KR20180126966A - method of obtaining fatty acids and manufactured ester oil from by-product of omega3 and engine oil including ester oil manufactured by the same - Google Patents

Abstract

The present invention relates to a method for acquiring purified fatty acid derived from omega-3 byproducts. More specifically, the present invention relates to a method for acquiring purified fatty acid derived from omega-3 byproducts, comprising the following steps: (1) adding an oil-repellent agent to the omega-3 byproducts to separate an upper organic layer; (2) saponifying the organic layer to separate fatty acid formed on the upper layer; (3) adding acid to the separated fatty acid to perform a neutralization reaction; and (4) after the neutralization reaction, separating and removing a lower water layer by adding the oil-repellent agent, and then recovering the oil-repellent agent to acquire purified fatty acid.

Description

TECHNICAL FIELD The present invention relates to a method for producing refined fatty acids derived from omega-3 by-products, and a method for producing an ester oil and an engine oil comprising the ester oil produced thereby the same}

The present invention relates to a method for synthesizing a fatty acid and an ester oil from a byproduct generated during the process of producing omega-3, and more particularly, to a method for producing a fatty acid by reacting a fatty acid with a polyhydric alcohol, The present invention relates to a process for producing omega-3 by-product purified fatty acids and a process for producing ester oil, which comprises synthesizing an ester oil which is high-quality oil which can be used for engine oil.

Omega-3 has shown that a German oriental herb has played an important role in reducing the heart disease and mortality of fatty acids (Omega-3) in omega-3s through the eating habits of Eskimos. Omega-3 is found in fish oil, plankton, seafood, soybean oil, and breast milk. It helps normal development especially in newborns and adolescents. Deficiency can lead to depression, schizophrenia, attention deficit hyperactivity disorder, , Heart disease, and the like, and it is known that stress can be increased. One of the important functions of omega-3 is to prevent platelets from sticking to the blood vessel wall. When a person's body is injured, the platelets become entangled to prevent the wound. When a wound is created in the blood vessel, it is entangled in the blood vessel wall and blocks the blood vessel. This causes stroke, cerebral infarction, angina pectoris, myocardial infarction, and so on. Omega-3 blocks platelet aggregation and reduces heart attack.

Examples of omega-3 fatty acids include alpha-linolenic acid (LNA), docosahexaenoic acid, also known as DHA, eicosapentaenoic acid (EPA), stearidonic acid (SDA) There is ETA (eicosatetraenoic acid). DHA is an important polyunsaturated fatty acid that constitutes the central nervous system and is important for the maintenance of brain and eye health. EPA has a powerful anti-cardiovascular function. Molecular structure of the cell membrane is very soft, faster information transmission and cell function is improved.

Omega-3 is becoming increasingly popular as a dietary supplement, and the demand for Omega-3 products is steadily increasing.

Therefore, the technology to manufacture omega-3 is also rapidly evolving. The main components of omega-3 are eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), and their standard contents are 18% EPA and 12% DHA, respectively.

Currently, we have reached a level of technology that can increase the purity of omega-3 by more than 50%, up to 99%, through supercritical extraction, supercritical chromatography, and distillation.

The main source of omega-3 are small blue fish with little contamination in the South Pacific. Fish oil is made by moving the fishes by boats, squeezing them under pressure, separating the solids, and separating the water and oil. Most of the oil is then used as animal feed after a polishing process that involves several washes with water. Some of these products are consumed by people. The bleaching and deodorizing process is carried out at 160 to 200 ° C. Triglyceride containing EPA and DHA in 18/12 is the raw material. When the raw materials are received, the Omega-3 manufacturing company will receive the raw materials and proceed with the refining process.

This process is costly, but it is a necessary process for producing higher quality oils. Typical fish oils contain 30% omega-3, but the remaining 70% contain ingredients such as saturated fatty acids, salts, heavy metals, alcohol and other processing chemicals.

Therefore, in order to obtain the omega-3 products that people ingest, the purification process must be included. At this time, saturated fatty acids and contaminants as by-products are discharged together with the washing water and are being disposed.

Korean Patent No. 10-1586029 Korean Patent No. 10-1357298

The present invention provides a method for obtaining omega-3 by-product purified fatty acid so as to synthesize an ester oil from by-products generated in the process of manufacturing omega-3 in order to solve the above problems. do.

Another object of the present invention is to provide a process for producing an ester oil derived from omega-3 by-products, which synthesizes an ester oil by synthesizing the obtained fatty acid and a polyhydric alcohol.

Another object of the present invention is to provide an engine oil containing an ester oil produced by the above method.

According to an aspect of the present invention,

(1) adding an oil-repellent agent to omega-3 by-products to separate the upper organic layer;

(2) saponifying the organic layer to separate the fatty acid formed in the upper layer;

(3) adding an acid to the separated fatty acid to neutralize the fatty acid; And

(4) after the neutralization reaction, adding a water repellent agent to separate and remove the lower water layer, and then recovering the oil repellent agent to obtain a purified fatty acid, which comprises obtaining omega-3 by-product purified fatty acid Method is provided.

According to another aspect of the present invention,

There is provided a method for synthesizing an ester oil derived from omega-3 by-products, which comprises esterifying an ester oil by adding a polyhydric alcohol to the fatty acid obtained by the above fatty acid obtaining method.

Further, in order to solve still another problem of the present invention,

There is provided an engine oil containing an ester oil produced by the method for synthesizing an ester oil.

The present invention relates to a process for producing an omega-3 by-product, which is environmentally friendly and which can reduce the disposal cost of the omega-3 by-product, since the ester oil can be synthesized by reacting the fatty acid with a polyhydric alcohol as well as a high- .

In addition, since the ester oil synthesized from the omega-3 by-product can be used as a high-performance ester lubricant for automobiles and industrial, it can compete with existing ester oils in terms of price.

1 is a flow chart showing the method for obtaining purified omega-3 by-product fatty acid of the present invention.

The present invention relates to a method for synthesizing a fatty acid and an ester oil from byproducts generated during the process of producing omega-3, and the present invention will be described in detail with reference to the accompanying drawings.

According to an aspect of the present invention,

(1) adding an oil-repellent agent to omega-3 by-products to separate the upper organic layer;

(2) saponifying the organic layer to separate the fatty acid formed in the upper layer;

(3) adding an acid to the separated fatty acid to neutralize the fatty acid; And

(4) after the neutralization reaction, adding a water repellent agent to separate and remove the lower water layer, and then recovering the oil repellent agent to obtain a purified fatty acid, which comprises obtaining omega-3 by-product purified fatty acid Method is provided.

1 is a flow chart showing the method for obtaining purified omega-3 by-product fatty acid of the present invention.

Referring to FIG. 1, in step (1), an oil-repellent agent is added to omega-3 by-products to separate an upper organic layer. This corresponds to the step (2) and the pretreatment step for the saponification reaction.

Specifically, the omega-3 by-product has an ammonia embrittlement state, and when the saponification reaction is performed for recovering saturated fatty acid in the state where the water is not removed due to the state of suspension in which water and oil are emulsified, There is a problem that arises. Accordingly, in the present invention, it is possible to prevent the generation of foam during the saponification reaction by separating the omega-3 by-product into a lower water layer and an upper organic layer by adding a water repellent agent to the omega-3 by-product in the step (1).

In addition, the separated upper organic layer is subjected to a filter treatment to remove impurities. In addition, residual moisture is removed through a moisture removing filter, and then acid clay is used to adsorb and filter impurities such as closterol And removed.

In addition, the step (1) is preferably carried out at 50 to 200 ° C, preferably at 70 to 100 ° C.

The oil repellent agent may be added in an amount of 0.001 to 1% by weight, preferably 0.01 to 0.1% by weight, based on the omega-3 by-product. The oil repellent agent may include hydrophilic and hydrophobic Is not particularly limited as long as it reduces the surface tension of one of water and oil to break the emulsification of water and oil, and the oil-water separator used in the refining process may be included therein.

Next, step (2) of the present invention is a saponification reaction step in which the organic layer is subjected to a saponification reaction to separate the fatty acid formed in the upper layer.

Specifically, in the step (2), a basic component is added to the organic layer to saponify the structure esterified with an alcohol into a basic substance, and the alcohol and the water layer (lower layer) .

At this time, the removal of the alcohol and the aqueous layer may be omitted, but it is preferable to remove the alcohol and the aqueous layer to prepare the purified fatty acid.

The basic component is not particularly limited as long as it is a substance used in the saponification reaction, but is preferably NaOH or KOH.

The saponification reaction temperature is 30 to 150 ° C, preferably 60 to 100 ° C. After the saponification reaction is completed, the saponification reaction is cooled to 50 ° C or less.

Next, step (3) of the present invention is a step of neutralizing the separated fatty acids.

Specifically, the step (3) is a step of adding an acid to the saponified fatty acid to neutralize it. In order to minimize heat generation, the acid added is an aqueous solution of 5 to 50%, preferably 10 to 40% .

In this case, the acid is not particularly limited, and after completion of the neutralization reaction, the pH is adjusted to 5 to 8, and the reaction is allowed to stand and cooled.

Next, in the step (4) of the present invention, after the neutralization reaction, a water-repellent agent is added to separate and remove the lower water layer, and then the water-repellent agent is recovered to obtain a purified fatty acid.

In detail, in the step (4), after the neutralization reaction is completed, a water repellent agent is added to separate the upper layer of the oil layer and the lower layer of the water layer, and the lower layer containing the brine is removed. Thereafter, the upper layer from which the aqueous layer (lower layer) has been removed is re-distilled to recover the water-wettable agent to obtain a purified fatty acid.

At this time, the water-repellent agent is not particularly limited, but is preferably n-hexane which is excellent in separability from water and low in boiling point and easy to be recovered.

Further, the fatty acid obtained at this time is characterized by being a saturated fatty acid.

According to an aspect of the present invention,

There is provided a process for producing an omega-3 by-product ester oil, characterized in that an ester oil is synthesized by adding a polyhydric alcohol to the fatty acid obtained by the above-mentioned fatty acid obtaining method to cause an ester reaction.

Specifically, the esterification reaction is characterized in that the fatty acid and the polyhydric alcohol obtained are reacted with each other under an acidic catalyst at a temperature of 100 to 250 ° C, preferably 150 to 200 ° C for 20 hours or less.

In this case, if the reaction time is within 20 hours, not only the production suitability but also the reaction time is longer than 20 hours, the ester oil may be thermally changed. Accordingly, a solvent which is azeotropic with water can be used for rapid reaction, and the reaction can be promoted by accelerating the removal rate of water with a device such as vacuum, but the present invention is not limited thereto.

Also, the polyhydric alcohol is not particularly limited and may be ethylene glycol, propylene glycol, glycerol, pentaerythritol entaerythritol, or sorbitol.

The acidic catalyst is not particularly limited, but is preferably an organometallic catalyst or an organic acid catalyst, and the content of the acidic catalyst is preferably 0.001 to 1.0% by weight.

Further, the acidic catalyst is more preferably characterized by containing a sulfonic acid group.

The catalyst containing the sulfonic acid group may be selected from the group consisting of p-xylene-2-sulfonic acid, methylene sulfonic acid dihydrate, benzenesulfonic acid, p-toluenesulfonic acid monohydrate p-toluenesulfonic acid monohydrate, dodecylbenzenesulfonic acid, 1-methyl-2-propynyl p-toluenesulfonate or 2-amino-1-naphthalenesulfonic acid (2-Amino-1-naphthalene sulfonic acid).

In the present invention, the ester oil produced by the above method has an acid value of not more than 0.5 mg KOH / g, preferably not more than 0.1 mg KOH / g, a hydroxyl value of not more than 10 mg KOH / g, preferably not more than 4 mg KOH / g Or less, and may further include an additive such as an antioxidant to improve physical properties.

According to an aspect of the present invention,

There is provided an engine oil including an ester oil produced by the method for producing an ester oil from the omega-3 by-product.

Specifically, the engine oil is prepared by using the ester oil and PAO produced according to the method for producing an ester oil from the omega-3 production by-products.

More specifically, an engine oil is prepared by using the ester oil, PAO, and various additives prepared from the omega-3 production by-products.

This is similar to that of the existing high-grade synthetic engine oil, which is produced from 5 to 30% of ester oil, 60 to 85% of PAO and 7 to 13% of various additives mixed with PAO because the cost of ester oil is high, The unit cost can be lowered by preparing the ester oil from omega-3 production by-products, and the ester oil is used at a maximum value of 30%.

In addition, the PAO base oil may be adjusted depending on the content of the ester oil and the additive in the range of 10 to 90%.

As the above-mentioned additive, 0.001 to 5% of an antioxidant or a corrosion inhibitor may be used for oxidation and thermal stability of the synthesized ester oil. In order to reduce the viscosity change due to the drop in viscosity and the temperature difference and to improve the viscosity index, 0.001 to 5% of a reducing agent or a viscosity improver may be used.

In case of oil contamination, it is possible to use 0.001 ~ 5% of detergent and dispersant to remove contaminants and 0.001 ~ 5% of defoamer to prevent air bubbles.

In addition, 0.001 to 5% of a wear-resistant agent or an extreme pressure agent can be applied to improve the wear resistance and the anti-polarity property.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Example

Example 1: Omega-3 by-product fatty acid was obtained

1 kg of omega-3 by-product was collected and put into a lower corrosion reactor. Thereafter, 0.1 wt% of Ethylene oxide-added nonyl phenol was added, the temperature was raised to 90 ° C, and the mixture was stirred for 1 hour and allowed to stand for 30 minutes.

When the layer was separated, the aqueous layer having the lower ammonia odor was removed, and the upper oil layer was recovered. The acid value was measured using a titrimetric method, and saponification reaction was carried out by adding 20% of NaOH to the equivalent amount. When the temperature of saponification reaction is low, the reaction may become hard due to the reaction, so that the whole reaction may be difficult. Therefore, the temperature is raised to 90 ° C and the viscosity is lowered to complete the reaction.

As the saponification reaction proceeds, the alcohol is recovered because the saturated fatty acid, a by-product, is discharged in a state of being bound to the lower alcohol.

When the saponification reaction was completed, the alcohol was not recovered any more. At this time, the neutralization reaction was performed while slowly injecting 30% hydrochloric acid aqueous solution into the dropping funnel in the same manner as the equivalent amount of the added NaOH. After the final addition was complete, the pH was measured to 5 to 8, and the reaction was allowed to settle and allowed to cool.

After the addition of 300 g of n-hexane, the lower salt layer was removed by stirring. The upper oil layer was heated to recover n-hexane by vacuum decompression at 60 ° C. The remaining organic acid was acid- And the mixture was stirred for 1 hour. Then, the remaining salt and cleesterol were adsorbed and separated by filtration to obtain a purified fatty acid.

<Example 2> Production of ester oil derived from omega-3 by-product

(1) Production of ester oil using omega-3 by-product fatty acid and TMP

3 moles of the purified fatty acid of Example 1 and 1.1 moles of trimethylolpropane (TMP) prepared from the purified omega-3 by-product having an acid value of 180 mg / KOH were introduced into a 2 liter reactor to obtain 0.05 wt. %, And the temperature was raised to 180 ° C to carry out the ester synthesis reaction.

At this time, the reaction proceeded and water was removed, and the degree of the reaction was confirmed by sampling the acid value at any time. The reaction was terminated when the acid value was 0.1 mg / KOH, and the reaction time was 18 hours.

The viscosity of the ester oil thus prepared was 46 cSt at 40 ° C and 9.4 cSt at 100 ° C. The pour point was -27 ° C and the flash point was 268 ° C.

(2) Production of ester oil using omega-3 by-product fatty acid and PE

4 moles of the purified fatty acid of Example 1 and 1.1 moles of pentaerythritol (PE) having a hydroxyl value of 4, which were prepared from purified omega-3 by-product having an acid value of 180 mg / KOH, were fed into a 2 liter reactor, %, And the temperature was raised to 180 ° C to carry out the ester synthesis reaction.

At this time, the reaction proceeded and water was removed, and the degree of the reaction was confirmed by sampling the acid value at any time. The reaction was terminated when the acid value was 0.1 mg / KOH, and the reaction time was 19 hours.

The viscosity of the prepared ester oil was 65 cSt at 40 ° C and 11 cSt at 100 ° C, and the pour point was -18 ° C and the flash point was 296 ° C.

Example 3 Production of engine oil using ester oil prepared in Example 2- (1)

15 wt% of the ester oil prepared in Example 2- (1), 60 wt% of PAO base oil, 15 wt% of engine oil additive additive pack (antiwear, detergent inhibitor etc.) and 10 wt% of viscosity improver, And physical properties were analyzed.

The engine oil thus produced was found to have a flash point of 235 ° C., viscosities at 40 ° C. and 100 ° C. of 79 cSt and 14 cSt, respectively, and a viscosity index of 183, .

Comparative Example

(1) Preparation of ester oil prepared with 2-ethyl hexanoic acid and TMP

3 mol of 2-ethylhexanoic acid and 1.1 mol of trimethylolpropane (TMP) were fed into a 2-liter reactor, and 0.05 wt% of an acid catalyst was added thereto. Respectively.

At this time, the reaction proceeded and water was removed, and the degree of the reaction was confirmed by sampling the acid value at any time. The reaction was terminated when the acid value was 0.1 mg / KOH, and the reaction time was 15 hours.

The viscosity of the ester oil thus prepared was 7 cSt at 40 ° C. and 2 cSt at 100 ° C. The pour point was -54 ° C. and the flash point was 198 ° C.

From the above results, it can be seen that an ester oil can be synthesized by using the omega-3 by-product to obtain a fatty acid.

In addition, the omega-3 by-product ester oil exhibits similar or improved physical properties as the ester oil synthesized using a commercially available fatty acid.

While the present invention has been described in connection with certain exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, And various modifications and variations are possible within the scope of the appended claims.

Claims (4)

(1) adding an oil-repellent agent to omega-3 by-products to separate the upper organic layer;
(2) saponifying the organic layer to separate the fatty acid formed in the upper layer;
(3) adding an acid to the separated fatty acid to neutralize the fatty acid; And
(4) after the neutralization reaction, adding a water repellent agent to separate and remove the lower water layer, and then recovering the water repellent agent to obtain a purified fatty acid, which comprises obtaining omega-3 by-product purified fatty acid Way.
The method according to claim 1,
The method for obtaining purified omega-3 by-product fatty acid according to claim 1, wherein the oil repellent agent in step (1) is contained in an amount of 0.001 to 1% by weight based on the omega-3 by-product.
A process for producing an ester oil derived from omega-3 by-product, which comprises the step of synthesizing an ester oil by adding a polyhydric alcohol to the fatty acid obtained according to the method of claim 1 or 2 to carry out an ester reaction.
An engine oil comprising an ester oil produced according to the process of claim 3.

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