KR102177450B1 - Method for manufacturing sorbitan fatty acid esters - Google Patents

Abstract

An aspect of the present invention provides a method for manufacturing sorbitan fatty acid esters comprising the following steps: (a) treating fat and oil resources with acids for degumming the same; (b) conducting a reaction of the degummed fat and oil resources with first alcohol in the presence of a first catalyst; (c) conducting a reaction of a product of the step (b) with second alcohol in the presence of a second catalyst; and (d) dehydrating liquid sorbitol, and conducting a reaction with product of the step (c) in the presence of a third catalyst. The present invention is environmentally friendly, and at the same time, it is possible to increase the reactivity and efficiency of a reaction accompanying an entire process.

Description

Manufacturing method of sorbitan fatty acid ester {METHOD FOR MANUFACTURING SORBITAN FATTY ACID ESTERS}

The present invention relates to a method for producing a sorbitan fatty acid ester, and more particularly, to a method for producing a sorbitan fatty acid ester using a high acid value maintenance waste resource as a raw material.

The sorbitan fatty acid ester is a nonionic surfactant formed by ester bonding a polyhydric alcohol such as sorbitol or sorbitan with a fatty acid. The sorbitan fatty acid ester has relatively high lipophilicity and low toxicity, so it is widely used in food and pharmaceutical fields. A sorbitan fatty acid ester is used as an intermediate, and it is widely used as an intermediate to prepare a polysorbate surfactant by ethoxylation.

In general, the sorbitan fatty acid ester may be prepared through a process of converting sorbitol into sorbitan by an internal etherification reaction and a process of esterifying sorbitan with a fatty acid. These reactions usually occur almost simultaneously in a single step, since there are several sites in the reaction where internal etherification and esterification can occur. The product according to this reaction mechanism is generally a mixture of isomers, and multiple esterifications are possible, resulting in a wider range of changes in the molecular structure.

On the other hand, in recent years, as promoting eco-friendliness through reuse of resources has emerged as a topic in the industry as a whole, a process for producing sorbitan fatty acid esters using oil and fat resources has been proposed. In this case, the sorbitan fatty acid ester may be prepared through an esterification reaction, a transesterification reaction, or the like of the waste oil.

However, waste oils and fats, which are the raw materials necessary to produce sorbitan fatty acid esters, generally have a high acid value. In addition to triglycerides, which are the main components of fats and oils, there are many impurities that affect the quality of fats such as phospholipids, proteins, neutral salts, and moisture. Included as. When the maintenance waste resource in this state is esterified with glycerin, an unnecessary intermediate product may be generated by a side reaction between the impurity and glycerin, and the intermediate product has a problem of lowering the efficiency and yield of the subsequent transesterification reaction. .

Therefore, in order to use the waste oil and fat as a raw material, it is important to first perform degumming to remove impurities such as phospholipids, thereby lowering the acid value of the ester reaction product and suppressing side reactions.

In crude oil of vegetable oil, which is one of these oil and fat resources, about 2% of phospholipids are present, about 70% of hydrated phospholipids are mostly removed by hydration degumming, and about 30% of non-hydrated phospholipids are removed by acid degumming. Can be. If the efficiency of the degumming process is low, it may adversely affect subsequent processes such as esterification and transesterification.

The present invention is to solve the problems of the prior art described above, and an object of the present invention is to produce sorbitan fatty acid ester using high acid value maintenance waste resources, so that it is environmentally friendly and accompanying esterification and transesterification reactions. It is to provide a method for producing a sorbitan fatty acid ester that can increase the reactivity and efficiency of.

One aspect of the present invention, (a) degumming by treating the maintenance resource with an acid; (b) reacting the degumming resource with a first alcohol in the presence of a first catalyst; (c) reacting the product of step (b) with a second alcohol in the presence of a second catalyst; And (d) dehydrating the liquid sorbitol, and reacting with the product of step (c) in the presence of a third catalyst. It provides a method for producing a sorbitan fatty acid ester.

In one embodiment, the amount of acid used may be 0.1 to 2 parts by weight based on 100 parts by weight of the maintenance resource.

In one embodiment, the first to third catalysts are respectively potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium peroxide, sodium peroxide, lithium peroxide, potassium carbonate, sodium carbonate, lithium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, and carbonic acid. Lithium hydrogen, potassium methylate, sodium methylate, lithium methylate, potassium ethylate, sodium ethylate, lithium ethylate, potassium propylate, sodium propylate, lithium propylate, potassium butyrate, sodium butyrate, lithium butyrate , Boron trifluoride, titanium acrylate, tetrabutyl titanate, tetrapropyl titanate, titanium isopropoxide, aluminum isopropoxide, tin octoate, sodium acetate, calcium acetate, tin acetate, zinc acetate, antimony trioxide , Butylstanic acid, monobutyltin hydrate, monobutylchlorotindihydroxide, stenosoxalate, dibutyltindiacetate, dibutyltinoxide, dibutyltindilaurate, dibutyltindimethoxide, dibutyltindibutoxide , Titanium dioxide, and may be one selected from the group consisting of a combination of two or more of them.

In one embodiment, the amount of the first catalyst used may be 0.01 to 0.3 parts by weight based on 100 parts by weight of the degummed maintenance resource.

In one embodiment, the first alcohol may be a polyhydric alcohol.

In one embodiment, the acid value of the product of step (b) may be 3mgKOH/g or less.

In one embodiment, the (c) step, (c1) the first mixture produced by reacting the product of step (b) with a second alcohol in the presence of the second catalyst, a first supernatant and a first lower layer After separating into a liquid, removing at least a portion of the first lower layer liquid; (c2) after the second mixture produced by reacting the first supernatant in the presence of the additional second catalyst is stagnated and separated into a second supernatant and a second lower liquid, at least part of the second lower liquid is Removing; And (c3) distilling the second supernatant.

In one embodiment, the amount of the second catalyst used in steps (c1) and (c2) may be 1 to 5 parts by weight and 0.1 to 0.5 parts by weight, respectively, based on 100 parts by weight of the product of step (b).

In one embodiment, the second alcohol may be a monohydric alcohol.

In one embodiment, the step (d) is performed in the presence of a surfactant, and the amount of the surfactant may be 1 to 20 parts by weight based on 100 parts by weight of the product of step (c).

The method for producing a sorbitan fatty acid ester according to an aspect of the present invention is eco-friendly by using a fat or oil resource degumming by an acid as a raw material, and transesterification reaction between a fatty acid methyl ester and a dehydrated liquid sorbitol as an intermediate product. At the same time, it is possible to increase the reactivity and efficiency of the reaction accompanying the entire process.

The effects of the present invention are not limited to the above effects, and should be understood to include all effects that can be deduced from the configuration of the invention described in the detailed description or claims of the present invention.

1 is a schematic diagram of a method for preparing a sorbitan fatty acid ester according to an embodiment of the present invention.

Hereinafter, the present invention will be described with reference to the accompanying drawings. However, the present invention may be implemented in various different forms, and therefore is not limited to the embodiments described herein.

Throughout the specification, when a part is said to be "connected" with another part, this includes not only "directly connected" but also "indirectly connected" with another part interposed therebetween. . In addition, when a part "includes" a certain component, it means that other components may be further provided, rather than excluding other components unless specifically stated to the contrary.

1 is a schematic diagram of a method for preparing a sorbitan fatty acid ester according to an embodiment of the present invention.

One aspect of the present invention, (a) degumming by treating the maintenance resource with an acid; (b) reacting the degumming resource with a first alcohol in the presence of a first catalyst; (c) reacting the product of step (b) with a second alcohol in the presence of a second catalyst; And (d) dehydrating the liquid sorbitol, and reacting with the product of step (c) in the presence of a third catalyst. It provides a method for producing a sorbitan fatty acid ester.

In the step (a), the oil and oil resources may be treated with an acid to degumming.

The oil and fat resources are, for example, soybean oil, rapeseed oil, corn oil, rapeseed oil, sunflower oil, castor oil, palm oil, linseed oil, poppy oil, walnut oil, peanut oil, cottonseed oil, rice bran oil, camellia oil, olive oil, beef tallow ), pork fat, Yangji, fish oil, diesel oil, diesel oil, waste oil whose acid value has been increased by repeated use, waste oil generated from vegetable oil refining process, and separated from glycerin during biodiesel process. It may be one selected from the group consisting of oil and a combination of two or more of them, but is not limited thereto.

In order to use the fat or oil resource as a raw material for producing sorbitan fatty acid ester, it is important to suppress side reactions in a subsequent step by performing degumming to remove impurities such as phospholipids.

For example, about 2% of phospholipids are present in crude oil of vegetable oil, which is one of the oil resources, and about 70% of hydrated phospholipids can be mostly removed by hydration degumming, and about 30% of non-hydrated phospholipids are removed. It can be separated and removed by treatment with an acid to convert it into a hydrophobic phospholipid. The hydrophobic phospholipid is not mixed with oil and can be dissolved in an acid solution and removed with separation and hydration.

The acid may be one selected from the group consisting of oxalic acid, citric acid, phosphoric acid, and a combination of two or more of them, and preferably, oxalic acid, but is not limited thereto.

The amount of acid used may be 0.1 to 2, preferably, 0.25 to 1.5 parts by weight based on 100 parts by weight of the maintenance resource. If the amount of the acid is less than 0.1 parts by weight based on 100 parts by weight of the maintenance resource, it is difficult to convert the non-hydrated phospholipid contained in the maintenance resource into a hydrated phospholipid, and if it exceeds 2 parts by weight, it is difficult to control the reaction accompanying the degumming. .

The acid can be used with a predetermined amount of water. The water may allow the acid to be substantially provided as an aqueous solution. The amount of water used may be 3 to 15 parts by weight, preferably 7 to 15 parts by weight, based on 100 parts by weight of the maintenance resource, and at this time, the concentration of the aqueous solution is 5 to 20% by weight, preferably, 10 to It may be 20% by weight, more preferably, 10 to 15% by weight, but is not limited thereto.

In consideration of reaction efficiency, energy efficiency, economy, etc., the degumming is performed at a temperature of 90 to 150°C, preferably 100 to 110°C, and 0.5 to 5 atm under normal pressure, preferably at normal to 1 atm. It may be made for 2 hours, preferably, 1 to 1.5 hours.

In the step (b), the fat and oil resources degumming in the presence of the first catalyst may be subjected to esterification reaction with the first alcohol.

The first catalyst is potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium peroxide, sodium peroxide, lithium peroxide, potassium carbonate, sodium carbonate, lithium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium hydrogen carbonate, boron trifluoride, titanium acrylic Rate, tetrabutyl titanate, tetrapropyl titanate, titanium isopropoxide, aluminum isopropoxide, tin octoate, sodium acetate, calcium acetate, tin acetate, zinc acetate, antimony trioxide, butylstannic acid, monobutyl tin Hydrate, monobutyl chlorotin dihydroxide, stenos oxalate, dibutyl tin diacetate, dibutyl tin oxide, dibutyl tin dilaurate, dibutyl tin dimethoxide, dibutyl tin dibutoxide, titanium dioxide, and two or more of these It may be one selected from the group consisting of a combination, and preferably, sodium hydroxide, dibutyl tin dilaurate, dibutyl tin oxide, or tetrabutyl titanate, but is not limited thereto.

The amount of the first catalyst to be used may be 0.01 to 0.3 parts by weight, preferably, 0.02 to 0.2 parts by weight, based on 100 parts by weight of the degummed maintenance resource.

The first alcohol may be a polyhydric alcohol. The polyhydric alcohol is, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, cyclohexylene glycol, trimethylolpropane, glycerin, pentaerythritol, sorbitol , Methyl glycoside, diglycerin, sucrose, and may be one selected from the group consisting of a combination of two or more of them, preferably, glycerin, but is not limited thereto. When the first alcohol is glycerin, the product of step (b) may be glyceride.

The amount of the first alcohol used may be 6 to 13 parts by weight, preferably 7.5 to 12 parts by weight, based on 100 parts by weight of the degummed maintenance resource.

In consideration of reaction efficiency, energy efficiency, economy, etc., the esterification reaction is 180 to 220°C, preferably, at a temperature of 200 to 210°C, and at normal pressure to 400 torr, preferably, 4 to 10 hours under pressure conditions of normal pressure. , Preferably, it may be made for 5 to 7 hours.

The acid value of the product of step (b) may be 3 mgKOH/g or less, preferably 2.5 mgKOH/g or less, more preferably 1.0 to 2.5 mgKOH/g. If the acid value of the product in step (b) is more than 3mgKOH/g, an excess of free fatty acids is neutralized with the second and third catalysts to produce fatty acid salts, and a repetitive washing process is required to remove them. There is a problem of lowering efficiency.

In the step (c), a fatty acid methyl ester (FAME) may be obtained by transesterification reaction of the product of step (b) with a second alcohol in the presence of a second catalyst.

The second catalyst is potassium methylate, sodium methylate, lithium methylate, potassium ethylate, sodium ethylate, lithium ethylate, potassium propylate, sodium propylate, lithium propylate, potassium butyrate, sodium butyrate, lithium It may be one selected from the group consisting of butyrate and a combination of two or more of them, preferably, sodium methylate, more preferably, a sodium methylate solution having a predetermined concentration, but is not limited thereto.

The second alcohol may be a monohydric alcohol. The monohydric alcohol is, for example, methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutanol, 2-butanol, tert-butanol, n-pentanol, isopentyl alcohol, 2-methyl-1-butanol, Neopentyl alcohol, diethyl kebinol, methylpropyl kebinol, methyl isopropyl kebinol, dimethyl ethyl kebinol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3 -Methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2-methyl-3- Tanol, 3-methyl-3-pentanol, 2,2-dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol , 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, and may be one selected from the group consisting of a combination of two or more thereof, preferably methanolyl However, it is not limited thereto.

In the step (c), (c1) the first mixture produced by reacting the product of step (b) with a second alcohol in the presence of the second catalyst is separated into a first supernatant and a first lower liquid, Removing at least a portion of the first lower layer liquid (first transesterification reaction); (c2) after the second mixture produced by reacting the first supernatant in the presence of the additional second catalyst is stagnated and separated into a second supernatant and a second lower liquid, at least part of the second lower liquid is Removing (second transesterification reaction); And (c3) distilling the second supernatant.

In the (c1) step (first transesterification reaction), the amount of the second alcohol used may be 20 to 30 parts by weight, preferably, 23 to 27 parts by weight, based on 100 parts by weight of the product of step (b), , The amount of the second catalyst used may be 1 to 5 parts by weight, preferably, 2 to 4 parts by weight.

The transesterification reaction in the step (c1) is 60 to 80°C, preferably, 65 to 70°C, and normal pressure to 2 atmospheres, preferably, atmospheric pressure, in consideration of reaction efficiency, energy efficiency, economy, etc. It can be made for 1 to 4 hours, preferably, 2 to 3 hours under a pressure condition of 0.5 atm. In addition, the stirring speed required for the reaction may be adjusted to 2,000-2,500 rpm.

After the end of the transesterification reaction, the product is held for 0.5 to 2 hours, preferably for 1 to 1.5 hours, to remove at least a part, preferably, the whole, of the mixture containing the first and second alcohols separated into the lower layer. I can.

When the lower layer liquid is separated from the first transesterification reaction product as described above, the sodium methylate used as a catalyst in the subsequent second transesterification reaction reacts with the free fatty acid and the soap produced is dissolved in the remaining glycerin and separated into the lower layer. In addition, by lowering the content of the soap content in the fatty acid methyl ester of the upper layer, subsequent processes such as solvent recovery and distillation can be smoothly performed.

In the step (c2) (second transesterification reaction), the amount of the second catalyst may be 0.1 to 0.5 parts by weight, preferably 0.1 to 0.3 parts by weight, more preferably 0.15 to 0.2 parts by weight.

In the transesterification reaction in the step (c2), in consideration of reaction efficiency, energy efficiency, economy, etc., at a temperature of 60 to 80°C, preferably, 65 to 75°C, and an atmospheric pressure to 2 atmospheres, preferably, It may be made for 0.5 to 2 hours, preferably, 0.8 to 1.5 hours under pressure conditions.

At least a portion of the mixture containing the first and second alcohols and soap powder separated into a lower layer by holding the product for 0.5 to 2 hours, preferably 1 to 1.5 hours after the end of the transesterification reaction, preferably all Can be removed.

In step (c3), the product of step (c2), that is, the second supernatant may be distilled to obtain fatty acid methyl ester.

The second supernatant may be a mixture containing a fatty acid methyl ester and a second alcohol. While stirring the second supernatant, the second alcohol is recovered by heating to 90 to 120° C., preferably 100 to 110° C., and further at a pressure of 50 to 200 torr, preferably 80 to 120 torr, 130 to After further recovering the second alcohol by heating to 170° C., preferably 140 to 160° C., at a pressure of 0 to 5 torr, preferably 1 to 3 torr, 210 to 250° C., preferably 220 to The fatty acid methyl ester can be recovered by heating to 230°C.

5 to 15 parts by weight, preferably 8 to 12 parts by weight of washing water is added to 100 parts by weight of the recovered fatty acid methyl ester, and while stirring, the fatty acid methyl ester, glycerin and monoglyceride are dissolved in water and separated. , 10 to 50 torr, preferably, at a pressure of 20 to 30 torr, heated to 90 to 130°C, preferably 100 to 110°C to dehydrate and remove moisture to recover pure fatty acid methyl ester.

In the step (d), after dehydrating the liquid sorbitol, it is reacted with the product of step (c) in the presence of a third catalyst to obtain a sorbitan fatty acid ester as the final product of the present invention.

The liquid sorbitol may be provided as an aqueous solution having a sorbitol concentration of 40 to 90% by weight, preferably, 50 to 80% by weight, more preferably, 60 to 80% by weight, and appropriately dehydrate it to the above (c) It can be transesterified with the product of the step.

In this dehydration, 0.1 to 0.5% of hypophosphorous acid, preferably 0.2 to 0.4% of the color stabilizer is added to 100 parts by weight of the liquid sorbitol, and then gradually stirred while blowing nitrogen as an inert gas to avoid contact with air. While stirring at a temperature of 120 to 160°C, preferably 130 to 150°C at normal pressure to 400 torr, preferably, at normal pressure for 2 to 5 hours, preferably 3 to 4 hours.

100 to 300 parts by weight of fatty acid methyl ester obtained in step (c), preferably 130 to 250 parts by weight of the dehydrated liquid sorbitol is added to cool, and the fatty acid methyl ester is 100 parts by weight. After adding 0.5 to 5 parts by weight of the third catalyst, preferably 1 to 3 parts by weight, and 0.05 to 1 parts by weight of sodium hypophosphate, preferably 0.05 to 0.5 parts by weight of the color stabilizer, the transesterification reaction can be carried out. have.

The third catalyst is potassium methylate, sodium methylate, lithium methylate, potassium ethylate, sodium ethylate, lithium ethylate, potassium propylate, sodium propylate, lithium propylate, potassium butyrate, sodium butyrate, lithium It may be one selected from the group consisting of butyrate and a combination of two or more of them, preferably, sodium methylate, more preferably, a sodium methylate solution having a predetermined concentration, but is not limited thereto.

In the transesterification reaction in step (d), in consideration of reaction efficiency, energy efficiency, economy, etc., a temperature of 200 to 260°C, preferably 230 to 250°C, and a pressure of atmospheric pressure to 400 torr, preferably atmospheric pressure It can be made for 4 to 10 hours, preferably, 5 to 7 hours under conditions.

The step (d) is performed in the presence of a surfactant (or emulsifier), and the amount of the surfactant is 1 to 20 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the product of step (c). , More preferably, it may be 5 to 10 parts by weight.

The surfactant may be one selected from the group consisting of cationic surfactants, anionic surfactants, amphoteric surfactants, nonionic surfactants, natural surfactants, and combinations of two or more of them.

The cationic surfactant is a quaternary ammonium compound, benzalkonium chloride, cetyltrimethylammonium bromide, chitosan, lauryldimethylbenzyl ammonium chloride, acylcarnitine hydrochloride, alkylpyridinium halide, cetylpyridinium chloride, cationic lipid , Polymethyl methacrylate trimethyl ammonium bromide, sulfonium compound, polyvinylpyrrolidone-2-dimethylaminoethyl methacrylate dimethyl sulfate, hexadecyl trimethyl ammonium bromide, phosphonium compound, benzyl-di (2-chloroethyl )Ethylammonium bromide, decyltriethylammonium chloride, decyldimethylhydroxyethylammonium chloride bromide, (C12-C15)dimethylhydroxyethylammonium chloride, (C12-C15)dimethylhydroxyethylammonium chloride bromide, myristyltrimethylammonium methyl Sulfate, lauryldimethylbenzyl ammonium chloride, lauryldimethylbenzylammonium bromide, lauryldimethyl (ethenoxy) tetraammonium chloride, lauryldimethyl (ethenoxy) tetraammonium bromide, N-alkyl (C12-C18) dimethyl Benzyl ammonium chloride, N-alkyl (C14-C18) dimethyl-benzyl ammonium chloride, N-tetradecyldimethylbenzyl ammonium chloride, derivatives thereof, and combinations of two or more thereof may be one selected from the group consisting of, but are limited thereto. no.

The anionic surfactants are ammonium lauryl sulfate, sodium 1-heptane sulfonate, sodium hexane sulfonate, sodium dodecyl sulfate, triethanol ammonium dodecylbenzene sulfate, potassium laurate, triethanolamine stearate, lithium dodecyl sulfate, sodium. Uryl sulfate, sodium laureth sulfate, sodium heptanoate, sodium gluconate, sodium cetyl sulfate, sodium thiosulfate, sodium chondroitin sulfate, sodium polyoxyethylene lauryl ether sulfate, alkyl polyoxyethylene sulfate, sodium alginate, dioctyl Sodium sulfosuccinate, disodium laureth sulfosuccinate, phosphatidylglycerol, phosphatidylinositol, phosphatidylserine, phosphatidic acid and salts thereof, glyceryl ester, sodium carboxymethylcellulose, bile acids and salts thereof, cholic acid, deoxycholic acid , Glycocholic acid, taurocholic acid, glycodeoxycholic acid, alkylsulfonate, arylsulfonate, alkylphosphate, alkylphosphonate, stearic acid and salts thereof, calcium stearate, phosphate, sodium carboxymethylcellulose, dioctylsulfosuccinate Nate, dialkyl esters of sodium sulfosuccinic acid, phospholipids and calcium carboxymethylcellulose sodium sulfate, derivatives thereof, and a combination of two or more of them may be one selected from the group, but the present invention is not limited thereto.

The nonionic surfactant is methanol, ethanol, isopropanol, butanol, benzyl alcohol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,6-hexanediol, 1,2-propanediol, 1 ,3-propanediol, trimethylolpropane, sorbitol, xylitol, glycerin, diglycerin, ethylene glycol, diethylene glycol, polyethylene glycol, ethylene glycol monomethyl ether, ethylene glycol phenyl ether, propylene glycol, dipropylene glycol, tripropylene glycol , Polypropylene glycol, propylene glycol monomethyl ether, propylene glycol phenyl ether, dibutyldiglycol, 3-methyl-3-methoxybutanol, 2-(2-butoxyethoxy)ethanol, polyoxyethylene alkyl ether, poly Oxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty alcohol, polyoxyethylene alkylphenyl ether, polysorbate, sorbitanolate, sorbitan laurate, sorbitan stearate, lactic acid, glucose, la Uryl glucoside, Brij TM, Solsperse TM, Triton TM X-100, derivatives thereof, and may be one selected from the group consisting of a combination of two or more of them, but is not limited thereto.

The amphoteric surfactant is an acetate (based), imidazole (based), betaine (based), phosphatide (based) compound, EDTA (ethylene diamine tetra acetic acid), derivatives thereof, and combinations of two or more of them It may be one selected from the group consisting of, but is not limited thereto.

The natural surfactant may be an enzyme, a vegetable oil such as soft nut, corn starch, potato starch, rice water, coconut oil, and a combination of two or more of them, but is not limited thereto.

Hereinafter, embodiments of the present invention will be described in detail.

(a) degumming reaction

In a 2L 4-neck flask, 1,000 g of dark oil (a by-product generated in the purification process of vegetable oil), 2.5 to 15 g of oxalic acid and 50 to 100 g of process water as a degumming catalyst are added, and then dark oil at 106°C for 60 minutes at normal pressure while stirring vigorously. Was degumming. The solution after degumming was transferred to a separatory funnel and held at 60° C. for 60 minutes to separate water generated in the lower layer. The amounts of reactants and products in the degumming step are shown in Table 1 below.

division Reactant product Dark oil
(g) Oxalic acid
(g) Process water
(g) Oxalic acid concentration
(%) Dark oil
(g) Separation water
(g) Example 1 1,000 2.5 50 5 906.6 139.2 Example 2 1,000 3.8 75 5 886.6 189.1 Example 3 1,000 5 100 5 894.7 199.4 Example 4 1,000 5 50 10 921.8 110.9 Example 5 1,000 7.5 75 10 962.8 115.5 Example 6 1,000 10 100 10 964.3 137.0 Example 7 1,000 7.5 50 15 900.5 157.0 Example 8 1,000 11.3 75 15 972.5 110.6 Example 9 1,000 15 100 15 966.5 142.2

Referring to Table 1, when dark oil is degumming with a certain amount of oxalic acid and process water, the yield of degumming dark oil ((degum dark oil (g)/dark oil (g)) * 100) is 88.6 to 97.3%. In particular, in Example 8 in which oxalic acid and process water were used at 11.3 parts by weight and 75 parts by weight, respectively, with respect to 100 parts by weight of dark oil, the yield of degumming dark oil was the highest at 97.3%.

(b) esterification reaction: glycerin ester production

Dark oil (degum dark oil obtained in Example 8 (Examples 8 to 10, acid value = 95 mgKOH / g), mitigum dark oil (Comparative Examples 1 to 5, acid value = 87 mgKOH / g)), glycerin And after the catalyst was added, nitrogen, an inert gas, was blown to avoid contact with air, and the esterification reaction was carried out while stirring at 200° C. and normal pressure for 6 hours while strongly stirring, and the acid value of the product was measured. The amounts and acid values of reactants and products in the esterification reaction are shown in Table 2 below.

division Reactant product Dark oil
(g) glycerin
(g) catalyst
(Kinds) catalyst
(g) product
(g) Acid
(mgKOH/g) Example 8 1,000 98 NaOH 1.4 989.2 2.1 Example 9 1,000 98 DBL-DL 0.2 981.6 0.7 Example 10 1,000 98 TnBT 0.2 1,009 2.7 Comparative Example 1 1,300 98 NaOH 2.8 1,284 1.6 Comparative Example 2 1,300 98 DBL-DL 0.5 1,268 1.5 Comparative Example 3 1,300 98 DBTO 0.5 1,273 3.1 Comparative Example 4 1,300 98 TnBT 0.5 1,277 2.8 Comparative Example 5 1,300 98 TDO 0.5 1,278 4.5

-NaOH: Sodium hydroxide

-DBT-DL: Dibutyltin dilaurate

-DBTO: Dibutyltin oxide

-TnBT: Tetra-N-butyl titanate

-TDO: Titanium dioxide

Referring to Table 2, the efficiency of the esterification reaction according to the Examples and Comparative Examples is shown to be similar, but in the case of the Example, it was found that similar efficiency was achieved with a small amount of dark oil compared to the Comparative Example, and the degumming dark oil of the Example was economical. , It can be seen that it is advantageous in terms of productivity.

(c) Transesterification reaction: production of fatty acid methyl ester

After adding the glycerin ester mixture (maintaining low acid value), methanol, and sodium methylate (SM, 30% methanol solution), which is a catalyst for the transesterification reaction, to a 2L four-neck flask with lowered acid value in step (b), and with strong stirring, 70℃ , After performing the first transesterification reaction at normal pressure for 2.5 hours, the stirring was stopped and the mixture was held for 1 hour to separate a mixture containing glycerin and methanol produced in the lower layer.

After adding sodium methylate (SM, 30% methanol solution) as a catalyst for the transesterification reaction to the unseparated mixture of the upper layer and the lower layer, the secondary transesterification reaction was carried out at 70°C and normal pressure for 1 hour with strong stirring. After the stirring was stopped and the mixture was held for 1 hour to separate the lower layer of glycerin, soap and methanol.

Here, the reason for separating the lower layer liquid after the first transesterification reaction is that when sodium methylate introduced as a catalyst in the second transesterification reaction reacts with the free fatty acid to generate soap, the remaining glycerin dissolves the soap and This is because it is possible to smoothly recover the solvent, distillation, water washing and dehydration, which are the subsequent processes by lowering the soap content in the fatty acid methyl ester (FAME) in the upper layer.

The mixture containing fatty acid methyl ester and methanol in the upper layer was heated to 110°C while stirring to recover residual methanol, and the residual methanol was recovered by heating to 150°C at 10 torr, and then heated to 230°C at a pressure of 3 torr or less to obtain fatty acid methyl. The ester was recovered. Washing water corresponding to 10% of the distilled fatty acid methyl ester was added, stirred at 60°C for 10 minutes, and then stopped to remove the washing water, and the temperature was raised from 10 torr to 110°C to remove moisture contained in the fatty acid methyl ester. The pure fatty acid methyl ester was recovered. The amounts of reactants and products in the first and second transesterification reactions are shown in Table 3 below, and the amounts of products according to distillation are shown in Table 4 below.

division 1st transesterification reaction Secondary transesterification reaction Keeping low acid prices
(g) Methanol
(g) SM
(g) Lower layer separation
(g) SM
(g) Upper floor
(g) substratum
(g) Example 8 989.2 250 23 120 2 954.7 49.9 Example 9 981.6 250 23 120 2 952.4 41.9 Example 10 1,009 250 23 120 2 927.3 102.4 Comparative Example 1 1,000 250 23 120 2 991.6 - Comparative Example 2 1,000 250 23 120 2 979 - Comparative Example 3 1,000 250 23 120 2 1,002.4 - Comparative Example 4 1,000 250 23 120 2 983.7 11.7 Comparative Example 5 1,000 250 23 120 2 998.4 4.8

division Upper distillation of products of secondary transesterification (FAME(g)/low acid price maintenance (g))*100
(%) FAME
(g, %) Residue
(g, %) Methanol loss
(g, %) Example 8 536.6
(56.2) 371.7
(38.9) 46.4
(4.9) 54.2 Example 9 603.6
(63.4) 312.6
(32.8) 36.2
(3.8) 61.5 Example 10 643.7
(69.4) 260.5
(28.1) 23.1
(2.5) 63.8 Comparative Example 1 107.3
(10.8) 869.3
(87.7) 15
(1.5) 10.7 Comparative Example 2 226.4
(23.1) 737.6
(75.3) 15
(1.5) 22.6 Comparative Example 3 224.5
(2.4) 762.9
(76.1) 15
(1.5) 22.5 Comparative Example 4 171.4
(17.4) 797.3
(81.1) 15
(1.5) 17.1 Comparative Example 5 185.6
(18.6) 797.8
(79.9) 15
(1.5) 18.6

Referring to Table 4, the yield of fatty acid methyl ester (FAME) with respect to the intermediate (glycerin ester) produced from degumming dark oil according to the Example is about 54.2-63.8%, which is about 50% or more, whereas comparison under the same conditions The yield of the fatty acid methyl ester according to the example was about 10.7 to 22.6%, and the effect of improving reactivity, productivity, and economy by degumming according to the present invention was more remarkable in the transesterification reaction.

(d) transesterification reaction: sorbitan fatty acid ester production

To a 1L 4-neck flask, add 360g of liquid sorbitol (70% aqueous solution) and 1.0g of hypophosphorous acid (HPA, 50% aqueous solution) as a color stabilizer, and then blow in nitrogen, an inert gas, at 140℃ while stirring to avoid contact with air. , Dehydration was performed at normal pressure for 3 hours. Here, 500 g of fatty acid methyl ester (FAME) recovered in Example 8 of step (c) was added and cooled, and then 0-50 g of sorbitan monooleate (SMO) and sodium methylate (SM, After adding 9.1 g of a 30% methanol solution) and 0.5 g of sodium hypophosphate (SHP), a transesterification reaction was performed at 230° C. and atmospheric pressure for 6 hours while vigorous stirring. Methanol flowing out through the reaction was quantified to check the reaction progress, and the amounts of reactants and products in the transesterification reaction are shown in Table 5 below.

When a fatty acid is used in the manufacture of sorbitan fatty acid ester, since the fatty acid has an inherent acid value, the progress of the transesterification reaction can be grasped by the acid value and the amount of reaction water generated, but when using fatty acid methyl ester, the acid value is about 0.5 Since it is very low in mgKOH/g, it is difficult to determine the progress of the transesterification reaction by measuring the acid value.

division Example 8 Example 11 Example 12 Example 13 Example 14 Sorbitol dehydration Liquid sorbitol
(g) 360 360 360 360 360 HPA
(g) 1.0 1.0 1.0 1.0 1.0 Dehydration
(mL) 108 108 111 111 111 Transesterification
reaction FAME
(g) 500 500 500 500 500 SMO
(g) 0 12.5 25 37.5 50 SM
(g) 9.1 9.1 9.1 9.1 9.1 SHP
(g) 0.5 0.5 0.5 0.5 0.5 product SMO
(g) 648.4 656.8 662.5 672.4 682.4 Methanol
(mL) 87 87 89 94 107 Hourly
Methanol
Generation
(mL) 0:00 20 19 17 18 19 0:30 32 26 29 31 37 1:00 42 37 43 48 55 1:30 52 49 58 59 71 2:00 60 59 69 68 81 2:30 67 65 76 76 88 3:00 74 71 79 82 94 3:30 78 76 81 85 98 4:00 81 80 84 88 100 5:00 85 85 88 91 104 6:00 87 87 89 94 107

Referring to Table 5, the amount of methanol produced after the reaction for 6 hours is 87 to 107 mL, and in particular, relative to Example 8 in the transesterification reaction conducted in the presence of a certain amount of sorbitan monooleate according to Examples 11 to 14. As a result, a lot of methanol was produced, indicating that sorbitan monooleate used as a surfactant further improved the reactivity, productivity, and economy of the transesterification reaction.

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

The scope of the present invention is indicated by the claims to be described later, and all changes or modified forms derived from the meaning and scope of the claims and the concept of equivalents thereof should be construed as being included in the scope of the present invention.

Claims (10)

(a) degumming by treating the oil and fat resources with an aqueous acid solution;
(b) reacting the degumming resource with a first alcohol in the presence of a first catalyst;
(c) reacting the product of step (b) with a second alcohol in the presence of a second catalyst; And
(d) dehydrating the liquid sorbitol and reacting with the product of step (c) in the presence of a third catalyst; and
The concentration of the acid aqueous solution is 5 to 20% by weight, a method for producing a sorbitan fatty acid ester. The method of claim 1,
The amount of the acid used is 0.1 to 2 parts by weight based on 100 parts by weight of the oil and fat resources, a method for producing a sorbitan fatty acid ester. The method of claim 1,
The first to third catalysts are respectively potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium peroxide, sodium peroxide, lithium peroxide, potassium carbonate, sodium carbonate, lithium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium hydrogen carbonate, potassium methylate , Sodium methylate, lithium methylate, potassium ethylate, sodium ethylate, lithium ethylate, potassium propylate, sodium propylate, lithium propylate, potassium butyrate, sodium butyrate, lithium butyrate, boron trifluoride, Titanium acrylate, tetrabutyl titanate, tetrapropyl titanate, titanium isopropoxide, aluminum isopropoxide, tin octoate, sodium acetate, calcium acetate, tin acetate, zinc acetate, antimony trioxide, butylstannic acid, mono Butyl tin hydrate, monobutyl chloro tin dihydroxide, stenos oxalate, dibutyl tin diacetate, dibutyl tin oxide, dibutyl tin dilaurate, dibutyl tin dimethoxide, dibutyl tin dibutoxide, titanium dioxide and among them One selected from the group consisting of a combination of two or more, a method for producing a sorbitan fatty acid ester. The method of claim 1,
The amount of the first catalyst used is 0.01 to 0.3 parts by weight based on 100 parts by weight of the degummed oil and fat resources, the method for producing a sorbitan fatty acid ester. The method of claim 1,
The first alcohol is a polyhydric alcohol, a method for producing a sorbitan fatty acid ester. The method of claim 1,
The acid value of the product of step (b) is 3mgKOH/g or less, a method for producing a sorbitan fatty acid ester. The method of claim 1,
The step (c),
(c1) after separating the first mixture produced by reacting the product of step (b) with a second alcohol in the presence of the second catalyst into a first supernatant and a first lower liquid, at least one of the first lower liquid Removing some;
(c2) after the second mixture produced by reacting the first supernatant in the presence of the additional second catalyst is stagnated and separated into a second supernatant and a second lower liquid, at least part of the second lower liquid is Removing; And
(c3) distilling the second supernatant; containing, a method for producing a sorbitan fatty acid ester. The method of claim 7,
In the steps (c1) and (c2), the amount of the second catalyst used is 1 to 5 parts by weight and 0.1 to 0.5 parts by weight, respectively, based on 100 parts by weight of the product of step (b). The method of claim 1,
The second alcohol is a monohydric alcohol, a method for producing a sorbitan fatty acid ester. The method of claim 1,
The step (d) is performed in the presence of a surfactant,
The amount of the surfactant used is 1 to 20 parts by weight based on 100 parts by weight of the product of step (c), a method for producing a sorbitan fatty acid ester.

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