JPH0358361B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polysaccharides. More specifically, the basic polymer (B) is brought into contact with a dilute aqueous solution containing polysaccharides (A), the polysaccharides are selectively adsorbed onto (B), and then the polysaccharides are removed using an eluent. The present invention relates to a method for producing concentrated polysaccharides by elution and concentration. Polysaccharides, such as plant polysaccharides, animal polysaccharides, and microbial polysaccharides, are widely distributed in the living world in large quantities. Chemically, there are many types of polysaccharides with significantly different compositions, and they are roughly divided into neutral polysaccharides and acidic polysaccharides having acidic groups.
Such polysaccharides include acidic polysaccharides that tend to be ionicly adsorbed, such as pectic acid, colominic acid, fucoidan, hyaluronic acid, chondroitin sulfate, delstan sulfate, clatan sulfate, heparin, heparan sulfate, and carrageenan. Pectin and carrageenan are used not only 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 due to their characteristic gel-forming ability. It is also used as a water retention and anti-aging agent for bread, as a coating agent for sugar fruits and frozen foods, 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 of citrus fruits, apples, and beets. is produced from. Pectin and carrageenan are produced by a method in which juice lees of citrus fruits, apples, beets, etc., and red algae and seaweed are extracted with an aqueous solution, the extract is then evaporated and concentrated, and pectin and carrageenan are coagulated. There is. Furthermore, general methods for producing these polysaccharides will be explained in detail using pectin as an example. Conventionally known methods for producing pectin include citrus fruits,
After washing the shredded juice lees of apples, beets, etc., extract the protopectin by hydrolysis with mineral acid, remove the strained extract lees, neutralize the obtained pectin extract, and then add water by heating. is distilled off, or ferric chloride or the like is added to the extract to precipitate it as a metal salt of pectin, which is then desalted. Generally employed is a method in which pectin is coagulated by adding a solvent, 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 squeezed lees from mandarin oranges, beets, etc., which is a raw material for pectin, is produced as a by-product, but these peels are only used for feed, fuel, and amino acid fermentation using molasses as a raw material. Industrialization has not been carried out. One of the major reasons for this is the high cost of manufacturing technology, especially the concentration process for extracts. In other words, concentration by water distillation method is 0.1~
It is necessary to concentrate the pectin extract containing 0.5% by weight of 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.Also, the extract contains ferric chloride, etc. The method of desalting after precipitating the metal salt of pectin by adding pectin has the disadvantage that the metal salt such as ferric chloride is expensive and requires complicated treatment for desalting. The production of polysaccharides other than pectin, such as carrageenan, has the same drawbacks as pectin. In view of these circumstances, the present inventors conducted intensive research to produce polysaccharides that can be easily and inexpensively concentrated as extracts and are of excellent quality. As a result, the basic polymer efficiently absorbs polysaccharides. They discovered that it can be attached and detached, and completed the method of the present invention. That is, the present invention provides an aqueous solution containing a polysaccharide.
(A) is brought into contact with a basic polymer (B) to adsorb the polysaccharide onto (B), and then the polysaccharide-adsorbed polymer is also brought into contact with an eluent to remove polysaccharides from the polysaccharide-adsorbed polymer. An object of the present invention is to provide a method for producing a concentrated polysaccharide, which comprises eluting and concentrating a polysaccharide. The dilute polysaccharide-containing aqueous solution to be treated in the method of the present invention is one of pectic acid, colominic acid, fucoidan, hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate, heparin, heparan sulfate, carrageenan, etc. Examples include aqueous solutions containing more than that amount. It is particularly suitable for aqueous solutions containing pectin and carrageenan. Aqueous solutions containing these polysaccharides can be produced by fragmenting and extracting citrus peel, fruit juice residue, fruit, or seaweed. In carrying out the method of the present invention, a basic polymer (B) is used as the polymer that adsorbs the polysaccharide used. Examples of the basic polymer (B) capable of adsorbing polysaccharides include resins having primary, secondary, tertiary and/or quaternary amino groups. More specifically, commercially available anion exchange resin Sumikaion KA-800 (resin with ethylene diamino group) Sumikaion KA-850 (resin with diethylenetriamino group) Sumikaion KA-890 (resin with diethylenetriamino group and quaternary ammonium salt) Duolite A-101D Duolite A-102D Duolite A-109 Duolite A-161 Duolite A-162 (Resins with primary and secondary amino groups, manufactured by Sumitomo Chemical) Duolite A-101D Duolite A-102D Duolite A-109 Duolite A-161 Duolite A-162 Duolite A-30B Duolite A-43B Duolite A-57 Duolite A-340 (Resin with tertiary and quaternary amino groups, Sumitomo Chemical Duolite A-2 Duolite A-7 (Resin having primary, secondary, and tertiary amino groups, manufactured by Sumitomo Chemical Co., Ltd., trade name) Duolite A-6 Duolite A-308 Duolite A -368 (Resin with tertiary amino group, manufactured by Diamond Shamlok Co., Ltd., trade name) Amberlite IRA-400 Amberlite IRA-401 Amberlite IRA-402 Amberlite IRA-405 Amberlite IRA-425 Amber Light IRA-900 Amberlite IRA-904 Amberlite IRA-938 Amberlite IRA-410 Amberlite IRA-411 Amberlite IRA-911 Amberlite IRA-910 (Resins with quaternary amino groups, ROHM
Amberlite IRA-68 Amberlite IRA-93 (Resin with tertiary amino group, manufactured by Diamond Shamlok Co., Ltd., trade name) Diaion SA-10A Diamondion SA-11A DIAION SA-20A DIAION PA-304 DIAION PA-308 DIAION PA-318 DIAION PA-418 (Resins with quaternary amino groups, Mitsubishi Chemical
Co., Ltd., trade name) Diaion WA-10 Diaion WA-20 Diaion CR-20 (Resins having primary and secondary amino groups, Mitsubishi Kasei Co., Ltd., trade name) etc. Examples include commercially available ion exchange resins. It was completely unexpected that polysaccharides in an aqueous solution could be adsorbed by using such a basic polymer, and that an aqueous solution containing concentrated polysaccharides could be produced by elution. In carrying out the present invention, an aqueous solution containing a polysaccharide
Contact between (A) and the basic polymer (B) may be carried out by selecting appropriate conditions. The contact method is not particularly limited, such as adding the basic polymer (B) to the polysaccharide-containing aqueous solution (A) and contacting it with stirring or shaking, or filling the basic polymer (B). A method of passing an aqueous solution containing a polysaccharide through a water column is preferably employed. In carrying out the method of the present invention, the amount of basic polymer used and the contact time are not particularly limited, and the polysaccharide concentration of the aqueous solution (A) containing the polysaccharide to be treated, the type of polysaccharide, etc. , the pH of the aqueous solution, and the type of basic polymer (B), but this can be determined by conducting appropriate preliminary experiments. The amount of the basic polymer (B) used is generally 10 to 1 part by weight of the polysaccharide in the polysaccharide-containing aqueous solution (A).
10,000 parts by weight of the basic polymer (B) may be brought into contact for generally 1 minute to 24 hours. The contact temperature between the polysaccharide-containing aqueous solution (A) and the basic polymer (B) is not particularly limited, but is usually 0 to 0.
It is carried out at a temperature of 100 °C. In carrying out the method of the present invention, the basic polymer adsorbed with polysaccharides from the polysaccharide-containing aqueous solution (A) by the above method is then brought into contact with an eluent, whereby the basic polymer adsorbed with polysaccharides is Elutes polysaccharides from the body. Such eluents include mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid, organic acids such as oxalic acid, malic acid, citric acid, and lactic acid, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide. Examples include basic drugs such as. The amount of these eluents used and the contact time are not particularly limited, but they depend on the amount of adsorption of the polysaccharide to the basic polymer, the type of basic polymer, the type of eluent, and the concentration of the eluent. This may vary depending on the situation, but this can be determined by conducting appropriate preliminary experiments. In general, the eluent may be 1 to 20 parts by weight of a 0.5 to 4N mineral acid or caustic alkali per weight of the polysaccharide-adsorbing basic polymer, and the contact time is generally 1 minute to 24 hours. Further, the contact temperature between the polysaccharide-adsorbing basic polymer and the eluent is not particularly limited, but may be 0 to 100°C,
It is generally carried out at room temperature. The polysaccharide eluate eluted from the polysaccharide-adsorbed basic polymer can be repeatedly used as an eluent to increase the polysaccharide content in the eluate. The polysaccharide eluate eluted from the polysaccharide-adsorbing basic polymer by the above method contains polysaccharides that are 10 times or more concentrated compared to the polysaccharide concentration in the liquid to be treated, so it is difficult to concentrate using known methods. This process is preferable in terms of the quality of the polysaccharide since it is not necessary to carry out the process again and it can be carried out without heat treatment as in conventional concentration methods. The polysaccharide eluate is then subjected to known techniques such as coagulation, spray drying, etc., if necessary. For coagulation of polysaccharides from the polysaccharide eluent, alcohol such as methanol, ethanol, isopropanol, etc. is generally used in the polysaccharide eluent in an amount of 30% by weight or more, preferably 50 to 150% by weight based on the polysaccharide eluent. The method will be adopted. If the amount of alcohol used is too small, impurities such as salts 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 efficiently remove impurities and is uneconomical. The polysaccharide obtained by the coagulation treatment can be used as it is or, if necessary, can be dried 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 concentrated using simple equipment, and polysaccharides of superior quality can be produced at low cost. Its industrial value is great for its production, food production, pharmaceutical use, etc. The method of the present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. Example 1 After washing 2,500 parts by weight of the squeezed peel of Satsuma mandarin orange with 5,000 parts by weight of water, and crushing the peel, the peel was heated to a temperature of
Pectin was extracted by adding to an aqueous sulfuric acid solution at 90°C and pH 1 and heating and stirring for 35 minutes. Next, 7500 parts by weight of water was added to 7500 parts by weight of the pectin extract obtained by filtration, and the mixture was filtered through a filter containing 750 parts by weight of activated carbon to remove fine particles. 10 parts by weight of hydroxide was added to the liquid. 15,000 parts by weight of an aqueous solution with a pectin concentration of 0.35% by weight, adjusted to pH 3 by adding sodium, was used as a pectin-adsorbing polymer, and 500 parts by volume of Sumikaion KA-890 (manufactured by Sumitomo Chemical Co., Ltd.) having primary and secondary amino groups was added. When the solution was passed through the packed resin tower for 3 hours, a treated solution with a pectin concentration of 0.01% by weight was obtained. Next, this pectin-adsorbed Sumikaion KA
-890 was washed with 1000 parts by volume of water, and 2000 parts by volume of a 10% by weight aqueous sodium hydroxide solution containing 2% by weight pectin was flowed from the top of the column in 1 hour as an eluent. 2000 parts by volume of eluent with pectin concentration were obtained. Next, 400 parts by weight of ethyl alcohol was added to 2000 parts by volume of this pectin concentrated eluate to coagulate pectin, and then filtered.
After drying, 88 parts by weight of pectin was obtained. IFT of the resulting pectin
The jelly grade according to Tpchnciogists) standards is
It was 235. Examples 2 to 4 The pectin concentration was determined in the same manner as in Example 1, except that the following three types of polymers were used instead of Sumikaion KA-890, which has primary and secondary amino groups as the basic polymer. When a 0.35% by weight aqueous solution was treated, the pectin yield and jelly grade obtained were as shown in Table 1. Sumikaion KA-850 (Resin with primary and secondary amino groups, manufactured by Sumitomo Chemical Co., Ltd., trade name) Sumikaion KA-800 (Resin with primary and secondary amino groups, manufactured by Sumitomo Chemical Co., Ltd., trade name) Duolite A-161 (Resin with quaternary amino group, manufactured by Diamond Shamlok Co., Ltd., trade name)

[Table] Examples 5 to 8 Example 1 except that 15,000 parts by weight of an aqueous lemon pectin solution with a pectin concentration of 0.13% by weight was used instead of pectin extracted from Satsuma mandarin oranges as the type of pectin.
When an aqueous pectin solution was treated in the same manner as above, the yield and jelly grade of pectin obtained were as shown in Table 2.

[Table] Comparative Example 1 15,000 parts by weight of the unshiu mandarin extract with the same pectin concentration of 0.35% by weight as obtained in Example 1 was added.
Distill water at 100 Torr and 60℃ for 10 hours to determine pectin concentration.
2000 parts by weight of a 2.5% by weight concentrate was obtained. Next, 400 parts by weight of ethyl alcohol was added to 2000 parts by weight of this pectin concentrate to coagulate pectin.
After filtering and drying, 50 parts by weight of pectin of jelly grade 157 was obtained. Example 9 100 parts by weight of the red seaweed Tsunomata was washed with water and crushed, containing 20 parts by weight of calcium hydroxide.
In addition to 10,000 parts by weight of an aqueous solution, 1000 parts by volume of Sumikaion, a basic polymer, was added to 10,050 parts by weight of a solution with a carrageenan concentration of 0.51% by weight, obtained by heating and extraction at 80 to 100°C for 15 hours. KA−850
(manufactured by Sumitomo Chemical Co., Ltd.) was added, and the mixture was immersed for 12 hours and stirred.
Next, the resin obtained by filtering this mixture was packed into a column, and 2000 parts by volume of 10% potassium hydroxide was added.
When the carrageenan adsorbed on Sumikaion KA-850 was eluted after running for 2 hours, the carrageenan was
1980 parts by volume of eluent with a concentration of 2.2% by weight were obtained. Then add 1980 parts by volume of this carrageenan concentrated eluent to 500
After adding parts by weight of ethyl alcohol to coagulate carrageenan, filtering and drying resulted in 41
Parts by weight of carrageenan were obtained. Comparative Example 2 100 parts by weight of red seaweed, Tsunomata, washed with water and crushed, containing 20 parts by weight of calcium hydroxide.
The mixture was added to 10,000 parts by weight of an aqueous solution and subjected to heating extraction treatment at 80 to 100°C for 15 hours, and then concentrated under reduced pressure to 10,050 parts by weight of the solution obtained by filtration with a carrageenan concentration of 0.51% by weight to 2,000 parts by weight. Next, the vacuum concentrated liquid 2000
After coagulating carrageenan by adding 500 parts by weight of ethyl alcohol, it was filtered and dried to obtain 39 parts by weight of carrageenan. From Examples 1 to 9 and Comparative Examples 1 and 2, the method for producing a polysaccharide of the present invention includes: from an aqueous solution containing a polysaccharide;
It is clear that polysaccharides can be easily concentrated without undergoing concentration operations such as heating and concentration, and polysaccharides of excellent quality can be produced, and that they are very useful industrially.

Claims (1)

[Claims] 1. An aqueous solution containing a polysaccharide (A) is a basic polymer.
(B) to adsorb the polysaccharide to (B), and then contact the polysaccharide-adsorbed polymer with an eluent to elute and concentrate the polysaccharide from the polysaccharide-adsorbed polymer. Method for producing polysaccharides. 2. The method for producing a polysaccharide according to claim 1, wherein the polysaccharide has an acidic group in the molecule. 3. The manufacturing method according to claim 1 or 2, wherein the polysaccharide is pectin or carrageenan. 4 The aqueous solution containing polysaccharides (A) is citrus peel,
Claims 1 and 2 are an aqueous solution obtained by subdividing and extracting fruit juice residue, fruit, or seaweed.
Or the method for producing a polysaccharide according to item 3. 5 Claim 1, wherein the eluent is hydrochloric acid, nitric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, magnesium hydroxide or calcium hydroxide,
The method for producing a polysaccharide according to item 2, 3 or 4. 6 Claim 1, characterized in that the polysaccharide is coagulated by further adding a solvent to the eluate concentrate.
The method for producing the polysaccharide described in Section 1. 7. The method for producing a polysaccharide according to claim 6, wherein the polysaccharide-containing aqueous solution (A) is an aqueous solution obtained by subdividing and extracting citrus peel, fruit juice residue, fruit, or seaweed. . 8. The method for producing a polysaccharide according to claim 6 or 7, wherein the eluent is hydrochloric acid, nitric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, magnesium hydroxide, or calcium hydroxide. 9. The method for producing a polysaccharide according to claim 6, 7, or 8, wherein the solvent is methyl alcohol, ethyl alcohol, or isopropyl alcohol.