesterification using an alkali soap such as Na as a catalyst.
US-A2628967 discloses a method for producing monoglyceride by reacting glycerin or ethylene glycol with fatty acid or glycerin polyester in the presence of a specific transition metal catalyst such as iron at high humidity. .

US-A2474740 and US-A2478354 US-A2478354 US-A2206167 US-A2628967

  An object of the present invention is to provide a monoglyceride-containing composition having a high monoglyceride content.

The present invention is a monoglyceride-containing composition that can be produced by reacting glycerin with a compound having at least one acyl group selected from fatty acids and glycerin esters, and at least selected from iron, cobalt, and manganese Provided is a monoglyceride-containing composition in which a reaction is carried out using a catalyst containing one kind of metal as a metal in an amount of 0.1 to 60 ppm (weight ratio to the total weight of the compound having glycerin and an acyl group, the same applies hereinafter).
Furthermore, the present invention is a monoglyceride-containing composition that can be produced by reacting glycerin with a compound having at least one acyl group selected from fatty acids and glycerin esters, wherein the glycerin reacts with the moon. A monoglyceride-containing composition having a step of maintaining the water content in the reaction system at 500 to 5000 ppm after the reaction rate on the basis of fatty acid reaches 90% or more or in the transesterification reaction between glycerol and glycerol ester. provide.

In US-A2474740 and US-A2478354, there is a problem that a considerable amount of unreacted fatty acid remains in addition to the system becoming a pressurized system in order to maintain the water content.
US-A2206167 also states that when unreacted glycerin is removed by distillation after the reaction, the alkali content must be neutralized at a high temperature in advance in order to prevent a decrease in monoglyceride content due to the reverse reaction. Another problem is that neutralized salts that cannot be separated by filtration remain in the product.
US-A2628967 does not require neutralization of the catalyst, but the amount used is 80 to 1700 ppm as a metal, so it is difficult to use as it is because there are many insolubles. However, since the reduction of the monoglyceride content due to the reverse reaction is promoted, there is a problem that the catalyst must be separated by filtration or decantation after cooling in advance. Moreover, there is a problem that the filtration rate is slow when glycerin remains in filtration, and the yield is poor in decantation. Moreover, when removing unreacted glycerol by distillation, there exists a point which is unpreferable also in the process of having to heat again.
The present invention provides a monoglyceride-containing composition having a high monoglyceride content from glycerin and a fatty acid or glycerin ester, which can be produced without using an expensive concentrator such as a molecular distiller or a special high-speed rotary stirring shearing machine. There is.
The present invention provides a monoglyceride-containing composition having a high monoglyceride content from glycerin and a fatty acid or glycerin ester, which can be easily produced without using an expensive concentrator such as a molecular distiller or a special high-speed rotary stirring shear machine. provide.
The glycerin used in the present invention is not particularly limited, but preferably has a purity of 95% by weight or more.

The compound having an acyl group selected from fatty acids and glycerin esters used in the present invention may have any of a branched chain, straight chain, saturated or unsaturated acyl group, but the effect of the present invention is more clearly understood. From this point of view, the acyl group preferably has 12 to 30 carbon atoms, more preferably 14 to 22 carbon atoms.
Specific examples of fatty acids used in the present invention include single fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, soybean oil fatty acid, rapeseed oil fatty acid, tall oil Examples include mixed fatty acids such as fatty acids. From the viewpoint of low-temperature fluidity related to the handleability of the monoglyceride-containing composition, those having an iodine value of 80 or more are preferable, and those having 130 or more are more preferable. Specifically, oleic acid, linoleic acid, linolenic acid, soybean oil fatty acid, rapeseed oil fatty acid, and tall oil fatty acid are preferred.
Examples of the glycerin ester used in the present invention include triesters, diesters and mixtures thereof containing the fatty acid and glycerin as constituent components. Moreover, monoester may be contained.

In the present invention, the reaction ratio between the glycerin and the compound having an acyl group is such that a monoglyceride-containing composition having a high monoglyceride content is obtained, and from the viewpoint of increasing the productivity per batch, 1 mol of the acyl group of the compound having an acyl group. On the other hand, 1 mol or more of glycerin is preferable, 1 to 3 mol is more preferable, and 1.5 to 3 mol is particularly preferable.
In the present invention, a catalyst may or may not be used, but when used, a catalyst containing at least one metal selected from iron, cobalt and manganese is preferable, and a simple metal selected from iron, cobalt or manganese, Or the compound is mentioned. Specifically, examples of the catalyst containing iron include reduced iron alone, iron sesquioxide (Fe ₂ 0 ₃ ), iron tetroxide (Fe ₃ 0 ₄ ), iron hydroxide (Fe00H), and other oxides and hydroxides. And metal soaps such as iron acetate, iron propionate, iron stearate and iron oleate, and chlorides such as iron (II) chloride and iron (III) chloride. Examples of the catalyst containing cobalt include cobalt alone, cobalt monoxide (CoO), cobalt tetroxide (Co ₃ 0 ₄ ), cobalt carbonate, cobalt stearate, and cobalt (II) chloride. Examples of the catalyst containing manganese include manganese alone, manganese dioxide, manganese trioxide, and manganese stearate. From the viewpoint of catalytic activity, handleability, and availability, a catalyst containing iron is preferable, and iron hydroxide is particularly preferable. The amount of the catalyst used is preferably 0.1 to 60 ppm, more preferably 0.5 to 10 ppm, and particularly preferably 0.5 to 5 ppm as a metal from the viewpoint of shortening the reaction time and reducing the filtration burden.

In the present invention, from the viewpoint of increasing the monoglyceride content and reducing the amount of free fatty acids, the reaction rate based on fatty acids (represented by the following formula (1)) reaches 90% or more in the reaction of glycerin and fatty acids. After the transesterification reaction becomes dominant over the esterification reaction or during the transesterification reaction between glycerin and glycerin ester, the water content in the reaction system is increased, the monoglyceride content is increased, and the free fatty acid content From the viewpoint of reducing the amount, it preferably has a step of controlling to 500 to 5000 ppm, more preferably 600 to 4000 ppm, more preferably 600 to 3000 ppm, and still more preferably 1000 to 3000 ppm. Although the role played by moisture in the method of the present invention is not clear, it is presumed that the glycerin ester is hydrolyzed in a small amount to liberate fatty acids, which act as a transesterification catalyst.
The moisture content is controlled by introducing an inert gas such as nitrogen into the reaction solution and / or the space above the reaction solution while measuring the moisture content of the reaction solution over time using a moisture meter. This can be done by adjusting the amount of the inert gas introduced into the. The inert gas is preferably supplied continuously or intermittently. In addition, in the case of a reaction in which water is insufficient, such as a reaction of glycerin and glycerin ester alone, water is added in advance, and if necessary, the water content in the system is combined with the introduction of an inert gas such as nitrogen into the reaction vessel. It is good to control to the above value.

Reaction rate (%) = 100 × (1- [weight of unreacted fatty acid]) / [weight of charged fatty acid] (I)
The temperature of the reaction between the glycerin and the compound having an acyl group is preferably 180 ° C. or higher from the viewpoint of improving the solubility of glycerin in the oil layer and improving the esterification reaction and transesterification reaction rate. From the viewpoint of suppressing the production of glycerin, 270 ° C. or lower is preferable.
Specifically, it is preferably 180 to 270 ° C, more preferably 200 to 260 ° C, and further preferably 240 to 255 ° C. As for the reaction time, heating for a long time at a high temperature increases the by-product amount of diglycerin, which is a condensate of glycerin, so there is a balance with the temperature. The time is further preferably 5 hours or less.

The monoglyceride-containing composition having a high monoglyceride content obtained by the method of the present invention can be used as it is, but when using glycerin and a catalyst, it is preferable to remove the metal-containing catalyst. When removing the catalyst containing glycerin and metal, it is preferable to distill glycerin in the presence of the catalyst containing metal from the viewpoint of productivity. That is, if it is attempted to filter the catalyst containing metal before distilling off glycerin, due to the heat resistance of the filter medium and the removal of the catalyst, it is once cooled to 100 ° C. Although there is a complexity in the process of having to leave, this complexity can be avoided in the present invention. Further, the method of filtering the metal-containing catalyst after distilling off glycerin has an advantage that the filtration rate is increased because glycerin having a high viscosity does not exist during filtration. Specifically, after the reaction, glycerin is distilled off under reduced pressure, and if necessary, water vapor is further supplied under reduced pressure to distill off glycerin, and then the catalyst containing metal is removed by filtration.
Distillation of glycerin can be performed batchwise or continuously using a thin film distiller. When glycerin is distilled off in a batch system, the temperature is preferably 200 ° C. or lower, more preferably 180 ° C. or lower, and the pressure is preferably 53 kPa or lower, more preferably 2.7 kPa or lower. Filtration can be easily performed using a zeta potential filter having an adsorption action by a so-called zeta potential.
The monoglyceride content in the present invention means a value obtained by GPC analysis (gel permeation chromatography) according to the following formula (II), and means the area ratio of monoglyceride in GPC analysis to the total of monoglyceride, diglyceride and triglyceride.

Monoglyceride content (area%) = 100 x MG / [MG + DG + TG] (II)
(Where MG: GPC monoglyceride area,
DG: GPC diglyceride area
TG: GPC triglyceride area. )
By the above method, a monoglyceride-containing composition with a high content of monoglyceride content of 55 area% or more can be obtained. From the viewpoint of productivity, the monoglyceride content can be increased to 75% by area. Specifically, a composition having a monoglyceride content of 55 to 75 area%, further 60 to 75 area% can be produced.
The monoglyceride-containing composition of the present invention has a high monoglyceride content of 55% or more, such as 65% or more or 75% or more.
Examples The monoglyceride content was determined by GPC analysis. TSKgelG2000HXL and TSKgelG1000HXL manufactured by Tosoh Corporation were connected in series as columns, RI (differential refractometer) was used as a detector, and THF (tetrahydrofuran) was used as an eluent.
The contents of glycerin and diglycerin were quantified by GC analysis (gas chromatography), and the iron content was quantified by ICP analysis (inductively coupled plasma emission analysis).

Example 1
In a 2L four-neck flask equipped with a stirrer, dehydration tube-cooling tube, thermometer, and nitrogen introduction tube, add 480g of glycerin and 750g of tall oil fatty acid [glycerin / fatty acid (molar ratio) = 2.0] and suspend in a small amount of water. Then, 2 ppm of iron hydroxide was added as iron, and the temperature was raised to 250 ° C. over about 1.5 hours with stirring at 400 r / min while flowing 100 mL / min of nitrogen through the liquid space. After reaching 250 ° C., the reaction was carried out at that temperature for 4 hours. As a result of analyzing the acid value, the amount of water, and the monoglyceride content over time, the amount of water at a fatty acid-based reaction rate of 90% or more was maintained at 700 to 1900 ppm. The monoglyceride content in the product after the reaction was 67 area%.
Subsequently, the reaction mixture was cooled to 170 ° C. by refluxing under reduced pressure, and glycerin was distilled off under reduced pressure at a pressure of 2.7 kPa or less. Further, after supplying water vapor at 150 ° C. and 2 kPa for 2 hours, Zeta Plus 30S A monoglyceride-containing composition was obtained by adsorption filtration under pressure using (Cuno Co., Ltd.). The monoglyceride content in the composition was 64 area%, the acid value was 0.2 mg KOH / g, the glycerin content was 0.3 wt%, the diglycerin content was 0.3 wt%, and the iron content was 0.1 ppm or less.

Example 2
The reaction was carried out in the same manner as in Example 1 except that iron hydroxide was changed to iron stearate, and adsorption filtration was performed in the same manner except for glycerin. The monoglyceride content in the product after the reaction was 65 area%, the water content was 600-1300 ppm when the reaction rate based on fatty acid was 90% or more. The monoglyceride content in the composition after adsorption filtration was 62 area%, the acid value was 0.2 mg KOH / g, the glycerin content was 0.4 wt%, the diglycerin content was 0.4 wt%, and the iron content was 0.1 ppm or less.
Example 3
The reaction was performed in the same manner as in Example 1 except that nitrogen was blown into the liquid at 100 mL / min and the reaction was performed for 6 hours. Similarly, glycerin was removed and adsorption filtration was performed. The monoglyceride content in the product after the reaction was 63 area%, the water content was 300-400 ppm when the reaction rate based on fatty acid was 90% or more. The monoglyceride content in the composition after adsorption filtration was 61 area%, the acid value was 0.3 mg KOH / g, the glycerin content was 0.4 wt%, the diglycerin content was 0.5 wt%, and the iron content was 0.1 ppm or less.

Example 4
The reaction was carried out in the same manner as in Example 1 except that iron hydroxide was changed to iron (II) chloride tetrahydrate and the addition amount was changed to 10 ppm as iron, and adsorption filtration was similarly performed except for glycerin. The monoglyceride content of the product after the reaction was 66 area%, and the water content was 600-1500 ppm when the reaction rate based on fatty acid was 90% or more. The monoglyceride content in the composition after adsorption filtration was 63 area%, the acid value was 0.2 mg KOH / g, the glycerin content was 0.5 wt%, the diglycerin content was 0.3 wt%, and the iron content was 0.1 ppm or less.
Example 5
Change tall oil fatty acid to soybean oil, change the feed amount to 2 mol of glycerin per mol of acyl group of soybean oil, change the addition amount of iron hydroxide to 10 ppm as iron and the reaction time to 10 hours The reaction was performed in the same manner as in Example 1 except that glycerin was removed and adsorption filtration was performed. The monoglyceride content in the product after the reaction was 64 area%, and the water content was 600-1400 ppm when the reaction rate based on fatty acid was 90% or more. In addition, the monoglyceride content in the composition after adsorption filtration was 61 area%, the acid value was 0.4 mg KOH / g, the glycerin content was 0.4 wt%, the diglycerin content was 0.9 wt%, and the iron content was 0.1 ppm or less. It was.

Example 6
Add 480 g of glycerin and 750 g of tall oil fatty acid [glycerin / fatty acid (molar ratio) = 2.0] to a 2 L four-necked flask equipped with a stirrer, a dehydrating tube, a thermometer, and a nitrogen introducing tube. The temperature was raised to 250 ° C. over about 1.5 hours under stirring at 400 rpm while flowing 100 mL / min into the space. After reaching 250 ° C., the reaction was carried out at that temperature for 6 hours. As a result of analyzing the acid value, moisture content and monovlyceride content over time, the reaction rate based on fatty acid when reaching 250 ° C is 93%, the moisture content when reaction rate based on fatty acid is 90% or more is 700-2200ppln, the reaction is completed The reaction rate was 99%, and the monoglyceride content was 61% by area.
Example 7
The reaction was performed at 250 ° C. for 6 hours in the same manner as in Example 6 except that nitrogen was blown into the liquid at 30 mL / min. The reaction rate based on fatty acid when reaching 250 ° C was 93%, the water content was 600-900 ppm when the reaction rate based on fatty acid was 90% or more, the reaction rate at the end of the reaction was 99%, and the monoglyceride content was 60 area%. It was.

Comparative Example 1
Reaction was carried out in the same manner as in Example 3 without adding iron hydroxide, and glycerin was removed in the same manner, followed by adsorption filtration. The monoglyceride content in the product after the reaction was 54 area%, the water content was 300-400 ppm when the reaction rate based on fatty acid was 90% or more. Further, the monoglyceride content in the composition after adsorption filtration was 51 area%, the acid value was 0.3 mg KOH / g, the glycerin content was 0.4 wt%, and the diglycerin content was 0.7 wt%.
Comparative Example 2
The reaction was performed in the same manner as in Example 3 except that iron hydroxide was changed to sodium hydroxide and 10 ppm was added as sodium, and glycerin was removed by distillation under reduced pressure without neutralization. The monoglyceride content in the product after the reaction was 62 area%, the water content was 300-400 pprn when the reaction rate based on fatty acid was 90% or more. The monoglyceride content in the composition after glycerin distillation was 48% by area, the glycerin content was 3.1% by weight, and the diglycerin content was 0.7% by weight.

Comparative Example 3
The reaction was performed at 250 ° C. for 6 hours in the same manner as in Example 6 except that nitrogen was blown into the liquid at 100 mL / min. The reaction rate based on fatty acids when reaching 250 ° C was 94%, the water content was 300-400 ppm when the reaction rate based on fatty acids was 90% or more, the reaction rate at the end of the reaction was 99%, and the monoglyceride content was 54 area%. It was.

Claims (13)

  Glycerol is reacted with at least one acyl-containing compound selected from the group consisting of fatty acids and glycerol esters; a catalyst containing at least one metal selected from the group consisting of iron, cobalt and manganese as a metal, containing glycerol and acyl The monoglyceride containing composition which can be obtained by the method including the process of using it in the quantity of 0.1-60 ppm as mass ratio with respect to the total mass of a compound.   The composition of claim 1 wherein at least 1 mole of glycerin is used and reacted per mole of acyl group in the acyl-containing compound.   A composition according to claim 1 or 2, wherein glycerin is reacted with an acyl-containing compound and then glycerin is distilled off in the presence of a catalyst.   The composition according to any one of claims 1 to 3, wherein the metal is iron.   After the method has been achieved, the degree of conversion in the reaction of glycerin and fatty acid is 90% or higher based on fatty acid; or during the transesterification reaction of glycerin and glycerin ester, The composition according to any one of claims 1 to 4, comprising holding at 500 to 5000 ppm.   The composition according to any one of claims 1 to 5, wherein the acyl group in the acyl-containing compound has 12 to 30 carbon atoms.   The composition according to any one of claims 1 to 6, wherein the reaction temperature is 180 to 270 ° C.   The composition according to any one of claims 1 to 7, wherein the monoglyceride content in the monoglyceride-containing composition as measured by GPC analysis is 55% or higher.   A method comprising a step of reacting glycerin with at least one acyl-containing compound selected from the group consisting of a fatty acid and a glycerin ester, wherein the amount of water is the degree of conversion in the reaction between glycerin and a fatty acid, Monoglyceride-containing composition obtainable by the above method, maintained at 500-5000 ppm in the reaction system after 90% or higher based on fatty acid or during the transesterification reaction between glycerin and glycerin ester .   10. The composition of claim 9, wherein at least 1 mole of glycerin is used and reacted per mole of acyl group in the acyl-containing compound.   The composition according to claim 9 or 10, wherein the acyl group in the acyl-containing compound has 12 to 30 carbon atoms.   The composition according to any one of claims 9 to 11, wherein the reaction temperature is 180 to 270 ° C.   The composition according to any one of claims 9 to 12, wherein the monoglyceride content in the monoglyceride-containing composition as measured by GPC analysis is 55% or higher.