JP2019205418A - Process for producing vanadium-reduced beverage and process for removing vanadium - Google Patents

Abstract

To provide: a process for producing vanadium-reduced beverage, that is excellent in vanadium removal efficiency; and a process for removing vanadium from vanadium-containing aqueous solution.SOLUTION: According to the present invention, a process for producing vanadium content-reduced beverage comprising a step in which a beverage or raw material liquid thereof and a polymer substrate carrying tannic acid are brought into contact, and a process for removing vanadium from vanadium-containing aqueous solution, comprising a step in which a vanadium-containing aqueous solution and a polymer substrate carrying tannic acid are brought into contact are provided.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a vanadium-reducing beverage and a method for removing vanadium. The present invention also relates to a method for recovering vanadium and a vanadium adsorbent.

  Vanadium has been confirmed to have health functionalities such as diabetes improvement effect and beauty effect, and has attracted attention as a functional food material. For this reason, in recent years, foods and beverages containing vanadium have been developed. On the other hand, vanadium is also a causative substance that causes problems related to beverage quality such as flavor deterioration, off-flavour, and precipitation in the field of beverage production.

  Vanadium exists as an ion in an aqueous solution, and various techniques have been disclosed so far for methods for reducing, removing, and recovering vanadium ions using their properties. As a representative technique, there is a method of reducing vanadium using a cation exchange resin column in vanadium-dissolved water (Patent Document 1). However, a plurality of metal ions are present in an aqueous solution such as natural water, and a method for selectively reducing or removing vanadium has been demanded. On the other hand, vanadium is widely used industrially as a rare metal, and a method for recovering vanadium from nature has been developed to satisfy demand (Patent Document 2).

Japanese Patent Laying-Open No. 2015-188848 JP 59-227728 A

  An object of this invention is to provide the manufacturing method of the vanadium reduction drink excellent in vanadium removal efficiency, and the method of removing vanadium from vanadium containing aqueous solution. Another object of the present invention is to provide a method for recovering vanadium from a vanadium-containing aqueous solution and a vanadium adsorbent.

  The inventors of the present invention have recently produced a nylon fiber body carrying tannic acid by a radiation graft polymerization method, and contacting the nylon fiber body with a vanadium-containing aqueous solution. As a result, the nylon fiber body has excellent vanadium removal. And the removal ability was found to be vanadium selective. The present inventors have also confirmed that the vanadium adsorbed on the nylon fiber can be recovered with high efficiency by subjecting the nylon fiber adsorbed with vanadium to a regeneration treatment. The present invention is based on these findings.

According to the present invention, the following inventions are provided.
[1] A method for producing a beverage with reduced vanadium content, comprising a step of bringing a beverage or a raw material solution thereof into contact with a polymer base material carrying tannic acid.
[2] The production method according to [1], wherein the beverage or the raw material liquid thereof contains vanadium.
[3] The production method according to [1] or [2] above, wherein the beverage has a vanadium content of 30 mg / 100 mL or less and a sodium content of 0.4 to 1.0 mg / 100 mL.
[4] The production method according to any one of [1] to [3], wherein the beverage having a reduced vanadium content is a container-packed beverage.
[5] The production method according to any one of [1] to [4], wherein the polymer base material is a polyamide resin.
[6] A method for removing vanadium from a vanadium-containing aqueous solution, the method comprising the step of bringing the vanadium-containing aqueous solution into contact with a polymer substrate carrying tannic acid.
[7] A method for recovering vanadium from a vanadium-containing aqueous solution, the step of bringing the vanadium-containing aqueous solution into contact with a polymer substrate supporting tannic acid, and the step of recovering vanadium from the polymer substrate A method for recovering vanadium, comprising:
[8] The method according to [7] above, wherein the vanadium-containing aqueous solution is seawater, groundwater, river water, or lake water.
[9] The method according to [7] or [8] above, wherein the step of recovering vanadium is performed by bringing the polymer substrate into contact with a neutral regenerant, an alkaline regenerator, or an acidic regenerant.
[10] The method according to any one of [7] to [9], wherein the step of recovering vanadium is performed at 1000 ° C. or lower.
[11] A vanadium adsorbent comprising a polymer base material carrying tannic acid.

  ADVANTAGE OF THE INVENTION According to this invention, the drink by which vanadium content was reduced with a high vanadium removal rate can be manufactured only by making a drink or its raw material liquid contact the polymer base material which carry | supports tannic acid. This polymer substrate is advantageous in that it can be processed into various shapes such as a fibrous shape, and can be easily produced without any handling problems and with a reduced vanadium content. Further, since vanadium adsorbed on a polymer substrate carrying tannic acid can be recovered with high efficiency, the present invention is advantageous in that vanadium, which is a kind of rare metal, can be efficiently recovered from nature.

Detailed description of the invention

  According to the present invention, a beverage with a reduced vanadium content can be produced. Here, “vanadium” is one of transition elements, and is used to mean not only metal vanadium, which is a single vanadium, but also vanadium ions and vanadium salts.

  Vanadium is widely distributed in the crust and is the fifth most abundant transition element. For example, groundwater around Mt. Fuji contains about 0.1 mg / L of vanadium and 0.002 mg / L of seawater. Groundwater, river water, lake water, and industrial water serve as water sources for tap water, and are used as water sources for raw water for soft drinks (hereinafter sometimes referred to as “raw water”) in the food industry. . Since raw water is used for the manufacture of beverages, the manufactured beverages may contain vanadium derived from raw water.

  The beverage and the raw material liquid to be brought into contact with the polymer base material carrying the tannic acid of the present invention (hereinafter sometimes referred to as “the polymer base material of the present invention”) shall contain vanadium. it can. In the production method of the present invention, the lower limit value of the vanadium concentration of the beverage and the raw material liquid to be brought into contact with the polymer base material can be 0.03 mg / L. The upper limit of the vanadium concentration can be 10 mg / L, preferably 1 mg / L. The vanadium concentration can be, for example, 0.03 to 10 mg / L, and preferably 0.03 to 1 mg / L.

  The measurement of the vanadium concentration of the beverage and the raw material liquid to be brought into contact with the polymer substrate of the present invention and the beverage produced by the production method of the present invention is performed by ICP (inductively coupled plasma) mass spectrometry as described in Examples below. According to the method, measurement may be performed using a commercially available apparatus (for example, 7500ce, manufactured by Agilent).

  In the present invention, the “beverage” is, for example, a soft drink (for example, natural water, natural water, natural mineral water, mineral water, near water, sports drink, cider, cola, ginger ale), tea drink (for example, green tea, Black tea, oolong tea, blended tea), brewed liquor (for example, malt fermented drinks such as beer and sparkling liquor, Japanese liquor, fruit liquor such as wine and cider, liqueur such as plum wine), distilled liquor (eg whiskey, shochu, brandy, Chuhai, highball), vegetable drinks (eg, tomato juice, carrot juice, tomato mix juice, carrot mix juice), fruit drinks (eg, apple juice, orange juice, fruit juice drink), fruit / vegetable mix juice, coffee drink Cereal milk (eg Soy milk, rice milk, coconut milk, almond milk), vinegar beverages (for example, fruit vinegar beverages) and non-alcohol beer-taste beverage.

  In the present invention, the “raw material liquid” includes, for example, raw water and liquid raw material liquid of each beverage. Raw material water from groundwater, river water, lake water, and industrial water may be used as raw material water suitable for beverages (raw water for beverages) through processes such as filtration, sterilization, and ion exchange. The raw material liquid of the present invention to be brought into contact with the polymer substrate may be raw water before the treatment step or raw water for beverage after the water treatment. The raw material water for beverages is used, for example, as dilution water for fruit juices and vegetable juices, extraction water for coffee beans and tea leaves, preparation water for sports drinks and carbonated beverages, and brewing water for fermented beverages. Moreover, some raw material water which uses groundwater etc. as a water source can be used for manufacture of mineral water, without passing through a treatment process.

  In the present invention, in addition to the above, “raw material liquid” refers to a preparation liquid obtained by adding various compounding ingredients to the raw material liquid, an extract obtained using the raw material liquid, a pre-fermentation liquid, and a fermentation after brewing. It shall be used in the meaning including liquid.

The production method of the present invention is characterized in that a polymer substrate formed by immobilizing tannic acid is used as the vanadium adsorption material. Here, “tannic acid” means tannic acid in a broad sense and m-galloyl gallic acid which is a tannic acid in a narrow sense (molecular formula: C ₁₄ H ₁₀ O ₉ , molecular weight 322.23, CAS number: 536-08-3). It is used in the meaning including. Tanninic acid in a broad sense is a general term for aromatic compounds having a large number of phenolic hydroxyl groups, and condensed tannin, which is a derivative of flavanol, and soluble tannin in which one or more gallic acids and sugars (usually glucose) are ester-bonded From the viewpoint of efficiently reducing vanadium contained in a beverage or its raw material liquid, preferably soluble tannin (tannic acid, molecular formula: C ₇₆ H ₅₂ O in which one or more gallic acids and glucose are ester-bonded) ₄₆ , molecular weight: 1701.2, CAS number: 1401-55-4) can be supported on the polymer substrate.

  In the polymer substrate of the present invention, for example, a polymerizable monomer containing an epoxy group is graft-polymerized onto the polymer substrate, and then tannic acid is immobilized on the epoxy group in the formed graft chain. Thus, tannic acid can be supported on the polymer substrate.

  Examples of the polymerizable monomer subjected to the graft polymerization reaction with the polymer base material include a polymerizable monomer containing an epoxy group. Examples of the polymerizable monomer containing an epoxy group include glycidyl methacrylate (GMA), glycidyl acrylate, glycidyl sorbate, glycidyl metaitaconate, ethyl glycidyl maleate, and glycidyl vinyl sulfonate.

  In the present invention, the graft polymerization is preferably performed by a radiation graft polymerization method, that is, a method in which a base material is irradiated with radiation and a polymerizable monomer is polymerized on the base material using radicals generated on the surface of the base material or inside the base material. Can be implemented.

  Ionizing radiation can be used as the radiation to irradiate the polymer substrate. Examples include α rays, β rays, γ rays, electron beams, and neutron rays. Gamma rays and electron beams having the ability to do so are preferred. The irradiation condition of radiation is not particularly limited as long as an appropriate functional group density is achieved, but it can be 5 to 200 kGy, preferably 15 to 100 kGy in a deoxygenated state. A method for bringing the reaction system into a deoxygenated state is known to those skilled in the art. For example, a treatment such as bubbling an inert gas such as nitrogen into the reaction system can be performed.

  When ionizing radiation is irradiated to the polymer substrate, radicals are generated on the surface and inside of the polymer substrate. When the irradiated substrate is brought into contact with the polymerizable monomer, the generated radical is used as a starting point for the irradiation. A monomer can be polymerized on the formed substrate. The graft polymerization method includes a simultaneous irradiation method in which a substrate is immersed in a polymerizable monomer solution and then irradiated with an electron beam, and a pre-irradiation method in which the substrate is irradiated with an electron beam and then immersed in the polymerizable monomer. However, either may be sufficient. The pre-irradiation method includes a vapor phase graft polymerization method in which the vapor of the polymerizable monomer and the substrate are brought into contact with each other, and a liquid phase graft polymerization method in which the solution of the polymerizable monomer and the substrate are brought into contact with each other. May be. In the liquid phase graft polymerization method, for example, the polymer base material can be immersed in a solution containing a polymerizable monomer.

  Here, the polymer substrate is not particularly limited as long as the graft polymerization reaction proceeds and the polymer substrate can be used for the vanadium reduction treatment. For example, polyolefin resin (for example, polyethylene, polypropylene), polyamide-based polymer Resins (eg, nylon) and cellulose can be mentioned. In addition, the shape of the polymer base material can be made into a fiber shape, a hollow fiber shape, a nonwoven fabric shape, or a bead shape from the viewpoint of efficiently performing the vanadium reduction treatment.

  The ratio (functional group density) of the polymerizable monomer subjected to graft polymerization per unit mass of the polymer substrate can be arbitrarily set according to the polymerizable monomer and the graft polymerization conditions. Further, the ratio of the polymerizable monomer graft polymerized to the polymer base material may be specified by the “graft ratio” defined in the examples below. The graft ratio in the polymer substrate of the present invention can be 80% or less, preferably 40% or less. Moreover, the ratio (functional group density) of the tannic acid immobilized on the graft chain per unit mass of the polymer substrate can be arbitrarily set according to the tannic acid and the graft polymerization conditions.

  In the present invention, the polymerizable monomer is graft-polymerized onto the polymer substrate as described above, and then tannic acid is immobilized on the epoxy group in the formed graft chain to carry tannic acid. A polymeric substrate can be made. The reaction between an epoxy group and tannic acid can be carried out according to a conventional method. For example, a fiber body obtained by graft polymerization of a monomer having an epoxy group is immersed in a 1 to 10% by mass tannic acid solution, and the temperature is 60 to 90 ° C. By reacting under conditions of 3 to 46 hours, tannic acid can be supported on the polymer substrate.

  When the polymer substrate of the present invention is brought into contact with a beverage or its raw material liquid, the shape and contact conditions of the polymer substrate are not particularly limited as long as vanadium is adsorbed on the polymer substrate. For example, carrying out the contacting step of the production method of the present invention by passing a beverage or its raw material liquid through a filter-like polymer substrate of the present invention or a column filled with the polymer substrate of the present invention Can do. Further, the contact time and contact temperature between the beverage or its raw material liquid and the polymer base material of the present invention can be appropriately determined according to the amount of vanadium to be removed with reference to examples described later.

  According to the production method of the present invention, a beverage having a reduced vanadium content can be produced. Here, the “beverage with reduced vanadium content” means a beverage with a reduced vanadium content compared to a beverage produced without contact with the polymer substrate of the present invention, for example, Examples include beverages having a vanadium content of 90% or less (preferably 80% or less, more preferably 70% or less) of the vanadium content of a beverage produced without being brought into contact with the polymer substrate of the present invention.

  In the production method of the present invention, the beverage or its raw material liquid is brought into contact with the polymer base material of the present invention, but whether to contact with the beverage or its raw material liquid depends on vanadium removal rate, production efficiency, and flavor. Can be determined for each beverage in consideration of the effects of For example, when producing a soft drink, the raw material water and the preparation liquid used for dilution and preparation can be brought into contact with the polymer base material of the present invention, and when producing drinking water such as mineral water, the container Raw material water to be packed can be brought into contact with the polymer substrate of the present invention. When manufacturing a tea beverage or a coffee beverage, not only the raw water used for extraction and dilution, but also a tea extract or a coffee extract can be brought into contact with the polymer substrate of the present invention.

  Further, when producing brewed liquor such as fermented malt beverage and fruit liquor, not only the raw water used for brewing and dilution, but also the pre-fermented solution or the fermented solution after brewing are brought into contact with the polymer substrate of the present invention. Can be made. Moreover, when manufacturing a fruit drink and a vegetable drink, not only the raw material water used for dilution and a preparation but concentrated fruit juice and concentrated vegetable juice can be made to contact with the polymer base material of this invention.

  In the manufacturing method of this invention, it can implement according to the manufacturing procedure of a normal drink except making a drink or its raw material liquid contact the polymer base material of this invention.

  For example, in the case of producing a soft drink, raw water obtained by contacting with the polymer base material of the present invention (raw water for drink) and, if necessary, a composition used for producing a normal soft drink Various soft drinks can be manufactured by adding components. In the case of producing a soft drink, various soft drinks are also produced by bringing the prepared liquid obtained by adding various blending ingredients into the raw water (beverage raw water) with the polymer substrate of the present invention. You can also Since the polymer base material of the present invention has high adsorption selectivity for vanadium with respect to sodium and potassium, the polymer base material of the present invention is applied to a preparation of a beverage containing a relatively rich amount of sodium and potassium such as isotonic beverages. Even in this case, it is advantageous in that vanadium is selectively adsorbed and the concentrations of sodium and potassium hardly change. Examples of the above ingredients include sweeteners, acidulants, fragrances, pigments, bitterings, preservatives, antioxidants, thickening stabilizers, emulsifiers, dietary fibers, pH adjusters, enzymes, and reinforcing agents. Although an agent is mentioned, it is not limited to these.

  Moreover, when manufacturing a tea beverage or a coffee beverage, a tea extract or a coffee extract is prepared using raw water obtained by contacting with the polymer base material of the present invention (raw water for beverage). If necessary, tea beverages and coffee beverages can be produced by adding compounding ingredients used in the production of ordinary tea beverages and coffee beverages to the extract. The tea extract is not only a tea extract extracted from tea leaves, but also commercially available tea extracts such as polyphenone (Mitsui Norin), sunphenon (Taiyo Kagaku), and theafuran (Itoen). Powders can be used, and those extracts and powders dissolved in water or hot water may be used. Examples of the above-mentioned blending components include sweeteners, acidulants, fragrances, dyes, bitterings, preservatives, antioxidants, thickening stabilizers, emulsifiers, dietary fibers, pH adjusters, enzymes, and reinforcing agents. Examples include, but are not limited to, food additives.

  In addition, when producing brewed liquor such as fermented malt beverage and fruit liquor, prepare a pre-fermentation solution using raw water (brewing water) obtained by contacting with the polymer base material of the present invention, A brewed liquor can be produced by adding blending components used in the production of an ordinary brewed liquor to the fermented liquor obtained by fermenting the pre-fermented liquor according to a conventional method, if necessary. Examples of the ingredients include sweeteners, acidulants, fragrances, pigments, foaming / foaming improvers, bitterings, preservatives, antioxidants, thickening stabilizers, emulsifiers, dietary fibers, pH adjusters, Although food additives, such as an enzyme and a fortifier, are mentioned, it is not limited to these.

  When the beverage produced by the production method of the present invention is drinking water, the beverage can have a vanadium content of 30 mg / 100 mL or less (preferably 3 mg / 100 mL) and a sodium content of 0.4 to 1. 0.0 mg / 100 mL.

  The beverage with reduced vanadium content produced according to the present invention can be provided as a container-packed beverage through steps such as a filling step and a sterilizing step in addition to the contact step and the blending step. For example, the blended liquid obtained in the blending step can be sterilized according to a conventional method and filled into a container. Sterilization may be before filling the container or after filling. The filling step and the sterilizing step are known in the art and can be appropriately determined according to the liquid type.

  The container used for the beverage produced according to the present invention may be any container that is usually used for filling beverages, and can be appropriately selected according to the liquid type. Examples of containers include metal cans, barrel containers, plastic bottles (for example, PET bottles, cups), paper containers, bottles, pouch containers, etc., preferably metal can / cask containers, plastic bottles ( For example, a PET bottle) and a bottle are mentioned. The container-packed beverage containing vanadium has a problem that turbidity or precipitation occurs due to long-term storage, but the production method of the present invention can efficiently remove vanadium and is therefore suitable for the production of a container-packed beverage. is there.

  Since the polymer base material used in the production method of the present invention can be processed into various shapes such as a fibrous shape, it is possible to easily produce a beverage with a reduced vanadium content without handling problems. it can. Moreover, since the maintenance process and the filtration process are unnecessary in the contact process with the polymer base material of the present invention, it is advantageous in that the process is simplified and the production efficiency is improved. Furthermore, since the polymer base material of the present invention is solid, it is advantageous in that there is no problem of swelling.

  According to another aspect of the present invention, the beverage or its raw material liquid is brought into contact with a polymer base material carrying tannic acid, and the vanadium content in the beverage or its raw material liquid is reduced. A method is provided. The vanadium content reduction method of the present invention can be carried out according to the description of the production method of the present invention.

  According to another aspect of the present invention, there is also provided a vanadium removal method comprising a step of bringing a vanadium-containing aqueous solution into contact with a polymer base material carrying tannic acid. The vanadium removal method of the present invention can be performed according to the description of the production method of the present invention, but the vanadium-containing aqueous solution applied to the removal method of the present invention is not particularly limited as long as it is an aqueous solution containing vanadium. Seawater, groundwater, river water, lake water, industrial water, and tap water can be used. The vanadium-containing aqueous solution applied to the removal method of the present invention is preferably groundwater, river water, lake water, industrial water, and tap water from the viewpoint of use as a source of raw water for soft drinks.

  According to still another aspect of the present invention, the method includes a step of bringing a vanadium-containing aqueous solution into contact with a polymer substrate supporting tannic acid, and a step of recovering vanadium from the polymer substrate. A method for recovering vanadium is provided.

  Vanadium has uses such as a storage battery such as a vanadium battery, an automobile steel plate, a turbo engine turbine, a nuclear fuel cladding tube, a titanium alloy additive, and the like, and is widely used industrially. However, since vanadium is a rare metal, there is almost no domestic production in Japan, and the current situation is that it relies on imported goods from overseas. Vanadium has a high melting point of 1890 ° C. and is therefore a very difficult material to recover, purify and process. According to the present invention, it is advantageous in that vanadium can be recovered from a vanadium-containing aqueous solution simply and efficiently using a polymer base material supporting tannic acid, and can be used for various applications described above. is there. Further, in the production method of the present invention, vanadium is adsorbed to a polymer base material that is brought into contact with raw material water for beverages and supports tannic acid. In this case, vanadium is absorbed using the polymer base material that adsorbs vanadium. Can also be recovered.

  The step of bringing the vanadium-containing aqueous solution and the polymer substrate carrying tannic acid into contact in the recovery method of the present invention can be carried out according to the description of the production method of the present invention. The vanadium-containing aqueous solution to be applied is not particularly limited as long as it is an aqueous solution containing vanadium, and seawater, fresh water, ground water, river water, lake water, industrial water, and tap water can be used. In the present invention, from the viewpoint of efficiently recovering vanadium, groundwater collected around volcanoes (including not only active volcanoes but also dormant volcanoes) can be used as the vanadium-containing aqueous solution of the recovery method of the present invention. In addition, as shown in the examples described later, the polymer base material of the present invention can selectively adsorb vanadium, so that vanadium can be selectively recovered from seawater containing various metal ions such as vanadium. This is advantageous.

  In the recovery method of the present invention, the lower limit value of the vanadium concentration of the vanadium-containing aqueous solution to be brought into contact with the polymer substrate is not particularly limited as long as the vanadium can be recovered. For example, 0.001 mg / L can do.

  The step of recovering vanadium from the polymer substrate in the recovery method of the present invention can be carried out, for example, by bringing the polymer substrate after vanadium adsorption into contact with a regenerant. The vanadium desorbed from the polymer substrate by the contact between the polymer substrate of the present invention and the regenerant can be used for the above-mentioned various purposes by appropriately performing the necessary treatment. It may be used for the various applications described above after obtaining high purity vanadium.

  The regenerant that desorbs vanadium from the used polymer base material is not particularly limited as long as it has a desorption ability, and may be any of a neutral regenerator, an alkaline regenerator, and an acidic regenerator. When using the recovered vanadium for food or drink, or when reusing the polymer base material that has regenerated the vanadium adsorption function to remove vanadium from food or drink, use a regenerant that is acceptable for food hygiene. Is desirable. Examples of the neutral regenerant include ion-exchanged water, and examples of the alkaline regenerator include one or more alkali components such as sodium hydroxide, sodium silicate, sodium hydrogen carbonate, sodium carbonate, and the like. Examples of the acidic regenerant include one selected from the group consisting of inorganic acids such as phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, hypochlorous acid, and organic acids such as citric acid. Or the aqueous solution which has 2 or more types of acids as a main component is mentioned.

  The recovery method of the present invention is characterized in that the step of recovering vanadium from the polymer substrate of the present invention can be carried out at a lower temperature than the conventional recovery method. The lower limit of the temperature of the step of recovering vanadium can be 0 ° C., for example, and preferably 10 ° C. Moreover, the upper limit of the temperature of the process which collect | recovers vanadium can be 1000 degreeC, for example, Preferably it is 600 degreeC, More preferably, it is 300 degreeC. The temperature of the step of recovering vanadium is, for example, 0 to 1000 ° C. or 10 to 300 ° C.

  In the recovery method of the present invention, the step of recovering vanadium from the polymer base material of the present invention is performed by contacting the polymer base material with a 0.1 to 0.4 M acidic regenerant (preferably a hydrochloric acid solution). The temperature in this case can be in the range of 0-100 ° C or 10-100 ° C. Before eluting vanadium from the polymer substrate of the present invention, the polymer substrate is washed with about 0.01M acid (preferably about 0.01M hydrochloric acid) thinner than 0.1 to 0.4M. By doing so, most of the alkaline earth metals such as calcium and magnesium can be eluted and removed, and the vanadium purity of the vanadium elution recovery liquid can be increased. When the vanadium-containing aqueous solution contains a transition metal other than vanadium, the transition metal is eluted by bringing the polymer substrate of the present invention into contact with an acidic regenerant (preferably a hydrochloric acid solution) of 1 M or more, It can be recovered.

  The recovery method of the present invention may include a step of bringing the polymer substrate after adsorption of vanadium into contact with a regenerant and then obtaining a polymer substrate with regenerated vanadium adsorption ability. In the recovery method of the present invention, by subjecting the polymer substrate used for adsorption of vanadium to a regeneration treatment, a polymer substrate having a regeneration function of vanadium can be obtained. The molecular substrate can again be used for vanadium adsorption. Thus, since the polymer substrate used in the production method of the present invention can be recycled, it can be used repeatedly and does not require disposal, which is advantageous in that the production cost can be reduced.

  In the recovery method of the present invention, the step of recovering vanadium from the polymer base material of the present invention may combust the polymer base material adsorbed with vanadium and recover vanadium from the combustion ash. The recovery of vanadium from the combustion ash can be carried out according to a known method. However, in the present invention, the object of combustion in the recovery process is a polymer substrate that adsorbs vanadium. This is advantageous in that it can be recovered.

  According to still another aspect of the present invention, there is provided a vanadium adsorbent comprising a polymer base material carrying tannic acid. The vanadium adsorbent of the present invention can be used in the production method of the present invention, the removal method of the present invention, and the recovery method of the present invention. The vanadium adsorbent of the present invention can be carried out according to the description of the production method of the present invention, the description of the removal method of the present invention, and the description of the recovery method of the present invention.

  The present invention will be described more specifically based on the following examples, but the present invention is not limited to these examples.

Example 1: Verification of vanadium adsorption ability of tannic acid-carrying fiber body (1) Production of tannic acid-carrying fiber body Radiation was generated by irradiating nylon fiber as a substrate with 20 kGy of γ-rays. The irradiated nylon fiber is immersed in a 10% methanol solution of glycidyl methacrylate (manufactured by Wako Chemical Co., Ltd.) (sometimes referred to as “GMA” in this specification) and reacted at 40 ° C. for 2 hours to give a GMA graft polymerized fiber body. Was made. The graft ratio of the GMA graft polymerized fiber body was 74%.

The graft ratio is a mass increase rate of the graft chain with respect to the substrate, and was calculated according to the following formula.

  Next, the GMA graft-polymerized fiber body was immersed in a tannic acid solution (3% by mass, solvent: water / isopropanol = 80/20 (mass ratio)) at 80 ° C. for 24 hours to form an epoxy group in the GMA graft chain. Tannic acid was fixed, and a fibrous body (sometimes referred to as “tannic acid-carrying fibrous body” in this specification) carrying 0.38 mmol of tannic acid per 1 g of base material was produced. As the tannic acid, pentaploid tannin (molecular weight: 1701, manufactured by Nacalai Tesque) was used.

(2) Treatment of tannic acid-carrying fiber body into vanadium-containing drinking water Obtained in the above (1) in drinking water containing 0.09 ppm of vanadium ("Mt. Fuji natural water", manufactured by Kirin Beverage Co., Ltd.) The tannic acid-carrying fibrous body was added to 0 (no addition), 0.05, 1.00, 5.00% by mass with respect to vanadium-containing drinking water, and contacted at 25 ° C. for 16 hours. Next, the vanadium-containing drinking water treated with the tannic acid-carrying fiber body (hereinafter referred to as “fiber body treated water”, test groups 1 to 3) and the tannic acid-carrying fiber body were removed. Untreated drinking water containing vanadium (control group) was obtained.

(3) Measurement of vanadium and mineral components The concentration of vanadium, sodium, calcium, potassium and magnesium of the vanadium-containing drinking water obtained in (2) above was measured. Various concentrations were measured using IPC-MS (7500ce, manufactured by Agilent) by ICP mass spectrometry.

(4) Results The results were as shown in Table 1.

  From the results in Table 1, it was confirmed that the tannic acid-carrying fiber body selectively adsorbs vanadium and has a high vanadium adsorption ability. Further, it was confirmed that the tannic acid-carrying fiber body hardly adsorbs minerals such as sodium and potassium.

Example 2: Isolation of vanadium using tannic acid-carrying fiber body (1) Production of tannic acid-carrying fiber body A tannic acid-carrying fiber body was produced according to the method described in Example 1 (1).

(2) Treatment of vanadium-containing drinking water with tannic acid-carrying fiber body The vanadium-containing drinking water contains 0.05% by mass of the tannic acid-carrying fiber body obtained in (1) above with respect to vanadium-containing drinking water. And contacted at 25 ° C. for 16 hours. Next, the tannic acid-carrying fiber body was removed, and vanadium-containing drinking water (fiber body treated water) treated with the tannic acid-carrying fiber body was obtained.

(3) Recovery of vanadium from tannic acid-carrying fiber body Next, using hydrochloric acid as an acid eluent, vanadium was recovered from the tannic acid-carrying fiber body obtained in (2) above. Specifically, 0.05% by mass of a tannic acid-carrying fiber body with respect to 0.1 M hydrochloric acid was immersed at 25 ° C. for 1 hour. Next, the tannic acid-carrying fiber body was removed to obtain an acid eluent. Transition metals other than vanadium could be eluted by immersing the tannic acid-carrying fiber body in 1 M or more hydrochloric acid (data not shown).

(4) Measurement of vanadium concentration Vanadium-containing drinking water not treated with a tannic acid-carrying fiber body (hereinafter referred to as “untreated water”), fiber body treated water obtained in (2) above, and obtained in (3) above. The vanadium concentration of the obtained acid eluent was measured according to the method described in Example 1 (3). In addition, the vanadium density | concentration showed the vanadium density | concentration of each sample when the vanadium density | concentration of untreated water was set to 100 with the relative value (ratio).

(4) Results The results were as shown in Table 2.

From the results in Table 2, it is confirmed that when vanadium-containing drinking water is treated with a tannic acid-carrying fiber body, 24% of vanadium in the vanadium-containing drinking water is removed by the adsorption of vanadium by the tannic acid-carrying fiber body. It was. Further, it was confirmed that when the tannic acid-carrying fiber body adsorbing vanadium was treated with an acid eluent, about 80% of the vanadium adsorbed on the tannic acid-carrying fiber body was isolated. From the above results, it was confirmed that vanadium can be efficiently adsorbed and removed by the tannic acid-carrying fiber body, and the adsorbed vanadium can be efficiently recovered.

Claims (11)

  A method for producing a beverage with reduced vanadium content, comprising a step of bringing a beverage or a raw material liquid thereof into contact with a polymer base material carrying tannic acid.   The manufacturing method of Claim 1 in which a drink or its raw material liquid contains vanadium.   The manufacturing method of Claim 1 or 2 whose vanadium content of the manufactured drink is 30 mg / 100mL or less, and whose sodium content is 0.4-1.0 mg / 100mL.   The manufacturing method as described in any one of Claims 1-3 whose drink with which vanadium content was reduced is a container stuffing drink.   The manufacturing method as described in any one of Claims 1-4 whose polymer base material is a polyamide resin.   A method for removing vanadium from a vanadium-containing aqueous solution, the method comprising the step of bringing the vanadium-containing aqueous solution into contact with a polymer substrate carrying tannic acid.   A method for recovering vanadium from a vanadium-containing aqueous solution, comprising the steps of bringing a vanadium-containing aqueous solution into contact with a polymer substrate supporting tannic acid, and recovering vanadium from the polymer substrate. A method for recovering vanadium.   The method according to claim 7, wherein the vanadium-containing aqueous solution is seawater, groundwater, river water, or lake water.   The method according to claim 7 or 8, wherein the step of recovering vanadium is performed by bringing the polymer substrate into contact with a neutral regenerant, an alkaline regenerant, or an acidic regenerant.   The method as described in any one of Claims 7-9 with which the process of collect | recovering vanadium is implemented at 1000 degrees C or less. A vanadium adsorbent comprising a polymer base material carrying tannic acid.