JP2006307205A - Inorganic salt of acid polysaccharide, inorganic salt of acid polysaccharide that holds adsorbent and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acid polysaccharide inorganic salt and its manufacturing method; a gel and/or a fiber of the acid polysaccharide inorganic salt; and the gel and/or the fiber of the acid polysaccharide inorganic salt that holds an adsorbent. <P>SOLUTION: The acid polysaccharide inorganic salt is the one in which the ratio of a monovalent inorganic salt of an acid polysaccharide which makes the main component to the whole acid polysaccharide inorganic salt, is ≥90 mol%, preferably ≥99.85 mol%, and particularly ≥99.9 mol%. The manufacturing method of the acid polysaccharide inorganic salt includes the step wherein an aqueous solution of the salt between the inorganic cations containing the monovalent inorganic cations that make the major component and the anions of the acid polysaccharide is dialyzed against a dialysis fluid containing monovalent inorganic cations (the ratio of the monovalent inorganic cations in the dialysis fluid is higher than the ratio of the monovalent inorganic cations that make the major component in the aqueous solution). The gel and/or the fiber of the acid polysaccharide inorganic salt is provided. Also provided is the gel and/or the fiber of the acid polysaccharide inorganic salt that holds the adsorbent, which has the gel and/or the fiber of the acid polysaccharide inorganic salt and the adsorbent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention mainly includes an acidic polysaccharide inorganic salt and a production method thereof, an acidic polysaccharide inorganic salt gel and / or fiber, an acidic polysaccharide inorganic salt gel product and / or a fiber product, and an acidic polysaccharide inorganic holding an adsorbent. The present invention relates to an acidic polysaccharide inorganic salt gel product and / or a fiber product that retains salt gel and / or fiber and adsorbent. The present invention further provides an acidic polysaccharide inorganic salt gel and / or fiber holding an adsorbent and / or an acidic polysaccharide inorganic salt gel product holding an adsorbent and / or a nutrient salt in salt water using the fiber product. Concentration reduction device, nutrient salt concentration reduction system in salt water, nutrient salt concentration reduction method in salt water, nutrient salt concentration reduction treatment water in salt water, and nutrient salt concentration reduction treatment water in salt water It also relates to the oceanic creatures produced.

Acidic polysaccharides have a carboxyl group (—COOH) or ester-type sulfuric acid (—SO ₃ H) in the molecule, and these have the ability to ion exchange bond with metal ions. Seaweed produces many acidic polysaccharides. Typical acidic polysaccharides produced by red algae seaweed are carrageenan, porphyran, funolan and the like. Typical acidic polysaccharides produced by brown algae are alginic acid and fucoidan. Typical acidic polysaccharides produced by the green alga seaweed are uronic acid-containing sulfate polysaccharides and the like.

It is known that a certain kind of acidic polysaccharide inorganic salt changes its presence state when the inorganic cation species are exchanged. Sodium alginate is water soluble, but calcium alginate is insoluble and forms a gel. Alginic acid is lead ion (Pb ²⁺ ), copper ion (Cu ²⁺ ), cadmium ion (Cd ²⁺ ), zinc ion (Zn ²⁺ ), nickel ion (Ni ²⁺ ), cobalt ion (Co ²⁺ ), manganese ion (Mn ²⁺ ). A divalent metal ion such as strontium ion (Sr ²⁺ ), barium ion (Ba ²⁺ ) and an alginate inorganic salt gel are prepared. Among divalent metal ions, magnesium ions (Mg ²⁺ ) and mercury ions (Hg ²⁺ ) do not form an alginate inorganic salt gel. The gel strength varies depending on the inorganic cation species, and is known to be in the order of Pb ²⁺ > Cu ²⁺ > Cd ²⁺ > Zn ²⁺ , Ni ²⁺ , Co ²⁺ > Mn ²⁺ . On the other hand, alkali metal salts, magnesium salts, and ammonium salts of alginic acid are water-soluble.

  However, acidic polysaccharide inorganic salts produced from living organisms because of natural materials contain many contaminating inorganic cations in addition to the main inorganic cation. For the purpose of producing an acidic polysaccharide inorganic salt gel or fiber that exhibits desired physical properties, a technique for producing a polysaccharide inorganic salt in which the ratio of a desired inorganic cation component is increased is required.

  For water-soluble acidic polysaccharide inorganic salts such as sodium alginate, the viscosity of the solution is important depending on the application. Sodium alginate, a water-soluble acidic polysaccharide inorganic salt, is widely used in the food industry, medicine, cosmetics, dyeing, textiles, papermaking, and other industries, taking advantage of its ability to dissolve in water and become a viscous liquid. ing. In the food industry, it is used as a food stabilizer, thickener, dispersant, and gelling agent. Each of the above uses has an appropriate viscosity range required for an aqueous sodium alginate solution.

  However, low turbidity sodium alginate is required for use in foods that require transparency, such as jelly and beverages. When an insoluble alginic acid inorganic salt such as calcium alginate is present as an impurity in the aqueous sodium alginate solution, the turbidity of the aqueous sodium alginate solution increases.

  Current methods for producing sodium alginate are mainly the acid (precipitation) method and the calcium (precipitation) method. Although the acid method and the calcium method are described in Comparative Examples 1 and 2, both have an acid treatment step and an alkali treatment step, and as a result, there is a probability that molecular chain scission of alginic acid occurs, resulting in a decrease in molecular weight. Get higher. MG ratio (alginic acid is composed of two types of uronic acids. The two types of uronic acids are mannuronic acid and guluronic acid. The ratio of mannuronic acid to guluronic acid is called the MG ratio. If the molecular weight decreases, the viscosity also decreases. That is, if the purification of sodium alginate is performed using the acid method and / or the calcium method, there is a high possibility of causing a decrease in molecular weight, that is, a decrease in viscosity.

  Therefore, there is a need for a technique for producing low-turbidity sodium alginate by removing inorganic cationic species that cause insoluble alginic acid inorganic salts from sodium alginate while maintaining the viscosity of sodium alginate that is required for foods and other applications. Yes.

  Carrageenan is highly used in the field of food processing, particularly in milk products, widely used as a paste, and also used as a pharmaceutical base. Carrageenan sodium salt is water-soluble, but carrageenan potassium and ammonium salts are insoluble and gelled.

These are natural and biological macromolecules (also referred to as biopolymers), and have an acidic group such as a carboxyl group (—COOH) or ester type sulfuric acid (—SO ₃ H) in the molecule to exchange ions with metal ions. Therefore, the crude water-soluble acidic polysaccharide inorganic salt contains salts of various inorganic cation species and acidic polysaccharide. In addition, there is also a high risk of acid polysaccharide chains being cleaved by acid or alkali treatment.

  Therefore, while maintaining the viscosity of the water-soluble acidic polysaccharide inorganic salt that is currently required for foods and other applications, the inorganic cation species that cause the insoluble acidic polysaccharide inorganic salt are removed and the low turbidity water-soluble acidic polysaccharide is removed. Sugar Inorganic Salt There is a need for a technique for producing a water-soluble acidic polysaccharide inorganic salt.

  Sodium alginate is a raw material for calcium alginate gel and fibers. If the raw material sodium alginate aqueous solution contains divalent metal ions that bind to and gel with alginic acid such as calcium ions, the viscosity of the sodium alginate aqueous solution will increase, turbidity will increase, Furthermore, when a sodium alginate aqueous solution is poured into a coagulation tank containing a coagulating solution such as a calcium chloride aqueous solution and gelation occurs, the gel solidifies in a non-uniform manner or clogs the nozzle. In particular, it has been a problem when adjusting the gel by spraying liquid from a thin nozzle. Furthermore, the strength of the prepared calcium alginate gel and / or fiber is also low.

  Therefore, high purity sodium alginate from which divalent metal ions such as calcium ions that bind to alginic acid and gel are removed as much as possible and a method for producing the same are demanded.

  On the other hand, alginic acid combined with magnesium or mercury ions does not gel and becomes a water-soluble alginate. When an aqueous solution of sodium alginate containing magnesium ions or mercury ions is used as a raw material for calcium alginate gels or fibers, the strength of the prepared calcium alginate gels or fibers may decrease because magnesium or mercury ions are bound. It was a problem.

  Therefore, high purity sodium alginate from which magnesium ions and mercury ions are removed as much as possible and a method for producing the same have been demanded. In particular, since calcium ions and magnesium ions are abundantly contained in seaweeds, which are the raw materials for sodium alginate, a technique for reducing calcium ions and magnesium ions from sodium alginate is most demanded.

  The present inventors have found that trace components in a solution can be removed by an abnormal adsorption chromatographic phenomenon and a pseudo-abnormal chromatographic adsorption phenomenon (Patent Document 1), and invented a method for producing a high purity sodium chloride crystal (patent). Reference 2). Furthermore, by applying the inventions described in Patent Documents 1 and 2 to removal of potassium ions in sodium chloride in particular, a low potassium sodium chloride medical material can be obtained (Patent Document 3), in particular magnesium ions in sodium chloride or It has already been discovered that an artificial seawater composition for algae growth can be obtained by applying it to calcium ion removal (Patent Document 4).

  However, a high-purity inorganic salt aqueous solution obtained by removing trace components in a solution by an abnormal adsorption chromatography phenomenon and a pseudo-abnormal chromatography adsorption phenomenon is a polysaccharide inorganic salt aqueous solution (in the present invention, a polysaccharide inorganic salt aqueous solution is When used as a dialysis solution for polysaccharide inorganic salts.), A high-purity polysaccharide inorganic salt aqueous solution (in the present invention, a high-purity polysaccharide inorganic salt aqueous solution having a high purity without increasing the molecular weight). It has not been known until now that it is possible to obtain water-soluble polysaccharide inorganic salts.

  When a high-purity sodium chloride aqueous solution obtained by removing trace components in a solution by abnormal adsorption chromatography and pseudo-abnormal chromatographic adsorption is used as a dialysate of sodium alginate aqueous solution, the purity is increased without reducing the molecular weight. It has not been known until now that it becomes possible to obtain a pure sodium alginate aqueous solution.

Insoluble polysaccharide inorganic salts;
When a polysaccharide inorganic salt is used as a fiber or gel, it may not be industrially usable unless its strength is high. It is the molecular weight of the polysaccharide inorganic salt that influences the strength of the polysaccharide inorganic salt fiber and / or polysaccharide inorganic salt gel, or the polysaccharide inorganic salt product made from them.

  Conventional purification methods for sodium alginate have been problematic in that molecular weight decreases and high-purity sodium alginate cannot be obtained. Therefore, a production method for increasing the purity of sodium alginate while maintaining the molecular weight has been demanded.

Disadvantages of powder adsorbents;
Unlike organic adsorbents, inorganic adsorbents are often powdered. Inorganic adsorbents exhibit excellent adsorption properties, but have several disadvantages because they are powdery.

  If the specific gravity is heavier than water, it will sink and the mixing rate will be poor. These drawbacks have caused a reduction in the adsorption efficiency of the powdery adsorbent.

  Moreover, since it is powdery, it cannot be packed in a column shape and cannot be used because it leaks under flowing water.

  Therefore, at present, there has been a demand for a polymer in which a powdery adsorbent is dispersed and immobilized.

Disadvantages of immobilizing polymers;
Unless it is a hydrophilic polymer, it cannot be used by adsorbing a hydrophilic substance such as nitrate ions.

  However, when a powdery adsorbent is immobilized on a conventional hydrophilic polymer, the adsorbing ability is reduced to 25% or less.

  There is a need for a polymer that immobilizes a powdered adsorbent without reducing the adsorption efficiency of the powdered adsorbent.

  In general, there are many organic polymers for immobilization, and there has been a problem that a harmful reagent must be used for the synthesis. Furthermore, it was practically difficult to recover the adsorbent immobilized on the polymer after the adsorption treatment was completed when it was immobilized on the organic polymer.

Moreover, it is desirable that the polymer for immobilizing the powdery adsorbent is a biodegradable polymer.
JP 2004-261636 A (Claims and others) JP 2004-262676 A (Claims and others) JP 2004-262766 A (Claims and others) JP 2004-261101 A (Claims and others)

  The present invention mainly comprises an acidic polysaccharide inorganic salt and a production method thereof, an acidic polysaccharide inorganic salt gel and / or fiber, an acidic polysaccharide inorganic salt gel product and / or a fiber product, and an acidic polysaccharide inorganic salt holding an adsorbent. It is an object of the present invention to provide an acidic polysaccharide inorganic salt gel product and / or a fiber product that retains a gel and / or fiber and an adsorbent. The present invention further provides an acidic polysaccharide inorganic salt gel and / or fiber holding an adsorbent and / or an acidic polysaccharide inorganic salt gel product holding an adsorbent and / or a nutrient salt in salt water using the fiber product. Concentration reduction device, nutrient salt concentration reduction system in salt water, nutrient salt concentration reduction method in salt water, nutrient salt concentration reduction treatment water in salt water, and nutrient salt concentration reduction treatment water in salt water The purpose is to provide produced oceanic organisms.

That is, the present invention relates to the following matters.
[Item 1]
The acidic polysaccharide inorganic salt whose ratio of the acidic polysaccharide monovalent | monohydric inorganic salt used as the main component with respect to all the acidic polysaccharide inorganic salts is 90 mol% or more.
[Item 2]
Item 10. The acidic polysaccharide inorganic salt according to Item 1, wherein the ratio of the acidic polysaccharide monovalent inorganic salt as a main component to all acidic polysaccharide inorganic salts is 99.85 mol% or more.
[Item 3]
Item 3. The acidic polysaccharide inorganic salt according to Item 2, wherein the ratio of the acidic polysaccharide monovalent inorganic salt as a main component to all acidic polysaccharide inorganic salts is 99.9 mol% or more.
[Item 4]
Item 4. The acidic polysaccharide inorganic salt according to any one of Items 1 to 3 for producing an acidic polysaccharide inorganic salt gel and / or fiber.
[Item 5]
Item 5. The acidic polysaccharide inorganic salt according to any one of Items 1 to 4, wherein the acidic polysaccharide is alginic acid.
[Item 6]
Item 6. The acidic polysaccharide inorganic salt according to any one of Items 1 to 5, wherein the acidic polysaccharide monovalent inorganic salt as the main component is an acidic polysaccharide sodium salt.
[Item 7]
Item 7. The acidic polysaccharide inorganic salt according to any one of Items 1 to 6, wherein the acidic polysaccharide monovalent inorganic salt as the main component is sodium alginate.
[Item 8]
A step of dialyzing an aqueous solution of a salt of an inorganic cation containing a monovalent inorganic cation and an acidic polysaccharide anion as a main component against a dialysis solution containing a monovalent inorganic cation (where the monovalent inorganic cation in the dialysis solution is Is higher than the ratio of the monovalent inorganic cation that is the main component in the aqueous solution).
[Item 9]
Item 9. The method for producing an inorganic salt of an acidic polysaccharide according to Item 8, wherein the acidic polysaccharide is alginic acid.
[Item 10]
Item 10. The method for producing an acidic polysaccharide inorganic salt according to Item 8 or 9, wherein the monovalent inorganic cation as the main component is sodium ion.
[Item 11]
The manufacturing method of the acidic polysaccharide inorganic salt in any one of 8-10 whose said acidic polysaccharide is alginic acid and whose monovalent | monohydric inorganic cation used as the said main component is a sodium ion.
[Item 12]
Item 12. The method for producing an acidic polysaccharide inorganic salt according to any one of Items 8 to 11, wherein the dialysate is a sodium chloride aqueous solution.
[Item 13]
Item 13. The method for producing an acidic polysaccharide inorganic salt according to Item 12, wherein the purity of sodium chloride in the aqueous sodium chloride solution is 99.99% by mass or more.
[Item 14]
Item 14. The method for producing an acidic polysaccharide inorganic salt according to Item 13, wherein the purity of sodium chloride in the aqueous sodium chloride solution is 99.999% by mass or more.
[Item 15]
Item 15. The method for producing an acidic polysaccharide inorganic salt according to any one of Items 12 to 14, wherein the sodium chloride aqueous solution is produced using an abnormal chromatography phenomenon or a pseudo-abnormal chromatography phenomenon.
[Item 16]
About the aqueous solution of the salt of the inorganic cation containing the monovalent inorganic cation as the main component and the acidic polysaccharide anion, the solution viscosity after the dialysis step is 90% or more of the solution viscosity before the dialysis step, Item 16. The method for producing an acidic polysaccharide inorganic salt according to any one of Items 8 to 15.
[Item 17]
With respect to an aqueous solution of a salt of an inorganic cation containing a monovalent inorganic cation as a main component and an acidic polysaccharide anion, the solution molecular weight after the dialysis step is 90% or more of the solution molecular weight before the dialysis step, Item 16. The method for producing an acidic polysaccharide inorganic salt according to any one of Items 8 to 15.
[Item 18]
About the aqueous solution of the salt of the inorganic cation containing the monovalent inorganic cation as the main component and the acidic polysaccharide anion, the solution viscosity after the dialysis step is 95% or more of the solution viscosity before the dialysis step, Item 18. A method for producing an inorganic salt of an acidic polysaccharide according to Item 16.
[Item 19]
With respect to an aqueous solution of a salt of an inorganic cation containing a monovalent inorganic cation as a main component and an acidic polysaccharide anion, the solution molecular weight after the dialysis step is 95% or more of the solution molecular weight before the dialysis step, Item 18. A method for producing an inorganic salt of an acidic polysaccharide according to Item 17.
[Item 20]
Acidic polysaccharide inorganic salt gel and / or fiber.
[Item 21]
An aqueous solution of an acidic polysaccharide inorganic salt (wherein, in the acidic polysaccharide inorganic salt, the ratio of the acidic polysaccharide monovalent inorganic salt as a main component to all acidic polysaccharide inorganic salts is 90 mol% or more), An acidic polysaccharide inorganic salt gel and / or fiber obtained by contacting with an aqueous inorganic salt solution.
[Item 22]
Item 22. The acidic polysaccharide inorganic salt gel and / or fiber according to Item 21, wherein the ratio of the acidic polysaccharide monovalent inorganic salt as a main component to all acidic polysaccharide inorganic salts is 99.85 mol% or more.
[Item 23]
Item 23. The acidic polysaccharide inorganic salt gel according to Item 22, wherein in the acidic polysaccharide inorganic salt, the ratio of the acidic polysaccharide monovalent inorganic salt as a main component to all the acidic polysaccharide inorganic salts is 99.9 mol% or more. And / or fiber.
[Item 24]
Item 24. The acidic polysaccharide inorganic salt gel and / or fiber according to any one of Items 20 to 23 for retaining the adsorbent.
[Claim 25]
Item 25. The acidic polysaccharide inorganic material according to any one of Items 20 to 24, wherein the tensile strength of the single fiber of the air-dried fiber is 1.5 g / denier or higher, or the tensile strength of the single fiber of the wet fiber is 0.15 g / denier or higher. Salt gel and / or fiber.
[Item 26]
Item 26. The acidic polysaccharide inorganic salt gel and / or fiber according to any one of Items 20 to 25, wherein the acidic polysaccharide is alginic acid.
[Item 27]
Item 27. The acidic polysaccharide inorganic salt gel and / or fiber according to any one of Items 21 to 26, wherein the acidic polysaccharide monovalent inorganic salt as the main component is an acidic polysaccharide sodium salt.
[Item 28]
Item 28. An acidic polysaccharide inorganic salt gel product and / or a fiber product, wherein the acidic polysaccharide inorganic salt gel and / or fiber according to any one of Items 20 to 27 is used as a raw material.
[Item 29]
Item 28. The acidic polysaccharide inorganic salt gel product and / or the fiber product having the adsorbent, the acidic polysaccharide inorganic salt gel product and / or the fiber product according to Item 28.
[Section 30]
Item 31. The acidic polysaccharide inorganic salt gel product and / or fiber holding the adsorbent according to Item 29, wherein the adsorbent is an adsorbent that adsorbs nutrient salts containing phosphorus and / or nutrient salts containing nitrogen. Product.
[Claim 31]
Item 28. The acidic polysaccharide inorganic salt gel and / or fiber having an adsorbent, comprising the acidic polysaccharide inorganic salt gel and / or fiber according to any one of Items 20 to 27.
[Item 32]
An aqueous solution of an acidic polysaccharide inorganic salt containing an adsorbent (wherein, in the acidic polysaccharide inorganic salt, the ratio of the acidic polysaccharide monovalent inorganic salt as a main component to all acidic polysaccharide inorganic salts is 90 mol% or more) And an acidic polysaccharide inorganic salt gel and / or fiber that retains the adsorbent, which is obtained by bringing the aqueous solution into contact with an aqueous inorganic salt solution.
[Claim 33]
Item 33. The acidic polysaccharide inorganic salt gel retaining the adsorbent according to Item 32, wherein the ratio of the acidic polysaccharide monovalent inorganic salt as a main component to all acidic polysaccharide inorganic salts is 99.85 mol% or more. Or fiber.
[Item 34]
Item 34. The acidic polysaccharide retaining salt according to Item 32, wherein the ratio of the acidic polysaccharide monovalent inorganic salt as a main component to all acidic polysaccharide inorganic salts in the acidic polysaccharide inorganic salt is 99.9 mol% or more. Polysaccharide inorganic salt gel and / or fiber.
[Claim 35]
Item 34. The acidic polysaccharide inorganic salt gel retaining an adsorbent according to any one of Items 31 to 33, wherein the adsorbent is an adsorbent that adsorbs a nutrient salt containing phosphorus and / or a nutrient salt containing nitrogen. And / or fiber.
[Claim 36]
Item 34. An acidic polysaccharide inorganic salt gel product and / or fiber product holding an adsorbent, the raw material being the acidic polysaccharide inorganic salt gel and / or fiber holding the adsorbent according to any one of Items 31 to 33.
[Section 37]
Calcium alginate gel and / or fiber.
[Section 38]
It is obtained by contacting an aqueous solution of an alginic acid inorganic salt (wherein the alginate inorganic salt has a ratio of sodium alginate as a main component with respect to all the alginic acid inorganic salts of 90 mol% or more) and an aqueous calcium ion solution. , Calcium alginate gel and / or fiber.
[Claim 39]
Item 40. The calcium alginate gel and / or fiber according to Item 39, wherein the ratio of sodium alginate as a main component to all inorganic alginate is 99.85 mol% or more.
[Claim 40]
40. The calcium alginate gel and / or fiber according to Item 39, wherein the ratio of sodium alginate as a main component to all alginate inorganic salts in the alginate inorganic salt is 99.9 mol% or more.
[Claim 41]
Item 41. The calcium alginate gel and / or fiber according to any one of Items 38 to 40 for retaining an adsorbent.
[Item 42]
42. The calcium alginate gel according to any one of Items 38 to 41, wherein the tensile strength of the single fiber of the air-dried fiber is 1.5 g / denier or higher, or the tensile strength of the single fiber of the wet fiber is 0.15 g / denier or higher. Or fiber.
[Item 43]
Item 43. A calcium alginate gel product and / or a fiber product, wherein the calcium alginate gel and / or fiber according to any one of Items 38 to 42 is used as a raw material.
[Item 44]
Item 54. The calcium alginate gel product and / or fiber product according to Item 43, and the adsorbent-containing calcium alginate gel product and / or fiber product having the adsorbent.
[Item 45]
Item 43. The calcium alginate gel and / or fiber having an adsorbent, the calcium alginate gel and / or fiber according to any one of Items 38 to 42, and the adsorbent.
[Item 46]
An aqueous solution of an alginic acid inorganic salt containing an adsorbent (herein, the ratio of sodium alginate as a main component to the entire alginic acid salt in the alginic acid inorganic salt is 90 mol% or more) and a calcium ion aqueous solution are contacted Calcium alginate gel and / or fiber holding the adsorbent, obtained by making it.
[Item 47]
Item 47. The calcium alginate gel and / or fiber holding the adsorbent according to Item 46, wherein the ratio of sodium alginate as a main component to all inorganic alginate is 99.85 mol% or more.
[Item 48]
48. A calcium alginate gel and / or fiber containing an adsorbent according to Item 47, wherein the ratio of sodium alginate as a main component to all alginate inorganic salts in the alginate inorganic salt is 99.9 mol% or more.
[Item 49]
Item 51. The calcium alginate gel containing the adsorbent according to any one of Items 45 to 48, wherein the adsorbent is an adsorbent that adsorbs nutrients containing phosphorus and / or nutrients containing nitrogen. fiber.
[Item 50]
50. A calcium alginate gel product and / or a fiber product holding an adsorbent, the raw material being the calcium alginate gel and / or fiber holding the adsorbent according to any one of Items 45 to 49.
[Item 51]
The acidic polysaccharide inorganic salt gel and / or fiber holding the adsorbent according to Item 31 to 35, the calcium alginate gel and / or fiber holding the adsorbent according to Item 45 to 49, Item 29, 30 and 36 Selected from the group consisting of the acidic polysaccharide inorganic salt gel product and / or the fiber product retaining the adsorbent described above, and the calcium alginate gel product and / or the fiber product retaining the adsorbent described in Item 44 and 50 An apparatus for reducing the concentration of nutrients in salt water.
[Item 52]
The nutrient salt for reducing the concentration is at least one selected from the group consisting of nitrate nitrogen, nitrite nitrogen, ammonia nitrogen, urea nitrogen, organic phosphorus, inorganic phosphorus and silicon. Item 52. The apparatus for reducing the concentration of nutrients in salt water according to Item 51.
[Item 53]
Item 51 or 52, a device for reducing the concentration of nutrients in salt water, a flow path switching device, a nitrification tank in which nitrifying bacteria are fixed, an oxygen supply tank, a foam separation tank, a precipitation tank, a pH adjustment water tank, a water temperature adjustment A system for reducing the concentration of nutrients in salt water, comprising at least one selected from the group consisting of a tank, a filtration tank, a circulation pump, and a biological breeding tank.
[Item 54]
The step of treating the salt water with at least one selected from the group consisting of the nutrient salt concentration reducing device according to Item 51 or 52 and the nutrient salt concentration reducing system according to Item 53. A method for reducing the concentration of nutrient salts in salt water.
[Item 55]
Item 55. Processed water for reducing the concentration of nutrients in salt water obtained by the method for reducing the concentration of nutrients in salt water according to Item 54.
[Section 56]
Item 55. An offshore organism produced in treated water with reduced concentration of nutrients in salt water according to Item 55.

Furthermore, the present invention relates to the following matters.
[Section 57]
Item 52. The apparatus for reducing the concentration of nutrients in salt water according to Item 51, comprising a flow path switching valve and a plurality of concentration reduction units connected to the flow path switching valve.
[Section 58]
58. The concentration reducing apparatus according to item 57, wherein the concentration reducing unit includes a salt water inflow side culture unit and a salt water outflow side culture unit.
[Section 59]
Nutrients to be reduced in concentration are at least one of nitrate nitrogen, nitrite nitrogen, ammonia nitrogen, urea nitrogen, organic phosphorus, inorganic phosphorus (such as orthophosphoric acid), and silicon (such as silicic acid). Item 57. The apparatus for reducing the concentration of nutrients in salt water according to Item 57 or 58.
[Section 60]
Item 60. The apparatus for reducing the concentration of nutrients in salt water according to any one of Items 57 to 59, wherein an adsorbent is introduced into the apparatus.
[Section 61]
Item 61. The apparatus for reducing the concentration of nutrient salts in salt water according to any one of Items 57 to 60, wherein the adsorbent is held in a polysaccharide inorganic salt.

  Hereinafter, the present invention will be described in more detail.

  In many cases, the inorganic salts of acidic polysaccharides currently industrially produced are formed by two or more inorganic cations with respect to a specific acidic polysaccharide anion. For example, an industrially produced alginic acid inorganic salt contains sodium alginate as a main component and also contains potassium alginate, magnesium alginate and calcium alginate exceeding the detection limit.

  The acidic polysaccharide inorganic salt can be used as a raw material for the acidic polysaccharide inorganic salt gel or fiber. The properties of the resulting acidic polysaccharide inorganic salt gel or fiber are the ratio of the monovalent inorganic salt (gel or fiber component) of the acidic polysaccharide that is the main component to all the acidic polysaccharide inorganic salts in the acidic polysaccharide inorganic salt (raw material). It varies depending on the molecular weight of the acidic polysaccharide monovalent inorganic salt, the solution viscosity of the acidic polysaccharide inorganic salt, and the like. Usually, the higher the ratio of the acidic polysaccharide monovalent inorganic salt (gel or fiber raw material component) that is the main component to all the acidic polysaccharide inorganic salts in the acidic polysaccharide inorganic salt (raw material), the more the pore size of the gel or fiber is aligned. High gel or fiber strength. Moreover, the larger the molecular weight of the acidic polysaccharide monovalent inorganic salt as the main component, the higher the gel or fiber strength. For example, when producing a calcium alginate gel or fiber using an alginate inorganic salt (raw material), the higher the ratio of sodium alginate (gel or fiber raw material component) that is the main component to all the alginate inorganic salts in the alginate inorganic salt, Calcium alginate gel or fiber has a uniform pore size and high gel or fiber strength. Moreover, the larger the molecular weight of sodium alginate as the main component, the higher the gel or fiber strength.

  In addition to the acidic polysaccharide monovalent inorganic salt that is the main component (becomes a gel or fiber component), other commercially available acidic polysaccharide inorganic salts are other acidic polysaccharide monovalent inorganic salts and acidic polysaccharide polyvalent inorganic salts. Is included. In addition, when the conventional acid polysaccharide inorganic salt is highly purified by an acid or calcium method, which is a conventional industrial extraction / purification method, the molecular weight is reduced by treatment with an acid and an alkali. For these reasons, a conventional commercially available acidic polysaccharide inorganic salt or an acidic polysaccharide inorganic salt fiber produced by using a highly purified product of the same by a conventional method as a raw material does not have the same pore size, gel or fiber strength. Is not high.

  In this invention, the acidic polysaccharide inorganic salt with which the ratio of the acidic polysaccharide monovalent inorganic salt used as the main component with respect to all the acidic polysaccharide inorganic salts was raised is provided.

  In the acidic polysaccharide inorganic salt of the present invention, the ratio of the acidic polysaccharide monovalent inorganic salt as the main component to all the acidic polysaccharide inorganic salts is usually 90 mol% or more, preferably 99.85 mol% or more, More preferably, it is 99.9 mol% or more.

  The acidic polysaccharide inorganic salt of the present invention is basically prepared by dialyzing an aqueous solution of an inorganic cation containing a monovalent inorganic cation as a main component and an acidic polysaccharide anion against a dialysate containing a monovalent inorganic cation. It is obtained by doing.

  An aqueous solution of a salt of an inorganic cation containing a monovalent inorganic cation as a main component and an acidic polysaccharide anion can be obtained by dissolving the acidic polysaccharide inorganic salt in a solvent.

  The acidic polysaccharide inorganic salt used for the preparation of the aqueous solution is usually a naturally derived acidic polysaccharide inorganic salt, but may be an artificially processed acidic polysaccharide inorganic salt. Here, the term “naturally-derived” means that it is obtained from any algae, plant or organism existing in nature. Such naturally-derived acidic polysaccharide inorganic salts can be extracted by known methods, but commercially available products may be used for convenience. Examples of the algae include brown algae (for example, Kombu seaweed, Wakame seaweed, Lessonia seaweed, Macrocystis seaweed, Kajime seaweed, Alameae seaweed, Ascophyllum, Davilia, etc.), red algae (for example, Giraffe seaweed, Ibaranori seaweed, Muchadenori seaweed, Tengusa seaweed, Ogonori seaweed, Funori seaweed, Amano seaweed, etc., green algae (for example, Mill seaweed, Aosa seaweed, Aonori seaweed, Iwatsuki seaweed, Seaweed seaweed, etc.) Etc. Examples of plants include citrus fruits, sugar beets and apples. Examples of other organisms include mammals, horseshoe crabs, squids, and bacteria.

  The molecular weight of the acidic polysaccharide inorganic salt used for the preparation of the aqueous solution is not particularly limited, but is, for example, 20,000 to 20,000,000, preferably 100,000 to 20,000,000, more preferably 200, 000 to 20,000,000. However, there is no particular problem as long as the acidic polysaccharide inorganic salt of the present invention has a desired effect even if a slight degradation product or condensate of an acidic polysaccharide having a molecular weight other than these is included.

The acidic polysaccharide is not particularly limited as long as it is composed of two or more monosaccharides and has an acidic functional group capable of forming a salt with an inorganic cation when dissolved in an aqueous solution. The monosaccharide that is a constituent unit of the acidic polysaccharide is not particularly limited. For example, neutral sugars such as glucose, galactose (D-form, L-form), xylose, mannose, rhamnose, fucose, fucose, arabinose, guluronic acid, Examples thereof include uronic acids such as iduronic acid, mannuronic acid, glucuronic acid and galacturonic acid, and amino sugars such as glucosamine and galactosamine. The acidic functional group, for example, -COOH (carboxyl group), - _SO 3 H (sulfo _group), - OSO 3 _H, although -CH 2 OSO ₃ H and the like, without limitation.

  Typical acidic polysaccharides include alginic acid, agaropectin, carrageenan (carrageenan), hyaluronic acid, porphyran, fucoidan (sulfated fucan), ascofilan, preferably alginic acid, agaropectin, carrageenan (carrageenan), particularly preferably alginic acid. For example, but not limited to.

  In the acidic polysaccharide inorganic salt used for the preparation of the aqueous solution, the inorganic salt means a salt formed by an anion of the acidic polysaccharide with a metal ion or a positive basic group. Examples of inorganic salts include sodium salt, potassium salt, lithium salt, ammonium salt, nickel salt, silver salt, magnesium salt, calcium salt, cobalt salt, barium salt, strontium salt, manganese salt, lead salt, copper salt, cadmium. Salt, zinc salt, mercury salt and the like can be mentioned.

  The acidic polysaccharide inorganic salt used for the preparation of the aqueous solution contains an acidic polysaccharide monovalent inorganic salt as a main component and an acidic polysaccharide monovalent inorganic salt and / or an acidic polysaccharide polyvalent other than the main component as a subcomponent. Inorganic salts may be included. In the present invention, “acidic polysaccharide monovalent inorganic salt (or monovalent inorganic cation) as a main component” means that a plurality of monovalent inorganic salts (or monovalent inorganic cations) exist for a specific acidic polysaccharide. In this case, it means a monovalent inorganic salt (or monovalent inorganic cation) present in the largest proportion. For example, a monovalent inorganic salt of alginic acid is a monovalent inorganic salt having a sodium salt as a main component when sodium salt is most present among sodium salts, potassium salts, lithium salts and the like.

  In the acidic polysaccharide inorganic salt used for the preparation of the aqueous solution, the acidic polysaccharide monovalent inorganic salt as the main component is preferably a sodium salt of acidic polysaccharide.

  The solvent of the aqueous solution is usually water, but may be a solvent containing water as a base and further containing another solvent as long as the acidic polysaccharide inorganic salt of the present invention has a desired effect.

  In the present invention, an aqueous solution of a salt of an inorganic cation containing a monovalent inorganic cation as the main component and an acidic polysaccharide anion is dialyzed against a dialysate containing a monovalent inorganic cation.

  The dialysate contains a monovalent inorganic cation that is the same kind as the monovalent inorganic cation as the main component in the aqueous solution described above at a higher ratio than the aqueous solution. That is, the ratio of the monovalent inorganic cation in the dialysate is higher than the ratio of the monovalent inorganic cation as the main component in the aqueous solution. For example, when the monovalent inorganic cation that is the main component in the aqueous solution is sodium ion, the ratio of sodium ion in the dialysate is higher than the ratio of sodium ion that is the main component in the aqueous solution. The monovalent inorganic cation in this document is a monovalent metal ion or a positive basic group, and does not include hydrogen ions.

  As the dialysate, a high-purity monovalent inorganic salt aqueous solution is basically used.

  A high-purity monovalent inorganic salt aqueous solution is obtained by dissolving a high-purity monovalent inorganic salt in a solvent (usually water or a water-based solvent).

  The purity of the high-purity monovalent inorganic salt is, for example, 99.9% by mass or more, preferably 99.99% by mass or more, and more preferably 99.999% by mass or more.

  In a preferred embodiment of the present invention, the dialysate is a high purity sodium chloride aqueous solution.

  In a preferred embodiment of the present invention, the dialysate is a high-purity sodium chloride aqueous solution produced using an abnormal chromatography phenomenon or a pseudo-abnormal chromatography phenomenon.

  In a preferred embodiment of the present invention, the dialysate is a high-purity sodium chloride aqueous solution having a sodium chloride purity of 99.99% by mass or higher, preferably 99.999% by mass or higher.

  It is particularly preferable that the dialysate does not substantially contain an inorganic cation which is not a main component (subcomponent) in the aqueous solution or contains a lower ratio than the aqueous solution. In this way, by using a dialysate that is substantially free of inorganic cations that are not the main component or in a lower ratio than the aqueous solution, the inorganic cations that are not the main component move from the aqueous solution to the dialysate, The proportion of no inorganic cation is reduced.

  In a preferred embodiment of the present invention, the dialysate is substantially free of inorganic cations that are not the main component in the aqueous solution.

  In a preferred embodiment of the present invention, the dialysate has a high purity substantially free from one, more preferably two, and even more preferably all three selected from the group consisting of magnesium ions, calcium ions, and potassium ions. Sodium chloride aqueous solution.

  The solvent of the dialysate is usually water, but may be a solvent containing water and another solvent as long as the acidic polysaccharide inorganic salt of the present invention has a desired effect.

  The dialysis membrane is not particularly limited as long as it does not pass the acidic polysaccharide anion and passes the monovalent inorganic cation.

  Although the molecular weight cut off of the dialysis membrane is not particularly limited, it is, for example, 3,500 to 60,000, preferably 3,500 to 10,000, and more preferably 3,500 to 8,000.

  The material of the dialysis membrane is not particularly limited, and examples thereof include cellulose (for example, regenerated cellulose and cellulose acetate), polyacrylonitrile, polysulfone, polymethyl methacrylate, and the like.

  In the present invention, a commercially available dialysis membrane can be suitably used. As a commercially available dialysis membrane, for example, when the molecular weight of acidic polysaccharide is about 100,000 to 1,000,000, Spectra / Pore dialysis tube (manufactured by Spectrum), disposable dialysis cassette Slide-A- Suitable examples include Lyzer (manufactured by PIERCE).

  The dialysis temperature is usually 4 to 50 ° C, preferably 4 to 30 ° C, more preferably 4 to 25 ° C, but is not particularly limited.

  The dialysis time is not particularly limited, and is appropriately selected according to the composition of the aqueous solution, the composition of the dialysis solution, the dialysis conditions, the desired effect, and the like. Dialysis is preferably performed until the ratio of monovalent inorganic cations reaches a state where the aqueous solution and the dialysate are substantially equal to each other or a state close thereto.

  By the dialysis step, the ratio of the acidic polysaccharide monovalent inorganic salt as a main component to all the acidic polysaccharide inorganic salts is high (preferably 99.9 mol% or more). An aqueous solution can be obtained.

  After dialysis, if necessary, the aqueous solution of the acidic polysaccharide inorganic salt of the present invention is concentrated, diluted or dried (dried) by a conventional method, so that the aqueous solution of the acidic polysaccharide inorganic salt of the present invention has a predetermined concentration. (Including sol-like aqueous solutions) or solids.

  Thus, the acidic polysaccharide inorganic salt obtained by the production method of the present invention using dialysis is not usually subjected to low molecular weight compared to the conventional method using acid or alkali treatment.

  The degree of molecular weight reduction that the acidic polysaccharide inorganic salt has undergone in the dialysis process can be known, for example, using the physical properties (for example, solution viscosity) of the acidic polysaccharide inorganic salt before and after the dialysis process as an index. . That is, for example, for an aqueous solution of an acidic polysaccharide inorganic salt (ie, an aqueous solution of an inorganic cation containing a monovalent inorganic cation as a main component and an acidic polysaccharide anion), the solution viscosity before the dialysis step and after the dialysis step By comparing with the solution viscosity, the degree of molecular weight reduction that the acidic polysaccharide inorganic salt received in the dialysis step can be examined. At this time, the solution volume after the dialysis step is concentrated or diluted so as to be the same as the solution volume before the dialysis, and the solution viscosity after the dialysis step is compared with the solution viscosity before the dialysis step. The greater the degree of molecular weight reduction received by the acidic polysaccharide inorganic salt in the dialysis step, the lower the solution viscosity after the dialysis step compared to the solution viscosity before the dialysis step.

  In the present invention, for an aqueous solution of an acidic polysaccharide inorganic salt (that is, an aqueous solution of an inorganic cation containing a monovalent inorganic cation as a main component and an acidic polysaccharide anion), the solution viscosity after the dialysis step is the dialysis. For example, it is 90% or more, preferably 95% or more, more preferably 100% or more of the solution viscosity before the process. Here, the solution viscosity can be measured according to a viscosity measurement method of a reference example described later.

  In the present invention, for an aqueous solution of an acidic polysaccharide inorganic salt (that is, an aqueous solution of a salt of an inorganic cation containing a monovalent inorganic cation as a main component and an acidic polysaccharide anion), the solution molecular weight after the dialysis step is the dialysis. It is 90% or more, preferably 95% or more, more preferably 100% or more of the solution molecular weight before the process.

  In the conventional acid method or calcium method, the acidic polysaccharide inorganic salt is broken and the solution viscosity and the solution molecular weight are greatly reduced. However, if the present invention is used, the solution viscosity and the solution molecular weight of the acidic polysaccharide inorganic salt are greatly reduced. And the purity can be increased.

  According to the present invention, an acidic polysaccharide inorganic salt gel and / or fiber is provided.

  Such an acidic polysaccharide inorganic salt gel and / or fiber is basically obtained by bringing the aqueous solution of the above-mentioned acidic polysaccharide inorganic salt of the present invention into contact with the aqueous inorganic salt solution.

  Although the density | concentration of acidic polysaccharide inorganic salt aqueous solution is not specifically limited as long as a desired gel or fiber is obtained when it contacts with inorganic salt aqueous solution, For example, 0.1-10 mass%, Preferably it is 1-5 mass %, More preferably 2 to 5% by mass.

  The inorganic salt aqueous solution is not particularly limited as long as the inorganic cation in the inorganic salt aqueous solution forms a salt with the acidic polysaccharide anion in the acidic polysaccharide inorganic salt aqueous solution of the present invention to be solidified or gelled.

  The inorganic salt aqueous solution is appropriately selected according to the type of the acidic polysaccharide. For example, calcium salt, magnesium salt, other divalent inorganic salt, potassium salt, other monovalent inorganic salt, preferably calcium salt It is an aqueous solution. For example, when the acidic polysaccharide is alginic acid, the inorganic salt aqueous solution is preferably an aqueous solution containing calcium ions (usually a calcium salt aqueous solution). For example, when the acidic polysaccharide is carrageenan, the inorganic salt aqueous solution is preferably a potassium salt aqueous solution or an ammonium salt aqueous solution.

  Although the density | concentration of inorganic salt aqueous solution is not specifically limited as long as a desired gel or fiber is obtained when it contacts with acidic polysaccharide inorganic salt aqueous solution, For example, 0.1-20 mass%, Preferably it is 1-20 mass. %, More preferably 5 to 20% by mass.

  The method for bringing the acidic polysaccharide inorganic salt aqueous solution and the inorganic salt aqueous solution of the present invention into contact with each other may be any method.

  The method of contacting in the case of producing fibers is, for example, a method of injecting an acidic polysaccharide inorganic salt aqueous solution into the inorganic salt aqueous solution in a thin liquid flow, and injecting an inorganic salt aqueous solution into the acidic polysaccharide inorganic salt aqueous solution in a thin liquid flow Or the like is used.

  When the solution is contacted with a thin liquid flow, the thin liquid flow can be achieved by passing the aqueous solution through a liquid leveling device. Examples of the liquid amount adjusting device include a nozzle, a capillary, a pipe, a hose, a container with a hole, and a syringe. Moreover, you may use a some liquid quantity adjusting device together. The inner diameter of the tip portion (aqueous solution outlet) of the liquid amount adjusting device is not particularly limited, but is, for example, 0.01 to 5.0 mm, preferably 0.1 to 2.5 mm, and more preferably 0.25 mm to 1 mm.

  For example, (1) a sol-like acidic polysaccharide inorganic salt aqueous solution is put into a container (for example, from a hole formed in the bottom or side of the container) and the inorganic salt aqueous solution is infiltrated. Method, (2) A method of directly contacting a sol-like acidic polysaccharide inorganic salt aqueous solution with an inorganic salt aqueous solution, (3) A hole formed in the bottom or side of a container containing a sol-like acidic polysaccharide inorganic salt aqueous solution. Cover with a dialysis membrane and place in a container containing an inorganic salt aqueous solution to allow the inorganic salt to permeate through the dialysis membrane. (4) Cover a sol-like acidic polysaccharide inorganic salt aqueous solution with a dialysis membrane and place in a container containing an inorganic salt aqueous solution. For example, a method of allowing an inorganic salt to permeate from a dialysis membrane is used.

  In a preferred embodiment of the present invention, a calcium alginate gel and / or a sodium alginate solution of the present invention having a high ratio (preferably 99.9 mol% or more) and an aqueous calcium chloride solution are brought into contact with each other. Fiber is obtained.

  The acidic polysaccharide inorganic salt gel and / or fiber of the present invention particularly preferably has an air-dried fiber single fiber tensile strength of about 1.5 g / denier or higher, or a wet fiber single fiber tensile strength of about 0.00. 15 g / denier or more. The tensile strength of single fibers of air-dried fibers and wet fibers can be measured by JIS L1069 “Fiber Tensile Test Method” method.

  In this invention, the gel product and / or fiber product which use the said acidic polysaccharide inorganic salt gel and / or fiber as a raw material are provided. Gel products and / or fiber products include gels only, fibers only, and those made from both gels and fibers.

  The form of the gel product is not particularly limited, and examples thereof include a plate, a pole, a string, a sphere, a film, a network, and a dice.

  Although the form of a textile product is not specifically limited, A textile fabric, a knitted fabric, a net | network, a nonwoven fabric, a thread | yarn, a string, a rope, paper etc. are mentioned.

  The form of the gel product and / or the fiber product may be, for example, a form provided with a recess or a notch capable of holding the adsorbent.

  You may provide the instrument for installing or collect | recovering said gel products / fiber products, such as a metal fitting, a rope, and a string, in a part of gel products and / or fiber products.

  In the present invention, an acidic polysaccharide inorganic salt gel product and / or a fiber product having an adsorbent and an acidic polysaccharide inorganic salt gel product and / or a fiber product having an adsorbent are provided.

  The acidic polysaccharide inorganic salt gel product and / or fiber product retaining such an adsorbent is obtained, for example, by causing the acidic polysaccharide inorganic salt gel product and / or fiber product to retain at least a part of the adsorbent. It is done. For example, it is achieved by embedding at least a part of the adsorbent in the product. Alternatively, for example, the product is formed by wrapping the adsorbent with the product, or the product is processed (for example, molded) into a shape having a concave portion, the adsorbent is put into the concave portion of the product, and the product is covered with the lid. It is made by.

  ADVANTAGE OF THE INVENTION According to this invention, the acidic polysaccharide inorganic salt gel and / or fiber which hold | maintain an adsorption agent which has an acid polysaccharide inorganic salt gel and / or fiber, and an adsorption agent are provided.

  The acidic polysaccharide inorganic salt gel and / or fiber holding the adsorbent is basically obtained by bringing the acidic polysaccharide inorganic salt aqueous solution of the present invention containing the adsorbent into contact with the inorganic salt aqueous solution.

  Any method may be used for the contact.

  As the method of contacting in the case of producing fibers, as described above, for example, a method of injecting the acidic polysaccharide inorganic salt aqueous solution of the present invention containing an adsorbent into the inorganic salt aqueous solution in a thin liquid flow, an inorganic salt aqueous solution, The method of inject | pouring into the acidic polysaccharide inorganic salt aqueous solution of this invention containing an adsorbent with a thin liquid flow is mentioned.

  Examples of the method for contacting in the case of producing a gel include: (1) placing an aqueous sol-like acidic polysaccharide inorganic salt solution in which at least a part of an adsorbent is embedded in a container; (2) A method of infiltrating an aqueous solution of an inorganic salt) (2) A method of directly contacting an inorganic salt aqueous solution of the sol-like acidic polysaccharide, (3) An inorganic salt of an acidic polysaccharide of the sol A method of covering the bottom or side surface of a container containing an aqueous solution with a dialysis membrane, attaching it to a container containing an inorganic salt aqueous solution, and infiltrating the inorganic salt from the dialysis membrane, (4) the sol-like acidic polysaccharide inorganic salt A method in which the aqueous solution is covered with a dialysis membrane, attached to a container containing the inorganic salt aqueous solution, and the inorganic salt permeates from the dialysis membrane is used. At this time, the adsorbent is preferably disposed in the sol-form acidic polysaccharide inorganic salt aqueous solution at predetermined intervals.

  According to the present invention, a gel product and / or a fiber product using an acidic polysaccharide inorganic salt gel and / or fiber holding such an adsorbent as raw materials is provided. The form and characteristics of the product are as described above.

As adsorbents, known adsorbents for nitrogen and phosphorus may be widely used. Among them, oxoanionic adsorbents for the purpose of adsorbing nutrient salts in salt water with many interfering ions (nanospace control) It is preferable to use a nitrogen adsorbent or a phosphorus adsorbent which is also called an adsorbent. The oxoanion adsorbent has a high adsorption rate, high adsorption capacity, and the ability to efficiently desorb adsorbed nitrogen and phosphorus even in the presence of other mixed ions in salt water. Examples of the oxo anion adsorbent (also referred to as nano-space control adsorbent) and nitric acid adsorbent include, for example, a hydroxide containing Ni—Fe having a heat-treated product of a composite metal hydroxide crystal as an active ingredient. Nitric acid adsorbent (Patent Document 5) containing layered double hydroxide (LDH) synthesized from the active ingredient, and M ^II _1-x M ^III _x (OH) ₂ A ^n- _y · mH as phosphoric acid adsorbent A phosphorus adsorbent containing a heat-treated product of a composite metal hydroxide crystal represented by ₂ O as an active ingredient can be cited as an example (Patent Document 6).

  Known nitric acid adsorbents that adsorb nitric acid as nutrient salts include, for example, tributylamino group-containing ion exchange resins (Patent Document 7), graphite and nitric acid intercalation compounds (Patent Document 8), and three-dimensional cross-linked polymers. Synthetic polymer adsorbent (Patent Document 9), a secondary amine type substituent and a tertiary amine type substituent chemically bonded to the basic skeleton, and a three-dimensional copolymer of styrene and divinylbenzene as the basic skeleton A styrene-based three-dimensional copolymer (Patent Document 10) characterized by having a phosphate group and an amino group in at least a part of the benzene nucleus can be used. As the ammonium ion adsorbent, zeolite or the like can be used.

  As a known phosphoric acid adsorbent that adsorbs phosphorus as nutrient salts, for example, slag produced by melting treatment of industrial waste is subjected to iron removal treatment and then finely pulverized, and calcium oxide therein is removed by alkali treatment. From an inorganic adsorbent for removing phosphorus made porous (Patent Document 11), a phosphorus removing material formed by molding a substance containing allophane as a main component and calcined at 300 to 600 ° C. (Patent Document 12), fluidized bed boiler A dephosphorizing material for wastewater consisting of a hardened body mainly containing discharged ash (Patent Document 13), a remover of phosphorus dissolved in water containing hydrotalcite as an active ingredient (Patent Document 14), calcareous material A dephosphorization material (Patent Document 15) made of a reaction product of a raw material, a siliceous raw material, and zeolite can be used.

  As adsorbents, adsorbents that adsorb phosphorus-containing components as described above, adsorbents that adsorb nitrogen-containing components, adsorbents that adsorb sulfur-containing components, adsorbents that adsorb boron-containing components, etc. Can be used.

  There may be one kind of adsorbent, or two or more kinds. Moreover, when using 2 or more types of adsorbents, the adsorbent which shows the same effect may be sufficient, and the adsorbent which shows a different effect may be sufficient. For example, a combination of an adsorbent that adsorbs nutrient salts containing phosphorus and an adsorbent that adsorbs nutrient salts containing nitrogen is used.

The form of the adsorbent may be any form, and examples thereof include powder, granules, tablets, fine particles, particles, films, and threads.
According to the present invention, there is further provided an acidic polysaccharide inorganic salt gel and / or fiber holding an adsorbent, and / or an acidic polysaccharide inorganic salt gel product and / or fiber product holding an adsorbent. An apparatus for reducing the concentration of nutrients is provided.

  In the present invention, salt water includes sea water and brackish water. As salt water, although it may be seawater derived from a fish culture tank, for example, it is not limited to this.

  By using the nutrient salt concentration reducing device of the present invention, for example, nitrate nitrogen, nitrite nitrogen, ammonia nitrogen, urea nitrogen, organic phosphorus, inorganic phosphorus (such as orthophosphoric acid), silicon ( The concentration of at least one nutrient selected from the group consisting of silicic acid and the like can be suitably reduced.

  According to the present invention, in addition to the nutrient salt concentration reducing device described above, a flow path switching device, a nitrification tank in which nitrifying bacteria are fixed, an oxygen supply tank, a foam separation tank, a precipitation tank, a pH adjustment water tank, a water temperature There is provided a system for reducing the concentration of nutrients in salt water, further comprising at least one selected from the group consisting of a regulating tank, a filtration tank, a circulation pump, a seaweed growth tank, and a biological breeding tank.

  According to the present invention, the method includes the step of treating salt water in any one selected from the group consisting of the concentration reducing device for nutrient salts in the salt water and the concentration reducing system for nutrient salts in the salt water. A method for reducing the concentration of nutrients in salt water is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the concentration reduction processing water of the nutrient salt in salt water obtained by the density | concentration reduction method of nutrient salt in salt water is provided. The nutrient-reduced nutrient water in the salt water of the present invention is useful as breeding water for organisms that are difficult to grow if the nutrient salt concentration in the salt water is high, such as giraffe rhinoceros of the open oceanic red algae large seaweed. .

  ADVANTAGE OF THE INVENTION According to this invention, the open-sea creature produced in the concentration reduction processing water of the nutrient salt in salt water is provided.

  Examples of the offshore organisms produced in the present invention include shellfish, algae, protozoa, sponges, cnidarians, and comb animals.

  The organism produced using the treated water for reducing the concentration of nutrient salts in the salt water of the present invention can be used for ornamental purposes or as a raw material for useful substances. For example, useful proteins, carbohydrates, and the like can be obtained from giraffe rhinoceros, a large open-sea red alga seaweed. The apparatus for reducing the concentration of nutrients in salt water according to the present invention includes a batch method (batch method), an intermittent flow pouring method, a continuous pouring method, or a combination thereof. It can be used in any method or system. In the case of the pouring method, the concentration of nutrient salts can be effectively reduced by using a nutrient salt concentration reducing device or system having a flow path switching valve. FIG. 4 shows a schematic diagram of a flow path switching valve and a device for reducing the concentration of nutrients in salt water having the same. The flow path switching valve usually includes a switching valve, a valve, a liquid feed pump, and the like. As the switching valve, a multi-directional valve can be used. For example, an eight-way valve, a six-way valve, or a combination thereof can be used. The valve may be electromagnetic or manual. The pump may be operated continuously, or may be temporarily stopped (for example, before and after the flow path switching). Further, the nutrient salt concentration reducing device in the salt water of the present invention may be aerated as necessary.

  The unit on the right side of unit 1 (denoted as U1) is unit 2 (U2) in FIG. The solenoid valve is composed of two three-way switching valves (FIG. 5). One three-way switching valve is connected to the inlet and outlet of each unit. The solenoid valve may be replaced with a manual flow path switching valve. The pump may be temporarily stopped before, after, or before and after the valve flow path switching operation.

  It is also possible to reduce the concentration of nutrients in salt water using a nutrient concentration reducing device E (FIG. 6a) having a flow path switching program different from that in FIG.

  Unlike FIG. 4b, salt water with high nutrient concentration is connected to the inlet of U1 through the 8-way valve A, and salt water is returned to the environment from the outlet of U2 through the 8-way valve B (FIG. 6a, FIG. 6). 6b).

  One example program is described below.

I 0 to 6 hours after the start of salt water feeding, each unit contains 10 liters of salt water and an appropriate amount of adsorbent in advance.

  The outlet of each unit is connected to the inlet of the unit on the left with two flow path switching valves (may be solenoid valves) (for example, the U1 outlet is connected to the U8 inlet) .) However, the U1 inlet and the U2 outlet are disconnected, and the U1 inlet is connected to a salt water supply source having a high nutrient concentration through the 8-way valve A.

  The U2 outlet is connected to the water tank for treated water through the 8-way valve A.

  In this state, the salt water is started to flow from the source of salt water having a high nutrient salt concentration to the nutrient salt concentration reducing apparatus E at a flow rate of 40 liters / day. The salt water flowing out from U2 is stored in the treated water tank until 6 hours have passed since the supply of salt water having a high nutrient salt concentration to U1. Measure the concentration of nutrients in the salt water of the treated water tank, confirm that the nutrient concentration is below the standard value, and return it to the surrounding water area (environment).

II After 6-12 hours from the start of salt water feeding, when the salt water starts flowing from a salt water source with a high nutrient concentration, the operations of II-1 to 4 are performed almost simultaneously.
(II-1) The eight-way valve A is switched to change the salt water flow path from the salt water supply source having a high nutrient concentration from the U1 inlet to the U2 inlet.
(II-2) Switching the U1 inlet switching valve (or a solenoid valve) and the U2 outlet switching valve (or a solenoid valve) to shut off the flow path between the U1 inlet and the 8-way valve A, The flow paths of the U1 inlet and the U2 outlet are connected.
(II-3) Switching the U3 inlet switching valve (or a solenoid valve) and the U2 outlet switching valve (or a solenoid valve) to cut the flow path between the U3 outlet and the U2 inlet, The flow path between the inlet and the 8-way valve B is connected.
(II-4) The 8-way valve B is switched so that the running water from the U3 outlet is connected to the treated water tank. Measure the concentration of nutrients in the salt water of the treated water tank, confirm that the nutrient concentration is below the standard value, and return it to the surrounding water area (environment).

III After 12 to 18 hours from the start of the salt water feeding, when the salt water is started to flow from the salt water supply source having a high nutrient concentration, the operations of III-1 to 4 are performed almost simultaneously.
(III-1) The eight-way valve A is switched to change the salt water flow path from the salt water supply source having a high nutrient salt concentration from the U2 inlet to the U3 inlet.
(III-2) Switching the U2 inlet switching valve (may be a solenoid valve) and the U3 outlet switching valve (may be a solenoid valve) to shut off the flow path between the U2 inlet and the 8-way valve A, The flow path between the U2 inlet and the U3 outlet is connected.
(III-3) A U4 outlet switching valve (or a solenoid valve) and a U3 inlet switching valve (or a solenoid valve) may be switched to cut off the flow path between the U4 outlet and the U3 inlet. The flow path between the inlet and the 8-way valve B is connected.
(III-4) The 8-way valve B is switched so that the flowing water from the U4 outlet is connected to the treated water tank. Measure the concentration of nutrients in the seawater tank for treated water, make sure that the nutrient concentration is below the reference value, and return it to the surrounding waters (environment).

IV After 18 to 24 hours from the start of feeding the salt water, when the salt water is started to flow from the salt water supply source having a high nutrient concentration, the operations of IV-1 to IV-4 are performed almost simultaneously.
(IV-1) The eight-way valve A is switched to change the salt water flow path from the salt water supply source having a high nutrient salt concentration from the U3 inlet to the U4 inlet.
(IV-2) Switching the U3 inlet switching valve (or electromagnetic valve) and U4 outlet switching valve (or electromagnetic valve) to shut off the flow path between the U3 inlet and the 8-way valve A, The flow path between the U3 inlet and the U4 outlet is connected.
(IV-3) Switching the U5 outlet switching valve (or a solenoid valve) and the U4 inlet switching valve (or a solenoid valve) to cut the flow path between the U5 outlet and the U4 inlet; The flow path between the inlet and the 8-way valve B is connected.
(IV-4) Switch the 8-way valve B so that the running water from the U5 outlet is connected to the treated water tank. Measure the concentration of nutrients in the salt water of the treated water tank, confirm that the nutrient concentration is below the standard value, and return it to the surrounding water area (environment).

V After 24 to 30 hours from the start of feeding the salt water, when the salt water is started to flow from the salt water supply source having a high nutrient concentration, the operations of V-1 to 4 are performed almost simultaneously.
(V-1) The eight-way valve A is switched to change the salt water flow path from the salt water supply source having a high nutrient salt concentration from the U4 inlet to the U5 inlet.
(V-2) Switching the U4 inlet switching valve (or electromagnetic valve) and U5 outlet switching valve (or electromagnetic valve) to shut off the flow path between the U4 inlet and the 8-way valve A; The flow paths of the U4 inlet and the U5 outlet are connected.
(V-3) A U6 outlet switching valve (or a solenoid valve) and a U5 inlet switching valve (or a solenoid valve) may be switched to cut off the flow path between the U6 outlet and the U5 inlet. The flow path between the inlet and the 8-way valve B is connected.
(V-4) The 8-way valve B is switched and connected so that the flowing water from the U6 outlet is collected in the water tank for treated water. Measure the concentration of nutrients in the salt water of the treated water tank, confirm that the nutrient concentration is below the standard value, and return it to the surrounding water area (environment).

  In V, the seawater eluted from the U6 outlet is seawater retained for 24 hours in a nutrient salt concentration reducing device in salt water by an adsorbent. In V (24 passes after starting to feed salt water from a source of salt water having a high nutrient concentration), the salt water that first flows into U1 in I elutes from the nutrient concentration reducing device.

VI After 30 to 36 hours from the start of salt water feeding, when the salt water is started to flow from the salt water supply source having a high nutrient concentration and 30 hours have passed, the operations of VI-1 to 4 are performed almost simultaneously.
(VI-1) The eight-way valve A is switched to change the salt water flow path from the salt water supply source having a high nutrient salt concentration from the U5 inlet to the U6 inlet.
(VI-2) Switching the U5 inlet switching valve (or solenoid valve) and U6 outlet switching valve (or solenoid valve) to shut off the flow path between the U5 inlet and the 8-way valve A, Connect the flow path between the U5 inlet and the U6 outlet.
(VI-3) Switching the U7 outlet switching valve (or solenoid valve) and the U6 inlet switching valve (or solenoid valve) to cut the flow path between the U7 outlet and U6 inlet; The flow path between the inlet and the 8-way valve B is connected.
(VI-4) Switch the 8-way valve B so that the flowing water from the U7 outlet is connected to the treated water tank. Measure the concentration of nutrients in the salt water of the treated water tank, confirm that the nutrient concentration is below the standard value, and return it to the surrounding water area (environment).

VII 36 to 42 hours after the start of the salt water feeding, the operation of VII-1 to 4 is carried out almost simultaneously when 36 hours have passed since the salt water started flowing from the salt water supply source having a high nutrient concentration.
(VII-1) The eight-way valve A is switched to change the salt water flow path from the salt water supply source having a high nutrient salt concentration from the U6 inlet to the U7 inlet.
(VII-2) Switching the U6 inlet switching valve (or electromagnetic valve) and U7 outlet switching valve (or electromagnetic valve) to shut off the flow path between the U6 inlet and the 8-way valve A, The flow path between the U6 inlet and the U7 outlet is connected.
(VII-3) A U8 outlet switching valve (or a solenoid valve) and a U7 inlet switching valve (or a solenoid valve) may be switched to cut off the flow path between the U7 outlet and the U6 inlet. The flow path between the inlet and the 8-way valve B is connected.
(VII-4) The 8-way valve B is switched so that the flowing water from the U7 outlet is connected to the treated water tank. Measure the concentration of nutrients in the salt water of the treated water tank, confirm that the nutrient concentration is below the standard value, and return it to the surrounding water area (environment).

VIII 42 to 48 hours after the start of the salt water feeding, the operation of VIII-1 to 4 is carried out almost simultaneously when 42 hours have passed since the salt water began to flow from the salt water supply source having a high nutrient salt concentration.
(VIII-1) The eight-way valve A is switched to change the salt water flow path from the salt water supply source having a high nutrient salt concentration from the U7 inlet to the U8 inlet.
(VIII-2) Switching the U7 inlet switching valve (or electromagnetic valve) and U8 outlet switching valve (or electromagnetic valve) to shut off the flow path between the U7 inlet and the eight-way valve A; The flow path between the U7 inlet and the U8 outlet is connected.
(VIII-3) Switching the U1 outlet switching valve (or a solenoid valve) and the U8 inlet switching valve (or a solenoid valve) to cut the flow path between the U8 outlet and the U7 inlet; The flow path between the inlet and the 8-way valve B is connected.
(VIII-4) The 8-way valve B is switched so that the running water from the U1 outlet is connected to the treated water tank. Measure the concentration of nutrients in the salt water of the treated water tank, confirm that the nutrient concentration is below the standard value, and return it to the surrounding water area (environment).

IX 48 to 54 hours after the start of the salt water feeding, the operation of IX-1 to 4 is carried out almost simultaneously when 48 hours have passed since the salt water started flowing from the salt water supply source having a high nutrient concentration.
(IX-1) The eight-way valve A is switched to change the salt water flow path from the salt water supply source having a high nutrient salt concentration from the U8 inlet to the U1 inlet.
(VIII-2) Switching the U8 inlet switching valve (or a solenoid valve) and the U1 outlet switching valve (or a solenoid valve) to shut off the flow path between the U7 inlet and the 8-way valve A, The flow path between the U8 inlet and the U1 outlet is connected.
(VIII-3) Switching the U2 outlet switching valve (or a solenoid valve) and the U1 inlet switching valve (or a solenoid valve) to cut the flow path between the U1 outlet and the U8 inlet; The flow path between the inlet and the 8-way valve B is connected.
(VIII-4) The 8-way valve B is switched so that the running water from the U2 outlet is connected to the treated water tank. Measure the concentration of nutrients in the salt water of the treated water tank, confirm that the nutrient concentration is below the standard value, and return it to the surrounding water area (environment).

  As for salt water flow, the IX state is the same as the original I state.

X Repeat the switching of two switching valves (or electromagnetic valves) every 6 hours after 54 hours from the start of salt water feeding, and the switching of the 8-way valve A and B-way valve B to reduce the concentration of nutrients in salt water .

  The adsorbent that has absorbed nutrients in each unit and proliferated can be isolated from salt water at any time, and a new adsorbent should be put into each unit instead of the adsorbent that has adsorbed nutrients. Can do. The timing can also be determined by the nutrient adsorption capacity of the adsorbent, the amount of adsorbent introduced into the unit, and the concentration of the nutrient in the brine.

  After the salt water from the salt water source with high nutrient concentration is introduced to the unit containing the adsorbent (state I), until the unit is connected to the treated water tank through the 8-way valve ( when the replacement of the adsorbent IX state) as prospect, adsorbent newly introduced becomes to be utilized in the nutrient concentration reduction in the brine for 48 hours.

The nutrient salt concentration reduction apparatus of FIG. 6 has a time period of 48 hours for reducing the concentration of nutrient salts in salt water by the adsorbent, which is longer than 18 hours in FIG. The nutrient concentration of the treated seawater produced by the reduction treatment device E is lower than the nutrient salt concentration of the treatment saltwater produced by the concentration reduction treatment device C for the nutrient salts in the salt water of FIG. Therefore, it is considered to be a more effective means than FIG. 4 when the nutrient salt concentration in the salt water is high.
JP 2004-130200 A (Claims and others) Japanese Patent Application No. 2004-89760 (Claims and others) US Pat. No. 4,479,877 (Claims and others) Japanese Patent Publication No. 60-18605 (Claims and others) JP-A-5-15776 (Claims and others) JP-A-7-238113 (Claims and others) Japanese Patent Laid-Open No. 3-68445 (claims and others) JP 63-39632 A (claims and others) Japanese Patent Laid-Open No. 5-261378 (Claims and others) JP 2000-24658 A (Claims and others) JP 2001-9470 A (Claims and others)

  The present invention relates to an acidic polysaccharide inorganic salt and a production method thereof, an acidic polysaccharide inorganic salt gel and / or fiber, an acidic polysaccharide inorganic salt gel product and / or a fiber product, an acidic polysaccharide inorganic salt gel holding an adsorbent, and Provided is an acidic polysaccharide inorganic salt gel product and / or a fiber product that retains fibers and / or adsorbents. The present invention further provides an acidic polysaccharide inorganic salt gel and / or fiber holding an adsorbent and / or an acidic polysaccharide inorganic salt gel product holding an adsorbent and / or a nutrient salt in salt water using the fiber product. Concentration reduction device, nutrient salt concentration reduction system in salt water, nutrient salt concentration reduction method in salt water, nutrient salt concentration reduction treatment water in salt water, and nutrient salt concentration reduction treatment water in salt water Providing the oceanic creatures produced.

  The acidic polysaccharide inorganic salt gel and / or fiber holding the adsorbent of the present invention, or the acidic polysaccharide inorganic salt gel product and / or fiber product holding the adsorbent is (1) compared to the adsorbent alone. Since the adsorbent does not settle in the apparatus or collect in a place where the water flow is slow (for example, at the corner of the apparatus), the concentration of nutrients can be reduced efficiently. (2) Concentration of nutrients can be reduced more efficiently by making them present in the saccharide inorganic gel and / or fiber at a predetermined distribution (for example, at equal intervals). , The adsorbent can be easily recovered together with the acidic polysaccharide inorganic gel and / or fiber, (4) the clogging of the drain filter by the adsorbent can be avoided, (5) the adsorbent is acidic polysaccharide inorganic Supported on gel and / or fiber Because the adsorbent collides with each other or the adsorbent collides with another substance (for example, the bottom or side wall of the apparatus), the wear of the adsorbent can be prevented. (6) In particular, alginic acid gel and / or fiber have moderate hydrophilicity, so that salt water containing nutrient salt is appropriately passed, and excellent gel and / or fiber strength can be obtained. Therefore, the adsorbent can be firmly supported, and the advantages of having desirable properties as a support for the adsorbent in salt water can be obtained. Furthermore, (7) while general synthetic gels cannot avoid the use of harmful reagents and organic solvents during synthesis, alginic acid gels do not contain reagents harmful to preparation. (8) Since the acidic polysaccharide inorganic salt gel such as calcium alginate gel can be easily returned to the water-soluble acidic polysaccharide aqueous solution by exchanging cations, the retained adsorbent can be recovered. In a synthetic gel, it is often difficult to recover the adsorbent retained. (9) Since the calcium alginate gel can recover the adsorbent that has been retained, it is possible to recover the nutrients adsorbed on the adsorbent.

  Furthermore, in the case of an acidic polysaccharide inorganic salt gel and / or fiber prepared using a high-purity acidic polysaccharide inorganic salt aqueous solution, an acidic polysaccharide inorganic salt prepared using an acidic polysaccharide inorganic salt aqueous solution containing a contaminating inorganic cation Compared with gels and / or fibers, advantages of gel strength, fiber strength and salt water resistance are obtained. For this reason, there is little leakage of the adsorbent currently hold | maintaining from acidic polysaccharide inorganic salt gel and / or a fiber. This is remarkable when the acidic polysaccharide inorganic salt gel and / or fiber is calcium alginate gel and / fiber, and the acidic polysaccharide inorganic salt aqueous solution is a sodium alginate aqueous solution.

  Examples of the present invention will be described below, but the examples do not limit the present invention.

Reference example 1

Purity of high grade sodium chloride crystals;
The purity of sodium chloride grade sodium chloride was measured. Any analysis method may be used for cation determination and anion determination in an aqueous sodium chloride solution, but in this specification, sodium ion, calcium ion, magnesium ion and potassium ion are determined. Was performed by atomic absorption analysis, and sulfate ions (SO ₄ ²⁻ ) and chloride ions (Cl ⁻ ) were quantified using ion chromatography. In the present specification, sodium chloride having a sodium purity of 99.86% by mass or more and less than 99.90% by mass is also referred to as high grade sodium chloride. Commercially available salt is also referred to as commercially available salt.

  A 10% saline solution was prepared by dissolving 1 g of higher grade sodium chloride crystals in 10 ml of distilled water. The measured value is an average of actually measured values of 10 lots of sodium chloride high grade sodium chloride crystals. Sodium chloride 99.840% by mass, calcium sulfate 0.0010% by mass, calcium chloride 0.0120% by mass, magnesium chloride 0.0310% by mass, potassium chloride 0. It was 0620 mass%. The mass% by ion of sodium chloride crystals of higher grade sodium chloride was 39.903 mass% sodium ion, 0.0046 mass% calcium ion, 0.0079 mass% magnesium ion, and 0.0252 mass% potassium ion. The mass% of each inorganic cation relative to the total inorganic cations (sodium ion, calcium ion, magnesium ion and potassium ion: equivalent to 39.34284% by mass in sodium chloride crystals of higher grade sodium chloride) is 99.8855% by mass of sodium ions, They were 0.0117 mass% calcium ion, 0.0201 mass% magnesium ion, and 0.0826 mass% potassium ion. That is, the purity of sodium chloride was 99.8940% by mass of sodium chloride, and the purity of the main component of the inorganic cation with respect to all inorganic cations was 99.8855% by mass of sodium ions. In addition, in this invention, an inorganic cation is a metal ion or a positive basic group, and a hydrogen ion is not contained.

Reference example 2

Purity of commercial salt;
Sodium ion, potassium ion, magnesium ion and calcium ion were quantitatively analyzed for the commercially available salt by atomic absorption analysis, and the mass% and mol% of each inorganic cation with respect to the total of four kinds of inorganic cations were calculated. As a result, in a 1M commercial saline solution, sodium ion was 22274 ppm (968.43 mmol / l), potassium was 20.14 ppm (0.52 mmol / l), and magnesium ion was 11.45 ppm (0.47 mmol / l). In addition, 1.80 ppm (0.04 mmol / l) of calcium ions was contained.

  The 1M commercial saline solution has a total of 4307.39 ppm (969.46 mmol / l) of four kinds of inorganic cations, 99.85% by mass (99.89 mol%) of sodium ions, and 0.09% by mass of potassium ions ( 0.05 mol%), magnesium ions were 0.05 mass% (0.05 mol%), and calcium ions were 0.01 mass% (0.005 mol%).

  Thus, it is clear that commercial salt contains magnesium ions and calcium ions as impurities. Attempts have been made to remove magnesium ions and calcium ions from aqueous sodium chloride by adding chemicals such as soda ash, but in order to process a large amount of sodium chloride, a large-scale facility is required. The long time required for processing has been a big problem.

Reference example 3

Purity of commercially available sodium alginate preparation of a 1% by weight aqueous sodium alginate solution;
In order to prepare a sodium alginate aqueous solution of about 1% by mass (W / V), about 3.3 g each of five types of commercially available sodium alginate A, B, C, D, and E were weighed and 300 The mixture was added to a milliliter beaker and allowed to stand for 30 minutes, and then stirred to prepare a total volume of 300 milliliters and dissolve. The amounts weighed were 3.3003 g of commercially available sodium alginate A, 3.3001 g of sodium alginate B, 3.3004 g of sodium alginate C, 3.2959 g of sodium alginate D, and 3.3004 g of sodium alginate E.

Sodium ion concentration;
The sodium ion in the aqueous solution of about 1% by mass sodium alginate prepared by atomic absorption analysis after diluting the about 1% by mass aqueous sodium alginate solution 10 times and then diluting 100 times with 0.1N hydrochloric acid. The concentration was determined. As a result, 1075.8 ppm (46.77 mmol / l) for A, 938.7 ppm (40.81 mmol / l) for B, 903.1 ppm (39.27 mmol / l) for C, and 826.5 ppm (35. 93 mmol / l) and E was 981.8 ppm (42.69 mmol / l). The calculation was performed assuming that the molecular weight of sodium was 23.0.

Contaminated inorganic ion concentration;
The aqueous solution of about 1% by mass sodium alginate is diluted 10-fold with 0.1N hydrochloric acid, and the resulting precipitate is removed with a filter. The solution after analysis is subjected to atomic absorption spectrometry to measure potassium ions, calcium ions, magnesium ions, manganese. Ions, cobalt ions, iron ions, nickel ions and zinc ions were quantified. The potassium ion concentration in the about 1% sodium alginate aqueous solution was 10.35 ppm (0.26 mmol / l) for A, 4.99 ppm (0.13 mmol / l) for B, and 13.70 ppm (0.35 mmol / l) for C. l), D was 73.85 ppm (1.89 mmol / l), and E was 5.75 ppm (0.15 mmol / l). The magnesium ion concentration in the about 1% by mass sodium alginate aqueous solution was 1.44 ppm (0.059 mmol / l) for A, 1.00 ppm (0.041 mmol / l) for B, and 1.38 ppm (0.057 mmol) for C. / L), D was 1.19 ppm (0.049 mmol / l), and E was 1.25 ppm (0.051 mmol / l). The calcium ion concentration in the about 1% by mass sodium alginate aqueous solution was 4.14 ppm (0.103 mmol / l) for A, 13.66 ppm (0.341 mmol / l) for B, and 3.00 ppm (0.075 mmol) for C. / L), D was 10.99 ppm (0.274 mmol / l), and E was 13.28 ppm (0.331 mmol / l). Calculation was made assuming that the molecular weight of potassium was 39.1, the molecular weight of magnesium was 24.3, and the molecular weight of calcium was 40.1. Manganese ions, cobalt ions, iron ions, nickel ions, and zinc ions were below the detection limit.

  From the above, it is apparent that the approximately 1% by mass aqueous sodium alginate solution contains potassium ions, magnesium ions, and calcium ions as contaminant components in addition to sodium ions, which are inorganic cation main components. Sodium alginate is derived from brown algae and exists as a salt of a divalent inorganic cation in the algae. Contaminating ions in the approximately 1% by mass aqueous sodium alginate solution are considered to be derived from the raw material.

Sodium purity;
The mass% and mol% of each inorganic cation relative to the total inorganic cation of sodium ion, potassium ion, magnesium ion and calcium ion were calculated.

  In the about 1% by mass (W / V) sodium alginate aqueous solution A, the total inorganic cation total is 1091.73 ppm (47.19 mmol / l), the sodium ion is 98.54% by mass (99.11 mol%), and the potassium ion is 0.95 mass% (0.55 mol%), magnesium ions were 0.13 mass% (0.13 mol%), and calcium ions were 0.38 mass% (0.22 mol%).

  In the about 1% by mass (W / V) sodium alginate aqueous solution B, the total inorganic cation is 958.35 ppm (41.32 mmol / l), the sodium ion is 97.95% by mass (98.77 mol%), and the potassium ion is 0.52 mass% (0.31 mol%), magnesium ion was 0.10 mass% (0.10 mol%), and calcium ion was 1.43 mass% (0.83 mol%).

  In the about 1% by mass (W / V) sodium alginate aqueous solution C, the total inorganic cation total is 922.18 ppm (39.75 mmol / l), the sodium ion is 98.04% by mass (98.79 mol%), and the potassium ion is It was 1.49 mass% (0.88 mol%), magnesium ion was 0.15 mass% (0.14 mol%), and calcium ion was 0.33 mass% (0.19 mol%).

  In the about 1% by mass (W / V) sodium alginate aqueous solution D, the total inorganic cation is 912.53 ppm (38.14 mmol / l), the sodium ion is 90.57% by mass (94.20 mol%), and the potassium ion is The content was 8.09 mass% (4.96 mol%), magnesium ion was 0.13 mass% (0.13 mol%), and calcium ion was 1.20 mass% (0.72 mol%).

  In the about 1% by mass (W / V) sodium alginate aqueous solution E, the total inorganic cation is 1002.08 ppm (43.22 mmol / l), the sodium ion is 97.98% by mass (98.77 mol%), and the potassium ion is 0.57 mass% (0.35 mol%), magnesium ion was 0.12 mass% (0.12 mol%), and calcium ion was 1.33 mass% (0.77%).

  The five types of commercially available sodium alginate had a sodium purity of 90.57 to 98.54% by mass (94.20 to 99.11 mol%), which is an inorganic cation main component. From this, it is clear that it is difficult to efficiently purify the commercially available sodium alginate by dialysis using sodium chloride having a sodium purity of less than 99% by mass.

  Since the commercially available sodium chloride described has a sodium purity of less than 99% by mass, it is unsuitable as a dialysate for increasing the purity of the commercially available sodium alginate.

  It can be understood that the higher the purity of sodium chloride, the better the dialysate for increasing the purity of the commercially available sodium alginate.

Reference example 4

Abnormal adsorption chromatography phenomenon, pseudo-abnormal adsorption chromatography phenomenon;
As a result of intensive studies to efficiently remove a trace amount of impurities contained therein from an aqueous solution of a water-soluble compound, the present inventors have made an adsorption column containing the same substance as the impurity in advance. When an aqueous solution to be treated is passed through this, an abnormal adsorption chromatographic phenomenon occurs, and a fraction with a high impurity concentration is formed. It has already been found that an aqueous solution containing a water-soluble compound with high purity removed can be obtained (Patent Document 1).

  That is, when an aqueous solution containing a water-soluble compound containing at least one trace impurity is passed through a column packed with an adsorbent that selectively adsorbs the impurity, an abnormal adsorption chromatography phenomenon is caused in removing the impurity. A method for removing trace impurities in a solution, comprising forming a fraction having an impurity concentration higher than the trace impurity concentration in an original solution and removing the fraction.

  In general, when passing an aqueous solution of a water-soluble compound containing at least one trace impurity, for example, a sodium chloride solution containing a trace amount of potassium ions, through a column packed with an adsorbent that selectively adsorbs potassium ions, such as ammonium ion zeolite. In addition, if the adsorbent is previously adsorbed with the same substance as the trace impurities, that is, potassium ions, the sodium ions as the main components are replaced with the potassium ions present in the pores, and this is combined with the potassium ions contained as impurities. The fraction which flows out and whose concentration is higher than the concentration of potassium ions originally contained in the aqueous solution is obtained.

  The sodium ions temporarily adsorbed by this adsorbent are replaced again with the potassium ions in the subsequent aqueous solution. At this time, in order to generate an activated adsorption point, it is more than the case of the normal adsorption chromatography phenomenon. Abnormal adsorption chromatography phenomenon that adsorbs a large amount of potassium ions.

  This is a method for obtaining a water-soluble compound with improved purity by removing trace impurities contained in a water-soluble compound aqueous solution by utilizing such an abnormal adsorption chromatography phenomenon.

This abnormal adsorption chromatography phenomenon is usually characterized by the presence of the following processes. That is, when chromatography was performed using a column pre-filled with an adsorbent containing trace impurities,
(1) A process of producing an eluate fraction enriched in trace impurities until a volume of eluate from the column reaches 5 times the column volume after introducing a concentrated solution of a predetermined substance containing trace impurities into the column. ,
(2) Next, the process of producing an eluate fraction whose trace impurities monotonously decrease,
(3) Subsequently, a process of generating an eluate fraction in which the trace impurity concentration becomes constant at a value smaller than the initial concentration (concentration in the stock solution),
(4) Further, a process of producing an eluate fraction in which the impurity concentration continuously increases monotonously at a value smaller than the initial concentration, and (5) an eluate fraction in which the impurity concentration is optionally greater than the initial concentration. Process.

  In this method for removing trace impurities in the solution, the same applies to the abnormal adsorption chromatography phenomenon (hereinafter referred to as pseudo-abnormal adsorption chromatography phenomenon) lacking the process (1) among the processes (1) to (5). Is available.

  As the water-soluble compound aqueous solution containing trace impurities treated by the trace impurity removal method in this solution, various aqueous solutions can be applied, but an inorganic salt aqueous solution is preferable. The concentration of the water-soluble compound aqueous solution varies depending on the type of the water-soluble compound, the type of adsorbent used, and the chromatography conditions such as temperature, pressure, and the flow rate through the column. The lower limit is selected, and the upper limit is selected in the range of saturated concentration, preferably in the range of 2 to 30% by mass, more preferably in the range of 2 to 10% by mass.

  Further, the concentration of trace impurities contained as components other than the main component in the aqueous solution of the water-soluble compound is desirably 20 times or less, preferably 1/50 or less of the concentration of the water-soluble compound as the main component.

The adsorbent used in the method for removing trace impurities in this solution depends on the kind of trace impurities in the aqueous solution to be removed. When the impurities are metal ions, cationic zeolite, for example, ammonium ion type Zeolite, H ⁺ type natural zeolite or the like or a cation exchange resin is used. When trace impurities are organic substances, silica gel, aluminum oxide, activated carbon, cellulose, chemically modified silica gel, Sephadex, polyacrylamide gel and the like are used. These adsorbents are usually used as particles having a particle size of 0.1 to 2.5 mm. In addition, the linear velocity at the time of liquid passage is usually selected in the range of 0.1 to 300 cm / hr, preferably 0.1 to 100 cm / hr.

  In this method for removing trace impurities in a solution, it is necessary to previously adsorb the same substance as the impurity to an adsorbent that selectively adsorbs the impurity. In this case, the adsorption amount is preferably in the range of 1.0 to 10 μmol per 1 g of the adsorbent. In this case, if an adsorbent that has already adsorbed the same substance as the impurity is used, it is not necessary to perform a process for adsorbing the same substance as the impurity.

  In order to suitably perform the method for removing trace impurities in this solution, the entire fraction of the column eluate of the aqueous solution of water-soluble compound passed through the column is collected, and the concentration of the desired component in each fraction is measured. Collect approximate fractions. In this way, a concentrated solution of the desired component can be obtained by collecting the concentrated fractions of the specific component together, and the concentration of trace impurities is lower than the initial concentration. By collecting the water, a highly pure water-soluble compound can be obtained.

  Further, by desorbing a predetermined component temporarily adsorbed on the column with an appropriate eluent, a solution in which the component is concentrated can be obtained.

  A preferred embodiment of the method for removing trace impurities in this solution will be described by taking a sodium salt aqueous solution having a concentration of 2.3% by mass containing a trace amount of potassium salt as an example. When the aqueous solution is passed through ion-type zeolite, potassium ions adsorbed on the adsorbent are eluted into the mobile phase, and the fraction until the volume of the eluate introduced into the column reaches 5 times the column volume (hereinafter referred to as the first fraction). In the fraction), the concentration is higher than the impurity concentration in the stock solution. After that, when the aqueous solution is further passed, the amount of trace impurities adsorbed from the mobile phase to the adsorbent becomes greater than the amount of trace impurities desorbed from the adsorbent to the mobile phase, which is lower than the concentration in the stock solution. The eluate fraction appears. At this time, the change in the concentration of the trace impurities fluctuates in the range of 100 times or more to 1/100 or less of the concentration of the stock solution. Up to more than that, depending on conditions.

  The operation in the method for removing trace impurities in the solution can be carried out in the same manner as in ordinary adsorption chromatography. As operation conditions at this time, room temperature and atmospheric pressure are usually selected.

  In this method for removing trace impurities in a solution, whether or not an abnormal adsorption chromatography phenomenon has occurred can be confirmed by fractionating and analyzing each fraction of the column eluate.

  Next, the method for removing trace impurities in this solution will be described in more detail by way of example.

  Separation of impurities from 1M sodium chloride aqueous solution containing potassium ions 13 mg / liter, magnesium ions 4 mg / liter, calcium ions 2 mg / liter as impurities using an apparatus comprising a liquid feed pump, an adsorbent column and a fraction collector It was.

That is, an H ⁺ type natural zeolite (made by Sun Zeolite Co., Ltd., clinoptilolite, trade name “Sun”) having adsorbed about 7 μmol / g of potassium ions as an adsorbent on a glass column (inner diameter 50 mm, height 200 mm). “Zeolite” (average particle size 0.5 mm) was filled to a height of 70 mm, and the above sodium chloride aqueous solution was passed at a temperature of 50 ° C. at a flow rate of 1 ml / min.

  Next, the eluate from the column was fractionated into 2 ml fractions, and the potassium ion concentration, magnesium ion concentration and calcium ion concentration were quantitatively analyzed for each fraction, and the results are shown in FIG. 1 as a graph. In the figure, A is a graph of potassium ions, B is a magnesium ion, and C is a calcium ion.

  The vertical axis in FIG. 1 is the potassium ion concentration, magnesium ion concentration, calcium ion concentration (mg / liter) in the eluate, and the horizontal axis is the ratio of the eluate volume to the column volume. From this figure, it can be seen that, in the initial stage, a fraction enriched with potassium ions and magnesium ions is eluted, and then a fraction from which potassium ions and magnesium ions are removed is eluted. It can also be seen that calcium ions are removed without being concentrated.

  In accordance with this method for removing trace impurities in a solution, an aqueous solution of a water-soluble compound containing trace impurities is introduced into a column packed with an adsorbent that is selective for trace impurities, thereby efficiently utilizing trace adsorption impurities and trace impurities. Can be removed. Further, it is possible to concentrate trace components during regeneration of the adsorbent, and the adsorbent can be used repeatedly.

Reference Example 5

A method for obtaining sodium chloride crystals having a purity of 98% by mass or more, particularly a purity of 99.99% by mass or more;
Next, the present inventors have conducted extensive research to efficiently remove potassium ions, magnesium ions, and calcium ions contained in the sodium chloride aqueous solution as impurities. If an aqueous solution of sodium chloride to be treated is passed through an adsorption column containing the same ions, abnormal adsorption chromatography occurs, and a fraction with a high impurity concentration is formed, which is removed. As a final treatment liquid after passing, an aqueous solution containing sodium chloride from which impurities have been removed is produced, so that a sodium chloride crystal is crystallized from this, and a solid-liquid separation process and a drying process are performed. In particular, it has been found that high-purity sodium chloride crystals having a purity of 99.99% by mass or more can be separated and recovered (Patent Document 2).

  That is, a concentrated sodium chloride aqueous solution containing at least one ion selected from potassium ion, magnesium ion and calcium ion as a trace impurity and having a solid content of 50 g / liter or more is contained in potassium. The solution is passed through a column packed with an adsorbent that selectively absorbs at least one ion selected from ions, magnesium ions, and calcium ions, and trace impurities are removed using abnormal adsorption chromatography. A purity of 98% by mass or more, in particular, a purity of 99.99% by mass, characterized in that sodium chloride is crystallized from the treatment liquid after the treatment to be removed and separated and recovered by performing a solid-liquid separation step and a drying step. This is a method for producing the above high purity sodium chloride crystal.

  In general, when a sodium chloride aqueous solution containing a small amount of potassium ions is passed through an adsorbent that selectively adsorbs potassium ions, for example, a column packed with ammonium ion-type zeolite, potassium ions are adsorbed to the adsorbent in advance. And sodium ions, which are the main components, are replaced with potassium ions present in the pores, and flow out together with potassium ions originally contained in the aqueous solution, so that the concentration is higher than the concentration of potassium ions contained in the aqueous solution. Is obtained.

  The sodium ions temporarily adsorbed by this adsorbent are replaced again with the potassium ions in the subsequent aqueous solution. At this time, in order to generate an activated adsorption point, it is more than the case of the normal adsorption chromatography phenomenon. Abnormal adsorption chromatography phenomenon that adsorbs a large amount of potassium ions.

  A method for obtaining high-purity sodium chloride crystals having a purity of 98% by mass or more, particularly 99.99% by mass or more, utilizes such an abnormal adsorption chromatographic phenomenon and uses potassium ions and magnesium contained in an aqueous sodium chloride solution. This is a method of obtaining sodium chloride with improved purity by removing trace impurities such as ions and calcium ions.

This abnormal adsorption chromatography phenomenon is usually characterized by the presence of the following processes. That is, when chromatography was performed using a column pre-packed with an adsorbent containing the same substance as trace impurities,
(1) A process of producing an eluate fraction enriched in trace impurities until a volume of eluate from the column reaches 5 times the column volume after introducing a concentrated solution of a predetermined substance containing trace impurities into the column. ,
(2) Next, the process of producing an eluate fraction whose trace impurities monotonously decrease,
(3) Subsequently, a process of generating an eluate fraction in which the trace impurity concentration becomes constant at a value smaller than the initial concentration (concentration in the stock solution),
(4) Further, a process of producing an eluate fraction in which the impurity concentration continuously increases monotonously at a value smaller than the initial concentration, and (5) an eluate fraction in which the impurity concentration is optionally greater than the initial concentration. Process.

  In the method for obtaining high purity sodium chloride crystals having a purity of 98% by mass or more, particularly 99.99% by mass or more, the process (1) among the processes (1) to (5) is performed. Abnormal adsorption chromatographic phenomena lacking (hereinafter referred to as pseudo-abnormal adsorption chromatographic phenomena) can be used in the same manner.

  In the method of obtaining a high purity sodium chloride crystal having a purity of 98% by mass or more, particularly a purity of 99.99% by mass or more, the concentration of the sodium chloride aqueous solution used as a raw material is the type of adsorbent used, chromatography conditions, For example, it varies depending on the temperature, pressure, flow rate through the column, etc., but usually 1% by mass is the lower limit, and the upper limit is in the range of saturated concentration, preferably in the range of 2-30% by mass, usually containing solids The amount is selected at 50 g / liter or more.

  On the other hand, the concentration of trace impurities contained in this aqueous sodium chloride solution is 1/20 or less, preferably 1/50 or less, of the concentration of the main component sodium chloride.

  As the adsorbent used in the method for obtaining a high purity sodium chloride crystal having a purity of 98% by mass or more, particularly 99.99% by mass or more, an adsorbent used in usual chromatography such as silica gel and alumina is used. However, an ion exchange material exhibiting excellent adsorptivity to potassium ion, magnesium ion or calcium ion, for example, ammonium ion type zeolite, cellulosic ion exchanger, Sephadex ion exchanger and the like are suitable. These are usually used as particles having a particle size of 0.2 to 2.0 mm packed in a chromatography tube, that is, a column.

  In the method of obtaining high purity sodium chloride crystals having a purity of 98% by mass or more, particularly 99.99% by mass or more, the same substances as trace impurities are previously added to the adsorbent because of the abnormal chromatographic phenomenon. Although it is necessary to make it adsorb | suck, as an adsorption amount in this case, the range of 1.0-10 micromol per 1g of adsorption agent is preferable. In this case, if an adsorbent that has already adsorbed the same substance as the impurity is used, the process of adsorbing the same substance as the impurity can be omitted.

  The method for obtaining high-purity sodium chloride crystals having a purity of 98% by mass or more, particularly 99.99% by mass or more, is first selected from potassium ions, magnesium ions and calcium ions in a column packed with this adsorbent. In addition, one or more metal ions are adsorbed and then passed through a predetermined concentrated aqueous sodium chloride solution. As the liquid passing speed at this time, the linear speed is usually 0.1 to 300 cm / hr, preferably 0.1 to 100 cm / hr. In passing this liquid, the passage can be promoted by pressurizing or depressurizing as desired.

  In this way, high-purity sodium chloride having an impurity concentration of 1% by mass or less based on the solid content mass can be finally obtained. The adsorbent column that has adsorbed impurities after passing through the concentrated aqueous sodium chloride solution can be regenerated and reused by passing, for example, an aqueous solution of hydrogen chloride or ammonium chloride. At this time, the fractions enriched in potassium ions, the fractions enriched in magnesium ions, or the fractions enriched in calcium ions are collected and subjected to the above regeneration operation, respectively, potassium ions, Since a fraction rich in magnesium ions or calcium ions can be obtained, the corresponding salts, that is, potassium chloride, magnesium chloride, and calcium chloride, can be recovered by concentrating the fraction. The concentration of the aqueous solution of hydrogen chloride or aqueous solution of ammonium chloride used for this regeneration is not particularly limited, but a range of 0.55 M-concentration is appropriate from the viewpoint of ease of handling.

  Next, in order to obtain sodium chloride crystals from a concentrated aqueous solution of sodium chloride after removing impurities through the column, it is most common to evaporate to dryness, but in addition, alcohols such as methyl alcohol, ethyl alcohol are used in the treatment liquid. Sodium propyl alcohol may be added to crystallize sodium chloride. Further, sodium hydroxide is further added to the treatment solution to form a precipitate, and then the precipitate is filtered off, and then alcohol is added to crystallize sodium chloride to obtain higher purity sodium chloride.

  For example, fractions with a low potassium ion concentration are collected, concentrated, and then added with alcohols (preferably ethyl alcohol) to obtain sodium chloride crystals. If sodium chloride is thick (20% or more), it is possible to obtain crystals without concentration. That is, by adding an alcohol (preferably ethyl alcohol) to a concentrated sodium chloride solution, sodium chloride crystals can be obtained in a high yield. Under normal conditions, the purity of sodium chloride is low, so the purity may be reduced due to the contamination of impurities. However, since the original mother liquor is a high-purity solution having a sodium chloride purity of 99.95% by mass or more, potassium, calcium, magnesium There is almost no decrease in purity due to contamination.

  Crystallization of ultrahigh-purity sodium chloride (sodium chloride purity: 99.99% by mass or more) by addition of alcohols is also performed with ultrahigh-purity sodium chloride from the magnesium ion-removed fraction after the magnesium ion selective ion exchanger treatment. It is also effective for crystallization or crystallization of ultra-high purity sodium chloride (sodium chloride purity: 99.99% by mass or more) from the calcium ion-removed fraction after the calcium ion selective ion exchanger treatment.

  In order to suitably perform a method for obtaining a high purity sodium chloride crystal having a purity of 98% by mass or more, particularly a purity of 99.99% by mass or more, one or more kinds of potassium ions, magnesium ions and calcium ions which are impurity components are used. Collect all fractions of the column eluate of concentrated sodium chloride aqueous solution containing ions (evaporated dry matter content: 100 g / l, purity of sodium chloride in evaporated dry matter: 90% by mass or more), potassium ion, magnesium Analyzing the concentration of one or more types of ions among ions and calcium ions, and collecting similar fractions having one or more types of ion concentrations among potassium ions, magnesium ions, and calcium ions. A more concentrated sodium chloride mother liquor can be obtained by collecting fractions having lower ion concentrations of potassium ions, magnesium ions, and calcium ions than the initial concentration.

  Ultra high purity sodium chloride (sodium chloride purity: 99.99 mass% or more) can be produced by crystallization of the concentrated sodium chloride mother liquor thus obtained by evaporation crystallization or reaction crystallization. it can.

  In the method for obtaining a high-purity sodium chloride crystal having a purity of 98% by mass or more, particularly 99.99% by mass or more, when a potassium ion selective ion exchanger is used, ammonium ions or Proton is suitable. Since the selective ion exchanger of potassium ions has high affinity with potassium ions, potassium ions cannot be sufficiently removed only by treatment with hydrochloric acid. Therefore, ion exchange treatment (preferably treatment with an ammonium chloride solution) with ammonium ions having an ionic radius similar to potassium ions is effective.

  Although the ammonium ion type can be used directly for removing potassium ions, ammonium chloride may be mixed during crystallization of sodium chloride. In that respect, if the proton type is used, hydrochloric acid will not be precipitated, so that it is guaranteed to obtain high-purity sodium chloride. However, if the hydrochloric acid treatment is performed, the adsorbent is dissolved and the constituent elements are likely to be eluted. This hydrochloric acid cleaning is not limited to the above, but is also effective for removing magnesium ions when using a magnesium ion selective ion exchanger or removing calcium ions when using a calcium ion selective ion exchanger.

Next, a method for obtaining high-purity sodium chloride crystals having a purity of 98% by mass or more, particularly a purity of 99.99% by mass or more will be described in more detail by way of example.
Using an apparatus consisting of a liquid feed pump, an adsorbent column and a fraction collector, impurities from a 30% by mass aqueous sodium chloride solution containing potassium ions 9 mg / liter, magnesium ions 1 mg / liter, calcium ions 0.8 mg / liter as impurities Removal was performed.

  That is, in a glass column (inner diameter 10 mm, height 500 mm), as an adsorbent, ammonium ion type natural zeolite (manufactured by Octa zeolite, clinoptilolite, trade name “octa zeolite”, average particle size 0.5 mm) ) To a height of 450 mm, and the sodium chloride aqueous solution was passed at a temperature of 50 ° C. at a linear velocity of 9 cm / hr.

  In this way, the relationship between the ratio of the eluate volume to the column volume and the concentration of each component (mg / liter) was determined and shown as a graph in FIG. From this figure, it can be seen that a remarkable abnormal adsorption chromatographic phenomenon has occurred for potassium ions, and it can be seen that the potassium ion concentration has decreased to 0.05 mg / liter.

  Next, a fraction having a low potassium ion was collected, and a 2-fold volume of ethyl alcohol was added to precipitate crystals, thereby obtaining high-purity sodium chloride crystals.

  The high purity sodium chloride crystals thus obtained were vacuum-dried and then dissolved in water to give a 10% by mass aqueous solution. When analyzed by atomic absorption spectrophotometry, the potassium ion concentration was 0.3 mg / liter, the magnesium ion concentration was 0.03 mg / liter, and the calcium ion concentration was 0.04 mg / liter.

  According to the method for obtaining a high purity sodium chloride crystal having a purity of 98% by mass or more, particularly 99.99% by mass or more, it contains at least one impurity selected from potassium ion, magnesium ion and calcium ion. By using the abnormal adsorption chromatography phenomenon from the concentrated sodium chloride aqueous solution, high-purity sodium chloride crystals can be obtained.

Purification of sodium chloride for dialysate from higher grade sodium chloride;
High grade sodium chloride aqueous solution was prepared by dissolving high grade sodium chloride in distilled water. Using an apparatus consisting of a feed pump, an adsorbent column and a fraction collector, 1M-salt high grade grade containing potassium ions 18.99 mg / liter, magnesium ions 4.63 mg / liter, calcium ions 2.70 mg / liter as impurities Separation of impurities from the aqueous sodium chloride solution was performed.

That is, an H ⁺ type natural zeolite (made by Sun Zeolite Co., Ltd., clinoptilolite, trade name “Sun”) having adsorbed about 7 μmol / g of potassium ions as an adsorbent on a glass column (inner diameter 50 mm, height 200 mm). “Zeolite” (average particle size 0.5 mm) was filled to a height of 70 mm, and the above sodium chloride aqueous solution was passed at a temperature of 25 ° C. at a flow rate of 1 ml / min.

  Subsequently, the eluate from the column was fractionated into 2 ml fractions, and the potassium ion concentration, magnesium ion concentration and calcium ion concentration were quantitatively analyzed for each fraction, and the results are shown in FIG. 3 as a graph. In the figure, hollow circles are potassium ions, hollow squares are magnesium ions, and hollow triangles are calcium ions.

  The vertical axis in FIG. 3 is the potassium ion concentration, magnesium ion concentration, calcium ion concentration (mg / liter) in the eluate, and the horizontal axis is the ratio of the eluate volume to the column volume. From this figure, it can be seen that, in the initial stage, a fraction enriched with potassium ions and magnesium ions is eluted, and then a fraction from which potassium ions and magnesium ions are removed is eluted. From this figure, it can be seen that a remarkable abnormal adsorption chromatographic phenomenon has occurred for potassium ions, and it can be seen that the potassium ion concentration has decreased to 0.33 mg / liter. For magnesium ions, a 1M-salt high grade sodium chloride aqueous solution is introduced into the column, and then the eluate fraction enriched with magnesium ions is produced until the eluate volume from the column reaches 5 times the column volume. It is understood that the magnesium ion concentration is reduced to 2.29 mg / liter by taking the process and then the process of producing an eluate fraction in which magnesium ions monotonously decrease. As for calcium ions, it is understood that calcium ions are removed without being concentrated first by taking a process of producing an eluate fraction in which the monotonous decrease occurs. It can be seen that the calcium ion concentration is reduced to 0.40 mg / liter or less.

  Fractions having a potassium ion concentration of 0.50 mg / liter or less, a magnesium ion concentration of 3.80 mg / liter or less, and a calcium ion concentration of 0.35 mg / liter or less were collected. Fractions corresponding to fraction number 750 to number 1350 were collected and concentrated with a rotary evaporator, and then ethyl alcohol was added to precipitate crystals. The crystals were separated by filtration, washed with ethyl alcohol and dried to obtain high purity sodium chloride crystals.

  The sodium chloride crystals thus obtained were dissolved in water and analyzed to determine the mass% by compound. The sodium chloride was 99.99984 mass%, potassium chloride was 0.000014 mass%, and magnesium chloride was 0.00010. % By mass and calcium chloride were 0.000043% by mass. The mass% by ion was 39.3394 mass% for sodium ions, 0.000007 mass% for potassium ions, 0.000026 mass% for magnesium ions, and 0.000016 mass% for calcium ions. The mass% of each inorganic cation with respect to the total inorganic cations (sodium ion, calcium ion, magnesium ion and potassium ion: corresponding to 39.339449 mass% in the purified high-purity sodium chloride crystal) is the sodium ion 99.99998 mass%. The potassium ions were 0.000018 mass%, the magnesium ions were 0.000066 mass%, and the calcium ions were 0.000041 mass%. That is, as the purity of sodium chloride, the concentration of sodium chloride was 99.99984% by mass, and the purity of the inorganic cation main component with respect to all inorganic cations was 99.99998% by mass of sodium ions.

  The above operation of purifying sodium chloride for dialysate from high-grade sodium chloride was repeated, and high-purity sodium chloride crystals for dialysate for obtaining high-purity sodium alginate were collected and stored.

High purity sodium alginate using high purity sodium chloride as dialysate;
About 1% by mass (W / V) of a commercially available sodium alginate aqueous solution B described in Reference Example 3, about 1% by mass (W) based on the 1M sodium chloride aqueous solution prepared from the high-purity sodium chloride crystal purified in Example 1. / V) commercial sodium alginate aqueous solution C and about 1% by mass (W / V) commercial sodium alginate aqueous solution E were dialyzed to try to increase the purity of sodium alginate.

The purification of sodium alginate by dialysis was performed by an operation including the following steps (1) to (4).
(1) Dialysis step using high-purity sodium aqueous solution The above-mentioned approximately 1% by mass of three types of commercially available sodium alginate aqueous solutions B, C, and E are each separated disposable dialysis cassettes (fraction molecular weight is 3,500, material is regenerated cellulose, Thickness is 25 microns, volume is 3 ml each, and a buoy is attached to the cassette, containing 3 liters of 1M sodium chloride aqueous solution prepared from the high purity sodium chloride crystals purified in Example 1. In addition, each was put in a separate 3 liter beaker, and dialysis was performed while stirring the dialysis external solution with a stirrer bar. The dialysis solution was exchanged at an appropriate time. The dialysis time may be an appropriate time as long as dialysis is efficiently performed. In Example 2, dialysis was performed for 20 hours.

(2) Dialysis step with distilled water Next, a disposable dialysis cassette filled with a commercially available sodium alginate aqueous solution was taken out from a 3 liter beaker, attached to a 1 liter beaker containing 1 liter of distilled water, and the dialysis external solution was stirred with a stirrer bar. Dialysis was performed. The dialysis was performed every hour by replacing the distilled water as the external dialysis solution. Chloride ions (Cl ⁻ ) in the outer dialyzate were quantified by ion chromatography, and this process was continued until the chloride ions (Cl ⁻ ) in the inner dialyzate were sufficiently removed.

(3) chloride ions in the extraction process external dialysis solution of dialyzate (Cl ^-) are Once sufficiently excluded, removed disposable dialysis cassette full of commercial sodium alginate aqueous solution of 1 liter beaker, syringe and dialyzed solution I took it out.

(4) Concentration process of dialysis internal solution Since the volume of the dialysis internal solution was increased by dialysis, it was concentrated to the volume before dialysis. Concentration of the sodium alginate aqueous solution can be carried out by various methods, but natural drying at low temperature (air drying) and drying in a vacuum dryer are preferable, and concentrating by using a rotary evaporator at low temperature saves time.

  After dialysis treatment of a commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) B by the above operation, the dialysis internal solution (sodium alginate aqueous solution) is taken out and concentrated to the volume before the dialysis treatment to obtain a dialysis treatment solution B1. It was. After dialysis treatment of commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) C by the above operation, the dialysis internal solution (sodium alginate aqueous solution) is taken out and concentrated to the volume before dialysis treatment to obtain dialysis treatment solution C1. It was. After dialysis treatment of a commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) E by the above operation, the dialysis internal solution (sodium alginate aqueous solution) is taken out and concentrated to the volume before the dialysis treatment to obtain a dialysis treatment solution E1. It was. Next, the purity of the dialysis treatment liquids B1, C1, and E1 was measured.

Sodium ion concentration;
The sodium ion concentration in the dialysis treatment solution B1 of a commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) was 938.6 ppm (40.81 mmol / l), and the sodium ion concentration in the dialysis treatment solution C1 was 903.0 ppm (39 .26 mmol / l), and the sodium ion concentration in the dialysis treatment solution E1 was 981.7 ppm (42.68 mmol / l).

Contaminated inorganic ion concentration;
Quantification of potassium ion, calcium ion, and magnesium ion in the dialysis solution (about 1% by mass aqueous sodium alginate solution) was performed by atomic absorption analysis.

  As a result, the potassium ion concentration was 0.175 ppm or less (0.0045 mmol / l or less) for the dialysis treatment solutions B1, C1, and E1 of a commercially available sodium alginate aqueous solution (about 1 mass% sodium alginate aqueous solution).

  Magnesium ion concentration was 0.10 ppm or less (0.0041 mmol / l or less) for dialysis treatment solutions B1, C1, and E1 of commercially available sodium alginate aqueous solution (about 1 mass% sodium alginate aqueous solution).

  The calcium ion concentration was 0.20 ppm or less (0.0050 mmol / l or less) for all commercially available sodium alginate aqueous solutions (about 1% by mass sodium alginate aqueous solutions) B1, C1, and E1.

  From the above, in the dialysis treatment solutions B1, C1, and E1 of a commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution), potassium ions, magnesium ions, and calcium ions total 0.475 ppm or more (0.0136 mmol). It is clear that it is not included.

Sodium purity;
From the results of Reference Example 3, the potassium ion concentration in the about 1% by mass aqueous sodium alginate solution was 4.99 ppm (0.13 mmol / l) for B, 13.70 ppm (0.35 mmol / l) for C, and 5 for E. It was 0.775 ppm (0.15 mmol / l). The magnesium ion concentration in the about 1% by mass sodium alginate aqueous solution was 1.00 ppm (0.041 mmol / l) for B, 1.38 ppm (0.057 mmol / l) for C, and 1.25 ppm (0.051 mmol) for E. / L). The calcium ion concentration in the aqueous solution of about 1% by mass sodium alginate was 13.66 ppm (0.341 mmol / l) for B, 3.00 ppm (0.075 mmol / l) for C, and 13.28 ppm (0.331 mmol) for E. / L).

  By dialysis treatment with a high-purity sodium chloride aqueous solution, potassium ions in a dialysis treatment solution of a commercially available sodium alginate aqueous solution are 0.175 ppm or less (0.0045 mmol / l or less), and magnesium ions are 0.10 ppm or less (0.0041 mmol / l or less). ), Calcium ions are reduced to 0.20 ppm or less (0.0050 mmol / l or less). From the above, it can be seen that the purity of sodium alginate is increased more than expected by the dialysis treatment using the high-purity sodium chloride aqueous solution prepared from the high-purity sodium chloride crystal purified in Example 1 as the dialysate. Potassium ions, magnesium ions, and calcium ions, which are contaminated ions, are obtained by dialysis using the high-purity sodium chloride aqueous solution prepared from the high-purity sodium chloride crystal having a purity of 99.999% by mass or more purified in Example 1 as a dialysate. It is clear that a high-purity sodium alginate aqueous solution with reduced water content is obtained. Dialysis treatment solution B1 of sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) has a sodium purity of 99.94% by mass or more (99.96% by mol or more), and C1 has a sodium purity of 99.94% by mass or more (99.99% by mass). It is clear that E1 has a sodium purity of 99.95% by mass or more (99.96% by mol or more).

  In order to increase the purity of the commercially available sodium alginate, it can be understood that the higher the sodium chloride purity of the sodium chloride aqueous solution used as the dialysate, the higher the efficiency of the purification.

  High-purity sodium alginate can be obtained easily from inexpensive sodium alginate for food use.

A variant of Example 2;
In addition, sodium alginate was purified as described below by the same method as described above, except that the dialysis treatment was performed for 5 hours instead of the dialysis treatment for 20 hours in the dialysis step using a high-purity sodium aqueous solution. .

  After dialysis treatment of the commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) B by the above operation, the dialysis internal solution (sodium alginate aqueous solution) is taken out and concentrated to the volume before dialysis treatment to obtain dialysis treatment solution B2. It was. After dialysis treatment of a commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) C by the above operation, the dialysis internal solution (sodium alginate aqueous solution) is taken out and concentrated to the volume before the dialysis treatment to obtain a dialysis treatment solution C2. It was. After dialysis treatment of a commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) E by the above operation, the dialysis internal solution (sodium alginate aqueous solution) is taken out and concentrated to the volume before the dialysis treatment to obtain a dialysis treatment solution E2. It was. Next, the purity of the dialysis treatment liquids B2, C2, and E2 was measured.

Sodium ion concentration;
The sodium ion concentration of the commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) in the dialysis treatment solution B2 was 938.6 ppm (40.81 mmol / l), and the sodium ion concentration in the dialysis treatment solution C2 was 903.0 ppm (39 .26 mmol / l), and the sodium ion concentration in the dialysis solution E2 was 981.7 ppm (42.68 mmol / l).

Contaminated inorganic ion concentration;
Quantification of potassium ion, calcium ion, and magnesium ion in the dialysis solution (about 1% by mass aqueous sodium alginate solution) was performed by atomic absorption analysis.

  As a result, the potassium ion concentration was 0.700 ppm or less (0.0180 mmol / l or less) for the dialysis treatment liquids B2, C2, and E2 of a commercially available sodium alginate aqueous solution (about 1 mass% sodium alginate aqueous solution).

  Magnesium ion concentration was 0.400 ppm or less (0.0164 mmol / l or less) for dialysis treatment liquids B2, C2, and E2 of commercially available sodium alginate aqueous solution (about 1 mass% sodium alginate aqueous solution).

  The calcium ion concentration was 0.800 ppm or less (0.020 mmol / l or less) for the dialysis treatment solutions B2, C2, and E2 of a commercially available sodium alginate aqueous solution (about 1 mass% sodium alginate aqueous solution).

  From the above, in the dialysis treatment liquids B2, C2, and E2 of a commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution), potassium ions, magnesium ions, and calcium ions total 1.900 ppm or more (0.0544 mmol). It is clear that it is not included.

  By dialysis treatment with a high-purity sodium chloride aqueous solution, potassium ions in a dialysis treatment solution of a commercially available sodium alginate aqueous solution are 0.700 ppm or less (0.0180 mmol / l or less), and magnesium ions are 0.400 ppm or less (0.0164 mmol / l or less). ), Calcium ions are reduced to 0.800 ppm or less (0.0200 mmol / l or less). From the above, it can be seen that the purity of sodium alginate is increased more than expected by the dialysis treatment using the high-purity sodium chloride aqueous solution prepared from the high-purity sodium chloride crystal purified in Example 1 as the dialysate. Potassium ions, magnesium ions, and calcium ions, which are contaminated ions, are obtained by dialysis using the high-purity sodium chloride aqueous solution prepared from the high-purity sodium chloride crystal having a purity of 99.999% by mass or more purified in Example 1 as a dialysate. It is clear that a high-purity sodium alginate aqueous solution with reduced water content is obtained. The dialysis solution B2 of an aqueous sodium alginate solution (about 1% by mass sodium alginate aqueous solution) has a sodium purity of 99.79% by mass or more (99.86 mol% or more), and C2 has a sodium purity of 99.79% by mass or more (99.99% by mass). 86 mol% or more), E2 clearly has a sodium purity of 99.80 mass% or more (99.87 mol% or more).

  It is clear that the sodium alginate aqueous solution can be purified to a purity of 99.85 mol% or more even by a short dialysis treatment.

High purity of sodium alginate using chelate solution and high purity sodium chloride as dialysate;
Instead of using the 1M sodium chloride aqueous solution prepared from the high-purity sodium chloride crystals purified in Example 1 as the dialysate in the dialysis step (1) of Example 2, the high-purity sodium chloride purified in Example 1 was used. About 1% by mass (W / V) of a commercially available sodium alginate aqueous solution B described in Reference Example 3 with respect to a solution containing 0.05M sodium ethylenediaminetetraacetate in a 0.1M sodium chloride aqueous solution prepared from the crystals, about 1 High purity of sodium alginate was attempted by dialyzing a mass% (W / V) commercial sodium alginate aqueous solution C and about 1 mass% (W / V) commercial sodium alginate aqueous solution E.

The purification of sodium alginate by dialysis was performed by an operation including the following steps (1) to (5).
(1) Dialysis step using high-purity sodium aqueous solution The above-mentioned approximately 1% by mass of three types of commercially available sodium alginate aqueous solutions B, C, and E are each separated disposable dialysis cassettes (fraction molecular weight is 3,500, material is regenerated cellulose, Thickness is 25 microns, volume is 3 ml each, and a buoy is attached to the cassette, and 0.05 M sodium ethylenediaminetetraacetate is added to the 0.1 M sodium chloride aqueous solution purified in Example 1 Dialysis was carried out while stirring the external dialysate with a stirrer bar in each 3 liter beaker containing 3 liters of saliva. The dialysis time may be an appropriate time as long as dialysis is efficiently performed. In Example 3, dialysis was performed for 20 hours.
(2) Dialysis step using 0.1 M sodium chloride aqueous solution purified in Example 1 Next, a disposable dialysis cassette packed with a commercially available sodium alginate aqueous solution was taken out from a 3 liter beaker and 0.1 M sodium chloride purified in Example 1 was used. The sample was placed in a 3 liter beaker containing 3 liters of aqueous solution, and dialysis was performed while stirring the dialysis external solution with a stirrer bar. The dialysis time may be an appropriate time as long as dialysis is efficiently performed. In Example 3, dialysis was performed for 20 hours.
(3) Dialysis step with distilled water Next, a disposable dialysis cassette filled with a commercially available sodium alginate aqueous solution was taken out of the 3 liter beaker, attached to a 1 liter beaker containing 1 liter of distilled water, and the dialysis external solution was stirred with a stirrer bar. Dialysis was performed. The dialysis was performed every hour by replacing the distilled water as the external dialysis solution. Chloride ions (Cl ⁻ ) in the outer dialyzate were quantified by ion chromatography, and this process was continued until the chloride ions (Cl ⁻ ) in the inner dialyzate were sufficiently removed.
(4) Chloride ion in extraction processes external dialysis solution of dialyzate (Cl ^-) After sufficiently excluded, removed disposable dialysis cassette full of commercial sodium alginate aqueous solution of 1 liter beaker, syringe and dialyzed solution I took it out.
(5) Concentration process of dialysis internal solution Since the volume of the dialysis internal solution was increased by dialysis, it was concentrated to the volume before dialysis. Concentration of the sodium alginate aqueous solution can be carried out by various methods, but natural drying at low temperature (air drying) and drying in a vacuum dryer are preferable, and concentrating by using a rotary evaporator at low temperature saves time.

  After dialysis treatment of commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) B by the above-mentioned operation, the dialysis internal solution (sodium alginate aqueous solution) is taken out and concentrated to the volume before dialysis treatment to obtain dialysis treatment solution B3. It was. After dialysis treatment of a commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) C by the above operation, the dialysis internal solution (sodium alginate aqueous solution) is taken out and concentrated to the volume before the dialysis treatment to obtain a dialysis treatment solution C3. It was. After dialysis treatment of a commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) E by the above operation, the dialysis internal solution (sodium alginate aqueous solution) is taken out and concentrated to the volume before the dialysis treatment to obtain a dialysis treatment solution E3. It was. Next, the purity of the dialysis treatment liquids B3, C3, and E3 was measured.

Sodium ion concentration;
The sodium ion concentration in the dialysis treatment liquid (about 1 mass% sodium alginate aqueous solution) B3 of a commercially available sodium alginate aqueous solution (about 1 mass% sodium alginate aqueous solution) was 938.4 ppm (40.80 mmol / l). The sodium ion concentration in C was 902.8 ppm (39.25 mmol / l), and the sodium ion concentration in the dialysis treatment solution E3 was 981.5 ppm (42.67 mmol / l).
Contaminated inorganic ion concentration;
Quantification of potassium ion, calcium ion, and magnesium ion in the dialysis solution (about 1% by mass aqueous sodium alginate solution) was performed by atomic absorption analysis.

  As a result, the potassium ion concentration was 0.175 ppm or less (0.0045 mmol / l or less) for the dialysis treatment solutions B3, C3, and E3 of a commercially available sodium alginate aqueous solution (about 1 mass% sodium alginate aqueous solution).

  Magnesium ion concentration was 0.10 ppm or less (0.0041 mmol / l or less) for dialysis treatment liquids B3, C3, and E3 of a commercially available sodium alginate aqueous solution (about 1 mass% sodium alginate aqueous solution).

  The calcium ion concentration was 0.20 ppm or less (0.0050 mmol / l or less) for all commercially available sodium alginate aqueous solutions (about 1 mass% sodium alginate aqueous solutions) B3, C3, and E3.

  From the above, in the dialysis treatment liquids B3, C3, and E3 of a commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution), potassium ions, magnesium ions, and calcium ions total 0.475 ppm or more (0.0136 mmol). It is clear that it is not included.

Sodium purity;
From the results of Reference Example 3, the potassium ion concentration in the about 1% by mass aqueous sodium alginate solution was 4.99 ppm (0.13 mmol / l) for B, 13.70 ppm (0.35 mmol / l) for C, and 5 for E. It was 0.775 ppm (0.15 mmol / l). The magnesium ion concentration in the about 1% by mass sodium alginate aqueous solution was 1.00 ppm (0.041 mmol / l) for B, 1.38 ppm (0.057 mmol / l) for C, and 1.25 ppm (0.051 mmol) for E. / L). The calcium ion concentration in the aqueous solution of about 1% by mass sodium alginate was 13.66 ppm (0.341 mmol / l) for B, 3.00 ppm (0.075 mmol / l) for C, and 13.28 ppm (0.331 mmol) for E. / L).

  By dialysis treatment with a high-purity sodium chloride aqueous solution, potassium ions in a dialysis treatment solution of a commercially available sodium alginate aqueous solution are 0.175 ppm or less (0.0045 mmol / l or less), and magnesium ions are 0.10 ppm or less (0.0041 mmol / l or less). ), Calcium ions are reduced to 0.20 ppm or less (0.0050 mmol / l or less). From the above, it can be seen that the purity of sodium alginate is increased more than expected by the dialysis treatment using the high-purity sodium chloride aqueous solution prepared from the high-purity sodium chloride crystal purified in Example 1 as the dialysate. Potassium ions, magnesium ions, and calcium ions, which are contaminated ions, are obtained by dialysis using the high-purity sodium chloride aqueous solution prepared from the high-purity sodium chloride crystal having a purity of 99.999% by mass or more purified in Example 1 as a dialysate. It is clear that a high-purity sodium alginate aqueous solution with reduced water content is obtained. The dialysis treatment solution B3 of the sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) has a sodium purity of 99.94% by mass or more (99.96% by mol or more), and C3 has a sodium purity of 99.94% by mass or more (99.99% by mass). It is apparent that E3 has a sodium purity of 99.95% by mass or more (99.96% by mol or more).

  In order to increase the purity of the commercially available sodium alginate, it can be understood that the higher the sodium chloride purity of the sodium chloride aqueous solution used as the dialysate, the higher the efficiency of the purification.

Comparative Example 1

High purity test of commercial sodium alginate using saline solution as dialysate;
Instead of using the 1M sodium chloride aqueous solution prepared from the high-purity sodium chloride crystal purified in Example 1 as the dialysate, the same operation as in Example 2 was performed except that 1M commercial saline solution was used as the dialysate. High purity of sodium alginate was attempted by dialyzing commercially available sodium alginate B, C, and E of Reference Example 3.

The purification of sodium alginate by dialysis was performed by an operation including the following steps (1) to (4).
(1) Dialysis step with 1M-commercial saline solution The above-mentioned approximately 1% by mass of three commercially available sodium alginate aqueous solutions B, C, and E are separated into separate disposable dialysis cassettes (fractionated molecular weight is 3,500, material is regenerated cellulose) Inject 3ml each into PIERCE, attach a buoy to the cassette, attach it to a separate 3 liter beaker containing 3 liters of 1M commercial saline solution and stirrer bar The dialysis was performed while stirring the dialysis external solution. The dialysis time may be an appropriate time as long as dialysis is efficiently performed. In Comparative Example 1, the same dialysis time as in Example 2, that is, 20 hours was dialyzed.
(2) Dialysis step with distilled water Next, a disposable dialysis cassette filled with a commercially available sodium alginate aqueous solution was taken out from a 3 liter beaker, attached to a 1 liter beaker containing 1 liter of distilled water, and the dialysis external solution was stirred with a stirrer bar. Dialysis was performed. The dialysis was performed every hour by replacing the distilled water as the external dialysis solution. Chloride ions (Cl ⁻ ) in the outer dialyzate were quantified by ion chromatography, and this process was continued until the chloride ions (Cl ⁻ ) in the inner dialyzate were sufficiently removed.
(3) Step of taking out dialysate solution The same procedure as in Example 2 was performed.
(4) Concentration step of dialyzed internal solution The same procedure as in Example 2 was performed.

  After dialysis treatment of commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) B by the above operation, the dialysis internal solution (sodium alginate aqueous solution) is taken out and concentrated to the volume before dialysis treatment to obtain dialysis treatment solution B4. It was. After dialysis treatment of commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) C by the above-mentioned operation, the dialysis internal solution (sodium alginate aqueous solution) is taken out and concentrated to the volume before dialysis treatment to obtain dialysis treatment liquid C4. It was. After dialysis treatment of a commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) E by the above operation, the internal dialysis solution (sodium alginate aqueous solution) is taken out and concentrated to the volume before the dialysis treatment to obtain a dialysis treatment solution E4. It was. Next, the purity of the dialysis treatment liquids B4, C4, and E4 was measured.

Sodium ion concentration;
The sodium ion concentration of the commercially available sodium alginate aqueous solution (about 1% by mass sodium alginate aqueous solution) in the dialysis treatment solution (about 1% by mass sodium alginate aqueous solution) B4 was 947.37 ppm (41.19 mmol / l). The sodium ion concentration was 909.52 ppm (39.54 mmol / l) in C, and the sodium ion concentration in the dialysis treatment solution E4 was 990.68 ppm (43.07 mmol / l).
Contaminated inorganic ion concentration;
Quantification of potassium ion, calcium ion, and magnesium ion in the dialysis solution (about 1% by mass aqueous sodium alginate solution) was performed by atomic absorption analysis.

  As a result, the potassium ion concentration was 1.54 ppm (0.039 mmol / l) for dialysis solution B4, 1.84 ppm (0.047 mmol / l) for C4, and 1.55 ppm (0.040 mmol / l) for E4. there were.

  Magnesium ion concentrations were 6.66 ppm (0.274 mmol / l) for dialysis treatment solution B4, 7.36 ppm (0.303 mmol / l) for C4, and 7.31 ppm (0.301 mmol / l) for E4.

  The calcium ion concentration was 2.43 ppm (0.061 mmol / l) for dialysis solution B4, 2.25 ppm (0.056 mmol / l) for C4, and 2.45 ppm (0.061 mmol / l) for E4.

  As a result of Reference Example 3, the potassium ion concentration in the aqueous solution of about 1% by mass sodium alginate was 4.99 ppm for B, 13.70 ppm for C, and 5.75 ppm for E. The magnesium ion concentration in the about 1% by mass aqueous sodium alginate solution was 1.00 ppm for B, 1.38 ppm for C, and 1.25 ppm for E. The calcium ion concentration in the about 1% by mass sodium alginate aqueous solution was 13.66 ppm for B, 3.00 ppm for C, and 13.28 ppm for E.

Sodium chloride purity;
In the dialysis treatment solution B4 [about 1% by mass (W / V) sodium alginate aqueous solution], the total inorganic cation was 958.00 ppm (41.56 mmol / l), and the sodium ion was 98.89% by mass (99.11 mol%). ), 0.16 mass% (0.094 mol%) of potassium ions, 0.70 mass% (0.659 mol%) of magnesium ions, and 0.25 mass% (0.147 mol%) of calcium ions. there were.

  In the dialysis solution C4 [about 1% by mass (W / V) sodium alginate aqueous solution], the total inorganic cation was 927.97 ppm (39.95 mmol / l), and sodium ions were 98.76% by mass (98.97 mol%). ), 0.20 mass% (0.118 mol%) of potassium ions, 0.80 mass% (0.758 mol%) of magnesium ions, and 0.24 mass% (0.140 mol%) of calcium ions. there were.

  In the dialysis solution E4 [about 1% by mass (W / V) sodium alginate aqueous solution], the total inorganic cation total is 1001.99 ppm (43.47 mmol / l), and the sodium ion is 98.87% by mass (99.08 mol%). ), Potassium ion is 0.15 mass% (0.092 mol%), magnesium ion is 0.73 mass% (0.692 mol%), and calcium ion is 0.24 mass% (0.140 mol%). there were.

  In dialysis treatment with a commercially available saline solution, potassium ions and calcium ions in a commercially available sodium alginate aqueous solution were reduced, but magnesium ions were increased.

  From the above, it can be seen that the purity of sodium alginate obtained after the dialysis treatment does not increase so much in the dialysis treatment using a commercial saline solution as the dialysis solution.

  In the dialysis treatment using a commercially available saline solution as a dialysate, it is clear that a high-purity sodium alginate aqueous solution in which potassium ions, magnesium ions, and calcium ions, which are contaminating ions in commercially available sodium alginate, are reduced has not been obtained.

  Since the commercially available sodium chloride described has a sodium purity of less than 99.9% by mass, it is unsuitable as a dialysate for increasing the purity of the commercially available sodium alginate.

  It can be understood that the higher the purity of sodium chloride, the better the dialysate for increasing the purity of the commercially available sodium alginate.

Reference Example 6

Method for measuring the molecular weight of sodium alginate and the relationship between viscosity and molecular weight;
As a method for measuring the molecular weight of sodium alginate, there is a method by measuring osmotic pressure using an osmometer. In addition, the viscosity of a 1% mass aqueous solution of sodium alginate increases with an increase in molecular weight (sodium alginate is a polymer and may be expressed as a degree of polymerization) (Non-patent Document 1).
Industrial Chemistry Magazine Vol.56 (April 1968) 252-253

Reference Example 7

Relationship between molecular weight and viscosity;
As already reported, when the viscosity is high, the molecular weight is high (Non-patent Document 2).
The molecular weight (or degree of polymerization) of sodium alginate is estimated from the viscosity measurement using the above relationship.
Fragrance Journal, 73, 100, 1985

Viscosity measurement and molecular weight measurement experiment using a rotational viscometer;
The viscosity of sodium alginate was measured with a B-type rotational viscometer by preparing a 1% by mass (w / v) aqueous solution of sodium alginate.

  Sodium alginate subjected to high-purity treatment by dialysis as described in Example 2 [dialysis method high-purity sodium alginate, dialysis treatment liquid by high-purification treatment, contaminated ions (magnesium, calcium, potassium ions, etc.) in sodium alginate by dialysis method ) And reduced viscosity of sodium alginate (also referred to as untreated sodium alginate) that was not purified by dialysis.

  Since the highly purified aqueous sodium alginate solution was reduced in concentration by dialysis as described in Example 2, the viscosity was measured after concentration to 1% by mass. Concentration of the sodium alginate aqueous solution can be carried out by various methods, but natural drying at low temperature (air drying) and drying in a vacuum dryer are preferable, and concentrating by using a rotary evaporator at low temperature saves time.

  The viscosity of a 1% by mass aqueous solution of untreated sodium alginate was 500 cp (centipoz). On the other hand, the viscosity of 1% by mass of dialysis-purified sodium alginate was 530 cp.

Comparative Example 2

Viscosity measurement of highly purified sodium alginate by a part of acid method There are two methods of producing alginic acid from seaweed: acid method (also called acid precipitation method) and calcium method (also called calcium precipitation method).

  In the acid method, sodium alginate is roughly extracted from seaweed with an alkali such as sodium carbonate, mineral acid (such as sulfuric acid) is added to the processed crude extract, and sodium alginate is precipitated as alginic acid (acid). In this method, the solution is neutralized with sodium carbonate, fractionated as soluble sodium alginate, and dehydrated to obtain purified sodium alginate. In the acid method, the calcium content as a contaminant in the atrium alginate is 0.01 to 0.05% by mass and the calcium method (the calcium content as a contaminant in the atrium alginate in the calcium method is 0.2 to 1%). (0.0 mass%). However, when an acid is used, hydrolysis of the glycosidic bond of the polysaccharide is likely to occur, and it is not often used for extraction and purification of polysaccharides except in special cases. On the other hand, alkali has a weaker ability to hydrolyze glycosidic bonds than acid, but has an action of oxidatively degrading from the reducing end of a polysaccharide. Furthermore, the ester bond of polysaccharide is also susceptible to hydrolysis by alkali (Non-patent Document 3).

  In the calcium method, calcium chloride is added to an aqueous solution of sodium alginate instead of acid, fractionated as a calcium alginate precipitate, hydrochloric acid is added to form an alginate gel, and the alginate gel is neutralized with sodium carbonate to purify the sodium alginate. Is the method.

  Instead of performing purification by dialysis in Example 2, attempts were made to increase the purity of sodium alginate by a part of the acid method. A sample of commercially available sodium alginate whose viscosity of a 1% by mass aqueous solution is 500 cp (also referred to as untreated sodium alginate in the present specification since it was not purified) was used as a sample.

  Sulfuric acid was added to a commercially available sodium alginate aqueous solution to separate it as alginate. Next, sodium carbonate was added to the separated alginic acid in the presence of alcohol and neutralized to obtain water-soluble sodium alginate. The aqueous sodium alginate solution was dried to obtain a sodium alginate powder (also referred to herein as purified sodium alginate compliant with part of the acid method).

  The viscosity of the obtained sodium alginate highly purified by the acid method (also referred to as acid method highly purified sodium alginate) was measured.

The viscosity of 1% by mass of the acid method highly purified sodium alginate was 110 cp. Thus, it is clear that the viscosity decreases when the purity of sodium alginate is increased in accordance with a part of the acid method. The decrease in viscosity is a decrease in the molecular weight of sodium alginate, and this is thought to be due to the use of acid and alkali for purification.
Biochemical Experimental Method 20 Polysaccharide Separation / Purification Method, edited by Kazuo Matsuda, Society Publishing Center, 1987, pp. 17-

Comparative Example 3

Viscosity measurement of highly purified sodium alginate by some methods of calcium method;
Instead of purifying by dialysis in Example 2, sodium alginate was purified by the calcium method. A sample of commercially available sodium alginate whose viscosity of a 1% by mass aqueous solution is 500 cp (also referred to as untreated sodium alginate in the present specification since it was not purified) was used as a sample.

  Calcium chloride was added to a commercially available sodium alginate aqueous solution and separated as a precipitate as calcium alginate. Next, hydrochloric acid was added to the separated calcium alginate to obtain alginic acid. Then, sodium carbonate is added to the alginic acid thus obtained in the presence of alcohol and neutralized to obtain water-soluble sodium alginate. The aqueous sodium alginate solution was dried to obtain sodium alginate (also referred to herein as purified sodium alginate compliant with the calcium method partly).

  The viscosity of highly purified sodium alginate (also referred to as calcium method highly purified sodium alginate) was measured by a method based on a part of the obtained calcium method.

  The 1 mass% viscosity of the calcium method highly purified sodium alginate was 120 cp.

  From these facts, it can be seen that when the purity of sodium alginate is increased in accordance with a part of the procedure of the calcium method, a significant decrease in viscosity occurs. The decrease in the viscosity is considered to be caused by the decrease in the molecular weight of the alginic acid molecule (polysaccharide) due to the acid or alkali during the purification operation.

Reference Example 8

Molecular Weight Measurement The viscosity average molecular weight of sodium alginate was determined as follows.

The concentration of sodium alginate was changed to 5 levels (g / l) (5 levels consisting of 0.2%, 0.4%, 0.6%, 0.8%, 1.00%, etc.) Aqueous solutions were prepared, and the respective viscosities were measured using a B-type rotational viscometer to determine the intrinsic viscosity intrinsic viscosity [η: eta], and the Smidsrod equation (O. Midsrod and
A. Haug, Acta Chem. Scand. , 22, 797, 1968)
[Η] = 2.0 × 10 ⁻⁵ × M _W (20 ° C., 0.1 M NaCl solution)
M _W: by applying the viscosity-average molecular weight was calculated molecular weight M _W.

Sodium alginate was used, the viscosity by a B type rotational viscometer 1 wt% aqueous solution 795Cp (centipoise), average molecular weight _{M W} was 642,500. A digital rotary viscometer DVL-B type manufactured by Toki Sangyo Co., Ltd. was used.

Experiments for producing calcium alginate fibers by injecting from an aqueous sodium alginate solution into an aqueous calcium chloride solution;
A sodium alginate aqueous solution was extruded through a nozzle of a syringe (or a spinning machine) into a calcium chloride aqueous solution as a coagulation liquid to prepare fibrous calcium alginate, which was then washed with water.

Specifically, a 4.5 (absolutely dry w / w)% sodium alginate (also referred to as AlgNa) aqueous solution (dope) is put into a syringe (or a storage tank of a spinning machine), and a nozzle hole (diameter 1.0 mm, or diameter) 0.5 mm), the solution was extruded by hand into a coagulation tank containing a 0.5 M (molar concentration) aqueous solution of calcium chloride (CaCl ₂ ) as a coagulation liquid at a speed at which the liquid continuously appeared without interruption. Becomes calcium alginate fiber. The ends were pulled immediately so as to be linear, and kept for several minutes until they were not wrinkled (or linear fibers were achieved by winding in a coagulation tank of a spinning machine). After that, it was kept in the coagulation tank for 2 hours or more, and the water washing was performed 6 times or more using deionized water, and it was carried out for 2 hours or more (or rolled up continuously after 2 water washing tanks of the spinning machine). , Water washing was completed). After washing with water, it was put in a polyethylene bag containing deionized water, stored in a refrigerator at 4 ° C., and used for experiments.

Stretching;
It is also possible to add a stretching process during winding.

  After leaving the coagulation tank, the calcium alginate fiber was drawn by pulling the fiber length to about 1.3 times in the water washing stage. Orientation occurred in the winding and traveling direction of the fiber, and the fiber strength was improved.

In detail, after winding the calcium alginate fiber produced in the coagulation tank and leaving the coagulation tank, the winding speed was increased 1.3 times in the first washing tank and the fiber length was pulled 1.3 times. And stretched. In the case of two-stage drawing, orientation in the winding / traveling direction of the fiber has improved, and in the case of two-stage stretching, the winding speed is increased by 1.2 times in the second washing tank after the first washing tank. Stretched 1.5 times. Under soft fiber conditions, two-stage drawing is possible.

Experiment of measuring tensile strength of calcium alginate monofilament;
When the tensile strength of the control calcium alginate monofilament was measured by the JIS method, the air-dried fiber had a tensile strength of about 1.7 (1.5 to 2.2) grams per denier (g / d), and the tensile strength of the wet fiber. The strength was about 0.35 (0.15 to 0.40) g / d. The strength of the wet single fiber was measured in a state where the wet single fiber stored in water in a polyethylene bag was not dried.

  When powder (powder adsorbent) is added, the tensile strength of air-dried single fibers is about 1.0 (0.25 to 1.5) g / d, and the tensile strength of wet single fibers is about 0.10 ( 0.042-0.20) g / d. The powder was treated with 270 mesh (53 microns) and then mixed with an aqueous sodium alginate solution. The concentration of the powder in the aqueous sodium alginate solution was 10% by mass. The powdered sodium alginate aqueous solution was injected into the calcium chloride aqueous solution with a 0.5 mm diameter nozzle to prepare calcium alginate fibers.

  Specifically, the control experiment was performed as follows. The tensile strength of single fiber of calcium alginate was measured by JIS L1069 “Fiber tensile test method” method. The single fiber was chucked at an interval of 2 cm, and both ends of the air-dried single fiber were bonded to glossy paper with the instant adhesive Aron Alpha. Glossy paper was held and fixed with upper and lower chucks. Autograph AG100A manufactured by Shimadzu Corporation, load cell 100 kgf, tensile speed 20 mm / min, measurement chamber 16-19 ° C., 35-42 RH%. The average of two or more measurements was taken. In the case of wet monofilament, qualitative filter paper No. is used instead of adhesion to glossy paper. A wet fiber was sandwiched between two sheets 2 and tightened with a chuck and a tensile load was applied, and a value cut at the center of a 2 cm single fiber was adopted.

Strength of calcium alginate fibers from various sodium alginate;
The same operation as in Example 5 was performed to obtain calcium alginate fibers from 4.5 (absolutely dry w / w)% highly purified untreated sodium alginate aqueous solution (dope). The strength of the obtained fiber was about 1.7 (1.5 to 2.2) g / d.

  Dialysis method high purity sodium alginate aqueous solution described in Example 2 [dialysis treatment solution of commercially available sodium alginate aqueous solution (about 1 mass% sodium alginate aqueous solution E)] E1 was concentrated, and 4.5 (absolutely dry w / w)% Dialysis method A calcium alginate fiber was obtained from a highly purified sodium alginate aqueous solution (dope). The strength of the obtained fiber was about 2.6 (2.4 to 2.9) g / d.

  From the above, it is clear that the strength of the manufactured calcium alginate single fiber is low when magnesium is contained as an impurity in the sodium alginate aqueous solution that is the dope. On the other hand, the calcium alginate monofilament produced from the dialysis method high-purity sodium alginate aqueous solution (dope) in which magnesium, calcium and potassium ions in the sodium alginate are reduced by dialysis is the alginic acid produced from high-purity untreated sodium alginate. It can be seen that the strength is higher than the calcium monofilament.

Reference Example 9

Effect of aqueous sodium alginate viscosity on strength of calcium alginate fiber products Alginate paper was used as a product made from calcium alginate fibers. The tensile strength of the prepared calcium alginate paper was measured according to the JIS method, and it was found that the higher the molecular weight of sodium alginate (that is, the higher the viscosity), the higher the strength of the manufactured calcium alginate fiber.

Specifically, the prepared calcium alginate long fibers produced by a spinning machine were cut into 3 mm, disaggregated and dispersed in water, paper was prepared with a TAPPI paper machine, and the tensile strength of the paper was measured according to JIS method. Molecular weight of about 280,000 daltons, molecular weight of about 480,000 daltons. And three types of sodium alginate having a molecular weight of about 640,000 daltons.
As a result, the molecular weight is about 280,000 daltons and the molecular weight is about 480,000 daltons. And the strength (zero span breaking length (Km)) of calcium alginate fiber paper made from sodium alginate having a molecular weight of about 640,000 daltons is 4.71, 5.06, and 5.47, respectively. there were. That is, it has been clarified that the strength of the calcium alginate fiber produced increases as the molecular weight of sodium alginate increases. Since the zero span break length is proportional to the strength of the single fiber, it is clear that the single fiber strength increases as the molecular weight of sodium alginate as a raw material increases. Therefore, it can be seen that the single fiber strength of calcium alginate fibers made from high molecular weight sodium alginate is increased.

Reference Example 10

Simple production method of calcium alginate fiber It is possible to easily prepare calcium alginate fiber or gel from an aqueous solution of sodium alginate, and it is possible to produce fiber or gel without stretching during production.

  Since the calcium alginate fiber obtained by putting sodium alginate into the storage tank and extruding it through the nozzle hole (the needle hole is shown here) into the calcium chloride aqueous solution as the coagulation liquid in the coagulation tank is not stretched, it is 1.3 times It is considered that the strength increases if it is stretched to the extent. The tensile strength of the single fiber was measured for air-dried fiber and wet fiber by JIS L1069 “Fiber tensile test method” method.

More specifically, a 4.5 (absolutely dry w / w)% sodium alginate (also referred to as AlgNa) aqueous solution (dope) is placed in a storage tank (a syringe or a storage tank of a spinning machine), and a nozzle hole (diameter 1.0 mm or diameter 0). .5mm), the liquid continuously comes out by hand (or machine) into the coagulation tank containing the 0.5M calcium chloride CaCl ₂ aqueous solution that is the coagulation liquid in the coagulation tank (petri dish or coagulation tank). Extruded at speed. Becomes calcium alginate fiber. The ends were pulled immediately so as to be straight, and kept for several minutes until wrinkles were not formed (or linear fibers were achieved by winding in a coagulation tank of a spinning machine). After that, it was kept in the coagulation tank for 2 hours or more, and the water washing was performed 6 times or more using deionized water, and it was carried out for 2 hours or more (or rolled up continuously after 2 water washing tanks of the spinning machine). Completed with water). After washing with water, it was put in a polyethylene bag containing deionized water, stored in a refrigerator at 4 ° C., and used for experiments.

  The tensile strength of the single fiber was measured for air-dried fiber and wet fiber by JIS L1069 “Fiber tensile test method” method.

Reference Example 11

Stretching experiment (coagulation tank);
In the coagulation tank, it is possible to further increase the fiber strength by performing the following operations.

  In the coagulation tank, by stretching, the strength is increased due to uniform solidification and fiber orientation.

  In the case of 0.5 M calcium chloride coagulation solution, the sodium alginate aqueous solution that has entered the coagulation tank immediately forms a calcium alginate film by ion exchange from the outer periphery of the fiber, and ion exchange proceeds inward and solidification and solidification proceed. Becomes calcium and hardens.

  During continuous solidification, that is, by stretching the single fiber whose outer periphery is solidified and whose inner solidification is in progress to a speed just before the winding speed is cut, it is possible to uniformize the inner / outer periphery of the solidification and lengthen the fiber Since the orientation toward the direction (winding direction) proceeds sufficiently, the strength can be increased. Since the fiber is stretched, the fiber becomes thinner than when the fiber is not stretched.

Reference Example 12

Equipment and instruments;
Examples of equipment necessary for producing calcium alginate fibers from an aqueous sodium alginate solution are given below. In the case of production of (1) control alginate fiber, and (2) production of alginate fiber containing additives, the production apparatus / flow of alginate (calcium) fiber is described.
(1) In the case of control alginate fiber
[Storage tank: Preparation of sodium alginate aqueous solution (dope) concentration 5%]
[Coagulation tank: Preparation of coagulation solution sodium chloride aqueous solution, concentration 0.5M]
[Fiberification in the coagulation tank: extrusion from the nozzle hole into the coagulation tank]
[Washing tank: Winding]
[Stretching in washing tank: There is stretching due to increased winding speed]
[Storage: Refrigerator 4 ° C]

[Storage tank (syringe): Preparation of sodium alginate aqueous solution (dope) concentration 5%]
[Coagulation tank (petri dish): Preparation of coagulation liquid sodium chloride aqueous solution concentration 0.5M]
[Fiberification in the coagulation tank: extrusion from the nozzle hole (syringe hole) into the coagulation tank]
[Washing tank: Distilled water exchange]
[Stretching in washing tank: No stretching]
[Storage: Refrigerator 4 ° C]

(2) In the case of alginate fiber containing additives
[Storage tank: Preparation of powdered sodium alginate 5% aqueous solution (dope)]
[Coagulation tank: Preparation of 0.5M sodium chloride aqueous solution for coagulation]
[Fiberification in the coagulation tank: extrusion from the nozzle hole (syringe hole) into the coagulation tank]
[Washing tank: Winding]
[Stretching in washing tank: There is stretching due to increased winding speed]
[Storage: Refrigerator 4 ° C]

[Reservoir syringe: Preparation of powdered sodium alginate 5% aqueous solution (dope)]
[Coagulation Petri dish: Preparation of Coagulation Solution 0.5M Sodium Chloride]
[Fiberification in the coagulation tank: extrusion from the nozzle hole into the coagulation tank]
[Washing tank: Distilled water exchange]
[Stretching in washing tank: No stretching]
[Storage: Refrigerator 4 ° C]

Relationship between the molecular weight of sodium alginate and the strength of calcium alginate gels;
Sodium alginate aqueous solution having a polymerization degree of 500 (also described as DP500) and a polymerization degree of 80 (also described as DP80) (concentration, 0.5, 1.0, 2.0, 3.0, 4.0, 5.0 mass%) Is put into a polypropylene syringe, extruded into a polypropylene container containing a calcium chloride aqueous solution (concentration 0.05, 0.2, and 0.5M) with a syringe, and gelled into a fiber having a diameter of about 1.0 mm. After holding for 4 hours, washing with water was performed for 2 hours (exchange of distilled water three times). Then cut to a length of 10 cm and soak in 8 ml of filtered seawater. After 4 hours, the solution was changed once and left overnight (at room temperature of 28 ° C.). The strength and seawater resistance of various calcium alginate gels were evaluated. The results are shown in Table 1.

The following results were obtained.
Result 1: When there is no seawater resistance, the gel that was initially opaque when immersed in seawater becomes transparent, becomes surface-null, and can be easily broken when pulled. Result 2: DP500> DP80 when strong and stretched. The AlgNa (sodium alginate) concentration of 5%, 3%, and 2% had a thin shape, and the AlgNa 1% had a thick shape. Result 3: Strong, (as is the use of calcium chloride flocculant to agglomerate the sodium alginate) Combination of the AlgNa-CaCl ₂ extending: 5% strength sodium alginate of DP500, 3%, in 2% calcium chloride concentration It was 0.5M or 0.2M. When DP500 was sodium alginate and the concentration was 5%, the calcium chloride concentration was 0.05M. At a concentration of 5% with DP80 sodium alginate, the concentrations of nalsium chloride were 0.5M, 0.2M and 0.05M. Result 4: A gel having a high strength (hard and stretched) before immersion is strong even after immersion in seawater (maintaining shape, hard, and stretches without breaking when pulled).

  Although not shown in Table 1, a calcium alginate gel prepared from sodium alginate having a polymerization degree of 500 is not a fibrous gel but an alginic acid prepared from sodium alginate having a polymerization degree of 80. Gel strength and seawater resistance were stronger than calcium gel.

  Among the examples shown in Table 1, the maximum strength is obtained when a 5% aqueous solution of sodium alginate having a polymerization degree of 500 is coagulated with 0.5 M calcium chloride, and the durability of the gel in seawater is also maximum. there were. From the above, when preparing a calcium alginate gel from only sodium alginate, a calcium alginate gel having a degree of polymerization of 500 is stronger than a sodium alginate having a degree of polymerization of 80, and the gel does not easily collapse even in seawater. I understand that.

  It is clear that the higher the sodium alginate molecular weight, the higher the gel strength and the higher the durability of the gel in seawater. Higher molecular weight sodium alginate is preferable as a raw material even when the calcium alginate gel itself is used alone, or when it is used as a calcium alginate gel immobilization carrier used in seawater by immobilizing seaweed and / or adsorbent and the like. I understand that.

  The viscosity of a 1% by weight aqueous solution of sodium alginate in DP500 is about 500 cp, and the viscosity of a 1% by weight aqueous solution of sodium alginate in DP80 is about 80 cp.

  Regarding the sodium alginate aqueous solution containing seaweed and / or powder, the molecular weight (degree of polymerization) of sodium alginate, and the calcium alginate gel containing seaweed and / or powder prepared from the algae and its strength and seawater Resistance was evaluated. As a result, the calcium alginate gel has higher gel strength and higher gel durability in seawater as the molecular weight of sodium alginate is higher, similar to the results with the aqueous solution of sodium alginate that does not contain seaweed and / or powder. It turns out that it is obtained. In the present specification, any of the group consisting of seaweed spores, seaweed alga bodies, and seaweed slices is also referred to as seaweed.

Reference Example 13

Properties of nutrient adsorbents Nitrate ion adsorbents, new oxoanion adsorbents (nano-space control adsorbents);
A nitrate ion adsorbent, which is a hydroxide containing nickel and iron, was synthesized as follows (Japanese Patent Application Laid-Open No. 2004-130200 (claims and others)) by adding NaOH to a mixed solution of FeCl ₃ and NiCl _2. After co-precipitation and aging at 120 ° C. for 1 day, the precipitate was washed by filtration and dried for 1 day at 50 ° C. The nitrate adsorption capacity of the nitric acid adsorbent obtained by synthesis in seawater was measured. In the present invention, the synthesized nitric acid adsorbent is referred to as Ni-Fe type nitric acid adsorbent, and sodium nitrate is added to seawater to prepare seawater having a nitrate ion concentration of 1.86 mg / liter. Ni-Fe type nitric acid adsorbent 0.1 g was added to 1 liter of nitric acid-added seawater and allowed to stand for 72 hours at 25 ° C. Low concentration of nitrate ions in nitric acid-added seawater after 72 hours This was measured by a cadmium reduction method using an acid salt reagent set (manufactured by HACH) The nitric acid adsorption capacity of the Ni-Fe type nitric acid adsorbent was 4.203 mg nitrate nitrogen / g adsorbent. Nitrate nitrogen adsorption capacity of the aquarium nitrate adsorbent ion exchange resin etc. was measured, and as a result, the nitric acid adsorption capacity of the commercially available aquarium nitrate adsorbent was 1.47 mg nitrate nitrogen / g adsorbent or less. Nitric acid adsorption capacity of ion exchange resin is 0.23 mg nitrate nitrogen / g adsorbent or less, and nitric acid adsorption capacity of adsorbent composed of magnesium and aluminum is 0.23 mg nitrate nitrogen / g adsorbent or less, consisting of magnesium and iron The adsorbent has a nitric acid adsorption capacity of 1.12 mg nitrate nitrogen / g adsorbent, and an adsorbent composed of zinc and aluminum has a nitric acid adsorption capacity of 0.23 mg nitrate nitrogen. / G adsorbent or less, nitric acid adsorption capacity of commercially available nitric acid adsorbent is 0.23 mg nitrate nitrogen / g adsorbent or less, and nitric acid adsorption capacity of an adsorbent composed of Zr (OH) ₄ is 0.23 mg nitrate nitrogen From these results, the nitric acid adsorption capacity of the Ni-Fe type nitric acid adsorbent is about 3 times higher than the nitric acid adsorption capacity of the other adsorbents evaluated. It turns out that ability is excellent.

  Further, when the nitrate ion adsorption rate in seawater was measured, it was found that the Ni—Fe type nitrate adsorbent adsorbs nitrate ions of 80% of the adsorption capacity in 2 hours of reaction. From this result, Ni—Fe The type nitric acid adsorbent was found to have a very fast nitric acid adsorption rate. It was noted that nitrate ions of almost 100% of the adsorption capacity were adsorbed in 4 hours of reaction.

The pH dependence of the nitrate ion adsorption amount of the Ni—Fe type nitric acid adsorbent was determined by adding 0.1 g of adsorbent to 1 L of seawater whose pH was adjusted with HCl and NaOH to 1.86 mg / L of NaNO _{3 and} at 3 ° C. Went for days. The amount of nitrate ion adsorbed greatly depended on the pH of seawater, and reached a maximum near pH 8. From these results, the Ni—Fe type nitric acid adsorbent is promising as an adsorbent that selectively removes nitrate ions from seawater.

Powder adsorbent;
100 mM sodium nitrate was used as the salt water. The Ni—Fe type nitric acid adsorbent described in Reference Example 13 was used as the powder adsorbent.

  The powder adsorbent was screened using a 270 mesh screen. The pore size of 270 mesh is about 53 microns. At first, the powder adsorbent that passed through the sieve is called the powder adsorbent for immobilization.

  A 2 mg sodium alginate aqueous solution of 4.5 (absolutely dry w / w) was mixed at a ratio of 200 mg of the powder adsorbent for immobilization to prepare an aqueous sodium alginate solution containing the adsorbent.

An aqueous solution (dope) containing 4.5 (absolutely dry w / w)% sodium alginate (also referred to as AlgNa) containing an adsorbent was placed in a syringe and passed through a nozzle hole (diameter: 0.5 mm), 0.5 M as a coagulation liquid The solution was extruded by hand into a coagulation tank containing an aqueous solution of calcium chloride (CaCl ₂ ) at a speed at which the liquid continuously appeared without interruption. Since it became a calcium alginate fiber, both ends were pulled so that they were straight and kept for a few minutes until they did not wrinkle. Then, it hold | maintained in the coagulation tank for 2 hours or more, water washing was performed 6 times or more using deionized water, and was performed over 2 hours or more. After washing with water, it was put in a polyethylene bag containing deionized water and stored in a thermostatic bath at 10 ° C. until used for experiments. The calcium alginate fiber containing the adsorbent thus obtained is also referred to as an immobilized adsorbent fiber.

100 mM sodium nitrate was used as the salt water. Immobilized adsorbent fibers equivalent to 200 mg of the powder adsorbent for immobilizing adsorbent fibers were immersed in a 50 mL capacity screw tube containing 50 mL of 100 mM sodium nitrate aqueous solution, and the mixture was stirred at a speed of 100 rpm. After 4 days, the immobilized adsorbent fibers and the liquid were separated with a filter. The separated liquid was measured for nitrate ion concentration by ion chromatography.
As a result, the immobilized adsorbent fiber was able to reduce the concentration of nitrate ions to 93% of the original nitrate ions.

Comparative Example 4

  The adsorbing performance of nutrient salts was evaluated by directly attaching the powder adsorbent to the solution without immobilizing it on the gel. 200 g of the powder adsorbent was immersed in 50 ml of a 100 mM sodium nitrate aqueous solution, and subjected to tension at a speed of 100 rpm. After 4 days, the powder adsorbent and the liquid were separated by a filter. The separated liquid was measured for nitrate ion concentration by ion chromatography. As a result, the adsorbent was able to reduce the concentration of nitrate ions to 90.6% of the original nitrate ions.

  From the above, it is clear that calcium alginate fiber is a carrier that can be immobilized without reducing the performance of the powder adsorbent. Furthermore, since it was immobilized on a calcium alginate carrier, it was found that it exhibited 103% of the performance of the adsorbent that was not immobilized. Since the performance when immobilized with an organic carrier such as PVC is about 25% of the performance when not immobilized, the high performance of calcium alginate gel can be seen.

As a result of the adsorption experiment of nutrient salt using the immobilized adsorbent fiber described in Example 4, the immobilized adsorbent fiber has the following advantages compared with the powder adsorbent that is not immobilized. It was revealed.
(1) When salt water is used for pouring, if the adsorbent is not immobilized, the adsorbent will collect at a certain place or clog the filter, and the powder adsorbent will be substantially Can only be used in batch processing. On the other hand, the immobilized adsorbent fiber has the advantage that it can be used either in running water or in a column.
(2) In the immobilized adsorbent fiber, since the powder adsorbent is distributed in the immobilized fiber, the nitrate adsorbing rate of the immobilized adsorbent fiber is faster than the nitrate adsorbing rate of the powder adsorbent. It was. It can be used for quick adsorption treatment.
(3) Since calcium alginate is hydrophilic, the penetration of hydrophilic ions such as nitrate ions is good.
(4) The collection of the powder adsorbent is simple because the immobilized adsorbent fibers can be taken out.
(5) In order to be able to take out the adsorbent after the adsorption treatment with the adsorbent, the carrier itself for immobilizing the adsorbent must be a polymer that can be easily returned from fiber or solid to sol or aqueous solution. Although preferred, calcium alginate fibers have this property.

Further, the immobilized adsorbent fiber made from the high-purity sodium alginate aqueous solution E1 described in Example 2 obtained by high-purification treatment as a raw material is made from sodium alginate that has not been subjected to high-purity treatment (untreated). Compared to the immobilized adsorbent fiber, it had the following advantages.
(6) When culturing in running water, the gel strength was strong and the seawater resistance was high, so that no detachment of the immobilized adsorbent from the fibers was observed. On the other hand, in the immobilized adsorbent fiber made from sodium alginate not subjected to high-purity treatment (untreated), about 20% of the immobilized adsorbent was detached from the fiber.
(7) An immobilized adsorbent fiber was prepared using sodium alginate that had been highly purified by the acid method and the calcium method as a raw material, and a similar experiment was performed. However, the strength of the calcium alginate fiber was low and immobilized 30 % -40% sorbent leakage occurred.

  When high-purity sodium alginate was used as a raw material for calcium alginate fiber for immobilizing the adsorbent, an immobilized adsorbent fiber with performance that surpassed expectations could be obtained.

It is a figure which shows ratio of each eluate volume with respect to column volume, and each component density | concentration about the reference example 4. FIG. It is a figure which shows the ratio of the eluate volume with respect to column volume, and each component density | concentration about the reference example 5. FIG. FIG. 4 is a graph showing the ratio of the eluate volume to the column volume and the concentration of each component for Example 1. The schematic of an example of the flow-path switching machine with which the nutrient salt concentration reduction apparatus (especially in the case of a pouring method) of this invention is provided is shown. As shown in FIG. 4a, two 10 cubic liter polycarbonate cubic water tanks are connected by a tube to form one unit. A filter was installed between the polycarbonate water tank and the connecting tube to prevent the adsorbent from flowing out of the polycarbonate water tank. Aeration was performed in a polycarbonate water bath. It is preferable to insert a backflow prevention valve between the polycarbonate water tank and the connecting tube to prevent backflow of salt water. The nutrient salt concentration reducing apparatus employs a large unit structure in which eight units described above are connected (FIG. 4b). When reducing the concentration of nutrient salts in salt water, the adsorbent was added after injecting salt water to half the height of the polycarbonate water tank. That is, before flowing salt water from a source of salt water with high nutrient concentration into the nutrient concentration reducing device, 5 liters of environmental salt water (salt water) and adsorbent are put in each polycarbonate tank of the nutrient concentration reducing device in advance. did. Therefore, 10 liters of environmental salt water and an adsorbent are included per unit (also referred to as U). After the salt water from the nutrient water source with high nutrient concentration starts to flow into the nutrient concentration reduction device, the solenoid valve and the 8-way valve are switched every 6 hours, and the salt water source of the salt water with high nutrient concentration is switched. By changing the path, each water tank containing the adsorbent introduced into the nutrient concentration reduction device was brought into contact with salt water containing high concentration nutrients from a salt water source with high nutrient concentration. (Figure 4c). It is a figure which shows an example of the flow-path switching valve (an electromagnetic valve or a manual valve) of this invention. It is a figure which shows an example of the nutrient concentration reduction apparatus of the system of this invention. It is a figure which shows an example of the nutrient concentration reduction apparatus of the system of this invention.

Claims (56)

The acidic polysaccharide inorganic salt whose ratio of the acidic polysaccharide monovalent | monohydric inorganic salt used as the main component with respect to all the acidic polysaccharide inorganic salts is 90 mol% or more. 2. The acidic polysaccharide inorganic salt according to claim 1, wherein the ratio of the monovalent inorganic salt of the acidic polysaccharide as a main component to all the inorganic salts of acidic polysaccharide is 99.85 mol% or more. The acidic polysaccharide inorganic salt according to claim 2, wherein the ratio of the acidic polysaccharide monovalent inorganic salt as a main component to all acidic polysaccharide inorganic salts is 99.9 mol% or more. The acidic polysaccharide inorganic salt according to any one of claims 1 to 3, for producing an acidic polysaccharide inorganic salt gel and / or fiber. The acidic polysaccharide inorganic salt according to any one of claims 1 to 4, wherein the acidic polysaccharide is alginic acid. The acidic polysaccharide inorganic salt according to any one of claims 1 to 5, wherein the acidic polysaccharide monovalent inorganic salt as the main component is an acidic polysaccharide sodium salt. The acidic polysaccharide inorganic salt according to any one of claims 1 to 6, wherein the acidic polysaccharide monovalent inorganic salt as the main component is sodium alginate. A step of dialyzing an aqueous solution of a salt of an inorganic cation containing a monovalent inorganic cation and an acidic polysaccharide anion as a main component against a dialysis solution containing a monovalent inorganic cation (where the monovalent inorganic cation in the dialysis solution is Is higher than the ratio of the monovalent inorganic cation that is the main component in the aqueous solution). The method for producing an acidic polysaccharide inorganic salt according to claim 8, wherein the acidic polysaccharide is alginic acid. The manufacturing method of the acidic polysaccharide inorganic salt of Claim 8 or 9 whose monovalent | monohydric inorganic cation used as the said main component is a sodium ion. The manufacturing method of the acidic polysaccharide inorganic salt in any one of 8-10 whose said acidic polysaccharide is alginic acid and whose monovalent | monohydric inorganic cation used as the said main component is a sodium ion. The manufacturing method of the acidic polysaccharide inorganic salt in any one of Claims 8-11 whose said dialysate is sodium chloride aqueous solution. The manufacturing method of the acidic polysaccharide inorganic salt of Claim 12 whose purity of the sodium chloride in the said sodium chloride aqueous solution is 99.99 mass% or more. The manufacturing method of the acidic polysaccharide inorganic salt of Claim 13 whose purity of the sodium chloride in the said sodium chloride aqueous solution is 99.999 mass% or more. The method for producing an acidic polysaccharide inorganic salt according to any one of claims 12 to 14, wherein the aqueous sodium chloride solution is produced using an abnormal chromatography phenomenon or a pseudo-abnormal chromatography phenomenon. About the aqueous solution of the salt of the inorganic cation containing the monovalent inorganic cation as the main component and the acidic polysaccharide anion, the solution viscosity after the dialysis step is 90% or more of the solution viscosity before the dialysis step, The method for producing an acidic polysaccharide inorganic salt according to any one of claims 8 to 15. With respect to an aqueous solution of a salt of an inorganic cation containing a monovalent inorganic cation as a main component and an acidic polysaccharide anion, the solution molecular weight after the dialysis step is 90% or more of the solution molecular weight before the dialysis step, The method for producing an acidic polysaccharide inorganic salt according to any one of claims 8 to 15. About the aqueous solution of the salt of the inorganic cation containing the monovalent inorganic cation as the main component and the acidic polysaccharide anion, the solution viscosity after the dialysis step is 95% or more of the solution viscosity before the dialysis step, The method for producing an acidic polysaccharide inorganic salt according to claim 16. With respect to an aqueous solution of a salt of an inorganic cation containing a monovalent inorganic cation as a main component and an acidic polysaccharide anion, the solution molecular weight after the dialysis step is 95% or more of the solution molecular weight before the dialysis step, The method for producing an acidic polysaccharide inorganic salt according to claim 17. Acidic polysaccharide inorganic salt gel and / or fiber. An aqueous solution of an acidic polysaccharide inorganic salt (wherein, in the acidic polysaccharide inorganic salt, the ratio of the acidic polysaccharide monovalent inorganic salt as a main component to all acidic polysaccharide inorganic salts is 90 mol% or more), An acidic polysaccharide inorganic salt gel and / or fiber obtained by contacting with an aqueous inorganic salt solution. The acidic polysaccharide inorganic salt gel and / or fiber according to claim 21, wherein the ratio of the monovalent inorganic salt of the acidic polysaccharide as a main component to all the inorganic salts of acidic polysaccharide is 99.85 mol% or more. The acidic polysaccharide inorganic salt according to claim 22, wherein in the acidic polysaccharide inorganic salt, the ratio of the acidic polysaccharide monovalent inorganic salt as a main component to all the acidic polysaccharide inorganic salts is 99.9 mol% or more. Gel and / or fiber. The acidic polysaccharide inorganic salt gel and / or fiber according to any one of claims 20 to 23 for retaining an adsorbent. The acidic polysaccharide according to any one of claims 20 to 24, wherein the tensile strength of single fibers of air-dried fibers is 1.5 g / denier or higher, or the tensile strength of single fibers of wet fibers is 0.15 g / denier or higher. Inorganic salt gel and / or fiber. The acidic polysaccharide inorganic salt gel and / or fiber according to any one of claims 20 to 25, wherein the acidic polysaccharide is alginic acid. 27. The acidic polysaccharide inorganic salt gel and / or fiber according to any one of claims 21 to 26, wherein the acidic polysaccharide monovalent inorganic salt as the main component is an acidic polysaccharide sodium salt. The acidic polysaccharide inorganic salt gel product and / or fiber product which use the acidic polysaccharide inorganic salt gel and / or fiber in any one of Claims 20-27 as a raw material. The acidic polysaccharide inorganic salt gel product and / or fiber product according to claim 28, and the acidic polysaccharide inorganic salt gel product and / or fiber product having an adsorbent and having an adsorbent. 30. The acidic polysaccharide inorganic salt gel product retaining an adsorbent according to claim 29, wherein the adsorbent is an adsorbent that adsorbs nutrients containing phosphorus and / or nutrients containing nitrogen. Fiber products. The acidic polysaccharide inorganic salt gel and / or fiber which hold | maintains an adsorbent which has an acidic polysaccharide inorganic salt gel and / or fiber in any one of Claims 20-27, and an adsorbent. An aqueous solution of an acidic polysaccharide inorganic salt containing an adsorbent (wherein, in the acidic polysaccharide inorganic salt, the ratio of the acidic polysaccharide monovalent inorganic salt as a main component to all acidic polysaccharide inorganic salts is 90 mol% or more) And an acidic polysaccharide inorganic salt gel and / or fiber that retains the adsorbent, which is obtained by bringing the aqueous solution into contact with an aqueous inorganic salt solution. The acidic polysaccharide inorganic salt gel retaining an adsorbent according to claim 32, wherein the ratio of the acidic polysaccharide monovalent inorganic salt as a main component to all acidic polysaccharide inorganic salts is 99.85 mol% or more, and / Or fiber. The acidic polysaccharide inorganic salt retains the adsorbent according to claim 32, wherein a ratio of the acidic polysaccharide monovalent inorganic salt as a main component to all the acidic polysaccharide inorganic salts is 99.9 mol% or more. Acidic polysaccharide inorganic salt gel and / or fiber. The acidic polysaccharide inorganic salt retaining an adsorbent according to any one of claims 31 to 33, wherein the adsorbent is an adsorbent that adsorbs a nutrient salt containing phosphorus and / or a nutrient salt containing nitrogen. Gel and / or fiber. The acidic polysaccharide inorganic salt gel product and / or fiber product which hold | maintains an adsorbent which use the acidic polysaccharide inorganic salt gel and / or fiber which hold | maintain the adsorbent in any one of Claims 31-33 as a raw material. Calcium alginate gel and / or fiber. Obtained by contacting an aqueous solution of an alginic acid inorganic salt (wherein the alginate inorganic salt has a ratio of sodium alginate as a main component with respect to all the alginic acid inorganic salts of 90 mol% or more) and an aqueous calcium ion solution. , Calcium alginate gel and / or fiber. The calcium alginate gel and / or fiber according to claim 39, wherein a ratio of sodium alginate as a main component to all alginate inorganic salts is 99.85 mol% or more. 40. The calcium alginate gel and / or fiber according to claim 39, wherein a ratio of sodium alginate as a main component to all inorganic alginate in the alginate inorganic salt is 99.9 mol% or more. 41. The calcium alginate gel and / or fiber according to any one of claims 38 to 40 for retaining an adsorbent. The calcium alginate gel according to any one of claims 38 to 41, wherein the tensile strength of the single fiber of the air-dried fiber is 1.5 g / denier or higher, or the tensile strength of the single fiber of the wet fiber is 0.15 g / denier or higher. / Or fiber. A calcium alginate gel product and / or a fiber product obtained from the calcium alginate gel and / or fiber according to any one of claims 38 to 42. 44. A calcium alginate gel product and / or fiber product having an adsorbent, comprising the calcium alginate gel product and / or fiber product of claim 43 and an adsorbent. The calcium alginate gel and / or fiber which hold | maintains an adsorbent which has the calcium alginate gel and / or fiber in any one of Claims 38-42, and an adsorbent. An aqueous solution of an alginic acid inorganic salt containing an adsorbent (herein, the ratio of sodium alginate as a main component to the entire alginic acid salt in the alginic acid inorganic salt is 90 mol% or more) and a calcium ion aqueous solution are contacted Calcium alginate gel and / or fiber holding the adsorbent, obtained by making it. The calcium alginate gel and / or fiber holding the adsorbent according to claim 46, wherein a ratio of sodium alginate as a main component to all alginate inorganic salts is 99.85 mol% or more. 48. The calcium alginate gel and / or fiber holding an adsorbent according to claim 47, wherein the ratio of sodium alginate as a main component to all alginate inorganic salts in the alginate inorganic salt is 99.9 mol% or more. The calcium alginate gel holding an adsorbent according to any one of claims 45 to 48, wherein the adsorbent is an adsorbent that adsorbs nutrients containing phosphorus and / or nutrients containing nitrogen. Or fiber. A calcium alginate gel product and / or a fiber product holding an adsorbent, the raw material being the calcium alginate gel and / or fiber holding the adsorbent according to any one of claims 45 to 49. The acidic polysaccharide inorganic salt gel and / or fiber holding the adsorbent according to claim 31 to 35, the calcium alginate gel and / or fiber holding the adsorbent according to claim 45 to 49, and claims 29 and 30. And 36. An acidic polysaccharide inorganic salt gel product and / or a fiber product retaining the adsorbent according to claim 36, and a calcium alginate gel product and / or a fiber product retaining the adsorbent according to claim 44 and 50. An apparatus for reducing the concentration of nutrients in salt water, comprising at least one selected from the group. The nutrient salt for reducing the concentration is at least one selected from the group consisting of nitrate nitrogen, nitrite nitrogen, ammonia nitrogen, urea nitrogen, organic phosphorus, inorganic phosphorus and silicon. The apparatus for reducing the concentration of nutrients in salt water according to claim 51. 53. The apparatus for reducing the concentration of nutrients in salt water according to claim 51 or 52, and a flow path switching device, a nitrification tank in which nitrifying bacteria are fixed, an oxygen supply tank, a foam separation tank, a precipitation tank, a pH adjustment water tank, a water temperature A system for reducing the concentration of nutrients in salt water, comprising at least one selected from the group consisting of a regulating tank, a filtration tank, a circulation pump, and a biological breeding tank. The salt water is treated with at least one selected from the group consisting of the nutrient salt concentration reducing device in salt water according to claim 51 or 52 and the nutrient salt concentration reducing system according to claim 53. A method for reducing the concentration of nutrient salts in brine, comprising a step. 55. Processed water for reducing the concentration of nutrients in salt water obtained by the method for reducing the concentration of nutrients in salt water according to claim 54. 56. An offshore organism produced in treated water with reduced concentration of nutrients in salt water according to claim 55.

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