JP6667880B2 - Material recovery system, trapping hydrogel - Google Patents

Description

  The present invention relates to a substance recovery system, a trapping hydrogel, and a method for producing the same.

  In the case of decontaminating harmful ions from muddy water or muddy water, solids mixed therein are subjected to coagulation / precipitation treatment, removal treatment by pressure filtration using a filter press, or the like in advance. Thereafter, the adsorbent is charged into turbid water or the like to accumulate harmful ions. However, these processes require large-scale facilities and equipment, a large amount of consumables such as a flocculant and a precipitant, and also require a long processing time and a sufficient number of workers. There is also a problem in terms of cost.

  Examples of using a magnetic hydrotalcite complex for wastewater treatment and immobilization of harmful substances have been disclosed (Patent Documents 1 and 2). Regarding the accumulation using magnetism, the present inventors have hitherto proposed a magnetic induction type drug delivery system (Patent Documents 3 and 4) that can deliver an anticancer agent to a target site such as a cancer lesion by magnetic force, or from a nuclear contaminated water. Prussian blue-supported magnetic nanoparticles capable of removing radioactive cesium by magnetic force have been proposed (Patent Document 5).

  By the way, gel is a material that forms a three-dimensional network structure by cross-linking, and because it has properties intermediate between solid and liquid, it is used for software such as food-related products such as agar and gelatin and medical products such as contact lenses. It has been applied to various uses as a material, a superabsorbent material, a drug release controlling agent, and the like.

  For example, inexpensive glucomannan is a water-soluble dietary fiber (complex polysaccharide) that is not digested in the intestine and is purified from konjac potato. When this is dissolved in hot water and calcium hydroxide or the like is added, the dietary fiber changes to insoluble dietary fiber and solidifies. This is edible konjac, of which about 97% is water. Since calcium hydroxide is an alkaline agent, konjac is one of the few foods that exhibits alkalinity. Glucomannan absorbs water and swells about 10 times in 30 minutes and about 150 times in 6 hours. Utilizing this property, it is widely used as a gelling agent, a quality improving agent, a thickener, a humectant, an absorbent and the like.

WO 2015/083840 WO 2005/087664 Patent No. 4183 047 International Publication No. 2011/096223 Patent No. 4932054

  There is an urgent need for a technology capable of efficiently recovering decontamination substances such as harmful ions and resources such as rare metals from turbid water such as wastewater or muddy water.

  The present invention has been made in view of the above background, and a first object of the present invention is to provide a substance recovery system that can easily and efficiently capture a target substance. It is an object of the present invention to provide a trapping hydrogel suitably used in the above-mentioned substance recovery system and a method for producing the same.

The present inventors have conducted intensive studies in order to solve the problems of the present invention, and found that the problems of the present invention can be solved in the following embodiments, and have completed the present invention.
[1]: a capturing hydrogel for capturing a target substance in a liquid,
Magnetic force accumulating means for accumulating the trapping hydrogel adsorbing the target substance by magnetic force,
A substance recovery system, wherein the trapping hydrogel contains an adsorbent for trapping the target substance and magnetic powder.
[2]: The adsorbent is hydrotalcite, activated carbon, calcite, montmorillonite, kaolinite, birnessite, zeolite, illite, vermiculite, pyrophyllite, perlite, bentonite, cobalt oxide, neodymium oxide, indium oxide, silver oxide , Cerium oxide, titanium oxide, zirconium ferrite hydrate, titanium hydroxide, metal ferrocyanide, cation exchange resin, anion exchange resin, cation exchange fiber, anion exchange fiber, chelate resin, chelate fiber, Amphoteric ion exchange resin, amphoteric ion exchange fiber, molecular labeling gel, inorganic ion exchanger of porous crystal with niobium oxide skeleton, zirconium phosphate, aluminum oxide, polydextrose, sodium alginate, inulin, carrageenan, cellulose, hemi Cellulose material recovery system according to, lignin, chitin, characterized in that it is selected from the group consisting of chitosan and pectin [1].
[3]: magnetic powder,
Contains an adsorbent that captures the target substance in the liquid,
A trapping hydrogel for collecting substances that can be collected by magnetic force.
[4]: The adsorbent is hydrotalcite, activated carbon, calcite, montmorillonite, kaolinite, birnessite, zeolite, illite, vermiculite, pyrophyllite, pearlite, bentonite, cobalt oxide, neodymium oxide, indium oxide, silver oxide , Cerium oxide, titanium oxide, zirconium ferrite hydrate, titanium hydroxide, metal ferrocyanide, cation exchange resin, anion exchange resin, cation exchange fiber, anion exchange fiber, chelate resin, chelate fiber, Amphoteric ion exchange resin, amphoteric ion exchange fiber, molecular labeling gel, inorganic ion exchanger of porous crystal with niobium oxide skeleton, zirconium phosphate, aluminum oxide, polydextrose, sodium alginate, inulin, carrageenan, cellulose, hemi Cellulose, lignin, chitin, capture hydrogel according to, characterized in that it is selected from the group consisting of chitosan and pectin [3].
[5]: Step A of mixing at least a magnetic powder, an adsorbent for capturing a target substance, a gel component, and water;
After the step A, a step B of gelation is included.
A method for producing a trapping hydrogel containing the magnetic powder and the adsorbent.
[6]: The adsorbent is hydrotalcite, activated carbon, calcite, montmorillonite, kaolinite, birnessite, zeolite, illite, vermiculite, pyrophyllite, pearlite, bentonite, cobalt oxide, neodymium oxide, indium oxide, silver oxide , Cerium oxide, titanium oxide, zirconium ferrite hydrate, titanium hydroxide, metal ferrocyanide, cation exchange resin, anion exchange resin, cation exchange fiber, anion exchange fiber, chelate resin, chelate fiber, Amphoteric ion exchange resin, amphoteric ion exchange fiber, molecular labeling gel, inorganic ion exchanger of porous crystal with niobium oxide skeleton, zirconium phosphate, aluminum oxide, polydextrose, sodium alginate, inulin, carrageenan, cellulose, hemi Cellulose, lignin, chitin, manufacturing method of capturing hydrogel according to, characterized in that it is selected from the group consisting of chitosan and pectin [5].
[7]: The method for producing a trapping hydrogel according to [5] or [6], wherein the step A is performed in an alkaline environment.

  ADVANTAGE OF THE INVENTION According to the present invention, there is an excellent effect that a substance recovery system capable of easily and efficiently capturing a target substance can be provided. In addition, there is an excellent effect that it is possible to provide a trapping hydrogel and a method for producing the same, which are suitably used in the above-mentioned substance recovery system.

The flowchart figure of the target substance collection using the substance collection system concerning this embodiment. The schematic diagram which shows an example of the capture hydrogel which concerns on this embodiment. FIG. 1 is an explanatory diagram of a substance recovery system according to an embodiment. FIG. 1 is an explanatory diagram of a substance recovery system according to an embodiment. FIG. 1 is an explanatory diagram of a substance recovery system according to an embodiment. The schematic diagram which shows an example of the silicon plate upper surface used at the time of manufacture of the capture hydrogel which concerns on this embodiment. The schematic diagram which shows an example of the silicon plate side surface used at the time of manufacture of the capture hydrogel which concerns on this embodiment.

  Hereinafter, an example of an embodiment to which the present invention is applied will be described. It goes without saying that other embodiments are also included in the scope of the present invention as long as they conform to the gist of the present invention. Further, the sizes and ratios of the respective members in the following drawings are for convenience of explanation, and do not match actual ones.

  The substance recovery system according to the present embodiment relates to a system in which a target substance is adsorbed and captured by a magnetic force. More specifically, the present invention relates to a system in which a trapping hydrogel is put into a liquid containing a target substance to be accumulated, the target substance is adsorbed to the trapping hydrogel, and the adsorbed trapping hydrogel is collected by magnetic force. This trapping hydrogel refers to a substance collection gel that contains at least a magnetic powder and an adsorbent for trapping a target substance and can be recovered by magnetic force in a liquid.

  Here, the target substance is a target substance to be accumulated, and can be appropriately selected. For example, a decontamination substance such as harmful ions from muddy water or muddy water such as wastewater can be used as the target substance. For example, removal of heavy metals (arsenic, selenium, lead, hexavalent chromium, cadmium, nickel, mercury, cyan, copper, zinc, manganese, iron, etc.), harmful substances (fluorine, boron, ammonium ion, phosphate ion, nitrite) It can be used for removal of ions, normal hexane extract (mineral oil, animal and vegetable oil), halogen compounds such as chlorine (trihalomethane, dichloromethane, trichloroethylene, tetrachloroethylene, etc.) and decontamination of radioactive materials. Rare metals (the above metals, chromium, tungsten, molybdenum, vanadium, indium, gallium, tantalum, zirconium, niobium, platinum, neodymium, dysbrosium, terbium, cobalt, titanium, scandium, rare earth, yttrium, europium, dysprosium, lanthanum Aluminum or the like) may be aimed substance.

FIG. 1 shows a flowchart of the substance recovery system according to the present embodiment. The liquid applied to the present embodiment is not particularly limited as long as it does not deviate from the gist of the present invention. Preferable examples include an aqueous solvent and an aqueous solvent partially containing an organic solvent, but the present invention can also be applied to an organic solvent.
Specific examples include rainwater, groundwater, snowmelt water, seawater, rivers, lakes, ponds, reservoirs, etc., soil water containing contaminated soil, drainage from construction sites, drainage from landfill sites, drainage from tunnels, pollution Dispersed water of polluted dust, dispersed water of contaminated dust, washing water for contaminated debris, equipment, machinery, etc., transport of people, animals, luggage, etc. Water washed means, water supplied to waterworks, water supplied to sewers, water collected from sewers, sewage sludge, purified water sludge, dispersed water of incinerated ash containing target substances to be captured, milk, juice, Examples include drinking water containing tea and other foods, washing water for harvested tea leaves, etc., breast milk, serum and body fluids of internal A-bomb survivors, water, contaminated water, washing water derived from animals, plants and microorganisms, industrial wastewater, and experimental wastewater. it can. Note that the water supplied to the water supply and the central water supply includes, for example, water supplied to each household, industrial water, agricultural water, and water used in the forestry, livestock, and fisheries industries.

  First, a capturing hydrogel is introduced into a liquid containing a target substance to be collected (Step 1, FIG. 3). The trapping hydrogel is a gel having a three-dimensional network structure having both target substance trapping properties and magnetism. The input amount of the trapping hydrogel may be adjusted according to the amount of the target substance to be trapped in the liquid.

  FIG. 2 shows a schematic diagram of the trapping hydrogel. The trapping hydrogel 1 according to the present embodiment is a bead-like gel, and contains a magnetic powder 3, an adsorbent 4, and water 5 in a three-dimensional network structure 2. The main component of the trapping hydrogel is water 5. The three-dimensional network structure 2 forms the skeleton of the trapping hydrogel 1 and can use a known technique without limitation. For example, a polymer chain having a crosslinked structure can be used. The main component of the trapping hydrogel 1 is water. The shape of the trapping hydrogel 1 is arbitrary as long as it does not deviate from the gist of the present invention. The main solvent of the trapping hydrogel is water, but may contain other solvents without departing from the spirit of the present invention. For example, the organic solvent may be contained in a range of 30% or less.

  In the method for producing the trapping hydrogel 1 according to the present embodiment, at least a step A of mixing the magnetic powder 3, the adsorbent 4 for trapping a target substance in a liquid, the gel component constituting the three-dimensional network structure 2, and water 5 And a step B of gelling after the step A. The gelation step in the step B may be, for example, a step of constructing a three-dimensional network structure by heating. However, the present invention is not at all limited to the following manufacturing method.

  The three-dimensional network structure 2 is not particularly limited, and can be appropriately selected. Examples include konjac, glucomannan, agar, gelatin, agarose, carrageenan, guar gum, xanthan gum, guar bean enzyme decomposed product, locust bean gum, triblock copolymer, ring-active gel, nanocomposite gel, double network gel, polyampholyte gel , Protein gel using egg white (“Egg white is expected to be a new material with high strength for medical treatment, food, application”, Sankei Shimbun, Internet <URL: http://www.sankei.com/premium/news /180127/prm1801270026-n1.html>the article of January 27, 2018). In addition, gels described in JP-A-2017-171617, T. Nojima, T. Iyoda, "Water-Rich Fluid Material Containing Orderly Condensed Proteins", Angewandte Chemie 56, 1308-1312, (2017) and the like are used. It is also possible.

  As described above, konjac is obtained by dissolving glucomannan in hot water and adding calcium hydroxide, thereby changing the dietary fiber into insoluble dietary fiber and coagulating it. The alkali agent only needs to achieve the purpose of coagulation, and various compounds including sodium carbonate and the like can be used.

Also, polyampholyte gel described in WO 2016/027383, K. Haraguchi, et al., "
A nanocomposite gel described in A Unique Organic-Inorganic Network Structure with Extraordinary Mechanical, Optical, and Swelling / De-swelling Properties ”, Adv. Mater. 14, 1120-1124 (2002), Y. Okumura, et al., Ring ring gel disclosed in “The Polyrotaxane Gel: A Topological Gel by Figure-of-Eight Cross-links”, Adv. Mater. 13, 485-487 (2001), JP Gong, et al., “Double-Network Hydrogels 15, Extremely High Mechanical Strength, Adv. Mater. 15, 1155-1158 (2003), HJ Zhang, et al., “Tough Physical Double-Network Hydrogels Based on Amphiphilic Triblock Copolymers”, Y. Adv. Mater. 28, 4884-4890 (2016) Double network gel using triblock copolymer, T. Sakai, et al, “Design and Fabrication of a High-Strength Hydrogel with Ideally Homogeneous Network Structure from Tetrahedron-like Macromonomers”, UIChang Macromolecules, 41, 5379-5384 (2008) Can be.

  From the viewpoint of increasing the mechanical strength of the trapping hydrogel, a double network gel is preferred. Double network gels are gels formed by combining two different elements. For example, a structure including a plurality of network structures in which another polymer chain is entangled with a network structure serving as a base, or a structure in which a network structure serving as a base and another polymer chain are cross-linked to each other. Gels formed by combining three or more different elements are also preferably used.

  When a plurality of polymer chains are used, each of the polymer chains does not need to have a network structure, and it is sufficient that a network structure is constructed as a whole. In order to firmly hold the adsorbent 4 or / and the magnetic powder 3, the polymer chain is covalently bonded to the adsorbent 4 or / and the magnetic powder 3, ionic bond, hydrogen bond, complex, hydrophobic interaction, van der Waals A group having power may be provided. Further, the adsorbent 4 and the magnetic powder 3 may be firmly bonded by sintering.

  From the viewpoint of economy, it is preferable to use inexpensive konjac, glucomannan, agar, gelatin, carrageenan, locust bean gum and the like as gel components. Since konjac and glucomannan coagulated with alkali have high heat resistance and do not dissolve in boiling water, they are also suitable for high-temperature wastewater treatment. On the other hand, agar is 70 ° C. or higher, gelatin is 25 ° C. or higher, and carrageenan and locust bean gum are melted in an environment of 60 ° C. or higher.

  Konnyaku is odorless konnyaku that removes oxalic acid, calcium oxalate, amines that cause unpleasant odor (konnyaku smell), or konnyaku purified from konnyaku, from the viewpoint of extending the shelf life. It is more preferable to use mannan as a raw material. For purification of konjac mannan, for example, Ogasawara Shigen and two others, “An attempt of electrophoresis using konjac mannan as a support”, Biophysical Chemistry, Vol. 31, No. 3, 1987 (No. 155-158) Can be referred to.

  The size of the trapping hydrogel can be selected according to the purpose. Considering the dispersibility in the solution and the specific surface area, the particle size is preferably in the range of 0.5 to 3 mm. In addition, the range of 1 to 10 mm is preferable in consideration of the adsorption capacity and magnetic adsorption of the target substance. Of course, the size can be appropriately selected according to the application. The saturation magnetization of the trapping hydrogel is preferably 5 emu / g or more, more preferably 10 emu / g or more, from the viewpoint of increasing the integration efficiency by magnetic force. Further, it is more preferably at least 20 emu / g. In order to increase the efficiency of attracting the magnet, it is preferable that the saturation magnetization be higher.

  The trapping hydrogel can be obtained as a lump and crushed with a mixer or the like. In this case, the size distribution and shape (such as the shape of a polygonal polyhedron) can be adjusted by the crushing conditions. The shape or irregular shape in which a plurality of polygonal polyhedrons are continuous may be used. Alternatively, it may be manufactured by a method of extruding through pores of a device using a yarn konjac manufacturing machine or the like. A column-shaped trapping hydrogel may be produced by cutting a thread-like material, or a trapping hydrogel having a shape distribution can be obtained by crushing with a mixer or the like. Further, it may be formed at the time of alkali coagulation and designed in various shapes such as a spherical shape. In the heating step, a method using a mold or a method of steaming a sphere or the like in advance with a steamer or the like can be exemplified.

The magnetic powder 3 may be any as long as it satisfies the condition that the magnetic powder 3 is in the trapping hydrogel and has magnetism that can be integrated by the magnetic force integration means. Further, a material having high magnetic anisotropy having high magnetic induction characteristics even if the particle diameter is small is preferable. Preferred materials for the magnetic powder 3 include iron powder, stainless steel powder, iron oxide powder (magnetite (Fe ₃ O ₄ ), maghemite (Fe ₂ O ₃ ), iron monoxide (FeO)), cobalt powder, nickel powder, gadolinium. Powder, iron-silicon alloy powder, iron-nickel alloy powder, iron-cobalt alloy powder, iron-silicon-aluminum alloy powder, or nickel-zinc, magnesium-zinc, manganese-zinc ferrite powder, Examples include iron nitride, cobalt platinum chromium alloy, barium ferrite alloy, manganese aluminum alloy, iron platinum alloy, iron palladium alloy, cobalt platinum alloy, iron neodymium boron alloy, and samarium cobalt alloy. Further, a magnetic toner used in a copying machine or the like may be used. In order to improve the corrosion resistance of the magnetic nanoparticle surface, the surface may be coated with various metal oxides or the like. These particles may be coated with non-magnetic molecules to improve corrosion resistance. For example, high molecular weight polymer-coated magnetic microparticles, resin-coated magnetic microparticles, silica-coated magnetic microparticles, and the like may be used. The magnetic powder 3 is preferably an iron powder from the viewpoint of availability.

  The average particle size of the magnetic powder 3 can be appropriately designed according to the purpose, but from the viewpoint of easy handling, a magnetic powder having an average particle size of 1 to 500 μm is preferable, 10 to 200 μm is more preferable, and 20 to 100 μm is still more preferable. . By using a magnetic powder having an average particle diameter of 55 to 100 μm, rapid magnetic separation, economy, and handling safety can be improved. The magnetic powder 3 does not exclude nanoparticles. That is, one or more types of nanoparticles may be used alone or in combination with particles of other sizes as the magnetic powder. By using nanoparticles, the specific surface area can be increased and the interaction with the three-dimensional network structure can be enhanced. The size of the magnetic powder can be appropriately selected in consideration of the properties of the gel and the like.

  The content of the magnetic powder 3 can be appropriately designed according to the magnetic force of the magnetic powder. For example, it is about 0.01 to 0.25 times the mass of the trapping hydrogel.

  The adsorbent 4 may be any one that can capture the target substance to be captured, and a known adsorbent can be used without limitation. Examples of the adsorbent 4 include hydrotalcite, activated carbon, calcite, montmorillonite, kaolinite, birnessite, zeolite, illite, vermiculite, pyrophyllite, perlite, bentonite, and all ion exchangers (cation exchange resin, anion exchange resin Cation exchange fiber, anion exchange fiber), chelate resin, chelate fiber, amphoteric ion exchange resin, amphoteric ion exchange fiber, molecular labeling gel, inorganic ion exchanger of porous crystal with niobium oxide skeleton, metal ferrocyan Oxide, titanium hydroxide, zirconium phosphate, aluminum oxide, cobalt oxide, neodymium oxide, indium oxide, silver oxide, cerium oxide, titanium oxide, zirconium ferrite hydrate, illite, mica (mica), smectite (smectite) And other clay minerals Natural and artificial nanoporous materials, polydextrose, sodium alginate, inulin, carrageenan, cellulose, hemicellulose, lignin, chitin, chitosan, pectin, and other dietary fibers are effective. In addition, biobeads provided with an antibody are also suitable as the adsorbent. Examples of biobead products include AnaLig Cr-02 (manufactured by IBC Advanced Technologies). As the amphoteric ion exchange fiber, the technology described in JP-A-2012-030197 can be suitably used.

  JP-A-2010-71707 (page 20), JP-A-6-229994 (page 19), JP-T-2002-529714 (page 46), and JP-A-2000-126617 are examples of molecular labeling gels. And JP-A-2001-141710 (page 7) and gels described in RMIzatt, et al, American Laboratory, December, 28C (1994) and the like.

Specific products of the amphoteric ion exchange resin include SK1B, SK104, SK110, SK112, UBK08, UBK10, UBK12, PK208, PK212, PK216, PK218, PK220, PK228, SK104H, SK1BH, PK216H, RCP145H manufactured by Mitsubishi Chemical Corporation. , RCP160M, UBK530, UBK535, UBK530K, UBK535K, UBK555, WK40, WK10, WK11, WK100, SA10A, SA12A, SA11A, NSA100, UBA120 (uniform particle size product), PA306S, PA308, PA312, PA316, PA318L, HPA25, SA20A , SA21A, PA408, PA412, PA418, WA10, WA20, WA21J, WA30, SAF11AL, SAF12A, PAF308L, WA30C, AMP03, CR11, CR20, CRB03, CRB05, HP20, HP21, Sepabeads ^TM SP70, Sepabeads ^TM SP825, SP850, SP700 , Sepabeads ^™ SP207, HP20SS, Sepabeads ^™ SP20SS, SP207SS, HP2MG and the like. Further, the amphoteric ion exchange resin described in paragraph [0018] of JP-A-2014-184391 can be suitably applied.

As a specific item of other adsorbents available, by Sumika Chemtex Co., Ltd. of Duolite ^{TM A109D, A113LF, A113MA, A113MB} , A113OH, A116, A116LF, A134LF, A161JCL, A162LF, A368MS, A375LF, A378D, A561 , A568, C20J, C20JH, C20LF, C20LFH, C255LFH, C26A, C26CH, C26H / 2095, C26TRH, C433LF, C467, C476, C548, C747UPS, ES371N, PWA7, PWA7, S4LF, S874, S876, S877, S878, SC100 , SC200, SC300, SC400, SC500 , SC600, UP5000, UP6000, UP7000, XAD761 , etc., Imakku ^TM HP1220Na, HP333, HP555, etc., Sumikaion ^TM MB77, S8TR, etc., duo jet ^TM A1130CL, A1160CL, C2255H, etc., Sumikireto ^TM MC250, MC600H, MC700, MC760, MC760CA, MC770, MC850, MC900, MC960 , etc., Chelest Kiresuparu Co., Ltd. ^{TM CH112, CH351, CH400, SA110} , SB130, SB230, WB150 , and the like, CHELEST fiber ^{TM GRY-L, GRY-LW} , GRY-HW, IRY, IRY-L, IRY-LW, IRY-HW, etc., manufactured by Purolite Co., Ltd. A100, A103S, A110, A111S, A133S, A170 / 4675, A200, A300, A400, A500, A501P, A502PS, A503, A510, A520E, A532E, A600, A830W, A845, A847, A850, A860, A870, Bromide ^{Plus TM, C100, C100E, C100EAg} , C100x10, C100x12, C100x16MBH, C104, C106, C107E, C115E, C120E, C150, C160, FerrIX TM A33E, MB400, MB378LT, MB478LT, MN102, MN150, MN170, MN202, MN250, MN270 , MN500, MN502, NRW1000, NRW1600 , NRW2400, NRW600, NRW5010, NRW1600 / NRW600, NRW1600Li7 / NRW600, PAD300, PAD350, PAD400, PAD500, PAD550, PAD600, PAD610, PAD700, PAD900, PAD910, PAD950, Purogold TM A193, S106 , S108, S910, S914, S920 , S930 / 4922, S950, S985, SGA550, SGC650, SSTC60, SSTC60H, SSTC80DL, SSTC104, SSTA63, SSTA64 , etc., amber manufactured by organo Co., Ltd. light ^{TM 200CT, 252, FPC3500, FPX66} , IR120B, IR124, IRA67, IRA96SB, IRA98, IRA400J, IRA402BL, IRA404J, IRA410J, IRA411, IRA458RF, IRA478RF, IRA743, IRC76, IRC747, IRC747UPS, I RC748, IRA900J, IRA904, IRA910CT, IRA958, XAD-2, XAD4, XAD7HP, XAD1180N, XAD2000, XE583 and the like, Amba - jet ^TM 1020,1024,1060,1220,4400,4010, Amba - list ^TM 15DRY, 15JWET, 16WET , 31WET, 35WET, A21, MB -1, MB-2, MB-4, EG-4A-HG, EG-5A-HG, ESP-1, ESP-2 , etc., manufactured by Kyowa chemical industry Co., Ltd. of Kyowaad ^TM 200,500,600,700, etc., KW-2000 ^TM, etc., Nippon seawater made of READ-As, READ-B, READ-B (MC), READ-B (LC), READ-Cs (Co), A-19S of Amron Corporation, such as READ-Cs (Fe), READ-F, READ-F (HG), READ-F (PG), READ-Sb, READ-Sr1, READ-Sr2, READ-Sr3 , AC-1, CAMZ, CAMZ-S, CAMZ-W, CAPA-CT, MB4, TKS105, Ash Claw A, Ash Claw S, etc., MP-C, MP-CC, MP-HC, MP made by Astec Co., Ltd. Examples include Catenathio AB, AB-c, AB-e, AB-L, etc., manufactured by Japan Safety Co., Ltd., and Nova, etc., manufactured by Mizoguchi Business Co., Ltd.

  Further, the adsorbent disclosed in JP-A-2006-7601 can also be suitably used. In addition, examples of suitable adsorbents for rare metal recovery include the adsorbents described in the following documents. In other words, "Development of nickel plating wastewater recycling technology in factories", 2010-2011, Fukuoka Prefecture Industry and Science and Technology Promotion Foundation Industry-Academia-Government Joint Research and Development Project Research Results Report, [January 30, 2018 Search], the Internet <URL: http://www.ist.or.jp/randd/seikahoukokusyo/H23-2.pdf>, and Tetsuo Katsura, "Ions in separation analysis of copper, nickel and cobalt using ion exchange resin. Utilization of Exchange Resin "(2nd report), Analytical Chemistry, 10, 1961, 4, JP-A-2016-7601. In addition, Sumichelate MC960 (manufactured by Sumika Chemtex Co., Ltd.) as a chelate for indium adsorption, Sumichelate MC900 (manufactured by Sumika Chemtex Co., Ltd.) as a chelate for gallium adsorption, and Sumichelate MC700 (Sumichelate MC700) as an adsorbent for copper, nickel and zinc. And the like. When chromium is used as the target substance, a method using an ion-exchange resin is preferable (reference: “detoxification treatment of hexavalent chromium”, [searched on January 30, 2018]), Internet <URL: https http://jp.tech.misumi-ec.com/categories/surface_treatment_technology/st01/c0027.html> For terbium-adsorbed chelates, Setsu Kobayashi, et al., "Waste from chelating resins containing diethylenetriamine-polycarboxylic acid" Concentration and recovery of terbium in "Journal of the Ion Exchange Society of Japan / 3 (1992) 2".

Furthermore, regarding the adsorption chelate of uranium, gallium, indium, germanium, molybdenum, vanadium, gold, platinum, palladium, silver, copper, trivalent chromium, hexavalent chromium, cobalt, cerium, plutonium, zinc and radium, Masahide Hirai, "Chelate resin for recovering trace metals", Synthetic Organic Chemistry, Vol. 42, No. 11, 1984, p. Regarding manganese and lanthanum, Diaion ^™ CR series manufactured by Mitsubishi Chemical Corporation is suitable as a chelating resin. Regarding tungsten, tantalum, and titanium, Masazumi Tada and one others, “Quantitative determination of cobalt, titanium, and tantalum in ultra-high humidity alloys by anion exchange separation”, Analytical Chemistry, Vol. 12, No. 1963 (1963). The adsorbents described can be applied.

  Further, niobium, zirconium-adsorbed ion exchange resins and the like are preferable. Also, the adsorbent described in Koichi Oguma and one other, "Development of Steel Trace Component Analysis by Separation and Concentration", Iron and Steel, Vol. 100, 2014, No. 7, are suitable. As the rhodium adsorbent, the adsorbent described in JP-A-10-17953 can be suitably used.

As the lithium adsorbent, a specific alkali metal ion adsorbent (a porous crystal inorganic ion exchanger having a niobium oxide skeleton) described in Japanese Patent No. 4072624 can be used. Specifically, a proton-type adsorbent obtained by acid-treating Na ₈ Nb ₂₂ O ₅₉ and exchanging sodium ions for hydrogen ions, and an acid treatment for Rb ₈ Nb ₂₂ O ₅₉ to exchange rubidium ions for hydrogen ions and then water A lithium-type adsorbent in which the hydrogen ions are exchanged for lithium ions by contacting with a lithium oxide solution; a proton-type adsorbent in which Rb ₁₀ Zr ₂ Nb ₂₀ O ₅₉ is acid-treated to exchange rubidium ions for hydrogen ions; Rb ₁₃ Zr ₅ Nb ₁₇ O ₅₉ the acid-treated proton type adsorbent exchanged hydrogen ions rubidium _{ions, Rb 10 Ti 2 Nb 20 O} 59 the acid-treated proton type adsorbent was changed to hydrogen ions rubidium ions, or An example is a proton-type adsorbent obtained by treating Rb ₁₀ Sn ₂ Ta ₂₀ O ₅₉ with an acid and exchanging rubidium ions for hydrogen ions.

  In addition, the specific example of the said adsorbent is an illustration and is not limited to these. The adsorbent 4 may be in any form as long as it can be contained in the trapping hydrogel, and is not particularly limited, and examples thereof include powder, granules, fine particles, and small particles of about 0.1 μm to 1 mm. For the purpose of increasing the surface area of the adsorbent 4, the pulverization may be performed using a pulverizer X-TREME manufactured by Waring Co., Ltd. As the pulverizer, for example, various pulverizers of Osaka Chemical Co., Ltd. can be used.

  The content of the adsorbent 4 can be appropriately designed according to the magnetic force of the magnetic powder. For example, it is about 0.005 to 0.5 times the mass of the trapping hydrogel.

  The spatial movement of the adsorbent 4 and / or the magnetic powder 3 is restricted by the three-dimensional network structure 2. From the viewpoint of strengthening the holding power of the magnetic powder 3 and the adsorbent 4, it is preferable to make the crosslinked structure dense as long as entry and exit of the substance or ions for the purpose of adsorption are not hindered.

  When the target substance is, for example, heavy metals (arsenic, selenium, lead, hexavalent chromium, cadmium, etc.), a common iron powder or iron oxide having both functions of an adsorbent and a magnetic powder may be used. When these heavy metals are captured, by using hydrotalcite in addition to iron powder and iron oxide, the accumulation efficiency can be further improved. Further, by adding hydrotalcite to these heavy metals, there is also an advantage that fluorine and boron can be removed.

  When iron powder is used, there is a problem that when it is wet with water, it is easily corroded and cannot be adsorbed, separated and recovered by magnetism. For this reason, when using iron powder as the magnetic powder 3, it is preferable to use it under an alkaline environment. From such a viewpoint, a combination of the adsorbent exhibiting alkalinity and the magnetic powder is more preferable. A preferred example is a combination of hydrotalcite and iron powder. Since hydrotalcite uses a strong alkali such as calcium hydroxide in the production process, it exhibits alkalinity when hydrotalcite is dispersed in water. For this reason, the hydrogel containing hydrotalcite and iron powder has the effect of significantly increasing the stability. As hydrotalcite, natural hydrotalcite may be used, or commercially available hydrotalcites may be used.

  Further, as a method for preventing rust of the iron powder, the hydrogel may be stored in an alkaline aqueous solution. Further, a method in which the liquid for recovering the target substance is made an alkaline environment is also suitable.

  The use of hydrotalcite can enhance the stability of iron powder, but when using an adsorbent that does not exhibit alkalinity, a pH adjuster may be added to make the trapping hydrogel alkaline. It may be adjusted appropriately. In addition to being effective in preventing rust of iron powder, making the environment alkaline is also suitable for coagulation of konjac, for example. However, iron ions are not preferred for coagulation of konjac, so removal of iron ions is preferred for accelerating coagulation.

  Preferable examples of the metal ferrocyanide include ferrocyanide metals such as iron ferrocyanide (Prussian blue), nickel ferrocyanide, cobalt ferrocyanide, and copper ferrocyanide.

  When the target substance to be captured is cesium, iron ferrocyanide, nickel ferrocyanide, cobalt ferrocyanide, zeolite, clay mineral, and pectin are particularly effective. In addition, polydextrose, sodium alginate, inulin, carrageenan, cellulose, hemicellulose, lignin, chitin, chitosan and the like are also effective. Prussian blue is also effective in removing thallium in addition to cesium. The adsorbent may be appropriately selected according to the radioactive substance to be captured.

  The adsorbent 4 may be subjected to a heat treatment or a pressure heat treatment as needed. For example, zeolite and the like can improve the cesium adsorption ability by heat treatment or pressure heat treatment. When it is desired to capture a plurality of types of radioactive substances, different types of adsorbents may be introduced into the covering magnetic nanoparticles, or a plurality of capturing hydrogels may be used. When the target substance to be captured is strontium, titanium hydroxide is particularly effective.

  In the case of particles having both magnetic performance and adsorption ability, the magnetic powder 3 and the adsorbent 4 may be composed of the same particles. Further, a composite of a magnetic powder and an adsorbent, such as a magnetic hydrotalcite composite, is also preferably used. The complexes may be linked to each other or unbound. As a bonding method, a known bonding method such as a covalent bond, an ionic bond, an intermolecular force, a hydrogen bond, and complex formation can be applied. When the magnetic powder 3 and the adsorbent 4 are bonded to each other, the magnetic powder 3 and the adsorbent 4 can be firmly held in the hydrogel by an additive / synergistic effect with the indirect connection by the three-dimensional network structure. . However, from the viewpoint of separation after accumulation, it is preferable that the magnetic powder and the adsorbent are separate particles.

  The magnetic powder 3 and the adsorbent 4 may be in any of a mode included in the inside of the trapping hydrogel (within a network having a three-dimensional network structure), a mode in which they are bonded to the surface, and a combination thereof. It is also suitable that the magnetic powder is taken into the trapping hydrogel and the adsorbent 4 is bonded to the surface of the trapping hydrogel. From the viewpoint of preventing the magnetic powder 3 and the adsorbent 4 from dropping from the trapping hydrogel, an embodiment in which the magnetic powder 3 and the adsorbent 4 are incorporated inside is preferable. By preventing the magnetic powder 3 from flowing out of the hydrogel, the reliability of magnetic recovery can be improved. Alternatively, a hydrogel containing only the magnetic powder and a hydrogel containing only the adsorbent may be produced, and a capturing hydrogel obtained by firmly binding them may be used.

  Further, depending on the type of the target substance, the magnetic powder alone and the trapping hydrogel may be used in combination as appropriate. For example, in the case of wastewater having a high arsenic content and containing a small amount of fluorine and / or boron, arsenic is mainly removed by using a large amount of inexpensive iron powder, and fluorine or / and cannot be removed by iron powder. By using a small amount of trapping hydrogel for boron and boron, wastewater treatment can be performed efficiently at low cost. According to such a method, it is possible to efficiently recover at low cost according to the characteristics of the target substance.

  Next, the target substance to be captured is captured by the capturing hydrogel 1 charged in the liquid containing the target substance to be collected (Step 2, see FIG. 4). If necessary, the liquid may be stirred, dispersed, heated, cooled, or the like. When recovering a rare metal or the like, an additive such as a liquid pH adjuster can be appropriately added to promote ionization of the metal.

  The target substance only needs to be able to be adsorbed on the trapping hydrogel, and the trapping form is not limited. Any of a mode of adsorbing on the surface of the trapping hydrogel, a mode of adsorbing the target substance inside the trapping hydrogel, and a combination thereof may be used. From the viewpoint of firm capture, it is preferable to include a mode in which the target substance is incorporated into the three-dimensional network structure holding the adsorbent (for example, Ogasawara Shigen and two others, “Electricity with Konjac Mannan as a support”). Trial of Electrophoresis ", Biophysical Chemistry, Vol. 31, No. 3, 1987 (No. 155-158)).

  Thereafter, the trapping hydrogel 1 is accumulated from the liquid by the magnetic accumulation means. Next, after the magnetic force accumulating means is separated from the liquid, the trapping hydrogel to be trapped is recovered by turning off the generation of magnetism (Step 3, see FIG. 5). That is, by the magnetic force of the magnetic force accumulating means, the trapping hydrogel 1 trapping the target substance to be trapped is accumulated and collected. According to such a method, the target substance to be captured can be easily and efficiently recovered. The magnetic force accumulating means may accumulate, separate, and collect the trapping hydrogel 1 by abutting or approaching the outer wall of the container without being immersed in the liquid.

  From the viewpoint of improving the ion adsorption efficiency, it is advantageous to reduce the size of the adsorbent as much as possible to increase the reaction surface area per unit weight. There is a disadvantage that processing takes time. According to the substance recovery method according to the present embodiment, the specific adsorbent and the magnetic particles having a large specific surface area are supported on the trapping hydrogel, so that high adsorptivity and rapid recovery ability can be satisfied at the same time. .

  A known technique can be appropriately used as the magnetic force integration means. Appropriate magnetic force accumulation means may be used according to the amount of liquid to be applied. For a relatively small amount of liquid, a magnetic separator (manufactured by Noritake Co., Ltd.) or the like is preferable from the viewpoint of saving space. When the substance recovery system according to the present embodiment is used for a large amount of liquid, a super-electromagnetic magnet or the like that can generate a strong magnetic field is suitable.

  As the magnetic force accumulating means, a means having a function capable of turning on and off a magnetic force and a moving mechanism may be used. Also, it is possible to control ON / OFF of the magnetic force by the permanent magnet and the shield means. Furthermore, the trapping hydrogel 1 is first recovered using a permanent magnet or the like, and then the trapping hydrogel 1 is recovered using a stronger electromagnet or a superconducting magnet, and then the magnetic force of the electromagnet or the superconducting magnet is turned off. This makes it possible to separate the trapping hydrogel 1.

  A compact magnet separator is also preferably used. For example, MDK-4 (-U), MDK-6 (-U), MDK-8 (-U), MDK-12 (-U), MDK-18 (-U), MDK-24 (-U), As described above, Noritake Co., Ltd. or the like can be preferably used. In addition, Daibar DB1, DB2, DB3, Diagrid DGS-200, DGS-250, DGS-300, DGH-200, DGH-250, DGH-300, Diacorner DCH-100, DCH-150 , DCH-200, DCH-250, DCH-300, DCH-350, DCH-400, DCS-100, DCS-150, DCS-200, DCV-100, DCV-150, DCV-200, DCV-250, DIA Self DAS (AMS), Dia Rotor DRP-200, DRP-250, DRP-300, DRP-400, DRP-500, Diacannon DKP-80, DKP-90, DKP-100, DKP-150, Diasler DSY-25 , DSY-32, DSY-40, DSY-50, DSI-25, DSI-40, DSI-50, DST-25, DST-40, DST-50, DST-60, DSH-40, DSH-50, DSH Magnet separators such as -60, DSH-70, DSH-80 and DSH-100 are also suitably used.

  When a permanent magnet is used, it is not particularly limited, but examples include ferrite, a Ne—Fe—B alloy, and a samarium-cobalt alloy. When a strong magnetic force is required, a Ne-Fe-B alloy is preferable. Even when an electromagnet, a superconducting magnet, or the like is used as the magnetic force accumulating means, it is effective to provide a shield means in order to impart directivity to the magnetic force lines of the magnet. In order to properly protect the magnetic force accumulation means from corrosion by seawater, a magnet or the like is sealed in the casing as necessary.

  Thereafter, the concentration of the target substance in the liquid 20 is measured again by a sensor, ICP-MS, lanthanum alizarin complexone (Lanthanum-Alizarin Complexone) absorption spectrophotometry (Step 4). Then, when it is determined that the target substance to be captured is required to be collected, the above Steps 1 to 3 are repeated. When it is determined that the collection of the target substance to be captured is unnecessary, the collection operation of the target substance to be captured is terminated. Step 4 can be performed on the supernatant liquid of step 2 and then step 3 can be performed. In that case, if the collection of the target substance is insufficient, steps 1 and 2 are repeated.

  Since most of the trapping hydrogel is water, incineration treatment, filter press dehydrator (“filter press to pressurize sludge in filtration chamber”, [Searched February 9, 2018] Internet <URL: https: / /kcr.kurita.co.jp/wtschool/052.html>), Belt press dewatering machine (“Mechanism of belt press and screw press”), [Searched February 9, 2018] Internet <URL: https: // kcr .kurita.co.jp / wtschool / 050.html>, screw press dehydrator, vacuum dehydrator (“Structure and use of vacuum dehydrator”, [Search February 9, 2018] Internet <URL: https: / /kcr.kurita.co.jp/wtschool/053.html>), centrifugal dehydrator ("Centrifugal dehydrator that separates using centrifugal force"), [February 9, 2018 search], Internet <URL: https : //kcr.kurita.co.jp/wtschool/051.html>) It is possible to reduce the volume. Becomes an adsorbent such as magnetic powder such as iron oxide, hydrotalcite, etc. In addition, since bovine rumen liquid, which is livestock waste generated during meat processing, contains cellulose-degrading enzymes, it is used as a component for decomposing with the rumen liquid. When a trapping hydrogel is produced from a raw material, it can be decomposed, such as konjac, which can be separated from hydrotalcite and iron powder by magnetic force after such treatment. Therefore, it can be reused.

  Different magnetic powders 3 can be used in combination with the trapping hydrogel 1. Similarly, the adsorbent may be used alone or in combination of two or more. In addition to using one kind of trapping hydrogel, a plurality of kinds of trapping hydrogels can be used in combination. By using a plurality of them, a plurality of target substances can be collected at a time. For this reason, there is an advantage that collection can be performed with high efficiency, particularly in the case of removing contaminants.

  When collecting target substances to be captured from muddy water, turbid water, and contaminated soil (hereinafter referred to as muddy water, etc.), trapping hydrogel is injected into the mixed liquid containing muddy water or contaminated soil. It is desirable that the magnetic material contained in muddy water or the like or the mixed solution of the contaminated soil be collected beforehand by magnetic separation. Thereby, the capture and recovery of the target substance to be captured by the capture hydrogel can be realized with high efficiency.

  The substance recovery system according to the present embodiment is not limited to the example of the present embodiment, and various modifications are possible. For example, the substance recovery system may include a liquid inlet, a mixing tank of a trapping hydrogel and a liquid, a trapping hydrogel collection tank by magnetic force, and a filtration device. For example, a trapping hydrogel set in advance according to the liquid injection amount, the degree of contamination, and the like is charged into the trapping hydrogel mixing tank with the liquid injection from the liquid injection port. Then, the liquid and the trapping hydrogel are mixed well in the trapping hydrogel mixing tank. Thereafter, the liquid containing the trapping hydrogel is moved to a trapping hydrogel collection tank by magnetic force, and the trapping hydrogel is collected by the magnetic integration means. After that, if necessary according to the application, it is passed through a filtration device. Such a material recovery system to be captured can be suitably used as, for example, a water purifier, a water and sewage treatment facility, a water treatment system for an apartment or the like, and a wastewater treatment facility of a factory.

  During storage and transportation of the trapping hydrogel, water may be reduced or removed. As a method of reducing or removing water, for example, sucrose, glucose, sugars such as maltose, sodium chloride, salts such as calcium chloride, ethanol, by mixing alcohols such as glycerin with the trapping hydrogel, There is a method using a pressure difference. Further, moisture may be removed by natural drying by standing, drying by warm air / low humidity air / low pressure / vacuum, freeze drying, forced drying by mixing a drying agent such as silica gel or powdery hydrotalcite. When used, the capture hydrogel can be regenerated by swelling by immersion in water.

  The substance recovery system according to the present embodiment is excellent in that harmful ions and the like can be directly magnetically separated from turbid water such as wastewater or muddy water without separating liquid and solid, even in an environment where suspended substances coexist. Has the effect. Further, according to the system of the present embodiment, the target substance to be captured can be recovered by turning on / off the magnetic force accumulation means, so that the operability is good and the efficiency is high. Moreover, the magnetic force accumulation means has an excellent merit that it can be used many times. It is also excellent in that it is not necessary to introduce special equipment and the like.

  The trapping hydrogel according to the present embodiment can be suitably used for the substance recovery system, but is not limited to the use in the system.

<Example>
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited at all by the following examples.

(Example 1)
0.25 g of KW-2000 (hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd.) and 10 mL of distilled water were mixed well in a polypropylene 15 mL centrifuge tube, and allowed to stand for 1 hour. Thereafter, the pH was confirmed to be 11.8 by pH measurement. Next, 1.5 g of iron powder RK-200 (manufactured by DOWA IP Creation Co., Ltd.) was added to the mixed solution and mixed well. When left standing for two weeks and observed, no rust was visually observed.

(Example 2)
In a 50 mL centrifuge tube made of polypropylene, 3 g of KW-2000 and 30 mL of distilled water were mixed well, and allowed to stand for 24 hours to collect a supernatant.

(Example 3)
In a polypropylene 15 mL centrifuge tube, 0.25 g of hydrotalcite KW-2000 (manufactured by Kyowa Chemical Industry Co., Ltd.) and 12.5 mL of distilled water were mixed well and allowed to stand for 1 hour. Thereafter, the pH was confirmed to be 11.8 by pH measurement. Next, 1.5 g of iron powder RK-200 (manufactured by DOWA IP Creation Co., Ltd.) was added, mixed well, and allowed to stand for 2 hours. The supernatant was removed as much as possible with a pipette, leaving the precipitated solids.

(Example 4)
0.75 g of konjac flour was added little by little to 15 mL of distilled water heated to 75 ° C. and stirred well for 5 minutes to obtain a soft gel.

(Example 5)
The soft gel obtained in Example 4 was added to the solid content obtained in Example 3, mixed well, and allowed to stand for 30 minutes. Further, 3 mL of the supernatant obtained in Example 2 was added, mixed well, and allowed to stand for 1 hour. These mixing steps were performed by the method of Japanese Patent No. 5907456. The mixture was placed in a 20 mL syringe fitted with a luer cap and kept free from hot water, and heated in a hot water at 75 ° C. for 30 minutes using a stainless steel beaker to obtain a hard gel-like lump. I got

(Example 6)
To the gel-like mass obtained in Example 5, 10 mL of the supernatant obtained in Example 2 was added and stored for 2 weeks. It was confirmed that there was no change in appearance including color tone such as rust.

(Example 7)
50 mL of distilled water was added to the gel-like mass obtained in Example 5, and the mixture was subjected to crushing for 1.5 seconds × 3 times using a mixer SKR-T250 (manufactured by Tiger Co., Ltd.). The size of the cut pieces was obtained. A 0.25 mm stainless steel mesh sieve was sieved to remove water.

(Example 8)
The washed gel obtained in Example 7 was stored at room temperature for 2 weeks. It was confirmed that there was no change in appearance including color tone such as rust.

(Example 9)
To the washed gel obtained in Example 7, 10 mL of the supernatant obtained in Example 2 was added and stored for 2 weeks. It was confirmed that there was no change in appearance including color tone such as rust.

(Example 10)
Each of a selenium standard solution (manufactured by WAKO Junyaku Kogyo Co., Ltd.), a fluoride ion standard solution (manufactured by Kishida Chemical Co., Ltd.) and a boron standard solution (manufactured by Kishida Chemical Co., Ltd.) is added to distilled water and mixed. The selenium concentration was adjusted to 1.2 mg / L, fluorine to 3.2 mg / L, and boron to 3.2 mg / L to produce simulated contaminated water.

(Example 11)
To 25 mL of the simulated water of Example 10 was added 2.5 g of the washed, crushed hydrotalcite / iron powder-dispersed trapping hydrogel (konjac) gel obtained in Example 7; Using a tube rotator-TR-350, stirring was performed at a speed of 15 rotations / minute for 24 hours. Thereafter, when the magnetic separation was performed, it was confirmed that the neodymium magnet of about 0.5 Tesla could be recovered within 2 seconds.

(Example 12)
The simulated contaminated water after performing the above steps was subjected to ICP-MS for quantification of selenium and boron, and lanthanum alizarin complexone (Lanthanum Alizarin Complexone) for the determination of fluorine by spectrophotometry. The concentration was 0.1 mg / L, fluorine was 1.6 mg / L, and boron was 1.9 mg / L, confirming that the trapping efficiency was high.

(Example 13)
In a polypropylene 15 mL centrifuge tube, 0.2 g of hydrotalcite KW-2000 (manufactured by Kyowa Chemical Industry Co., Ltd.) and 10 mL of distilled water were mixed well and allowed to stand for 1 hour. Thereafter, the pH was confirmed to be 11.8 by pH measurement. Next, 1.2 g of iron powder RK-200 (manufactured by DOWA IP Creation Co., Ltd.) was added, mixed well, and allowed to stand for 2 hours. The supernatant was removed as much as possible with a pipette, leaving the precipitated solids.

(Example 14)
0.75 g of odorless konjac powder (manufactured by Fuji Fine Laboratories) was added little by little to 10 mL of distilled water heated to 75 ° C., and the mixture was stirred well for 10 minutes to obtain a soft gel.

(Example 15)
The soft gel obtained in Example 14 was added to the solid content obtained in Example 13, mixed well, and allowed to stand for 30 minutes. Further, 4 mL of the supernatant obtained in Example 2 was added, mixed well, and allowed to stand for 1 hour. These mixing steps were performed by the method of Japanese Patent No. 5907456. The mixture was placed in a 20 mL syringe fitted with a luer cap and kept free from hot water, and heated in a hot water at 75 ° C. for 30 minutes using a stainless steel beaker to obtain a hard gel-like lump. I got

(Example 16)
10 mL of the supernatant obtained in Example 2 was added to the gel-like mass obtained in Example 15, and stored for 2 weeks. It was confirmed that there was no change in appearance including color tone such as rust.

(Example 17)
50 mL of distilled water was added to the gel-like mass obtained in Example 15, and crushing was performed three times for 1.5 seconds using a mixer SKR-T250 (manufactured by Tiger Co., Ltd.). The size of the cut pieces was obtained. A 0.25 mm stainless steel mesh sieve was sieved to remove water.

(Example 18)
The washed gel obtained in Example 17 was stored at room temperature for 2 weeks. It was confirmed that there was no change in appearance including color tone such as rust.

(Example 19)
To the washed gel obtained in Example 17, 10 mL of the supernatant obtained in Example 2 was added and stored for 2 weeks. It was confirmed that there was no change in appearance including color tone such as rust.

(Example 20)
To the washed gel obtained in Example 17, 10 grams of glucose was added and mixed well. Some water in the gel came out of the gel, and the volume of the gel decreased. After removing the water which came out, it was confirmed that no change in appearance including color tone such as generation of rust occurred even after storage for 2 weeks.

(Example 21)
When 30 mL of water was added to the gel obtained in Example 20 and mixed for 24 hours, the reduced gel volume was recovered. It was confirmed that there was no change in appearance including color tone such as generation of rust, and it could be recovered within 2 seconds with a neodymium magnet of about 0.5 Tesla.

  Examples 20 and 21 suggest that partial dehydration of the hydrogel using glucose leads to a reduction in the volume of the hydrogel, and thus may have advantages in storage and transportation.

(Example 22)
0.75 g of odorless konjac powder (manufactured by Fuji Fine Laboratories) and 0.1 g of powdered activated carbon (manufactured by WAKO Pure Chemical Industries, Ltd.) were added little by little to 10 mL of distilled water heated to 75 ° C. Stir well for a minute to obtain a soft gel.

(Example 23)
The soft gel obtained in Example 22 was added to the solid content obtained in Example 13, mixed well, and allowed to stand for 30 minutes. Further, 4 mL of the supernatant obtained in Example 2 was added, mixed well, and allowed to stand for 1 hour. These mixing steps were performed by the method of Japanese Patent No. 5907456. The mixture was placed in a 20 mL syringe fitted with a luer cap and kept free from hot water, and heated in a hot water at 75 ° C. for 30 minutes using a stainless steel beaker to obtain a hard gel-like lump. I got

(Example 24)
50 mL of distilled water was added to the gel-like mass obtained in Example 23, and crushing was performed for 3 seconds for 1.5 seconds using a mixer SKR-T250 (manufactured by Tiger Co., Ltd.). The size of the cut pieces was obtained. A 0.25 mm stainless steel mesh sieve was sieved to remove water.

(Example 25)
To 20 microliters of methylene blue stock solution (manufactured by WAKO Pure Chemical Industries, Ltd.), 5 mL of distilled water was added and mixed well. 20 mL of distilled water was added to 800 microliters of the obtained methylene blue diluent and mixed well to prepare blue simulated contaminated water.

(Example 26)
To 20 mL of the simulated water of Example 25, 3 g of the washed hydrotalcite / activated carbon / iron powder-dispersed trapping hydrogel (konjac) gel obtained in Example 24 was added. Using a tube rotator-TR-350, stirring was performed at a speed of 15 rotations / minute for 3 hours. Thereafter, when the magnetic separation was performed, it was confirmed that the neodymium magnet of about 0.5 Tesla could be recovered within 2 seconds. On the other hand, the simulated contaminated water after the treatment turned almost colorless and transparent, thus confirming that methylene blue was removed from the simulated contaminated water.

(Example 27)
A three-way cock was attached to a 10 mL syringe (A) with a polypropylene luer lock tip from which the piston was removed. After closing the stopcock, 0.15 g of KW-2000 (hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd.) and 1 mL of distilled water were put into the syringe (A). The hydrotalcite was sealed inside the syringe (A) by press-fitting the piston so that the tip of the piston was located at a site of a scale of 10 mL. The hydrotalcite was dispersed in water inside the syringe (A) by repeatedly inverting and mixing while keeping the position of the piston.

(Example 28)
An empty 10 mL syringe with a luer lock tip made of polypropylene (B) was connected to another part of the three-way cock to which the syringe (A) of Example 27 was connected. The syringe (A) -syringe (B) was opened by gradually opening the three-way cock. With the tip of the syringe (A) facing upward and taking care not to suck the hydrotalcite-dispersed water, pull the piston of the empty syringe (B) to remove most of the air inside the syringe (A). After removal, the three-way cock on the syringe (A) side containing the hydrotalcite-dispersed water was closed. The syringe (B) from which air was sucked was removed.

(Example 29)
A three-way cock was attached to a 10 mL syringe (C) with a polypropylene luer lock tip from which the piston was removed. After closing the three-way cock, 0.021 g of powdered activated carbon (manufactured by WAKO Pure Chemical Industries, Ltd.) and 1 mL of distilled water were put into the syringe (C). Activated powdered carbon was sealed inside the syringe (C) by press-fitting the piston so that the tip of the piston was positioned at the 10-mL scale. The powder activated carbon was dispersed in water inside the syringe (C) by repeatedly inverting and mixing while keeping the position of the piston.

(Example 30)
An empty 10 mL syringe with a luer lock tip made of polypropylene (D) was connected to another part of the three-way cock to which the syringe (C) of Example 29 was connected. By gradually opening the three-way cock, the space between the syringe (C) and the syringe (D) was opened. By pulling the piston of the empty syringe (D), with the tip of the syringe (C) facing upward and taking care not to suck the water in which the powdered activated carbon is dispersed, most of the air inside the syringe (C) Then, the three-way cock on the syringe (C) side containing water in which powdered activated carbon was dispersed was closed. The syringe (D) from which air was sucked was removed.

(Example 31)
Another part of the three-way cock connected to the syringe (A) filled with water in which hydrotalcite prepared in Example 28 was dispersed was connected with the syringe (C) filled with water in which powdered activated carbon prepared in Example 30 was dispersed. . After opening the three-way cock between the syringe (A) and the syringe (C), each piston was compressed alternately, and the contents of the syringe (A) and the syringe (C) were mixed well. Finally, the entire amount of the contents of both syringes was transferred into the syringe (A).

(Example 32)
A three-way cock was attached to a 10 mL syringe (E) with a luer lock tip made of polypropylene from which the piston was removed. After closing the stopcock, 0.6 g of iron powder RK-200 (manufactured by DOWA IP Creation Co., Ltd.) was put into the syringe (E). The iron powder was sealed inside the syringe (E) by press-fitting the piston so that the tip of the piston was located at the site of the scale of 10 mL. With the tip of the syringe (E) facing upward, open the three-way cock and carefully push in the piston, taking care not to let the iron powder fly up, to remove most of the air inside the syringe (E). .

(Example 33)
A three-way cock was attached to a 10 mL syringe (F) with a polypropylene luer lock tip from which the piston was removed. After closing the stopcock, 0.375 g of odorless konjac flour (manufactured by Fuji Fine Laboratories) was placed in the syringe (F). The odorless konjac powder was sealed inside the syringe (F) by press-fitting and mounting the piston so that the tip of the piston was positioned at a 10-mL scale. With the tip of the syringe (F) facing upward, open the three-way cock and carefully push in the piston, taking care not to let the odorless konjac powder fly up, to remove most of the air inside the syringe (F). Was.

(Example 34)
A three-way cock was attached to a 10 mL syringe (G) with a polypropylene luer lock tip from which the piston was removed. After closing the three-way cock, 5 mL of distilled water heated to 75 ° C. was put into the syringe (G). The heated distilled water was sealed inside the syringe (G) by press-fitting and mounting the piston so that the tip of the piston was positioned at the 10-mL scale. With the position of the piston fixed, the syringe (G) tip is turned upward, the three-way stopcock is opened, and the piston is gradually pushed in so that distilled water does not scatter, so that most of the air inside the syringe (G) Pulled out.

(Example 35)
The syringe (G) filled with the heated distilled water prepared in Example 34 was connected to another part of the three-way cock connected to the syringe (F) filled with the odorless konjac powder prepared in Example 33. After opening the three-way cock between the syringe (F) and the syringe (G), each piston is alternately compressed, and the contents of the syringe (F) and the syringe (G) are mixed well to form a soft konjac gel. Finally, the entire contents of both syringes were transferred into the syringe (G).

(Example 36)
The syringe (E) filled with iron powder prepared in Example 32 was connected to another part of the three-way cock connected to the syringe (G) filled with gel-like konjac prepared in Example 35. After opening the three-way cock between the syringe (G) and the syringe (E), the pistons are alternately compressed and the contents of the syringe (G) and the syringe (E) are mixed well, so that iron powder is added to the konjac gel. Was dispersed, and finally the entire contents of both syringes were transferred into the syringe (G).

(Example 37)
A syringe filled with water in which the hydrotalcite / powder activated carbon prepared in Example 31 is dispersed, at another site of the three-way cock connected to the syringe (G) filled with the gel-like konjac in which the iron powder prepared in Example 36 is dispersed. (A) was connected. After opening the three-way cock between the syringe (G) and the syringe (A), each piston was alternately compressed, and the contents of the syringe (G) and the syringe (A) were mixed well. Finally, the entire contents of both syringes were transferred into the syringe (A). It was confirmed that the alkali component of hydrotalcite reacted with the konjac and the hardness of the gel increased. The syringe (G) and the stopcock were removed.

(Example 38)
Aluminum foil prepared by cutting the konjac gel in which hydrotalcite / activated carbon / iron powder prepared in Example 37 was dispersed into a circular shape with a diameter of 13 cm from the tip of the syringe (A) and coated with silicon (Cook par & Asahi Kasei Home Products Co., Ltd.) Discharged and placed on top. At this time, the piston was gradually pushed out while moving the tip of the syringe on the aluminum foil little by little so as to draw a line. Specifically, the konjac gel is adjusted while adjusting the moving speed of the syringe tip and the pushing speed of the piston so that the konjac gel maintains a continuity and is as smooth as possible without overlapping, and has a cylindrical shape with a diameter of about 1.5 mm. Placed on aluminum foil.

(Example 39)
After tap water was poured to a height of about 80% of a steaming pot for a steamer having a diameter of 15 cm, the tap water was placed in a gas range, and the mixture was heated over a medium heat until boiling. A 13 cm diameter silicon-coated aluminum foil on which konjac gel prepared by dispersing hydrotalcite / activated carbon / iron powder prepared in Example 38 was transferred into a 15 cm diameter steamer and covered. The steamer was set in a steaming pot, and boiling was continued for 15 minutes while adding boiling water to the steaming pot as appropriate to prevent empty heating. After the fire was extinguished, it was cooled for 5 minutes.

(Example 40)
The konjac gel prepared in Example 39 was minced with stainless steel scissors to form a columnar hydrotalcite / activated carbon / iron powder having a diameter of about 1.5 mm × length 1.5 mm. Konjac gel) particles were obtained. The trapping hydrogel (konjac gel) particles were transferred to a 50 mL polypropylene tube, sealed with a cap, and stored while preventing drying.

(Example 41)
The gel obtained in Example 40 was stored at room temperature for 2 weeks. It was confirmed that there was no change in appearance including color tone such as rust.

(Example 42)
To 25 mL of the simulated water of Example 10 was added 2.5 g of a trapping hydrogel (konjac) gel in which the hydrotalcite / activated carbon / iron powder obtained in Example 40 was dispersed, and using a tube rotator-TR-350, Stirring was performed at a speed of 15 rotations / minute for 24 hours. Thereafter, when the magnetic separation was performed, it was confirmed that the neodymium magnet of about 0.5 Tesla could be recovered within 2 seconds.

(Example 43)
The simulated contaminated water after performing the above steps was quantified for selenium, boron and fluorine in the same manner as in Example 12, and the selenium concentration: 0.1 mg / L, fluorine: 1.2 mg / L, boron : 1.6 mg / L, and it was confirmed that the capture efficiency was high.

(Example 44)
FIGS. 6 and 7 are schematic diagrams of the silicon rubber plate. Two silicon rubber plates (K-125: manufactured by Togawa Rubber Co., Ltd.) having a size of 45 mm (length) × 45 mm (width) × 2 mm (thickness) were prepared. A hole 41 having a diameter of 1.5 mm was punched in the first silicon rubber plate 40 as shown in FIG. As shown in FIG. 7, the silicon rubber plate 40 was overlaid on the silicon rubber plate 50 having no holes, and the silicon rubber plate 40 was brought into close contact with the silicon rubber plate 50 by pressing.

(Example 45)
To the tip of the syringe (A) filled with konjac gel in which hydrotalcite / activated carbon / iron powder prepared in Example 37 was dispersed, a polypropylene female luer fitting (inner diameter 1.5 mm; VRF106: sold by Isis) was connected. Insert the tip of the female luer fitting into the hole having a diameter of 1.5 mm of the silicone rubber plate 40 prepared in Example 44, and slowly insert the konjac gel into the bottom of the silicone rubber plate 40 (silicon rubber plate 50). To the height of 1.5 mm, that is, up to the inserted luer fitting tip.

(Example 46)
After tap water was poured to a height of about 80% of a steaming pot for a steamer having a diameter of 15 cm, the tap water was placed in a gas range, and the mixture was heated over a medium heat until boiling. The silicone rubber plate 40 and the silicone rubber plate 50 filled with the konjac gel in which hydrotalcite / activated carbon / iron powder prepared in Example 45 were adhered were transferred into a steamer having a diameter of 15 cm and covered. The steamer was set in a steaming pot, and boiling was continued for 15 minutes while adding boiling water to the steaming pot as appropriate to prevent empty heating. After the fire was extinguished, it was cooled for 5 minutes.

(Example 47)
The silicon rubber plate 40 and the silicon rubber plate 50 prepared in Example 46 were brought into close contact with each other and taken out. The silicon rubber plate 40 and the silicon rubber plate 50 were separated by peeling. The tip of a cylindrical resin rod having a diameter of about 1.5 mm is pressed against a heated hydrotalcite / activated carbon / iron powder dispersed trapping hydrogel (konjac gel) remaining in the hole of the silicone rubber plate 40. Thus, the gel was extruded and collected in a 50 mL polypropylene tube to prevent drying. On the other hand, the heated gel adhered to the surface of the silicone rubber plate 50 was peeled off using tweezers, collected in a 50 mL polypropylene tube, and prevented from drying.

(Example 48)
The gel obtained in Example 47 was stored at room temperature for 2 weeks. It was confirmed that there was no change in appearance including color tone such as rust.

(Example 49)
To 25 mL of the simulated water of Example 10 was added 2.5 g of a trapping hydrogel (konjac) gel in which the hydrotalcite / activated carbon / iron powder obtained in Example 47 was dispersed, and using a tube rotator-TR-350, Stirring was performed at a speed of 15 rotations / minute for 24 hours. Thereafter, when the magnetic separation was performed, it was confirmed that the neodymium magnet of about 0.5 Tesla could be recovered within 2 seconds.

(Example 50)
The simulated contaminated water after performing the above steps was quantified for selenium, boron and fluorine in the same manner as in Example 12, and the selenium concentration: 0.1 mg / L, fluorine: 1.1 mg / L, boron : 1.5 mg / L, and it was confirmed that the capture efficiency was high.

(Example 51)
4 g of konjac flour (purchased from Bukchon liquor) into a 50 mL polypropylene tube, add 20 mL of an aqueous ethanol solution (50% v / v), close the cap, attach to the tube rotator TR-350, and rotate 15 times / Stirring was performed for 12 hours at a speed of minutes.

(Example 52)
The tube of Example 51 was removed from the tube rotator TR-350, and allowed to stand for 15 minutes. The cap was opened, and only the supernatant was carefully removed using a 5 mL pipette. Again, 20 mL of an aqueous ethanol solution (50% v / v) was added, the cap was closed, the tube was attached to a tube rotator TR-350, and stirring was performed at a speed of 15 rotations / minute for 12 hours. This operation was repeated once more.

(Example 53)
The tube of Example 52 was removed from the tube rotator TR-350, allowed to stand for 15 minutes, then the cap was opened, and only the supernatant was carefully removed using a 5 mL pipette. Again, a 20 mL ethanol aqueous solution (75% v / v) was added, the cap was closed, the tube was attached to a tube rotator TR-350, and stirring was performed at a speed of 15 rotations / minute for 12 hours.

(Example 54)
The tube of Example 53 was removed from the tube rotator TR-350, allowed to stand for 15 minutes, and then the cap was opened. Only the supernatant was carefully removed using a 5 mL pipette. Again, 8 mL of absolute ethanol was added, the cap was closed, the tube was attached to a tube rotator TR-350, and the mixture was stirred at a speed of 15 revolutions / minute for 15 minutes. This operation was repeated once more.

(Example 55)
The tube of Example 54 was removed from the tube rotator TR-350, and allowed to stand for 15 minutes. After opening the cap, only the supernatant was carefully removed using a 5 mL pipette. The precipitate was dried by putting it in an oven set at 60 ° C. for 3 hours and evaporating the ethanol to obtain ethanol-treated konjac powder in which impurities such as trimethylamine and oxalic acid were reduced.

(Example 56)
The ethanol-treated konjac flour obtained in Example 55 was used instead of the odorless konjac flour used in Example 33. That is, a three-way cock was attached to a 10 mL syringe (H) with a polypropylene luer lock tip from which the piston was removed. After closing the stopcock, 0.375 g of ethanol-treated konjac flour was placed in the syringe (H). The ethanol-treated konjac powder was sealed inside the syringe (H) by press-fitting and mounting the piston so that the tip of the piston was positioned at the 10-mL scale. With the tip of the syringe (H) facing upward, open the three-way cock and carefully push in the piston, taking care not to let the ethanol-treated konjac powder fly, to remove most of the air inside the syringe (H). I pulled it out.

(Example 57)
The syringe (G) filled with the heated distilled water prepared in Example 34 was connected to another part of the three-way cock connected to the syringe (H) filled with the ethanol-treated konjac powder prepared in Example 56. After opening the three-way cock between the syringe (H) and the syringe (G), the pistons are alternately compressed and the contents of the syringe (H) and the syringe (G) are mixed well to form a soft konjac gel. Finally, the entire contents of both syringes were transferred into the syringe (H).

(Example 58)
The syringe (E) filled with the iron powder prepared in Example 32 was connected to another part of the three-way cock connected to the syringe (H) filled with the gel-like konjac prepared in Example 57. After opening the three-way cock between the syringe (H) and the syringe (E), the pistons are alternately compressed and the contents of the syringe (H) and the syringe (E) are mixed well, so that iron powder is added to the konjac gel. Was dispersed, and finally the entire contents of both syringes were transferred into the syringe (H).

(Example 59)
Syringe filled with water in which hydrotalcite / activated carbon prepared in Example 31 was dispersed at another site of a three-way cock connected to a syringe (H) filled with gel-like konjac in which iron powder prepared in Example 58 was dispersed. (A) was connected. After opening the three-way cock between the syringe (H) and the syringe (A), each piston was alternately compressed, and the contents of the syringe (H) and the syringe (A) were mixed well. Finally, the entire amount of the contents of both syringes was transferred into the syringe (H). It was confirmed that the alkali component of hydrotalcite reacted with the konjac and the hardness of the gel increased. The syringe (A) and the stopcock were removed.

(Example 60)
The konjac gel prepared by dispersing the hydrotalcite / activated carbon / iron powder prepared in Example 59 from a syringe (H) tip into a circle having a diameter of 13 cm was cut into a silicon-coated aluminum foil in the same manner as in Example 38. , Discharged and placed.

(Example 61)
After tap water was poured to a height of about 80% of a steaming pot for a steamer having a diameter of 15 cm, the tap water was placed in a gas range, and the mixture was heated over a medium heat until boiling. A 13 cm diameter silicon-coated aluminum foil on which a konjac gel prepared by dispersing hydrotalcite / activated carbon / iron powder prepared in Example 60 was transferred into a steamer having a diameter of 13 cm was covered with a lid. The steamer was set in a steaming pot, and boiling was continued for 15 minutes while adding boiling water to the steaming pot as appropriate to prevent empty heating. After the fire was extinguished, it was cooled for 5 minutes.

(Example 62)
The konjac gel prepared in Example 61 was minced with stainless steel scissors to obtain a columnar hydrotalcite / activated carbon / iron powder-dispersed hydrogel (1.5 mm in diameter × 1.5 mm in length) ( Konjac gel) particles were obtained. The trapping hydrogel (konjac gel) particles were transferred to a 50 mL polypropylene tube, sealed with a cap, and stored while preventing drying.

(Example 63)
The gel obtained in Example 62 was stored at room temperature for 2 weeks. It was confirmed that there was no change in appearance including color tone such as rust.

(Example 64)
To 25 mL of the simulated water of Example 10 was added 2.5 g of a trapping hydrogel (konjac) gel in which the hydrotalcite / activated carbon / iron powder obtained in Example 62 was dispersed, and using a tube rotator-TR-350, Stirring was performed at a speed of 15 rotations / minute for 24 hours. Thereafter, when the magnetic separation was performed, it was confirmed that the neodymium magnet of about 0.5 Tesla could be recovered within 2 seconds.

(Example 65)
When the simulated contaminated water after performing the above steps was quantified for selenium, boron and fluorine in the same manner as in Example 12, the selenium concentration: 0.1 mg / L, fluorine: 1.3 mg / L, boron : 1.7 mg / L, and it was confirmed that the capture efficiency was high.

(Example 66)
The tip of a syringe (H) filled with konjac gel in which hydrotalcite / activated carbon / iron powder prepared in Example 59 was dispersed was connected with a female luer fitting made of polypropylene (inner diameter 1.5 mm; VRF106: sold by Isis). Insert the tip of the female luer fitting into a hole having a diameter of 1.5 mm of the plate 40 and the plate 50 prepared in Example 44 in close contact with each other, and slowly insert the konjac gel to the bottom of the plate 40 (plate 50 to the height of 1.5 mm, ie, to the inserted luer fitting tip.

(Example 67)
After tap water was poured to a height of about 80% of a steaming pot for a steamer having a diameter of 15 cm, the tap water was placed in a gas range, and the mixture was heated over a medium heat until boiling. A silicone rubber plate 40 and a silicone rubber plate 50 packed with konjac gel in which hydrotalcite / activated carbon / iron powder prepared in Example 66 were adhered were transferred into a 15 cm diameter steamer and covered. The steamer was set in a steaming pot, and boiling was continued for 15 minutes while adding boiling water to the steaming pot as appropriate to prevent empty heating. After the fire was extinguished, it was cooled for 5 minutes.

(Example 68)
The silicon rubber plate 40 and the silicon rubber plate 50 prepared in Example 67 were brought into close contact with each other, taken out, and separated by peeling off the silicon rubber plate 40 and the silicon rubber plate 50. The tip of a cylindrical resin rod having a diameter of about 1.5 mm is pressed against a heated hydrotalcite / activated carbon / iron powder dispersed trapping hydrogel (konjac gel) remaining in the hole of the silicone rubber plate 40. Thus, the gel was extruded and collected in a 50 mL polypropylene tube to prevent drying. On the other hand, the heated gel adhered to the surface of the silicone rubber plate 50 was peeled off using tweezers, collected in a 50 mL polypropylene tube, and prevented from drying.

(Example 69)
The gel obtained in Example 68 was stored at room temperature for 2 weeks. It was confirmed that there was no change in appearance including color tone such as rust.

(Example 70)
To 25 mL of the simulated water of Example 10, 2.5 g of the hydrotalcite / activated carbon / iron powder-dispersed hydrogel (konjac) gel obtained in Example 68 was added, and using a tube rotator-TR-350, Stirring was performed at a speed of 15 rotations / minute for 24 hours. Thereafter, when the magnetic separation was performed, it was confirmed that the neodymium magnet of about 0.5 Tesla could be recovered within 2 seconds.

(Example 71)
When the simulated contaminated water after performing the above steps was quantified for selenium, boron and fluorine in the same manner as in Example 12, the selenium concentration: 0.1 mg / L, fluorine: 1.3 mg / L, boron : 1.6 mg / L, and it was confirmed that the capture efficiency was high.

(Example 72)
A three-way cock was attached to a 10 mL syringe (I) with a polypropylene luer lock tip from which the piston was removed. After closing the three-way cock, 0.375 g of odorless konjac flour (manufactured by Fuji Fine Laboratories) and 0.067 g of crest fiber GRY-HW (manufactured by Crest Co., Ltd.) were put into the syringe (I). The odorless konjac powder was sealed inside the syringe (I) by press-fitting and mounting the piston so that the tip of the piston was positioned at the 10-mL scale. With the tip of the syringe (I) facing upward, the three-way cock is opened, and the piston is gradually pushed in while paying attention so that the odorless konjac powder and the crest fiber GRY-HW do not fly up. Most of the air was evacuated.

(Example 73)
The syringe (G) filled with the heated distilled water prepared in Example 34 was connected to another part of the three-way cock connected to the syringe (I) filled with the odorless konjac powder and the crest fiber GRY-HW prepared in Example 72. . After opening the three-way cock between the syringe (I) and the syringe (G), the pistons are alternately compressed, and the contents of the syringe (I) and the syringe (G) are mixed well, so that the crest fiber GRY-HW is obtained. Was obtained, and finally the entire contents of both syringes were transferred into the syringe (I).

(Example 74)
The syringe (E) filled with the iron powder prepared in Example 32 was connected to another part of the three-way cock connected to the syringe (I) filled with the gel-like konjac in which the killed fiber GRY-HW prepared in Example 73 was dispersed. did. After opening the three-way cock between the syringe (I) and the syringe (E), the pistons are alternately compressed, and the contents of the syringe (I) and the syringe (E) are mixed well, so that the Crest Fiber GRY-HW is obtained. Iron powder was dispersed in the konjac gel in which was dispersed, and finally the entire contents of both syringes were transferred into the syringe (I).

(Example 75)
A three-way cock was attached to a 10 mL syringe (J) with a luer lock tip made of polypropylene from which the piston was removed. After closing the stopcock, 0.15 g of KW-2000 (hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd.) and 2 mL of distilled water were put into the syringe (J). The hydrotalcite was sealed inside the syringe (J) by press-fitting the piston so that the tip of the piston was located at the site of the scale of 10 mL. The hydrotalcite was dispersed in water inside the syringe (J) by repeatedly inverting and mixing while keeping the position of the piston.

(Example 76)
An empty 10 mL syringe with a luer lock tip made of polypropylene (K) was connected to another part of the three-way cock to which the syringe (J) of Example 75 was connected. By gradually opening the three-way cock, the space between the syringe (J) and the syringe (K) was opened. With the tip of the syringe (J) facing upward and taking care not to suck in the hydrotalcite-dispersed water, pull the piston of the empty syringe (K) to remove most of the air inside the syringe (J). After removal, the three-way cock on the syringe (J) side containing the hydrotalcite-dispersed water was closed. The syringe (K) from which air was sucked was removed.

(Example 77)
The water in which the hydrotalcite prepared in Example 76 was dispersed was added to another site of the three-way cock connected to the syringe (I) filled with the gel-like konjac in which the crest fiber GRY-HW / iron powder prepared in Example 74 was dispersed. The filled syringe (J) was connected. After opening the three-way cock between the syringe (I) and the syringe (J), each piston was alternately compressed, and the contents of the syringe (I) and the syringe (J) were mixed well. Finally, the entire amount of the contents of both syringes was transferred into syringe (I). It was confirmed that the alkali component of hydrotalcite reacted with the konjac and the hardness of the gel increased. The syringe (J) and the stopcock were removed.

(Example 78)
The konjac gel prepared by dispersing the hydrotalcite / killest fiber GRY-HW / iron powder prepared in Example 77 from the tip of the syringe (I) into a circular shape having a diameter of 13 cm was coated with silicon by the same method as in Example 38. Discharged and placed on aluminum foil.

(Example 79)
After tap water was poured to a height of about 80% of a steaming pot for a steamer having a diameter of 15 cm, the tap water was placed in a gas range, and the mixture was heated over a medium heat until boiling. A 13 cm diameter silicon-coated aluminum foil on which konjac gel prepared by dispersing hydrotalcite / killest fiber GRY-HW / iron powder prepared in Example 78 was transferred into a 15 cm diameter steamer and capped. The steamer was set in a steaming pot, and boiling was continued for 15 minutes while adding boiling water to the steaming pot as appropriate to prevent empty heating. After the fire was extinguished, it was cooled for 5 minutes.

(Example 80)
The konjac gel prepared in Example 79 was finely sliced with stainless steel scissors, so that a columnar hydrotalcite / cylest fiber GRY-HW / iron powder having a diameter of about 1.5 mm and a length of about 1.5 mm was dispersed and captured. Hydrogel (konjac gel) particles were obtained. The trapping hydrogel (konjac gel) particles were transferred to a 50 mL polypropylene tube, sealed with a cap, and stored while preventing drying.

(Example 81)
The gel obtained in Example 80 was stored at room temperature for 2 weeks. It was confirmed that there was no change in appearance including color tone such as rust.

(Example 82)
To 25 mL of the simulated water of Example 10 was added 2.5 g of a trapping hydrogel (konjac) gel in which the hydrotalcite / killest fiber GRY-HW / iron powder obtained in Example 80 was dispersed, and a tube rotator-TR-350 was added. , Stirring was performed at a speed of 15 rotations / minute for 24 hours. Thereafter, when the magnetic separation was performed, it was confirmed that the neodymium magnet of about 0.5 Tesla could be recovered within 2 seconds.

(Example 83)
When the simulated contaminated water after performing the above steps was quantified for selenium, boron and fluorine in the same manner as in Example 12, the selenium concentration: 0.1 mg / L, fluorine: 1.3 mg / L, boron : 1.5 mg / L, and it was confirmed that the capture efficiency was high.

(Example 84)
The konjac gel prepared by dispersing the hydrotalcite / killest fiber GRY-HW / iron powder prepared in Example 77 was connected to a syringe (I) tip with a polypropylene female luer fitting (inner diameter 1.5 mm; VRF106: sold by Isis). . Insert the tip of the female luer fitting into a hole having a diameter of 1.5 mm about 0.5 mm into a plate having the plate 40 and the plate 50 closely contacted prepared in Example 44, and slowly put the konjac gel on the bottom of the plate 40 (plate 50 to the height of 1.5 mm, ie, to the inserted luer fitting tip.

(Example 85)
After tap water was poured to a height of about 80% of a steaming pot for a steamer having a diameter of 15 cm, the tap water was placed in a gas range, and the mixture was heated over a medium heat until boiling. The silicone rubber plate 40 and the silicone rubber plate 50 filled with the hydrotalcite / kirest fiber GRY-HW / iron powder-dispersed konjac gel prepared in Example 84 were transferred to a steamer having a diameter of 15 cm. Covered. The steamer was set in a steaming pot, and boiling was continued for 15 minutes while adding boiling water to the steaming pot as appropriate to prevent empty heating. After the fire was extinguished, it was cooled for 5 minutes.

(Example 86)
The silicon rubber plate 40 and the silicon rubber plate 50 prepared in Example 85 were brought into close contact with each other, taken out, and separated by peeling the silicon rubber plate 40 and the silicon rubber plate 50. A tip of a cylindrical resin rod having a diameter of about 1.5 mm is attached to a heated hydrotalcite / crest fiber GRY-HW / iron powder dispersed in a hole of the silicone rubber plate 40 in a trapping hydrogel (konjac). Gel), the gel was extruded and collected in a 50 mL polypropylene tube to prevent drying. On the other hand, the heated gel adhered to the surface of the silicone rubber plate 50 was peeled off using tweezers, collected in a 50 mL polypropylene tube, and prevented from drying.

(Example 87)
The gel obtained in Example 86 was stored at room temperature for 2 weeks. It was confirmed that there was no change in appearance including color tone such as rust.

(Example 88)
To 25 mL of the simulated water of Example 10 was added 2.5 g of a trapping hydrogel (konjac) gel in which the hydrotalcite / killest fiber GRY-HW / iron powder obtained in Example 80 was dispersed, and a tube rotator-TR-350 was added. , Stirring was performed at a speed of 15 rotations / minute for 24 hours. Thereafter, when the magnetic separation was performed, it was confirmed that the neodymium magnet of about 0.5 Tesla could be recovered within 2 seconds.

(Example 89)
When the simulated contaminated water after performing the above steps was quantified for selenium, boron and fluorine in the same manner as in Example 12, the selenium concentration: 0.1 mg / L, fluorine: 1.3 mg / L, boron : 1.4 mg / L, and it was confirmed that the capture efficiency was high.

(Example 90)
A three-way cock was attached to a 10 mL syringe (L) with a polypropylene luer lock tip from which the piston was removed. After closing the three-way cock, 0.375 g of odorless konjac powder (manufactured by Fuji Fine Laboratories) and 0.067 g of Kyrest Fiber IRY-HW (manufactured by Kirest Corporation) were put into the syringe (L). The odorless konjac powder was sealed inside the syringe (L) by press-fitting and mounting the piston so that the tip of the piston was positioned at the 10-mL scale. With the tip of the syringe (L) facing upward, the three-way cock is opened, and the odorless konjac flour and the crest fiber IRY-HW are carefully pushed so that the piston does not fly up, so that the piston is gradually pushed in. Most of the air was evacuated.

(Example 91)
The syringe (G) filled with the heated distilled water prepared in Example 34 was connected to another part of the three-way cock connected to the syringe (L) filled with the odorless konjac powder and the crested fiber IRY-HW prepared in Example 90. . After opening the three-way cock between the syringe (L) and the syringe (G), the pistons are alternately compressed, and the contents of the syringe (L) and the syringe (G) are mixed well, so that the crest fiber IRY-HW is obtained. Was obtained, and finally the entire contents of both syringes were transferred into the syringe (L).

(Example 92)
The syringe (E) filled with the iron powder prepared in Example 32 was connected to another part of the three-way cock connected to the syringe (L) filled with the gel-like konjac in which the killed fiber IRY-HW prepared in Example 91 was dispersed. did. After opening the three-way cock between the syringe (L) and the syringe (E), the pistons are alternately compressed, and the contents of the syringe (L) and the syringe (E) are mixed well, so that the crest fiber IRY-HW is obtained. Iron powder was dispersed in the konjac gel in which was dispersed, and finally the entire contents of both syringes were transferred into the syringe (L).

(Example 93)
The water in which the hydrotalcite prepared in Example 75 was dispersed was added to another site of the three-way stopcock connected to the syringe (L) filled with the gel-like konjac in which the crest fiber IRY-HW / iron powder prepared in Example 92 was dispersed. The filled syringe (J) was connected. After opening the three-way cock between the syringe (L) and the syringe (J), each piston was alternately compressed, and the contents of the syringe (L) and the syringe (J) were mixed well. Finally, the entire amount of the contents of both syringes was transferred into the syringe (L). It was confirmed that the alkali component of the hydrotalcite reacted with the konjac, increasing the hardness of the gel. The syringe (J) and the stopcock were removed.

(Example 94)
The surface of a konjac gel prepared by dispersing the hydrotalcite / killest fiber IRY-HW / iron powder prepared in Example 93 into a circular shape having a diameter of 13 cm from the tip of the syringe (L) in the same manner as in Example 38 was coated with silicon. Discharged and placed on aluminum foil.

(Example 95)
After tap water was poured to a height of about 80% of a steaming pot for a steamer having a diameter of 15 cm, the tap water was placed in a gas range, and the mixture was heated over a medium heat until boiling. A 13 cm diameter silicon-coated aluminum foil on which konjac gel prepared by dispersing the hydrotalcite / killest fiber IRY-HW / iron powder prepared in Example 94 was transferred into a steamer having a diameter of 15 cm and covered. The steamer was set in a steaming pot, and boiling was continued for 15 minutes while adding boiling water to the steaming pot as appropriate to prevent empty heating. After the fire was extinguished, it was cooled for 5 minutes.

(Example 96)
The konjac gel prepared in Example 95 was finely sliced with stainless steel scissors, so that a columnar hydrotalcite / cylest fiber IRY-HW / iron powder having a diameter of about 1.5 mm and a length of about 1.5 mm was dispersed and captured. Hydrogel (konjac gel) particles were obtained. The trapping hydrogel (konjac gel) particles were transferred to a 50 mL polypropylene tube, sealed with a cap, and stored while preventing drying.

(Example 97)
The gel obtained in Example 96 was stored at room temperature for 2 weeks. It was confirmed that there was no change in appearance including color tone such as rust.

(Example 98)
An indium standard solution (manufactured by WAKO Pure Chemical Industries, Ltd.) was added to and mixed with distilled water to adjust the indium concentration to 1.2 mg / L to produce a simulated rare metal water.

(Example 99)
To 25 mL of the simulated water of Example 98, 2.5 g of a trapping hydrogel (konjac) gel in which the hydrotalcite / killest fiber IRY-HW / iron powder obtained in Example 95 was dispersed was added, and a tube manufactured by As One Corporation was added. Using a rotator-TR-350, stirring was performed at a speed of 15 revolutions / minute for 24 hours. Thereafter, when the magnetic separation was performed, it was confirmed that the neodymium magnet of about 0.5 Tesla could be recovered within 2 seconds.

(Example 100)
The simulated rare metal water after performing the above steps was quantified for indium by ICP-MS, and the indium concentration was 0.1 mg / L, confirming that the capture efficiency was high.

(Example 101)
A konjac gel prepared by dispersing the hydrotalcite / killest fiber IRY-IW / iron powder prepared in Example 93 was connected to a syringe (L) tip with a polypropylene female luer fitting (inner diameter 1.5 mm; VRF106: sold by Isis). . Insert the tip of the female luer fitting into a hole having a diameter of 1.5 mm of the plate 40 and the plate 50 prepared in Example 44 in close contact with each other, and slowly insert the konjac gel to the bottom of the plate 40 (plate 50 to the height of 1.5 mm, ie, to the inserted luer fitting tip.

(Example 102)
After tap water was poured to a height of about 80% of a steaming pot for a steamer having a diameter of 15 cm, the tap water was placed in a gas range, and the mixture was heated over a medium heat until boiling. The silicon rubber plate 40 and the silicon rubber plate 50 filled with the hydrotalcite / killest fiber IRY-HW / iron powder dispersed konjac gel prepared in Example 101 were brought into close contact with each other, and transferred into a steamer having a diameter of 15 cm. Covered. The steamer was set in a steaming pot, and boiling was continued for 15 minutes while adding boiling water to the steaming pot as appropriate to prevent empty heating. After the fire was extinguished, it was cooled for 5 minutes.

(Example 103)
The silicon rubber plate 40 and the silicon rubber plate 50 prepared in Example 102 were brought into close contact with each other, taken out, and separated by peeling off the silicon rubber plate 40 and the silicon rubber plate 50. The tip of a cylindrical resin rod having a diameter of about 1.5 mm is connected to a heated hydrotalcite / crested fiber IRY-HW / iron powder dispersed in a hole of the silicone rubber plate 40 by a trapping hydrogel (konjac). Gel), the gel was extruded and collected in a 50 mL polypropylene tube to prevent drying. On the other hand, the heated gel adhered to the surface of the silicone rubber plate 50 was peeled off using tweezers, collected in a 50 mL polypropylene tube, and prevented from drying.

(Example 104)
The gel obtained in Example 103 was stored at room temperature for 2 weeks. It was confirmed that there was no change in appearance including color tone such as rust.

(Example 105)
To 25 mL of the simulated water of Example 98, 2.5 g of a trapping hydrogel (konjac) gel in which the hydrotalcite / killest fiber IRY-HW / iron powder obtained in Example 103 was dispersed was added, and a tube rotator-TR-350 was added. , Stirring was performed at a speed of 15 rotations / minute for 24 hours. Thereafter, when the magnetic separation was performed, it was confirmed that the neodymium magnet of about 0.5 Tesla could be recovered within 2 seconds.

(Example 106)
The simulated rare metal water after performing the above steps was quantified for indium by ICP-MS, and the indium concentration was 0.1 mg / L, confirming that the capture efficiency was high.

  From the above example, it was confirmed that hydrotalcite having a property of adsorbing harmful ions and the like exhibited strong alkalinity due to water dispersion. It was also confirmed that in a strong alkaline environment, rust of iron powder, which usually rusts easily, can be strongly prevented. In addition, konjac is a process that combines harmful heavy metals and useful rare metals from water with a variety of fine particles by combining the fact that even after coagulation with an alkali, the movement of low molecules and water is relatively easy. It has been confirmed that it can be integrated very few, instantaneously and at low cost.

1: Capturing hydrogel 2: Three-dimensional network structure 3: Magnetic powder 4: Adsorbent 5: Water 20: Liquid 21: Target substance 30: Magnetic force accumulating means 40: Perforated silicon rubber plate 41: Opening 50: Hole None silicone rubber plate

Claims (6)

A trapping hydrogel having a three-dimensional network structure,
In the three-dimensional network structure,
Magnetic powder,
An adsorbent that captures the target substance in the liquid,
Containing water and
The magnetic powder is iron powder,
A trapping hydrogel that exhibits alkalinity and can be recovered by magnetic force.   The capturing hydrogel according to claim 1, which is in the form of beads.   The adsorbent is hydrotalcite, activated carbon, calcite, montmorillonite, kaolinite, birnessite, zeolite, illite, vermiculite, pyrophyllite, perlite, bentonite, cobalt oxide, neodymium oxide, indium oxide, silver oxide, cerium oxide. , Titanium oxide, zirconium ferrite hydrate, titanium hydroxide, metal ferrocyanide, cation exchange resin, anion exchange resin, cation exchange fiber, anion exchange fiber, chelate resin, chelate fiber, amphoteric ion exchange resin , Amphoteric ion exchange fiber, molecular labeling gel, inorganic ion exchanger of porous crystal with niobium oxide skeleton, zirconium phosphate, aluminum oxide, polydextrose, sodium alginate, inulin, carrageenan, cellulose, hemicellulo Scan, lignin, chitin, capture hydrogel according to claim 1 or 2 is selected from the group consisting of chitosan and pectin. The three-dimensional network structure includes glucomannan, agar, gelatin, agarose, carrageenan, guar gum, xanthan gum, guar bean enzyme decomposed product, locust bean gum, polyampholite gel, protein gel using egg white, triblock copolymer, The trapping hydrogel according to any one of claims 1 to 3 , which is derived from a structure selected from a gel, a nanocomposite gel, and a double network gel. The trapping hydrogel according to any one of claims 1 to 4 , wherein the target substance is a decontamination substance or a rare metal. A capturing hydrogel according to any one of claims 1 to 5 , which captures the target substance in a liquid,
A magnetic force accumulating means for accumulating the trapping hydrogel adsorbing the target substance by magnetic force.

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