KR102109134B1 - Method for preparing monoglycerides - Google Patents

Abstract

The present application relates to a method for preparing monoglycerides, a method for recovering glycerin and catalysts after the process for preparing monoglycerides, and a process for preparing cyclic monoglycerides.

Description

Manufacturing method of monoglyceride {METHOD FOR PREPARING MONOGLYCERIDES}

The present application relates to a method for producing monoglycerides, a method for recovering glycerin and catalyst after the process for producing monoglycerides, and a process for producing cyclic monoglycerides.

Among fatty acids obtained from animals and plants, caprylic acid having 8 carbon atoms, capric acid having 10 individuals, lauric acid with 12 individuals, and the like are commonly referred to as medium chain fatty acids, stearic acid having 18 carbon atoms, palmitic acid with 16 individuals, and myristic acid with 14 individuals. It is distinguished from long-chain fatty acids made of and the like, and its importance is highlighted. Most of the fatty acids constituting the natural fat are long-chain fats having 14 or more carbon atoms (olive oil, canola oil, sesame oil, etc.), which are difficult to metabolize as energy and easily accumulate as body fat, but medium-chain fatty acids absorb 4 times faster than long-chain fatty acids and metabolize 10 It is said to be twice as fast, and accordingly, the speed of energy use is high. In addition, the medium-chain fatty acids affect the balance of microorganisms present in the digestive tract, and in particular, it is known to exhibit excellent antimicrobial effect against intestinal pathogenic microorganisms such as E. coli or Salmonella known as digestive pathogens.

In addition, glycerides of caprylic acid having 8 carbon atoms, capric acid having 10 carbon atoms, or a mixture thereof are added to cosmetics to exert the effect of skin moisturizers, skin softeners, emulsifiers, and thickeners. Because it is not, the oxidation stability is very high and the frequency of use is high. In addition, caprylic monoglyceride and capric monoglyceride, in which glycerin is bonded to caprylic acid and capric acid by one molecule, have broad spectrum antibacterial properties to bacteria, fungi, and yeast, in addition to functions such as skin moisturizers and emulsifiers. In addition, it has a relatively high stability against acid, alkali, and temperature, and its usage is rapidly increasing as a multifunctional preservative for cosmetics made from natural raw materials.

Transesterification to obtain monoglyceride by reacting oil and glycerin obtained from plants and animals under an alkali catalyst has been widely used as a manufacturing method since it has been widely used industrially in the past, but oil consists of several types of fatty acids. , Since it contains a lot of long-chain fatty acids, the oil obtained from animals and plants and the monoglyceride obtained from glycerin are mixtures containing a lot of long-chain fatty acids.

Another method for producing monoglycerides is to esterify fatty acids and glycerin directly under an acid catalyst. However, after the reaction is completed, a washing process for removing the catalyst is required, for example, a process of washing with water, and in this case, it is difficult to recover excess glycerin.

In addition, when preparing a glyceride by esterifying a fatty acid and glycerin under an acid catalyst, there is a problem that a mixture of monoglyceride, diglyceride and triglyceride is produced as follows:

Here, in order to increase the content of monoglycerides, 4 to 6 times the equivalent of glycerin is used compared to fatty acids, in which case monoglycerides are converted into yields of up to 75% to 80% (VLPSores, New applications for soybean biodiesel glycerol, Soybean-application and technology, p. 160, 2011). When the reaction is completed, it is a general method to separate the excess glycerin, remove or deactivate the used catalyst, and then increase the monoglyceride content.

In US Patent Publication No. 7,531,677B2, t-butanol is used as a reaction solvent, and p-toluenesulphonic acid is used as a catalyst in Example 5 to react lauric acid and glycerin, separate and remove glycerin, and then wash with water to remove the catalyst. Next, the glyceride layer was washed with hexane to obtain a high content of lauric monoglyceride. However, the use of fossil fuel-based reaction solvents and washing solvents, rather than large amounts of renewable natural raw materials, limits the use of cosmetics made of natural raw materials, recovers used solvents, or contains large amounts of water in the washed water. It is difficult to reuse glycerin.

After the completion of the reaction, another method used to remove and remove excess glycerin and to increase the content of the obtained monoglyceride is a molecular distillation method. The molecular distillation method is widely used because the product is prevented from being destroyed or denatured by temperature during distillation, even though the molecular distiller is an expensive device.

Chinese Patent Publication No. CN107935851 converts caprylic acid to caprylic acid methyl ester to produce high purity caprylic acid monoglyceride, and transesterifies the converted caprylic acid methyl ester and glycerin to produce high purity caprylic acid. Disclosed is the content of obtaining monoglycerides. However, in this method, a process of making caprylic acid methyl ester is added, and there is a process of filtering the combined catalyst and distilling glycerin after completion of the reaction.

Chinese Patent Registration No. CN102241586B tried to make glyceride from a mixture of fats and oils or fatty acids using a solid acid catalyst. The production of glycerides of a single fatty acid related herein is described in detail in Example 4. However, since a solid catalyst was used, the reaction temperature was raised to 230 ° C, and a mixture of 67.01% monoglyceride, 22.25% diglyceride, and 9.01% triglyceride was obtained. These results can be expected to have extremely poor reaction efficiency, even if diglycerides and triglycerides are recovered and reused, since a large amount of diglycerides and triglycerides were produced. In addition, since a solid acid catalyst was used, after the reaction was completed, the glyceride layer and the glycerin layer were separated using a centrifuge, and further filtered to reuse the obtained glycerin layer. Finally, two molecular distillations were required to increase the monoglyceride content in the glyceride layer obtained as above.

In China Patent Registration Publication CN103205315B, after completing the reaction and neutralizing to deactivate the catalyst, dehydration was performed in the first distillation, glycerin and unreacted fatty acids were removed in the second distillation, and monoglyceride was distilled in the third distillation to obtain the product. . However, since a solid catalyst or a neutralized catalyst is present in the distillation residue of the tertiary distillation, the glyceride layer is decolorized and recovered by centrifugation, and the lower layer made of glycerin or polyglycerin as a side reaction is extracted, desalted, and decolored again. , Glycerin or polyglycerin was recovered by distillation. In particular, a method of using the recovered polyglycerin as a raw material for making other products has been described, but it is judged that the method is complicated and there is no reality by using many devices.

In Chinese Patent Registration No. CN101724508A, despite the use of four high-priced molecular distillers to reuse glycerin, diglycerides and triglycerides, no mention is made of catalysts and other side-reactants.

The present application is intended to provide a method for producing monoglycerides, a method for recovering glycerin and catalyst after the monoglyceride production process, and a cyclic monoglyceride production process.

However, the problems to be solved by the present application are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

The first aspect of the present application includes: (a) esterifying a medium chain fatty acid having 8 to 12 carbon atoms and glycerin under an acid catalyst to obtain a reaction product; And (b) washing the reaction product with glycerin, followed by molecular distillation to obtain a monoglyceride.

The second aspect of the present application is a method for recovering glycerin and a catalyst after a monoglyceride production process, (a) esterifying a fatty acid and glycerin under a glycerin soluble acid catalyst to obtain a reaction product, and then restoring the reaction product To separate into a glycerin layer and a glyceride layer; And (b) washing the glyceride layer with glycerin, and then recovering the glycerin and the acid catalyst contained in the glycerin washed with the glycerin layer and the glyceride layer. .

The third aspect of the present application is (a) esterifying a fatty acid and glycerin under a glycerin soluble acid catalyst to obtain a reaction product, and then separating the reaction product into a glycerin layer and a glyceride layer; (b) washing the glyceride layer with glycerin, followed by molecular distillation to separate into low-boiling material glycerin and unreacted fatty acids, medium-boiling monoglyceride, and high-boiling material diglycerides and triglycerides; And (c) the glycerin layer containing the unreacted glycerin and the acid catalyst in (a), and washing the glyceride layer in (b) with glycerin containing the acid catalyst, and the molecular distillation. It provides a process for the production of a cyclic monoglyceride, comprising recovering the low-boiling material and the high-boiling material obtained by reuse in the production of monoglycerides.

The production method of the monoglyceride according to the embodiments of the present application, the recovery method of the glycerin and the catalyst after the production process of the monoglyceride, and the production process of the cyclic monoglyceride react at a low temperature under an acid catalyst, so there is no generation of impurities. It is possible to recover and reuse diglycerides and triglycerides without additional special treatment, and the catalyst can be recovered and reused as a glycerin layer, so that monoglycerides can be produced without generating by-products. In addition, it is a method of separating into a low-boiling-point substance, a medium-boiling-point substance, and a high-boiling-point substance with a single molecular distiller, and is a method of manufacturing monoglycerides in an economical and environmentally friendly manner to minimize the investment cost.

A method for producing a monoglyceride according to embodiments of the present application, a method for recovering glycerin and a catalyst after the monoglyceride production process, and a cyclic monoglyceride production process use a glycerin soluble acid catalyst and under low pressure or vacuum The method of direct esterification at a relatively low temperature was adopted. Thereby, it is possible to prevent the production of various by-products generated at a relatively high temperature, and to recover excess glycerin and by-products diglyceride and triglyceride without additional special treatment. In particular, the step of deactivating and separating the catalyst by using an organic acid soluble in glycerin as a catalyst is not required, and the catalyst is also recovered in a state dissolved in the glycerin in a process in which excess glycerin is recovered. Accordingly, a monoglyceride having a content of 85% by weight or more suitable for cosmetic use may be produced using only one molecular distillation device.

The production method of the monoglyceride according to the embodiments of the present application, the recovery method of the glycerin and the catalyst after the production process of the monoglyceride, and the production process of the cyclic monoglyceride are acid catalysts of medium chain fatty acids having 8 to 12 carbon atoms and glycerin. After standing under an esterification reaction under separation, most of the catalyst is recovered while being dissolved in the glycerin layer while separating the glycerin layer, and the glyceride layer is washed with glycerin to remove the catalyst remaining in the glyceride layer. The washed glyceride layer is separated using a molecular distiller into a low-boiling substance glycerin and unreacted fatty acids, a medium-boiling substance monoglyceride-oriented product, and a high-boiling substance diglyceride and triglyceride. After the esterification reaction, the glycerin obtained by standing still and washed, and the recovered glycerin and high boiling point diglycerides and triglycerides can be used in the next batch without special pretreatment.

1 is a schematic and exemplary flow chart of a method of making a monoglyceride according to embodiments herein.
2 is a schematic diagram of a molecular distiller that can be used in a method for producing monoglycerides according to embodiments herein.

Hereinafter, embodiments and examples of the present application will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains may easily practice. However, the present application may be implemented in various different forms and is not limited to the embodiments and examples described herein. In addition, in order to clearly describe the present invention in the drawings, parts irrelevant to the description are omitted, and like reference numerals are assigned to similar parts throughout the specification.

Throughout this specification, when a part is "connected" to another part, this includes not only "directly connected" but also "electrically connected" with another element in between. do.

Throughout this specification, when one member is positioned “on” another member, this includes not only the case where one member abuts another member, but also the case where another member exists between the two members.

Throughout this specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated.

As used herein, the terms “about”, “substantially”, and the like are used in or near the numerical values when manufacturing and material tolerances unique to the stated meanings are presented, to aid understanding of the present application Hazards are used to prevent unreasonable abuse by unscrupulous infringers of the disclosures that are either accurate or absolute.

The term “steps of ~” or “steps of ~” as used in the present specification does not mean “steps for”.

Throughout the present specification, the term “combination (s)” included in the expression of the marki form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the marki form, It means to include one or more selected from the group consisting of the above components.

Throughout this specification, the description of “A and / or B” means “A or B, or A and B”.

Hereinafter, embodiments of the present application have been described in detail, but the present application may not be limited thereto.

The first aspect of the present application includes: (a) esterifying a medium chain fatty acid having 8 to 12 carbon atoms and glycerin under an acid catalyst to obtain a reaction product; And (b) washing the reaction product with glycerin, followed by molecular distillation to obtain a monoglyceride.

In one embodiment of the present application, the medium chain fatty acid is caprylic acid, pelargonic acid, capric acid, undecyl acid, and lauric acid ) May include one or more selected from, but may not be limited thereto. For example, the medium chain fatty acid may include one or more selected from caprylic acid, capric acid, and lauric acid.

In one embodiment of the present application, the glycerin may be used in an amount of about 3 equivalents to about 5 equivalents to 1 equivalent of the medium chain fatty acid, but may not be limited thereto. For example, when the glycerin is used in an amount of less than about 3 equivalents based on 1 equivalent of the medium chain fatty acid, when the reaction is completed, the content of the monoglyceride is 60% by weight relative to the product obtained according to the method for preparing the monoglyceride It can be reduced as it is, and when the glycerin is used in excess of about 5 times, the content of monoglycerides increases, but the use of excess glycerin reduces the efficiency of the reactor, and the inconvenience of recovering and reusing excessive amounts of glycerin This can happen.

In one embodiment of the present application, the acid catalyst may be glycerin soluble. Here, the acid catalyst can be easily separated and reused after the esterification reaction by using an glycerin soluble acid catalyst. The acid catalyst may include one or more selected from sulfuric acid, p-toluene sulfonic acid, methane sulfonic acid, ethane sulfonic acid, and propane sulfonic acid, but may not be limited thereto. Further, the acid catalyst may be used as about 2 parts by weight or less or about 1 part by weight or less based on 100 parts by weight of the medium chain fatty acid and the glycerin, which are reactants of the esterification reaction, but may not be limited thereto.

In one embodiment of the present application, the esterification reaction may be performed under a pressure lower than atmospheric pressure, specifically, may be performed under a low pressure condition of about 300 mmHg to about 600 mmHg, but may not be limited thereto. For example, the esterification reaction is about 300 mmHg to about 600 mmHg, about 300 mmHg to about 500 mmHg, about 300 mmHg to about 400 mmHg, about 400 mmHg to about 600 mmHg, about 400 mmHg to about 500 mmHg, or It may be performed under a low pressure condition of about 500 mmHg to about 600 mmHg, but may not be limited thereto. In one embodiment of the present application, when water generated as a result of the esterification reaction is removed, the reaction proceeds by equilibrium movement, and when vacuum is gradually applied, water is easily leaked, but may not be limited thereto. have.

In one embodiment of the present application, the esterification reaction may be performed under low temperature conditions of about 80 ° C to about 130 ° C, but may not be limited thereto. For example, the esterification reaction is about 80 ℃ to about 130 ℃, about 80 ℃ to about 120 ℃, about 80 ℃ to about 110 ℃, about 80 ℃ to about 100 ℃, about 80 ℃ to about 90 ℃, about 90 ° C to about 130 ° C, about 90 ° C to about 120 ° C, about 90 ° C to about 110 ° C, about 90 ° C to about 100 ° C, about 100 ° C to about 130 ° C, about 100 ° C to about 120 ° C, about 100 ° C To about 110 ° C, about 110 ° C to about 130 ° C, about 110 ° C to about 120 ° C, or about 120 ° C to about 130 ° C, but may not be limited thereto. Here, while raising the temperature while stirring the reactor in which the medium chain fatty acid, the glycerin, and the acid catalyst are added, at this time, a reaction is performed at a relatively low temperature by acting a vacuum, and water, a by-product of the reaction, is easily leaked. Make it possible. For example, when the esterification reaction is performed under a condition of less than about 80 ° C, the reaction rate may be slow and unsuitable for industrialization, and when the esterification reaction is performed under a condition of greater than about 130 ° C, the reaction rate May be faster or an unknown side reaction product may be generated, and the color of the reaction product may be changed, but may not be limited thereto.

In one embodiment of the present application, the manufacturing method of the monoglyceride is to confirm whether the esterification reaction is completed depending on the amount of water distilled and discharged during the esterification reaction or the amount of the unreacted fatty acid in the reactor. It may include, but may not be limited to this. For example, the amount of unreacted fatty acid can be confirmed by gas chromatography, but may not be limited thereto. For example, the unreacted fatty acid is about 0.5 parts by weight to about 3 parts by weight, about 0.5 parts by weight to about 2.5 parts by weight, and about 0.5 parts by weight to about 2 parts by weight with respect to 100 parts by weight of the medium chain fatty acid initially used , About 0.5 parts by weight to about 1.5 parts by weight, about 0.5 parts by weight to about 1 part by weight, about 1 part by weight to about 3 parts by weight, about 1 part by weight to about 2.5 parts by weight, about 1 part by weight to about 2 parts by weight , About 1 part by weight to about 1.5 parts by weight, about 1.5 parts by weight to about 3 parts by weight, about 1.5 parts by weight to about 2.5 parts by weight, about 1.5 parts by weight to about 2 parts by weight, about 2 parts by weight to about 3 parts by weight , About 2 parts by weight to about 2.5 parts by weight, or about 2.5 parts by weight to about 3 parts by weight, but may not be limited thereto.

In one embodiment of the present application, the method for preparing the monoglyceride may further include separating the glycerin layer and the glyceride layer after obtaining the reaction product, but may not be limited thereto. In addition, in one embodiment of the present application, the glyceride layer may include washing the catalyst remaining after the esterification reaction with glycerin of (b), but may not be limited thereto.

In one embodiment of the present application, glycerin is added to the separated glyceride layer, stirred at about 50 ° C to about 70 ° C, and then allowed to stand again to separate the trace catalyst remaining in the glyceride layer to be transferred to the glycerin layer. However, even if the glyceride layer is distilled, there may be no change in composition, but may not be limited thereto. Here, the separated glycerin layer may be used as it is in the next batch, but may not be limited thereto.

In one embodiment of the present application, when the esterification reaction is completed, the temperature of the reactor may be lowered to separate excess glycerin, but may not be limited thereto. At this time, the separation temperature varies depending on the type of the medium chain fatty acid used. In general, separation is performed between about 50 ° C and about 70 ° C. The same temperature is maintained so that the separation can be performed well or can be applied directly to the next process. Although slightly different depending on the type of the medium chain fatty acid used, the product may be hardened at a temperature lower than 50 ° C. In addition, since most of the catalyst is dissolved in the separated glycerin, it can be used as it is in the next reaction. When the glycerin is separated, a glyceride layer remains, and the glyceride layer includes glycerin, trace catalyst, small amount of unreacted fatty acid, monoglyceride, diglyceride, and triglyceride. When the glyceride layer is analyzed by gas chromatography, about 70% to about 80% by weight of monoglyceride, about 15% to about 20% by weight of diglyceride, and about 1% to about 5% by weight Is converted to triglyceride, and about 0.5% to about 3% by weight of the unreacted fatty acid remains. However, it may not be limited to this.

In one embodiment of the present application, the reaction product washed with the glycerin of (b) by the molecular distillation is a low-boiling material glycerin and unreacted fatty acids, a medium-boiling monoglyceride, and a high-boiling material diglyceride And triglycerides, but may not be limited thereto.

In one embodiment of the present application, a general molecular distillation apparatus as shown in FIG. 2 may be used to perform the method for preparing the monoglyceride of the present application, but may not be limited thereto. At this time, the distillation conditions, that is, the heating temperature, the degree of vacuum, and the temperature of the condenser should be different according to the type of the fatty acid. For example, in the case of caprylic acid monoglyceride, the heating temperature is about 100 ° C to about 140 ° C. , Vacuum degree is about 0.5 mmHg, condenser is maintained at about 70 ℃ to about 75 ℃ while washing with glycerin to remove the catalyst little by little glyceride layer. Here, unreacted fatty acids and glycerin with the lowest boiling point are not condensed in a condenser, but are collected in a receiver (receiver, 2). The object containing about 85% by weight to about 90% by weight of monoglyceride is condensed and then taken out from the receiver (4). In addition, the receiver 3 receives a high-boiling-point distillation residue that has not yet evaporated, and consists of diglyceride and triglyceride. However, it may not be limited to this.

In one embodiment of the present application, the content of the monoglyceride may be from about 85% to about 95% by weight relative to the product obtained according to the method for preparing the monoglyceride. For example, the content of the monoglyceride is at least about 85% by weight, at least about 88% by weight, at least about 90% by weight, at least about 93% by weight, from about 85% by weight to about 95% by weight, from about 85% by weight to About 93%, about 85% to about 90%, about 85% to about 88%, about 88% to about 95%, about 88% to about 93%, about 88% to about 88% It may be about 90% by weight, about 90% by weight to about 95% by weight, about 90% by weight to about 93% by weight, or about 93% by weight to about 95% by weight, but may not be limited thereto.

According to one embodiment of the present application, the method for preparing the monoglyceride is to prepare a monoglyceride using the medium chain fatty acid having 8 to 12 carbon atoms, wherein the fatty acid and glycerin are acid catalysts, for example, sulfuric acid, After performing the esterification reaction directly under one or more acid catalysts selected from methanesulphonic acid, ethanesulphonic acid, propanesulphonic acid, and p-toluenesulphonic acid, it may include purifying the reactant. In particular, monoglycerides, which are frequently used for cosmetics, have a relatively high content of mono having a content of about 85% to about 95% by weight, about 85% to about 90% by weight, or about 90% to about 95% by weight. It provides an economical and environmentally friendly method for producing glycerides.

The second aspect of the present application is a method for recovering glycerin and a catalyst after a monoglyceride production process, (a) esterifying a fatty acid and glycerin under a glycerin soluble acid catalyst to obtain a reaction product, and then restoring the reaction product To separate into a glycerin layer and a glyceride layer; And (b) washing the glyceride layer with glycerin, and then recovering the glycerin and the acid catalyst contained in the glycerin washed with the glycerin layer and the glyceride layer. .

The detailed description of parts overlapping with the first aspect of the present application is omitted, but the description of the first aspect of the present application may be equally applied even if the description is omitted in the second aspect of the present application.

In one embodiment of the present application, glycerin of (a), which is a reactant of the esterification reaction with respect to 1 equivalent of the fatty acid, may be used in about 3 equivalents to about 5 equivalents, but may not be limited thereto. For example, when the glycerin is used in an amount of less than about 3 equivalents based on 1 equivalent of the fatty acid, when the reaction is completed, the content of the monoglyceride in the glyceride obtained in the manufacturing process of the monoglyceride is 60% by weight It can be reduced, and when the glycerin is used more than about 5 times, the content of the monoglyceride increases, but the use of excess glycerin decreases the efficiency of the reactor, and the inconvenience of recovering and reusing excessive amounts of glycerin This can happen.

In one embodiment of the present application, the fatty acid may include a medium chain fatty acid having 8 to 12 carbon atoms, but may not be limited thereto. In one embodiment of the present application, the medium chain fatty acid is caprylic acid, pelargonic acid, capric acid, undecyl acid, and lauric acid ) May include one or more selected from, but may not be limited thereto. For example, the medium chain fatty acid may include one or more selected from caprylic acid, capric acid, and lauric acid.

In one embodiment of the present application, the acid catalyst may include one or more selected from sulfuric acid, p-toluenesulphonic acid, methanesulphonic acid, ethanesulphonic acid, and propanesulphonic acid, but is not limited thereto. It may not.

In one embodiment of the present application, the esterification reaction may be performed under low pressure conditions of 300 mmHg to 600 mmHg and low temperature conditions of 80 ° C to 130 ° C, but may not be limited thereto.

In one embodiment of the present application, the esterification reaction may be performed under a pressure lower than atmospheric pressure, specifically, may be performed under a low pressure condition of about 300 mmHg to about 600 mmHg, but may not be limited thereto. For example, the esterification reaction is about 300 mmHg to about 600 mmHg, about 300 mmHg to about 500 mmHg, about 300 mmHg to about 400 mmHg, about 400 mmHg to about 600 mmHg, about 400 mmHg to about 500 mmHg, or It may be performed under a low pressure condition of about 500 mmHg to about 600 mmHg, but may not be limited thereto. In one embodiment of the present application, when water generated as a result of the esterification reaction is removed, the reaction proceeds by an equilibrium movement, and when the vacuum is gradually applied, water is easily leaked, but may not be limited thereto. have.

In one embodiment of the present application, the esterification reaction may be performed under low temperature conditions of about 80 ° C to about 130 ° C, but may not be limited thereto. For example, the esterification reaction is about 80 ℃ to about 130 ℃, about 80 ℃ to about 120 ℃, about 80 ℃ to about 110 ℃, about 80 ℃ to about 100 ℃, about 80 ℃ to about 90 ℃, about 90 ° C to about 130 ° C, about 90 ° C to about 120 ° C, about 90 ° C to about 110 ° C, about 90 ° C to about 100 ° C, about 100 ° C to about 130 ° C, about 100 ° C to about 120 ° C, about 100 ° C To about 110 ° C, about 110 ° C to about 130 ° C, about 110 ° C to about 120 ° C, or about 120 ° C to about 130 ° C, but may not be limited thereto. Here, while raising the temperature while stirring the reactor in which the medium chain fatty acid, the glycerin, and the acid catalyst are added, at this time, a reaction is performed at a relatively low temperature by acting a vacuum, and water, a by-product of the reaction, is easily leaked. Make it possible. For example, when the esterification reaction is performed under a condition of less than about 80 ° C, the reaction rate may be slow and unsuitable for industrialization, and when the esterification reaction is performed under a condition of greater than about 130 ° C, the reaction rate May be faster or an unknown side reaction product may be generated, and the color of the reaction product may be changed, but may not be limited thereto.

The third aspect of the present application is (a) esterifying a fatty acid and glycerin under a glycerin soluble acid catalyst to obtain a reaction product, and then separating the reaction product into a glycerin layer and a glyceride layer; (b) washing the glyceride layer with glycerin, followed by molecular distillation to separate into low-boiling material glycerin and unreacted fatty acids, medium-boiling monoglyceride, and high-boiling material diglycerides and triglycerides; And (c) the glycerin layer containing the unreacted glycerin and the acid catalyst in (a), and washing the glyceride layer in (b) with glycerin containing the acid catalyst, and the molecular distillation. It provides a process for the production of a cyclic monoglyceride, comprising recovering the low-boiling material and the high-boiling material obtained by reuse in the production of monoglycerides.

Detailed descriptions of parts overlapping with the first and second aspects of the present application have been omitted, but the descriptions of the first and second aspects of the present application may be applied in the same way even though the descriptions have been omitted in the third aspect of the present application. Can be.

In one embodiment of the present application, the fatty acid may include a medium chain fatty acid having 8 to 12 carbon atoms, but may not be limited thereto. In one embodiment of the present application, the medium chain fatty acid is caprylic acid, pelargonic acid, capric acid, undecyl acid, and lauric acid ) May include one or more selected from, but may not be limited thereto. For example, the medium chain fatty acid may include one or more selected from caprylic acid, capric acid, and lauric acid.

In one embodiment of the present application, the acid catalyst may include one or more selected from sulfuric acid, p-toluenesulphonic acid, methanesulphonic acid, ethanesulphonic acid, and propanesulphonic acid, but is not limited thereto. It may not.

In one embodiment of the present application, the esterification reaction may be performed under low pressure conditions of 300 mmHg to 600 mmHg and low temperature conditions of 80 ° C to 130 ° C, but may not be limited thereto.

In one embodiment of the present application, the esterification reaction may be performed under a pressure lower than atmospheric pressure, specifically, may be performed under a low pressure condition of about 300 mmHg to about 600 mmHg, but may not be limited thereto. For example, the esterification reaction is about 300 mmHg to about 600 mmHg, about 300 mmHg to about 500 mmHg, about 300 mmHg to about 400 mmHg, about 400 mmHg to about 600 mmHg, about 400 mmHg to about 500 mmHg, or It may be performed under a low pressure condition of about 500 mmHg to about 600 mmHg, but may not be limited thereto. In one embodiment of the present application, when water generated as a result of the esterification reaction is removed, the reaction proceeds by an equilibrium movement, and when the vacuum is gradually applied, water is easily leaked, but may not be limited thereto. have.

In one embodiment of the present application, the esterification reaction may be performed under low temperature conditions of about 80 ° C to about 130 ° C, but may not be limited thereto. For example, the esterification reaction is about 80 ℃ to about 130 ℃, about 80 ℃ to about 120 ℃, about 80 ℃ to about 110 ℃, about 80 ℃ to about 100 ℃, about 80 ℃ to about 90 ℃, about 90 ° C to about 130 ° C, about 90 ° C to about 120 ° C, about 90 ° C to about 110 ° C, about 90 ° C to about 100 ° C, about 100 ° C to about 130 ° C, about 100 ° C to about 120 ° C, about 100 ° C To about 110 ° C, about 110 ° C to about 130 ° C, about 110 ° C to about 120 ° C, or about 120 ° C to about 130 ° C, but may not be limited thereto. Here, while raising the temperature while stirring the reactor in which the medium chain fatty acid, the glycerin, and the acid catalyst are added, at this time, a reaction is performed at a relatively low temperature by acting a vacuum, and water, a by-product of the reaction, is easily leaked. Make it possible. For example, when the esterification reaction is performed under a condition of less than about 80 ° C, the reaction rate may be slow and unsuitable for industrialization, and when the esterification reaction is performed under a condition of greater than about 130 ° C, the reaction rate May be faster or an unknown side reaction product may be generated, and the color of the reaction product may be changed, but may not be limited thereto.

In one embodiment of the present application, the content of the monoglyceride may be about 85% to about 95% by weight relative to the product obtained according to the manufacturing process of the cyclic monoglyceride. For example, the content of the monoglyceride is at least about 85% by weight, at least about 88% by weight, at least about 90% by weight, at least about 93% by weight, from about 85% by weight to about 95% by weight, from about 85% by weight to About 93%, about 85% to about 90%, about 85% to about 88%, about 88% to about 95%, about 88% to about 93%, about 88% to about 88% It may be about 90% by weight, about 90% by weight to about 95% by weight, about 90% by weight to about 93% by weight, or about 93% by weight to about 95% by weight, but may not be limited thereto.

In one embodiment of the present application, the manufacturing process of the cyclic monoglyceride may be repeated about 1 to about 5 times. For example, the manufacturing process of the cyclic monoglyceride is about 1 to about 5 times, about 1 to about 4 times, about 1 to about 3 times, about 1 to about 2 times, about 2 times to It may be repeated about 5 times, about 2 times to about 4 times, about 2 times to about 3 times, about 3 times to about 5 times, about 3 times to about 4 times, or about 4 times to about 5 times, It may not be limited to this.

In one embodiment of the present application, when the manufacturing process of the cyclic monoglyceride is repeated, it may be performed by adding the fatty acid in an amount necessary for the reaction, but may not be limited thereto. Here, the amount of the fatty acid added to the reaction, the number of moles of glycerin recovered according to the manufacturing process of the cyclic monoglyceride, each mole of 'reused fatty acid, diglyceride, and triglyceride, and the fatty acid added' It is decided to be about 3 times to about 5 times the number agreement. That is, according to the molar ratio or equivalent ratio, (the sum of the number of moles of each of the fatty acids to be reused, diglycerides, and triglycerides, and the fatty acids to be added): (Glycerin recovered according to the manufacturing process of the cyclic monoglycerides ) = 1: The number of moles of the fatty acids to be added is determined to be about 3 to 5, and the amount of insufficient fatty acids is supplemented to the amount of the glycerin recovered. However, it may not be limited to this.

In one embodiment of the present application, the reuse method of recovered glycerin and the like is as follows: As shown in FIG. 1, the glycerin layer recovered by static separation and the catalyst dissolved therein, and the glyceride layer are washed and separated. Glycerin, glycerin recovered from molecular distillation, unreacted fatty acids, and diglycerides and triglycerides recovered from molecular distillation are added to the reactor and the appropriate amount of fatty acids is added to carry out the esterification reaction. You can get the same results as not.

[ Example ]

One. Monoglyceride  Manufacturing and separation

< Example  1>

A thermometer and a distillation device are attached to a 500 mL 4-neck flask, and 125 gr (0.62 mol) of lauric acid, 285 gr (3.1 mol) of glycerin and 0.2 gr of p-toluenesulphonic acid are added and heated to 120 ° C. After the temperature reaches 120 ° C, the internal pressure is lowered to 450 mmHg, and water starts to flow out. When a total of 11 gr of water flows out over 4.5 hours, the internal pressure is reduced to 150 mmHg to dry the interior sufficiently. When the internal temperature was lowered to 72 ° C, the layers were separated. The upper layer is a glyceride layer with a reaction target, and the lower layer is a glycerin layer containing a catalyst. The top layer weighed 250 gr and the catalyst-containing glycerin layer weighed 148 gr. When the upper layer of the glyceride layer was analyzed by gas chromatography, 75% by weight of monoglycerides, 19% by weight of diglycerides, and 3.5% by weight of triglycerides were excluded.

When 100 gr of glycerin is added to the glyceride layer separated in the previous step, and the mixture is stirred vigorously at 70 ° C. and left still, 125 gr of glycerin layer and 223 gr of glyceride layer are obtained. The composition of monoglyceride, diglyceride and triglyceride in the glyceride layer was unchanged.

< Example  2>

A thermometer and a distillation device are attached to a 500 mL 4-neck flask, and 125 gr (0.87 mol) of caprylic acid, 319 gr (3.47 mol) of glycerin and 0.2 gr of p-toluenesulphonic acid are added and heated to 100 ° C. When the temperature reaches 100 ° C and the internal pressure is lowered to 400 mmHg, water starts to flow out. When a total of 15.5 gr of water flows out over 5 hours, the internal pressure is reduced to 180 mmHg to dry the interior sufficiently. When the internal temperature was lowered to 60 ° C, the layers were separated. The upper layer is a glyceride layer with a reaction target, and the lower layer is a glycerin layer containing a catalyst. The top layer weighed 317 gr and the catalyst-containing glycerin layer weighed 125 gr. As a result of analyzing the glyceride layer of the upper layer by gas chromatography, it was 79% by weight of monoglycerides, 18.5% by weight of diglycerides, and 0.5% by weight of triglycerides excluding glycerin.

When 75 gr of glycerin is added to the glyceride layer separated from the above, and strongly stirred at 70 ° C. and left still, 90 gr of glycerin layer and 295 gr of glyceride layer are obtained. The composition of monoglyceride, diglyceride and triglyceride in the glyceride layer was unchanged.

< Example  3>

In the same manner as in Example 2, 0.15 gr of ethanesulfonic acid was used instead of 0.2 gr of p-toluenesulphonic acid as a catalyst. After completion of the reaction, as a result of analyzing the glyceride layer of the upper layer by gas chromatography, except for glycerin, it was 76% by weight of monoglycerides, 20.3% by weight of diglycerides, and 0.5% by weight of triglycerides.

< Example  4>

In the same manner as in Example 2, 0.1 gr of concentrated sulfuric acid was used instead of 0.2 gr of p-toluenesulfonic acid as a catalyst. After completion of the reaction, as a result of analyzing the glyceride layer of the upper layer by gas chromatography, 68% by weight of monoglycerides, 24.1% by weight of diglycerides, and 6.7% by weight of triglycerides were excluded.

< Example  5>

A thermometer and a distillation unit are attached to a 20 L bench-type reactor, 5 kg of caprylic acid, 13 kg of glycerin and 7 gr of p-toluenesulphonic acid are added and heated to 100 ° C. When the temperature reaches 100 ° C, the internal pressure is lowered to 400 mmHg, and water is removed while reacting for a total of 6 hours. After lowering the internal pressure to 180 mmHg to dry the interior sufficiently, lowering the internal temperature to 60 ° C separates the layers. The upper layer, that is, the glyceride layer was 12.5 kg, and the lower layer was 5.3 kg. As a result of analyzing the glyceride layer of the upper layer by gas chromatography, except for glycerin, it was 77.5% by weight of monoglycerides, 18.0% by weight of diglycerides, and 0.7% by weight of triglycerides.

3 kg of glycerin was added to the glyceride layer separated in the previous step, and after vigorous stirring at 70 ° C., 3.9 kg of glycerin layer and 11.5 kgr of glyceride layer were obtained. The composition of the monoglyceride, diglyceride and triglyceride of the glyceride layer was unchanged.

2. Molecular distillation

< Example  6>

While heating the heating section of the stainless steel thin film distiller having a heating area of 0.4 m 2 to 120 ° C., hot water at 70 ° C. is passed through the condensation section. Vacuum is applied to the inside at 0.5 mmHg. The glyceride obtained in Example 5 was injected at 0.7 kg / hr. The experimental results are in Table 1 below.

< Example  7 to 9>

Proceeding under the same conditions as in Example 6, the temperature of the condensation unit and the heating unit was changed as shown in Table 1 below. The experimental results are in Table 1 below:

[Table 1]

In [Table 1], Acid means caprylic acid, Mono means monoglyceride, Di means diglyceride, and Tri means triglyceride, respectively.

3. Reuse experiments such as glycerin

< Example  10>

620 gr in 5.2 Kg of glycerin layer obtained by standing in the 3 L reactor in Example 5 above, 450 gr in 3.9 kg of glycerin layer obtained by washing, and 360 gr in 3.9 kg of low-boiling isolate obtained in Example 6 and high boiling point separation After adding 110 gr of 950 gr of water and adding 465 gr of caprylic acid, the catalyst was reacted for 6.5 hours while maintaining the same temperature and pressure as in Example 5 without adding the catalyst.

After the reaction, the upper layer, that is, the glyceride layer was 1.35 kg, and the lower layer was 570 gr. As a result of analyzing the glyceride layer of the upper layer by gas chromatography, glycerin was 76.2% by weight of monoglycerides, 19.3% by weight of diglycerides, and 0.5% by weight of triglycerides.

< Comparative example  1>

In the same manner as in Example 10, 0.2 gr of the catalyst was added to react. The total reaction time was 5 hours, and the upper layer of the glyceride layer was analyzed by gas chromatography. As a result of glycerin, it was 77.1% by weight of monoglycerides, 18.5% by weight of diglycerides, and 0.5% by weight of triglycerides.

The above description of the present application is for illustrative purposes, and those skilled in the art to which the present application pertains will understand that it is possible to easily modify to other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the claims to be described later rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts should be interpreted to be included in the scope of the present application. .

1: reactant container
2: Receiver
3: Receiver
4: Receiver

Claims (24)

(a) esterifying a medium chain fatty acid having 8 to 12 carbon atoms and glycerin under an acid catalyst to obtain a reaction product; And
(b) After washing the reaction product with glycerin, molecular distillation to obtain monoglyceride
Including,
The acid catalyst is glycerin solubility, the production method of monoglyceride.
According to claim 1,
The medium chain fatty acid includes at least one selected from caprylic acid, pelargonic acid, capric acid, undecylic acid, and lauric acid. The production method of monoglyceride.
According to claim 1,
The glycerin is used in an amount of 3 to 5 equivalents based on 1 equivalent of the medium chain fatty acid, a method for producing monoglyceride.
delete According to claim 1,
The acid catalyst is sulfuric acid, p- toluene sulfonic acid, methane sulfonic acid, ethanesulfonic acid, and one or more selected from propane sulfonic acid, monoglyceride production method.
According to claim 1,
The esterification reaction is performed under a low pressure condition of 300 mmHg to 600 mmHg, a method for producing monoglyceride.
According to claim 1,
The esterification reaction is carried out under low temperature conditions of 80 ℃ to 130 ℃, the production method of the monoglyceride.
According to claim 1,
A method for producing a monoglyceride, comprising confirming whether the esterification reaction is completed according to the amount of water distilled and discharged during the esterification reaction or the amount of unreacted fatty acids in the reactor.
According to claim 1,
After the reaction product is obtained, the method further comprises separating into a glycerin layer and a glyceride layer by standing still, a method for producing a monoglyceride.
The method of claim 9,
A method for producing a monoglyceride, comprising washing the catalyst remaining after the esterification reaction in the glyceride layer with glycerin of (b).
According to claim 1,
The reaction product washed with glycerin of (b) by the molecular distillation is separated into low-boiling substance glycerin and unreacted fatty acid, medium boiling point monoglyceride, and high boiling substance diglyceride and triglyceride. , Monoglyceride production method.
According to claim 1,
The content of the monoglyceride is 85% to 95% by weight with respect to the product obtained according to the method for preparing the monoglyceride,
Process for the production of monoglycerides.
As a method for recovering glycerin and catalyst after the monoglyceride production process,
(a) esterifying a fatty acid and glycerin under a glycerin soluble acid catalyst to obtain a reaction product, and then separating the reaction product into a glycerin layer and a glyceride layer; And
(b) after washing the glyceride layer with glycerin, recovering the glycerin and the acid catalyst contained in the glycerin, and the glycerin washed with the glyceride layer
Recovery method comprising a.
The method of claim 13,
The glycerin of (a), which is a reactant of the esterification reaction with respect to 1 equivalent of the fatty acid, is used in 3 to 5 equivalents.
The method of claim 13,
The fatty acid is a method of recovering, comprising a medium chain fatty acid having 8 to 12 carbon atoms.
The method of claim 13,
The acid catalyst is sulfuric acid, p- toluene sulfonic acid, methane sulfonic acid, ethane sulfonic acid, and one or more selected from propane sulfonic acid, recovery method.
The method of claim 13,
The esterification reaction is carried out under low pressure conditions of 300 mmHg to 600 mmHg and low temperature conditions of 80 ℃ to 130 ℃, recovery method.
(a) esterifying a fatty acid and glycerin under a glycerin soluble acid catalyst to obtain a reaction product, and then separating the reaction product into a glycerin layer and a glyceride layer;
(b) washing the glyceride layer with glycerin, followed by molecular distillation to separate into low-boiling material glycerin and unreacted fatty acids, medium boiling point monoglyceride, and high boiling material diglycerides and triglycerides; And
(c) the glycerin layer containing the unreacted glycerin and the acid catalyst in (a), the glyceride layer in (b) washing the glycerin containing the acid catalyst, and by molecular distillation The obtained low-boiling-point material and the high-boiling-point material are recovered and reused in the production of monoglycerides
Including, cyclic monoglyceride production process.
The method of claim 18,
The fatty acid comprises a medium chain fatty acid having 8 to 12 carbon atoms, cyclic monoglyceride production process.
The method of claim 18,
The acid catalyst is sulfuric acid, p- toluene sulfonic acid, methane sulfonic acid, ethane sulfonic acid, and one or more selected from propane sulfonic acid, cyclic monoglyceride production process.
The method of claim 18,
The esterification reaction is carried out under a low pressure condition of 300 mmHg to 600 mmHg and a low temperature condition of 80 ℃ to 130 ℃, cyclic monoglyceride production process.
The method of claim 18,
The content of the monoglyceride is 85% by weight to 95% by weight relative to the product obtained according to the production process of the cyclic monoglyceride, the production process of cyclic monoglycerides.
The method of claim 18,
The manufacturing process of the cyclic monoglyceride is repeated one to five times, the manufacturing process of the cyclic monoglyceride.
The method of claim 18,
When repeating the manufacturing process of the cyclic monoglyceride, it is performed by adding the fatty acid in an amount necessary for the reaction, the manufacturing process of the cyclic monoglyceride.

Images