KR102065466B1 - Alginic acid propylene glycol ester production method containing fucoxanthin and fucoidan with reduced off-flavor - Google Patents

Abstract

The present invention already relates to a process for producing alginic acid propylene glycol esters containing fucoxanthin and fucoidan with reduced off-flavor. More specifically, in extracting fucoxanthin and fucoidan with reduced off-flavor from brown algae containing seaweed, kelp, and shellfish, the fat-soluble pigment fucoxanthin and fucoidan, a water-soluble acidic polysaccharide, can be emulsified and kept in a stable state. This is for extracting by converting to alginate propylene glycol ester form, and converting fucoxanthin and fucoidan from brown algae to propylene glycol ester when extracting fucoxanthin and fucoidan without using organic solvent or stepwise solvent fractionation. Fucoxanthin, which is easy to be added and preserved without using additional emulsifiers and preservatives when it is added during the product manufacturing process, as it is accompanied by the increase, emulsification stability and preservative properties of propylene glycol alginate. Containing fucoidan Relates to a process for preparing alginic acid propylene glycol esters.

Description

Alginic acid propylene glycol ester production method containing fucoxanthin and fucoidan with reduced off-flavor {omitted}

The present invention already relates to a process for producing alginic acid propylene glycol esters containing fucoxanthin and fucoidan with reduced off-flavor. More specifically, in extracting fucoxanthin and fucoidan with reduced off-flavor from brown algae containing seaweed, kelp, and shellfish, the fat-soluble pigment fucoxanthin and fucoidan, a water-soluble acidic polysaccharide, can be emulsified and kept in a stable state. This is for extracting by converting to alginate propylene glycol ester form, and converting fucoxanthin and fucoidan from brown algae to propylene glycol ester when extracting fucoxanthin and fucoidan without using organic solvent or stepwise solvent fractionation. Fucoxanthin, which is easy to be added and preserved without using additional emulsifiers and preservatives when it is added during the product manufacturing process, because it is accompanied by the increase, emulsification stability and preservative properties of propylene glycol alginate. Containing fucoidan Relates to a process for preparing alginic acid propylene glycol esters.

Alginate is a kind of seaweed polysaccharide, which is composed of aL-gluronate [G] and β-D-manruronate [M], and homopolymer block of MM block and GG block. Or heteropolymer blocks, such as MG blocks, are alternating polysaccharides composed of a-1,4 or β-1,4 bonds.

The alginate has a property of forming a gel when reacted with a metal ion. Such a gel has a property of adsorbing a metal ion. The reaction zone where alginate binds to metal ions is known to form a three-dimensional network gel by combining metal ions between the carboxyl groups of uronic acid, which is a component of alginate. The metal ions between the polyguluronic acid segment (G) of the alginate salt and the polymannuronic acid segment (M) form a crosslink to form a network structure, and uronic acid. It is reported that the array type of is related to the metal ion binding ability, and the lower the M / G ratio, the better the removal ability of heavy metals.

In addition, alginate can be used as an anti-tumor agent, wound healing agent, and medicinal agents such as wound dressings. Particularly, alginate can be used as a wound dressing, firstly, alginic acid forms a hydrophilic gel to quickly absorb body fluids. In addition, even when adhering to the wound, the addition of saline to the coating material converts insoluble calcium salts into soluble sodium alginate, which facilitates peeling. Third, the fibers remaining on the wound have biodegradation properties.

Therefore, in recent years, it has been applied chemically in various fields by using these advantages of alginic acid, and researches are being conducted to prepare alginate as a gel to use as an enzyme stabilizer or to prepare a film formulation and a capsule. . In addition, the function of alginate as a dietary fiber is known, and alginate is also used as a dietary supplement by applying that it has the property of releasing harmful metals in vitro by combining with harmful metals.

Fucoidan is a major polysaccharide that forms brown algae with laminaran and alginate, and is contained in kelp and seaweed 3 to 5%. Fucoidan is a sulfated heteropolysaccharide, containing galactose, mannose, xylose, glucuronic acid, etc., mainly having L-fucose as a-1,2 or a-1,3 bond. In addition, fucoidan has been reported to have the pharmacological efficacy exhibited in polyanionic charges, for example anticoagulant, anti-cancer, anti-virus (anti- HIV (including HIV), anti-tumor, immune function improvement, antioxidant effects are known.

On the other hand, fucoxanthin is one of the most carotenoid compounds present on the earth, accounting for about 10% of the total carotenoid compounds. Fucoxanthin is a compound that contains a variety of biological activities. To date, various biological activities of fucoxanthin have been identified through cell experiments and animal experiments. For example, the antioxidant, anti-inflammatory, anti-cancer, hepatoprotective, antidiabetic and antihyperlipidemic activities of fucoxanthin have been identified by various researchers. Others include skin protection, angiogenesis inhibition, bone protection, eye protection and antimalarial activity. Effects have been reported. In addition, the most actively studied field among the various physiological activities of fucoxanthin is the anti-obesity effect. In other respects, the anti-obesity effect of fucoxanthin is one of the most obvious physiological activities, and it is the most commercially challenging field for product development.

Investigating the current industrially developed products related to fucoxanthin, most of them reduce body fat in relation to the anti-obesity effect. The raw materials of these products are mainly brown seaweed such as kelp and seaweed. The form of fucoxanthin added to the product is brown algae extract.

Propylene glycol alginate (PGA) is a propylene glycol ester of alginic acid, a mixed polymer of D-mannuronic acid and L-guluronic acid units, the ratio of which depends on the specific seaweed extracted. The chemical formula of propylene glycol alginate is (C ₉ H ₁₄ O ₇ ) _n , and the chemical structure is shown in FIG. 2. Its properties are white to yellowish, slightly coarse or fine powder, odorless and almost tasteless. The molecular weight is (243) _n , _n is from 100 to 800, insoluble in alcohol, chloroform, benzene and petroleum ether, and becomes a colloidal solution viscous in cold water and hot water, and stable at pH 3-4.

Propylene Glycol Alginate The standard for use is propylene glycol alginate, which is set at 1% or less of food, and can be used for various foods. In Korea, as a food additive designated before 1975, standards are established in Japan, the United States, the EU, and Codex.

Conventionally, fucoxanthin or fucoidan and alginic acid are extracted from brown algae as a single substance and used for research and industrial purposes. Fucoxanthin is a fat-soluble carotenoid pigment, and fucoidan is a water-soluble acidic polysaccharide. Because of their fat-soluble and water-soluble solubility characteristics, they had to be accompanied by emulsifiers when added to the product. In addition, fucoxanthin has been used mainly for research purposes because it is extracted using an organic solvent and separated and purified using a stepwise solvent fraction and a chromatographic fraction. The barrier of commercial economics is high in the commercial market development.

Prior art document: Republic of Korea Patent Publication No. 2015-0010034 (2015.1.28 published)

The present invention has been made to solve the above problems, by converting fucoxanthin and fucoidan from brown algae to alginic acid propylene glycol ester when extracting fucoxanthin and fucoidan without using organic solvent or stepwise solvent fractionation process. Fucoxanthin, which is easy to be added and preserved without using additional emulsifiers and preservatives when it is added during the product manufacturing process, as it is accompanied by the increase, emulsification stability and preservative properties of propylene glycol alginate. It is an object of the present invention to provide a method for preparing alginic acid propylene glycol ester containing fucoidan.

Alginate propylene glycol ester production method containing fucoxanthin and fucoidan with reduced off-flavor according to the present invention in order to achieve the above object is to wash the seaweed with water to remove salt, dried and ground to prepare in powder form Raw material preparation step; Crude extract extraction step of extracting a crude extract containing fucoxanthin, fucoidan, and alginic acid by performing a hydrolysis of the raw material under a base catalyst; A first filtration step of removing unreacted residue remaining in the hydrolyzate in the crude extract extraction step; Crude extract crystallization step of inducing crystallization of alginic acid by adding citric acid to the alkaline hydrolyzed crude extract filtered in the first filtration step; A water content control step of filtering the crystallization reactant in the crude extract crystallization reaction step to compress the filtered crystal sludge to control a predetermined moisture content within; Deodorization and washing step of adding the anti-solvent including ethanol to the crystalline sludge of the water content control step to convert the water, neutral salts, odor components, chlorophyll into the anti-solvent layer to perform deodorization and washing; A second filtration step of filtering the crystal sludge having undergone the deodorization and washing step to remove the antisolvent and to obtain a crystallization product; Alginic acid propylene glycol esterification step of performing esterification by adding citric acid and propylene glycol to the crystallization recovered in the second filtration step; A third filtration step of filtering the ester reactant of the alginic acid propylene glycol esterification step to remove unreacted material and obtaining an esterified crystallization product; Drying and pulverizing the dry pulverized esterified crystallization of the third filtration step; And a powder obtaining step of obtaining the powder in the drying and grinding step.

In addition, the crude extract extraction step may include that the amount of addition of potassium hydroxide (KOH) relative to the amount of the raw material is 0.5% or more and 2% or less.

In addition, the crude extract crystallization step may include that the amount of the citric acid added to the amount of the raw material is 0.5% or more and 10% or less.

According to the present invention, in extracting fucoxanthin and fucoidan with reduced off-flavor from brown algae containing seaweed, kelp, and oyster, the fat-soluble pigment fucoxanthin and the water-soluble acidic polysaccharide fucoidan are emulsified to maintain a stable state. This is for extracting by converting to alginate propylene glycol ester form, and converting fucoxanthin and fucoidan from brown algae to propylene glycol ester when extracting fucoxanthin and fucoidan without using organic solvent or stepwise solvent fractionation. It can be extracted, and is accompanied by the increase and emulsification stability and antiseptic properties of propylene glycol alginic acid, it is effective in the addition and preservation without the use of separate emulsifiers and preservatives when added during the product manufacturing process.

1 is a flow chart of a method for preparing alginic acid propylene glycol ester containing fucoxanthin and fucoidan, which has already been reduced in odor, according to a preferred embodiment of the present invention.
2 is a chemical structure of propylene glycol alginic acid, and
Figure 3 is a chemical formula showing the conversion process of the alginic acid propylene glycol ester of the alginic acid propylene glycol ester production method containing fucoxanthin and fucoidan reduced odor according to a preferred embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. First, in adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible, even if shown on different drawings. In addition, in describing the present invention, if it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted. In addition, the following will describe a preferred embodiment of the present invention, but the technical idea of the present invention is not limited thereto and may be variously modified and modified by those skilled in the art.

1 is a flow chart of a method of preparing alginic acid propylene glycol esters containing fucoxanthin and fucoidan with reduced off-flavor according to a preferred embodiment of the present invention (S1000), FIG. 2 is a chemical structure of propylene glycol alginate, and FIG. According to a preferred embodiment of the present invention, the alginate propylene glycol ester conversion process of the alginic acid propylene glycol ester production method (S1000) containing fucoxanthin and fucoidan with reduced off-flavor is shown.

Referring to Figure 1, already, the alginate propylene glycol ester production method (S1000) containing fucoxanthin and fucoidan reduced odor is a raw material preparation step (S10), crude extract extraction step (S20), the first filtration step (S30) ), Crude extract crystallization reaction step (S40), water content control step (S50), deodorization and washing step (S60), second filtration step (S70), alginic acid propylene glycol esterification step (S80), third filtration step (S90), drying and pulverizing step (S100), and comprises a powder obtaining step (S110).

Hereinafter, the raw material preparation step (S10) will be described in detail.

Raw material preparation step (S10) is a step of washing the brown algae, including seaweed, kelp, and 로 with water to remove the salt, dried and ground to prepare in powder form.

Crude extract extraction step (S20) is a crude material containing fucoxanthine, fucoidan, and alginic acid by hydrolyzing the raw material under a base catalyst for 1 hour or more and 20 atmospheres or less, 80 ° C or more and 150 ° C or less for 1 hour or more and 2 hours or less. Extract the extract.

In addition, it is preferable to use potassium hydroxide (KOH) as the base catalyst of the crude extract extraction step (S20), and the weight of potassium hydroxide (KOH) relative to the weight of the raw material is added to 0.5% or more and 2% or less.

In particular, in the crude extract extraction step (S20), when the hydrolysis temperature is lower than 80 ℃, the diffusion rate of water into the raw material is slow, the hydrolysis reaction rate is reduced, and when the temperature is higher than 150 ℃, the hydrogen ion concentration of water increases Since the exchange capacity of alkali ions decreases, the hydrolysis reaction rate decreases, so that the hydrolysis proceeds at 80 ° C. or higher and 150 ° C. or lower.

In addition, in the crude extract extraction step (S20), the hydrolysis time is less than 1 hour, the progress of hydrolysis can be reduced, the hydrolysis yield can be reduced, and if more than 2 hours, peroxidation reaction and carbonization by prolonged heating exposure of the raw material The reaction proceeds and there is a risk of generating peroxide or carbide, and it is preferable to proceed for 1 hour or more and 2 hours or less.

In addition, potassium hydroxide (KOH), which is a base catalyst in the crude extract extraction step (S20), when less than 0.5% of the raw material weight is added, the swelling rate due to the hydration reaction of alginic acid decreases, so that Extraction yield is inhibited due to degradation of resolution, and when added in excess of 2%, swelling by the hydration reaction of alginic acid contained in the raw material rises sharply, requiring more than 20 times the amount of water compared to the amount of raw material. It is preferred to add it at 2% or less.

The first filtration step (S30) is to remove the unreacted residue remaining in the hydrolyzate in the crude extract extraction step (S20).

The unreacted residue refers to ash and insoluble fiber, which do not participate in hydrolysis.

In the crude extract crystallization reaction step (S40), citric acid is added to the alkaline hydrolyzed crude extract filtered in the first filtration step (S30) to induce crystallization of alginic acid.

In addition, in the crude extract crystallization reaction step (S40), it is preferable that the addition weight of citric acid to the raw material weight is 0.5% or more and 10% or less.

More specifically, when the citric acid addition weight to the raw material weight is less than 0.5%, the crystallization reaction does not occur due to the high degree of hydration of alginic acid, the crystal growth rate in the recrystallization step of alginic acid when the amount of citric acid addition to the raw material amount is more than 10% It is preferable to increase the amount of citric acid to 0.5% or more and 10% or less relative to the amount of the raw material because the amount of the citric acid increases rapidly due to the increase of the crystal size and the surface area of the crystal interface.

In the water content control step (S50), the crystallization reactant of the crude extract crystallization reaction step (S40) is filtered to compress the filtered crystal sludge to control a predetermined moisture content within.

More specifically, the water content is preferably controlled to 40% or more and 80% or less. If the water content is less than 40%, the dehydration of the crystallization reactant has a very high compression load, which increases the time of the filtration compression process and increases the production rate. This is because when the water content exceeds 80%, the use of the antisolvent is increased in the next step of deodorization and washing (S60).

Deodorization and washing step (S60) is added to the anti-solvent containing ethanol to the crystalline sludge of the water content control step (S50) to convert the water, neutral salts, odor components, and chlorophyll to the anti-solvent layer to perform deodorization and washing do.

In addition, in the deodorization and washing step (S60), ethanol acts as an antisolvent for the crystalline sludge and cannot dissolve or solubilize fucoxanthin, fucoidan, alginic acid, and the like, and the water, neutral salts, odors, and chlorophyll remaining in the crystallized sludge. And the like can be selectively dissolved and converted to an antisolvent layer.

In addition, if the amount of water in the crystallized sludge is less than 50% in the deodorizing and washing step (S60), it does not act as an anti-solvent, and is formed as a simple mixture, and has a significant effect when the amount of water in the crystallized sludge exceeds 500%. Since there is no deodorizing and washing step (S60), the amount of water in the crystallized sludge is preferably controlled to 50% or more and 500% or less.

In the second filtration step (S70), the crystal sludge from which the deodorization and washing step (S60) is performed is filtered to remove the antisolvent to obtain a crystallized product.

Referring to Figure 3, it shows a process of converting the alginic acid propylene glycol ester using alginic acid and propylene glycol, alginic acid propylene glycol esterification step (S80) is citric acid recovered in the crystallization recovered in the second filtration step (S70) And propylene glycol is added to carry out the esterification reaction.

In addition, the citric acid added in the alginate propylene glycol esterification step (S80) is preferably added at least 1% to less than 10% of the weight of the crystallization, when the amount of citric acid is less than 1% of the crystallization relative to the weight of the crystallization ester This is because the rate and conversion rate of the polymerization reaction is lowered, and when it is more than 10% of the crystallization rate, the initial reaction rate of esterification is increased, but the esterification reaction is terminated prematurely by inducing hardening of propylene glycol, thereby lowering the conversion rate.

In addition, the molecular weight of the alginic acid monomer is about 388g / mol, propylene glycol is 76g / mol, the molar ratio of the esterification reaction of propylene glycol alginate is 1: 1 mol. Therefore, the required esterification reaction of propylene glycol to alginic acid according to the minimum reaction mole ratio is 0.196 g per 1 g of alginic acid, which corresponds to about 20% mass ratio.

Accordingly, the amount of propylene glycol added in the alginate propylene glycol esterification step (S80) is preferably 20% or more and 120% or less, and the amount of propylene glycol added to alginic acid is greater than or equal to the minimum reaction mole ratio to alginic acid. If it exceeds 120%, there is no significant effect, and it is not desirable to increase the amount of propylene glycol to be removed after the reaction ends.

In the third filtration step (S90), the ester reactant of the alginic acid propylene glycol esterification step (S80) is filtered to remove the unreacted material to obtain an esterified crystallization product.

Drying and grinding step (S100) dry grinding the esterified crystallization of the third filtration step (S90).

Powder obtaining step (S110) to obtain the powder in the drying and grinding step (S100).

-Example-

1> Raw material preparation step (S10): washed with seaweed to remove salt, dried and pulverized to prepare 100g in the form of a powder.

2> crude extract extraction step (S20): 1 g of KOH and 2 L of purified water were added to 100 g of brown seaweed powder, and the mixture was stirred at 100 ° C. at 60 rpm for 1 hour to hydrolyze.

3> First filtration step (S30): The unreacted residue remaining in the hydrolyzed extract was filtered to obtain 1600 ml of seaweed alkali hydrolyzate.

4> Crude extract crystallization step (S40): 5 g of citric acid was added to 1600 ml of seaweed alkaline hydrolyzed crude extract to adjust the hydrogen ion concentration to pH 3 and stirred at 80 ° C. at 60 rpm for 1 hour.

5> Moisture content control step (S50): The crystallization reactant was filtered to compress the filtered crystal sludge to control the moisture content within 50%. The crystal sludge obtained at this time was 50 g.

6> Deodorization and washing step (S60): 50 g of the crystal sludge was added to 100 g of antisolvent (95% ethanol), stirred at 72 rpm at 60 ° C for 1 hour, and then deodorized and washed for 1 hour to remove moisture, neutral salts, odors, chlorophyll, etc. Was converted to an ethanol layer.

7> Second filtration step (S70): The deodorized / washed crystal sludge was filtered to remove the anti-solvent (95% ethanol) to obtain 25g of crystallization.

8> Alginate Propylene Glycol Esterification Step (S80): 0.75 g of citric acid was dissolved in 60 g of propylene glycol in 25 g of the recovered crystalline product, and 20.25 g were added three times every 20 minutes, followed by stirring at 120 ° C. at 60 rpm. The ester reaction was carried out for a total of 1 hour.

9> Third filtration step (S90): The ester reactant was filtered to remove unreacted material to obtain 55 g.

10> Drying and grinding step (S100), powder obtaining step (S110): Drying and grinding the esterified crystallized to give an alginate propylene glycol ester powder containing 30g fucoxanthin and fucoidan.

The above description is merely illustrative of the technical idea of the present invention, and various modifications, changes, and substitutions may be made by those skilled in the art without departing from the essential characteristics of the present invention. will be. Accordingly, the embodiments disclosed in the present invention and the accompanying drawings are not intended to limit the technical spirit of the present invention but to describe the present invention, and the scope of the technical idea of the present invention is not limited by the embodiments and the accompanying drawings. . The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present invention.

S10-raw material preparation step
S20-crude extract extraction step
S30-first filtration step
S40-crude extract crystallization reaction step
S50-moisture content control step
S60-Deodorization and Cleaning Steps
S70-second filtration step
S80-Alginic Acid Propylene Glycol Esterification Step
S90-third filtration step
S100-Drying and Grinding
S110-powder obtaining step
S1000-Alginic acid propylene glycol ester preparation containing fucoxanthin and fucoidan with reduced odor

Claims (3)

Washing the seaweed with water to remove salt, drying and pulverizing to prepare a raw material in powder form;
Crude extract extraction step of extracting the crude extract containing fucoxanthin, fucoidan, and alginic acid by performing a hydrolysis of the raw material under a base catalyst containing potassium hydroxide (KOH);
A first filtration step of removing unreacted residue remaining in the hydrolyzate in the crude extract extraction step;
Crude extract crystallization reaction step of inducing crystallization of alginic acid by adding citric acid to the alkali hydrolysis crude extract filtered in the first filtration step;
A water content control step of filtering the crystallization reactant in the crude extract crystallization reaction step to compress the filtered crystal sludge to control a predetermined moisture content within;
Deodorization and washing step of adding the anti-solvent containing ethanol to the crystalline sludge of the water content control step to convert the water, neutral salts, odor components, chlorophyll to the anti-solvent layer to perform deodorization and washing;
A second filtration step of filtering the crystal sludge having undergone the deodorization and washing step to remove the antisolvent and to obtain a crystallization product;
Alginic acid propylene glycol esterification step of performing esterification by adding citric acid and propylene glycol to the crystallization recovered in the second filtration step;
A third filtration step of filtering the ester reactant of the alginic acid propylene glycol esterification step to remove unreacted material and obtaining an esterified crystallization product;
A drying and grinding step of dry grinding the esterified crystallization of the third filtration step; And
Powder obtaining step of obtaining powder in the drying and grinding steps
Alginic acid propylene glycol ester production method comprising the fucoxanthin and fucoidan already reduced odor. The method of claim 1
The crude extract extraction step
Addition weight of potassium hydroxide (KOH) to raw material weight is 0.5% or more and 2% or less
Alginic acid propylene glycol ester production method comprising the fucoxanthin and fucoidan already reduced odor. The method of claim 1,
The crude extract crystallization step
Addition weight of citric acid to raw material weight is 0.5% or more and 10% or less
Alginic acid propylene glycol ester production method comprising the fucoxanthin and fucoidan already reduced odor.

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