JPS5971301A - Preparation of polysaccharides - Google Patents

Abstract

PURPOSE:To prepare a polysaccharide useful as a gelatinizing agent for producing foods, emulsifying agent, drugs, etc. easily, inexpensively, in high quality, by bringing a dilute aqueous solution containing a polysaccharide into contact with a porous polymer, adsorbing the polysaccharide on it, concentrating it. CONSTITUTION:An aqueous solution (e.g., an aqueous solution obtained by powdering the rind of citrus fruits, strained lees of fruit juice, fruits, seaweeds, arthropods, Crustacea, the outer layer of skin of insects, etc., followed by extracting it) containing a polysaccharide (e.g., pectin, carrageenan, chitosan, etc.) is brought into contact with a porous polymer, the polysaccharide is adsorbed selectively, the porous polymer is brought into contact with a smaller quantity of a polysaccharide-soluble eluant (e.g., an aqueous solution of NaOH, KOH, etc.) than that of a medium in the aqueous solution, the polysaccharide is eluted from the porous polymer, concentrated, and prepared. A porous polymer having >=5m<2>/g specific surface area and >=0.2cc/g pore volume of 200-10,000Angstrom pore diameter is preferably as the porous polymer.

Description

[Detailed description of the invention] The present invention relates to a method for producing polysaccharides.

More specifically, the porous polymer (B) is brought into contact with a dilute aqueous solution containing polysaccharides (A), and after the polysaccharides are selectively adsorbed onto (B), the polysaccharides are removed using an eluent. This invention relates to a method for producing concentrated polysaccharides by eluating and concentrating polysaccharides.

Polysaccharides, such as plant polysaccharides, animal polysaccharides, and microbial polysaccharides, are widely distributed in large amounts in the living world. Chemically, there are polysaccharides of significantly different compositions.

Due to their unique gel-forming ability, pectin and carrageenan are not only used as gelling agents in the production of foods such as jelly and jam, but also as emulsifiers in the production of foods such as mayonnaise and ice cream. It is also used as a water retention agent for bread, as an anti-aging agent, as a coating agent for sugar and frozen products, and in other pharmaceutical fields.

Pectin exists as a component of the cell membranes of plants such as fruits and vegetables, and is found in the juice lees of citrus fruits, apples, beets, etc., and carrageenan exists as a component of the cell membranes of red algae such as Tsunomata, Suginori, and Kirincho. It is produced from these seaweeds.

Pectin and carrageenan are produced by a method in which the juice residue of citrus fruits, apples, beets, etc., and red algae and seaweed are extracted with an aqueous solution, the extract is then heated and concentrated, and then pectin and carrageenan are coagulated. There is.

Furthermore, general methods for producing these polysaccharides will be explained in detail using pectin as an example.

Traditionally known pectin production methods include citrus fruits, apples,
After washing the shredded juice lees such as heat, extract the protopectin by hydrolysis with mineral acid, filter it and remove the extracted lees, neutralize the obtained pectin extract, and then distill the water by heating. A ferric chloride group is added to the solution or extract to precipitate it as a metal salt of pectin, which is then desalted, and the concentrated solution is treated with a bath medium such as ethyl alcohol, methyl alcohol, isopropyl alcohol, or acetone. Generally, a method is adopted in which pectin is coagulated by adding pectin, and the coagulated product is dried to form powdered pectin. In Europe, America, and Eastern Europe, the above method is commonly used, but in Japan it has not yet been industrialized and all imported products are used. In Japan, a large amount of juice residue from mandarin oranges, beets, etc., which is a raw material for pectin, is produced as a by-product, and these peels are used as feed,
Pectin is only used for fuel, amino acid fermentation using molasses raw material, etc., and pectin has not been industrialized.

The main reason for this is the high cost of the manufacturing technology, especially the process of concentrating the extract.

That is, concentration by water distillation method is 0.1 to 0.5% by weight.
It is necessary to concentrate the pectin extract containing pectin to a pectin concentration of about 3 to 5% by weight, which has the drawback of requiring a huge amount of energy for concentration, and the addition of ferric chloride etc. to the extract. The method of precipitating the metal salt of pectin and then desalting it has disadvantages in that the metal salt such as ferric chloride is expensive and requires complicated treatment for desalting treatment. The production of polysaccharides other than pectin, such as carrageenan, has the same drawbacks as pectin.

In view of these circumstances, the present inventors have conducted extensive research to produce polysaccharides that can be easily and inexpensively concentrated and have excellent quality. As a result, the porous polymer efficiently absorbs polysaccharides. They have discovered that it can be attached and detached, and have completed the method of the present invention.

That is, in the present invention, an aqueous solution containing a polysaccharide is brought into contact with a porous polymer, the polysaccharide is adsorbed onto (]3), and then the polysaccharide-adsorbed porous polymer is brought into contact with a porous polymer containing a polysaccharide. Provided is a method for producing a polysaccharide, which comprises contacting the polysaccharide with a polysaccharide-soluble eluent in a smaller amount than the medium in the aqueous solution (A) to elute and concentrate the polysaccharide from the polysaccharide-adsorbing porous polymer. It is in.

The polysaccharide of the present invention is in contact with the porous polymer (B)03)
There is no particular restriction on the compound as long as it contains carbohydrates, so-called glycans, as one of its molecular components, which are produced by dehydration condensation of two or more molecules of monosaccharides adsorbed by glycosidic bonds, but generally maltose, cellobiose, saccharose, and lactose are used. , gentiobiose, cellobiose, octa-O-acetylgentiobiose and other disaccharides and their derivatives, carrageenan, farcelan, pectin,
Single polysaccharides such as chitosan, dextran, elephant palm mannan, xylan, pectic acid, alginic acid, and chalonine; complex polysaccharides such as guaran, konjac mannan, heparin, chondroitin sulfate, hyaluronic acid, santancum, arahya gum, karaya gum, and guar gum. , p-aminophenacylcellulose ether, p-aminophenazoyl, ruboxymethyl cellulose ester, carboxymethyl cellulose, cellulose hydrazide, tri-methyl starch, carboxymethyl starch and other polysaccharide derivatives, covalent bonds with other polysaccharides, Due to ionic bonds, etc., compounds such as glycolipids, glycosides, and mixtures of these polysaccharides such as ceramide trihexoside, ceramide dihexoside, and fucoganglioside can be bonded to other sugar or non-saccharide components. Preferable examples include pectin, carrageenan, and chitosan.

Aqueous solutions containing these polysaccharides can be obtained by extraction from citrus peels, fruit juice dregs, fruits, seaweed, or the epidermis of arthropods, crustaceans, insects, and the like.

Examples of the porous polymer (B) that adsorbs polysaccharides used in carrying out the method of the present invention include diurnal polymers represented by B, E, and T. More specifically, commercially available porous polymers Sumikaion KA-800, Sumikaion KA-850
Sumikaion KA-890, Sumikilate 81c-90
SUMINALATE Q-10, SUMIKYLATE MC-50 SUMIKYLATE HQ-20 (trade name manufactured by Sumitomo Chemical Co., Ltd.) Teniolite S-861, Teniolite ES-862 Teniolite ES-863, Teniolite ES-866 Teyuolite S-37 (trade name manufactured by Diamond Jam Rock Co., Ltd.) Examples include commercially available porous polymers such as (trade name).

It is completely unexpected that polysaccharides in a water bath solution can be adsorbed using such porous polymers, and that a concentrated polysaccharide-containing aqueous solution can be produced by elution. child.

In carrying out this investigation method, an aqueous solution containing polysaccharides (Δ
) and the porous polymer (B) can be brought into contact by selecting appropriate conditions. The contact method is not particularly limited5, and the porous polymer (Bl) is mixed with an aqueous solution containing polysaccharides (A
) and stirring or shaking contact treatment, or passing an aqueous solution containing the polysaccharide through a column filled with the porous polymer (B) are preferably employed.

In implementing the method of the present invention, the amount of porous polymer used and the contact time are not particularly limited, and the concentration of polysaccharide in the aqueous F6 liquid (A) containing the polysaccharide to be treated, The pH of the aqueous solution varies depending on the volatilization frequency of the porous polymer (13) and the pH value of the aqueous solution, but this can be determined by conducting appropriate preliminary experiments.

The amount of the porous polymer (B) used is generally 10 to 10% of the polysaccharide INN in the polysaccharide-containing water bath liquid (A).
000 parts by weight of the porous polymer (B) and the contact time is generally from 1 minute to 24 hours. The contact temperature between the polysaccharide-containing aqueous solution (A) and the porous polymer (B) is not particularly limited, but it is usually carried out at a temperature of 0 to 1'00°C.

The porous polymer that has adsorbed the polysaccharide from the polysaccharide-containing aqueous solution (A) by the above method is then contacted with an eluent to elute the polysaccharide from the porous polymer that has adsorbed the polysaccharide. .

Such eluents include sodium hydroxide, magnesium hydroxide, potassium hydroxide, pyridine, aniline,
N,N-dimethylaniline, guanidine, guanidine hydrochloride, monochloroacetic acid, trichloroacetic acid, oxalic acid, citric acid4. Examples include organic bath media or aqueous solvents containing dimethyl sulfoxide, urine sulfoxide, phenol, and the like.

These eluents vary depending on the type of polysaccharide and porous polymer (B
) Since the vulgarity differs depending on the type, etc., preliminary experiments are conducted as appropriate to make a selection, but in general, sodium hydroxide,
Caustic alkaline water PM such as potassium hydroxide, magnesium hydroxide, calcium hydroxide, etc. is preferably used.

The amount and contact time of these eluents are not particularly limited, but will vary depending on the amount of polysaccharide adsorbed to the porous polymer, the type of porous polymer, the type of eluent, and the concentration of the eluent. However, this can be determined by conducting appropriate preliminary experiments.

In general, as a dispersing agent, 1 to 2 oxm parts of 0.5 to 4 N caustic alkali may be brought into contact with one weight of the polysaccharide-adsorbing porous polymer, and the contact time is generally 1 minute to 24 hours.

Further, the contact temperature between the polysaccharide-adsorbing porous polymer and the eluent is not particularly limited, but it is generally carried out at room temperature, ranging from 0 to 100°C.

The polysaccharide eluent eluted from the polysaccharide-adsorbed porous polymer is
It can be used repeatedly as an eluent to increase the polysaccharide content in the eluent.

The polysaccharide eluate separated from the polysaccharide-adsorbing porous monopolymer by the above method Iζ can contain polysaccharides that are 10 times or more concentrated compared to the polysaccharide concentration in the liquid to be treated. The concentration step of the known method does not need to be performed again and can be carried out without heat treatment as in conventional concentration methods, which is preferable in terms of polysaccharide quality.

Such polysaccharide elution dust is then subjected to coagulation treatment as necessary.
It is subjected to processing using known techniques such as spray drying.

Coagulation of polysaccharides from the polysaccharide eluent is generally carried out by adding an alcohol such as methanol, ethanol, isopropanol, etc. A method using 150% by weight is adopted. If the amount of alcohol used is too small, impurities contained in the polysaccharide eluent will mix into the polysaccharide, causing a decrease in the quality of the polysaccharide.

On the other hand, using more than a certain amount of alcohol does not contribute to the efficiency of removing impurities and is uneconomical.

The polysaccharide obtained by the coagulation treatment can be used as it is or, if necessary, can be subjected to a drying treatment to produce a powdered polysaccharide.

According to the method of the present invention as detailed above, compared to known polysaccharide production methods, polysaccharide extracts can be easily concentrated using simple equipment, and polysaccharides of superior quality can be produced at low cost. It has great industrial value for food production, pharmaceutical use, etc.

EXAMPLES The method of the present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.

Example: After washing 2,500 parts by weight of the squeezed peel of Satsuma mandarin with 5,000 parts by weight of water, the peel was crushed and heated at a temperature of 9.
The mixture was added to 100 parts of an aqueous sulfuric acid solution at 0°C and heated and stirred for 35 minutes to extract pectin. Then, 7,500 parts by weight of the pectin extract obtained by filtration was added with 7 parts of water.
500 parts by weight was added to the P solution, which was filtered using a filter having 750 parts of activated carbon to remove fine particles, and 10 parts by weight of sodium hydroxide was added to adjust the pH to 3. The pectin concentration was adjusted to 0. Water dissolution of 35% by weight approx. 15.0001.
3~1.5 tr4/f! Duolite S-86 is a porous polymer of styrene-divinylbenzene copolymer.
5 (manufactured by Diamond Jamrock Co., Ltd.) was added thereto, and the mixture was stirred and contacted for 12 hours, followed by filtration to separate the water bath liquid and the porous polymer. Next, the pectin 1-stage porous polymer obtained by filtration separation is packed into a column, and the column is heated to the top of the column (I).
1,000 parts by volume of a 10% sodium hydroxide aqueous solution was poured over 2 hours to obtain 1,000 parts of a pectin solution with a yield of 4.7M. Next, this pectin was concentrated and eluted and dried for 1,000 ml to obtain 48 parts by weight of pectin. 1. of the obtained pectin. F, T (In
5position of Food Technology
The jelly grade according to STS) standards was 280.

Examples 2 to 8 Duolite S used in Example 1 as a porous adsorbent
The pectin concentration was 0.35 in the same manner as in Example 1 except that the porous polymer shown in Table 1 was used instead of -861.
When an aqueous solution of % by weight was treated, the yield and jelly grade of pectin obtained were as shown in Table 1.

Comparative Example 1 The same pectin concentration as obtained in Example 1 with a pectin concentration of 0.85% by weight, 15,000 tangerine extracts! jft part 1
Water distillation was carried out at 00'I'0rr 60°C for 10 hours to obtain 2000 parts by weight of a concentrate having a pectin concentration of 2.5% by weight. Next, add 4 parts to 2000 parts by weight of pectin concentrate.
After adding 0.00 parts by weight of ethyl alcohol to coagulate pectin, it was filtered and dried to obtain 49 parts by weight of pectin with a jelly grade of 157.

Example 9 100 parts by weight of the red algae Tsunomata was washed with water and ground, added to 10,000 parts by weight of an aqueous solution containing 20 parts by weight of calcium hydroxide, and heated and extracted at 80 to 100°C for 15 hours. After that, approximately 10,000 yen of the retentate obtained by filtration
: 1000 parts by volume of the same porous polymer Duolite 8-865 used in Example 1 was added to the tit part, and the mixture was immersed for 24 hours and stirred. Next, this mixed solution was filtered, a column was filled with 4 tons of carrageenan-adsorbing porous polymer, and 2000 parts by volume of 10% by weight potassium hydroxide was added for 2 hours.
The carrageenan adsorbed on the porous polymer Duolite S-865 was eluted.
．． 2010 parts by volume of eluent having a concentration of 4% by weight were obtained.

Next, add 5 parts to 2,000 parts of this Karajiten concentrated eluent.
After adding 0.00 parts of ethyl alcohol to coagulate carrageenan, it was filtered and dried to obtain 45 parts by weight of carrageenan.

Comparative Example 2 In addition to 10.000 parts by weight of an aqueous solution containing 80 to 100 parts by weight of
After heating and extracting at °C for 15 hours, filter F solution 1.
A 0.000 N solution was concentrated under reduced pressure using 2000 parts by weight. Next, the vacuum concentrate 2000! After adding 500 M parts of ethyl alcohol to the ffi part to coagulate carrageenan, it was filtered and dried to obtain 39 parts by weight of carrageenan.

Examples 10 to 18 Crab shells were extracted by alkali treatment, and each polysaccharide of hyaluronic acid and chondroitin sulfate, commercially available from Glucomanna, which was extracted by hot water treatment of konjac powder, was added to 0.0%.
1'! Aqueous FB solution containing 80,000% of water was poured into a column filled with 500 parts by volume of a porous polymer as shown in Table 2 from the top of the column over a period of 2 hours. Next, 1,000 parts by volume of a 7% by weight aqueous sodium hydroxide solution was passed over 2 hours to elute the polysaccharide adsorbed on the porous polymer.
Approximately 1,000 parts by volume of each eluate containing polysaccharides at the concentrations shown in Table 2 were obtained. Next, 4()0 parts by volume of methyl alcohol was added to this polysaccharide concentrated eluent to coagulate the polysaccharides, and then filtered and dried. Obtained sugars.

It is clear that the method can easily concentrate polysaccharides from an aqueous solution containing polysaccharides without going through the concentration operation of heating concentration i. Furthermore, it is clear from Examples 1 to 8 and Comparative Example 1 that polysaccharides of excellent quality can be produced, and that W is always useful industrially.

that's all

Claims (1)

[Scope of Claims] ■) A porous polymer (IJ) containing a polysaccharide
The polysaccharide-adsorbing porous polymer is then brought into contact with a polysaccharide-soluble dispersant in a smaller amount than the medium in Ai (Ai), and the polysaccharide-adsorbing porous polymer is brought into contact with a polysaccharide-soluble dispersing agent in a smaller amount than the medium in Ai. A method for producing a polysaccharide, which comprises eluating and concentrating a polysaccharide from a sugar-adsorbing polymer. 2) A method for producing a polysaccharide according to claim 1, which is a polysaccharide, pectin, carrageenan, or chitosan. . 8) The polysaccharide-containing aqueous solution (A) is obtained by dividing and extracting citrus peel, fruit juice dregs, fruits, seaweed, or the epidermis of arthropods, crustaceans, and insects. Scope of patent claims @1. Or the method for producing a polysaccharide according to item 2. 4) The method for producing a polysaccharide according to claim 1, 2 or 8, wherein the eluent is a water bath solution of sodium hydroxide, potassium hydroxide, magnesium hydroxide or calcium hydroxide. The method for producing a polysaccharide according to claim 1.2.8 or 4, characterized in that the polysaccharide is 0,2 C1J9 or more. 7) The aqueous solution (A) containing polysaccharides is citrus peel,
Fruit juice residue, fruit, seaweed, or arthropods, crustaceans,
7. A method for producing polysaccharides according to claim 6, using an aqueous solution obtained by dividing insect epidermis and extracting it. 8) The method for procuring a polysaccharide according to claim 6 or 7, wherein the eluent is an aqueous solution of sodium hydroxide, potassium hydroxide, magnesium hydroxide or calcium hydroxide. 9) A method for producing a polysaccharide according to claim 6, 7 or 8, wherein the OW is methyl alcohol, ethyl alcohol or -isopropyl alcohol. The method for producing a polysaccharide according to claim 6.7.8 or 9, characterized in that pore 8[ is 0.2 (A/(1 or more) or more.