JP7193153B2 - Material recovery system, scavenging hydrogel, and manufacturing method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a material recovery system, a scavenging hydrogel, and a method for producing the same.

When decontaminating harmful ions from turbid water or muddy water, the solid content mixed in these is previously subjected to coagulation/sedimentation treatment, removal treatment by pressure filtration using a filter press, and the like. After that, an adsorbent is put into turbid water or the like to accumulate harmful ions. However, these processes require large-scale facilities and equipment, large amounts of consumables such as coagulants and precipitants, long processing times, and workers. Moreover, 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 accumulation using magnetism, the present inventors have so far developed a magnetic induction type drug delivery system (Patent Documents 3 and 4) that can deliver anticancer drugs to target sites such as cancer lesions by magnetic force, and We have proposed Prussian blue-supported magnetic nanoparticles that can remove radioactive cesium by magnetic force (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 in soft products such as food-related products such as agar and gelatin, and medical-related products such as contact lenses. It is used in various applications such as materials, highly absorbent materials, and drug release control agents.

For example, inexpensively available glucomannan is a water-soluble dietary fiber (complex polysaccharide) that is indigestible in the intestine and is purified from konjac yam. When this is dissolved in hot water and calcium hydroxide or the like is added, the dietary fiber turns into insoluble dietary fiber and coagulates. This is edible konnyaku, and about 97% of it is water. Since calcium hydroxide is an alkaline agent, konjac is one of the few foods that exhibit alkaline properties. Glucomannan absorbs water and expands about 10 times in 30 minutes and about 150 times in 6 hours. Taking advantage of this property, it is used in a wide range of fields as a gelling agent, quality improver, thickener, moisturizing agent, absorbent, and the like.

WO2015/083840 WO2005/087664 Patent No. 4183047 WO2011/096230 Patent No. 4932054

A technology capable of efficiently recovering decontamination substances such as harmful ions and resources such as rare metals from turbid water such as waste water and muddy water is desired.

The present invention has been made in view of the above background, and its first object is to provide a substance recovery system capable of easily and efficiently capturing a target substance. What is to be done is to provide a scavenging hydrogel suitable for use in the aforementioned material recovery system and a method for producing the same.

In order to solve the problems of the present invention, the present inventors have made extensive studies and found that the problems of the present invention can be solved in the following aspects, thereby completing the present invention.
[1]: A scavenging hydrogel that captures a target substance in a liquid,
magnetic force accumulating means for accumulating the scavenging hydrogel that adsorbs the target substance by magnetic force;
The substance recovery system, wherein the scavenging hydrogel contains an adsorbent that captures the target substance and magnetic powder.
[2]: The adsorbent includes hydrotalcite, activated carbon, calcite, montmorillonite, kaolinite, birnessite, zeolite, illite, vermiculite, pyrophyllite, pearlite, bentonite, cobalt oxide, neodymium oxide, indium oxide, and 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, porous crystal inorganic ion exchanger with niobium oxide skeleton, zirconium phosphate, aluminum oxide, polydextrose, sodium alginate, inulin, carrageenan, cellulose, hemicellulose, The substance recovery system according to [1], which is selected from the group consisting of lignin, chitin, chitosan and pectin.
[3]: Magnetic powder,
containing an adsorbent that captures the target substance in the liquid,
A scavenging hydrogel for material retrieval that can be retrieved by magnetic force.
[4]: The adsorbent includes hydrotalcite, activated carbon, calcite, montmorillonite, kaolinite, birnessite, zeolite, illite, vermiculite, pyrophyllite, perlite, bentonite, cobalt oxide, neodymium oxide, indium oxide, and 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, porous crystal inorganic ion exchanger with niobium oxide skeleton, zirconium phosphate, aluminum oxide, polydextrose, sodium alginate, inulin, carrageenan, cellulose, hemicellulose, The scavenging hydrogel according to [3], which is selected from the group consisting of lignin, chitin, chitosan and pectin.
[5]: Step A of mixing at least magnetic powder, an adsorbent that captures a target substance, a gel component and water;
After the step A, a step B of gelling,
A method for producing a scavenging hydrogel containing the magnetic powder and the adsorbent.
[6]: The adsorbent includes hydrotalcite, activated carbon, calcite, montmorillonite, kaolinite, birnessite, zeolite, illite, vermiculite, pyrophyllite, perlite, bentonite, cobalt oxide, neodymium oxide, indium oxide, and 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, porous crystal inorganic ion exchanger with niobium oxide skeleton, zirconium phosphate, aluminum oxide, polydextrose, sodium alginate, inulin, carrageenan, cellulose, hemicellulose, The method for producing a scavenging hydrogel according to [5], which is selected from the group consisting of lignin, chitin, chitosan and pectin.
[7]: The method for producing a scavenging hydrogel according to [5] or [6], wherein the step A is performed in an alkaline environment.

ADVANTAGE OF THE INVENTION According to this invention, there exists an outstanding effect that the substance collection|recovery system which can capture|acquire a target substance simply and efficiently can be provided. In addition, it has the excellent effect of being able to provide a scavenging hydrogel and a method for producing the same, which can be suitably used in the aforementioned substance recovery system.

FIG. 4 is a flow chart of target substance recovery using the substance recovery system according to the present embodiment. FIG. 1 is a schematic diagram showing an example of a scavenging hydrogel according to this embodiment. 1 is an explanatory diagram of a substance recovery system according to this embodiment; FIG. 1 is an explanatory diagram of a substance recovery system according to this embodiment; FIG. 1 is an explanatory diagram of a substance recovery system according to this embodiment; FIG. FIG. 4 is a schematic diagram showing an example of the upper surface of a silicon plate used when producing a scavenging hydrogel according to the present embodiment. FIG. 2 is a schematic diagram showing an example of the side surface of a silicon plate used when producing a scavenging hydrogel according to the present embodiment.

An example of an embodiment to which the present invention is applied will be described below. It goes without saying that other embodiments are also included in the scope of the present invention as long as they match the gist of the present invention. Also, the size and ratio of each member in the subsequent drawings are for convenience of explanation and do not match the actual ones.

A substance recovery system according to the present embodiment relates to a system that adsorbs a target substance and captures it by magnetic force. More specifically, the present invention relates to a system in which a scavenging hydrogel is introduced into a liquid containing a target substance to be accumulated, the target substance is adsorbed on the scavenging hydrogel, and the adsorbed scavenging hydrogel is recovered by magnetic force. This scavenger hydrogel is a substance recovery gel that contains at least magnetic powder and an adsorbent for capturing a target substance and that can be recovered in a liquid by magnetic force.

Here, the target substance is a target substance to be accumulated, and can be appropriately selected. For example, the target substance can be a decontamination substance such as harmful ions from turbid water such as waste water or muddy water. For example, removal of heavy metals (arsenic, selenium, lead, hexavalent chromium, cadmium, nickel, mercury, cyanide, copper, zinc, manganese, iron, etc.), harmful substances (fluorine, boron, ammonium ions, phosphate ions, nitrite It can be used for removal of ions, n-hexane extracts (mineral oils, animal and vegetable oils), halogen compounds such as chlorine (trihalomethane, dichloromethane, trichlorethylene, tetrachlorethylene, etc.), decontamination of radioactive materials, and resource recovery. Rare metals (the above metals, chromium, tungsten, molybdenum, vanadium, indium, gallium, tantalum, zirconium, niobium, platinum, neodymium, dysbrosium, terbium, cobalt, titanium, scandium, rare earths, yttrium, europium, dysprosium, lanthanum, aluminum, etc.) can be the target material.

FIG. 1 shows a flow chart of the material recovery system according to this embodiment. The liquid applied to this embodiment is not particularly limited as long as it does not deviate from the gist of the present invention. Suitable examples include water-based solvents and water-based solvents partially containing organic solvents, but organic solvent-based solvents are also applicable.
Specific examples include rainwater, groundwater, snowmelt water, seawater, water from rivers, lakes, ponds, water tanks, soil water including contaminated soil, wastewater from construction sites, wastewater from landfill sites, wastewater from tunnels, and pollution. Dispersed water of dust, dispersed water of contaminated dust, washing water for contaminated debris, equipment, machinery, etc., transportation of people, animals, luggage, etc. such as tricycles, bicycles, motorcycles, automobiles, trains, freight cars, ships, airplanes, helicopters, etc. Water used for washing means, water supplied to water supply, water supplied to gray water supply, water collected from sewage system, sewage sludge, purified water sludge, dispersed water of incineration ash containing target substances to be captured, milk, fruit juice, Drinking water containing food such as tea, washing water from harvested tea leaves, etc., breast milk, serum and body fluids of internal survivors, other water/contaminated water/washing water derived from animals, plants, and microorganisms, industrial wastewater, and laboratory wastewater are examples. can. The water supplied to the waterworks and the gray water supply includes, for example, water supplied to each household, industrial water, agricultural water, and water used in forestry, livestock industry, and fisheries.

First, a scavenging hydrogel is added to a liquid containing a target substance to be recovered (Step 1, FIG. 3). A scavenging hydrogel is a gel having a three-dimensional network structure that has both target substance scavenging properties and magnetism. The amount of scavenging hydrogel to be added may be adjusted according to the amount of target substance to be captured in the liquid.

FIG. 2 shows a schematic diagram of a scavenging hydrogel. A scavenging hydrogel 1 according to this embodiment is a bead-like gel, and contains magnetic powder 3 , adsorbent 4 , and water 5 within a three-dimensional network structure 2 . The main component of the scavenging hydrogel is water 5 . The three-dimensional network structure 2 forms the framework of the scavenger hydrogel 1, and known techniques can be used without limitation. For example, polymer chains having a crosslinked structure can be used. The main component of the entrapment 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 scavenging hydrogel is water, but other solvents can be included without departing from the scope of the present invention. For example, the organic solvent may be contained in the range of 30% or less.

The method for producing a scavenger hydrogel 1 according to the present embodiment includes a step A of mixing at least magnetic powder 3, adsorbent 4 that captures a target substance in liquid, a gel component that constitutes three-dimensional network structure 2, and water 5. and a step B of gelling after the step A. The gelation step of step B can be exemplified by, for example, a step of constructing a three-dimensional network structure by heating. However, the present invention is by no means limited to the following manufacturing method.

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

As described above, konjac is obtained by dissolving glucomannan in hot water and adding calcium hydroxide to convert dietary fiber into insoluble dietary fiber and coagulate it. The alkaline agent may be any compound as long as it can achieve the purpose of coagulation, and various compounds including sodium carbonate and the like can be used.

In addition, the polyampholite gel described in WO 2016/027383, K. Haraguchi, et al.,”
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., "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 with 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), 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) Tetra PEG gel and the like can be used.

A double network gel is preferable from the viewpoint of increasing the mechanical strength of the trapping hydrogel. A double network gel is a gel formed by combining two different elements. Examples thereof include a structure composed of a plurality of network structures in which other polymer chains are entwined with a base network structure, and a structure in which a base network structure and other polymer chains are mutually crosslinked. Gels formed by combining three or more different elements are also preferably used.

When using a plurality of polymer chains, each polymer chain 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 and/or the magnetic powder 3, the polymer chain and the adsorbent 4 and/or the magnetic powder 3 have covalent bonds, ionic bonds, hydrogen bonds, complexes, hydrophobic interactions, van der Waals A group or the like having power may be provided. Alternatively, 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, etc. as gel components. Alkali-coagulated konnyaku and glucomannan have high heat resistance and do not dissolve in boiling water, so they are suitable for high-temperature wastewater treatment. On the other hand, agar melts at 70° C. or higher, gelatin at 25° C. or higher, and carrageenan and locust bean gum at 60° C. or higher.

From the perspective of extending the shelf life of konnyaku, odorless konjac from which components such as oxalic acid, calcium oxalate, and amines that cause unpleasant odors (konnyaku odor) have been chemically removed, or konnyaku refined from konjac. It is more preferable to use mannan as a raw material. The purification of konnyaku mannan is described, for example, by Shigen Ogasawara and two others, "A trial of electrophoresis using konnyaku mannan as a support", Biophysical Chemistry, Vol.31, No.3, 1987 (No. 155-158). can be referred to.

The size of the entrapment hydrogel can be selected according to the purpose. Considering dispersibility in a solution and specific surface area, the particle size is preferably in the range of 0.5 to 3 mm. Also, considering the adsorption capacity of the target substance and magnetic adsorption, the range of 1 to 10 mm is preferable. Of course, the size can be appropriately selected depending on 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 enhancing the accumulation efficiency by magnetic force. Moreover, it is more preferably 20 emu/g or more. A higher saturation magnetization is preferable in order to increase the adsorption efficiency to the magnet.

The scavenging hydrogel can be obtained as a lump and crushed with a mixer or the like. In this case, the size distribution and shape (shape of polygonal polyhedron, etc.) can be adjusted depending on the crushing conditions. A shape in which a plurality of polygonal polyhedrons are connected or an irregular shape may be used. Alternatively, it may be produced by a method of extruding through the pores of a device using a yarn konjac making machine or the like. A cylindrical scavenging hydrogel may be produced by cutting a thread-like material, or a scavenging hydrogel with a shape distribution may be obtained by pulverizing it with a mixer or the like. Moreover, it may be designed into various shapes such as a spherical shape by molding during alkali solidification. In the heating step, a method using a mold, and a method of steaming a spherical shape or the like in advance using a steamer or the like can be exemplified.

The magnetic powder 3 may be any powder that satisfies the condition that it is present in the captive hydrogel and has magnetism capable of being accumulated by the magnetic force accumulation means. In addition, a material with high magnetic anisotropy that has high magnetic induction properties even if the particle size is small is preferred. 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, and gadolinium. powder, iron-silicon alloy powder, iron-nickel alloy powder, iron-cobalt alloy powder, iron-silicon-aluminum alloy powder, or nickel-zinc, magnesium-zinc or manganese-zinc ferrite powder, 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, samarium-cobalt alloy, and the like. Also, magnetic toner or the like used in copiers or the like may be used. In order to improve the corrosion resistance of the surface of the magnetic nanoparticles, the surface may be coated with various metal oxides. These particles may be coated with non-magnetic molecules to improve corrosion resistance. For example, polymer-coated magnetic microparticles, resin-coated magnetic microparticles, silica-coated magnetic microparticles, and the like may be used. The magnetic powder 3 is preferably 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 ease of handling, magnetic powder with an average particle size of 1 to 500 μm is preferable, 10 to 200 μm is more preferable, and 20 to 100 μm is even more preferable. . By using magnetic powder having an average particle size of 55 to 100 μm, it is possible to improve rapid magnetic separation, economic efficiency, and safety in handling. Note that nanoparticles are not excluded as the magnetic powder 3 . That is, as the magnetic powder, one type or multiple types of nanoparticles may be used alone or in combination with particles of other sizes. By using nanoparticles, it is possible to increase the specific surface area and enhance the interaction with the three-dimensional network structure. The size of the magnetic powder can be appropriately selected in consideration of the properties of the gel.

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 scavenging hydrogel.

As the adsorbent 4, any known adsorbent can be used without limitation as long as it can capture the target substance to be captured. As the adsorbent 4, hydrotalcite, activated carbon, calcite, montmorillonite, kaolinite, birnessite, zeolite, illite, vermiculite, pyrophyllite, perlite, bentonite, general 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, porous crystal inorganic ion exchanger with niobium oxide skeleton, metal ferrocyanine oxide, titanium hydroxide, zirconium phosphate, aluminum oxide, cobalt oxide, neodymium oxide, indium oxide, silver oxide, cerium oxide, titanium oxide, zirconium ferrite hydrate, illite, mica, smectite Clay minerals in general, known natural and artificial nanoporous materials, polydextrose, sodium alginate, inulin, carrageenan, cellulose, hemicellulose, lignin, chitin, chitosan, pectin and other dietary fibers are effective. Bio-beads to which antibodies are attached are also suitable as adsorbents. Examples of bio-bead products include AnaLig Cr-02 (manufactured by IBC Advanced Technologies). As the amphoteric ion exchange fiber, the technique described in JP-A-2012-030197 can be suitably used.

Examples of molecular label gels include JP-A-2010-71707 (page 20), JP-A-6-229994 (page 19), JP-A-2002-529714 (page 46), and JP-A-2000-126617. JP-A-2001-141710 (page 7), R.M.Izatt, et al, American Laboratory, December, 28C (1994), etc., can be exemplified.

Specific products of amphoteric ion exchange resins include SK1B, SK104, SK110, SK112, UBK08, UBK10, UBK12, PK208, PK212, PK216, PK218, PK220, PK228, SK104H, SK1BH, PK216H, and RCP145H manufactured by Mitsubishi Chemical Corporation. , RCP160M, UBK530, UBK535, UBK530K, UBK535K, UBK555, WK40, WK10, WK11, WK100, SA10A, SA12A, SA11A, NSA100, UBA120 (uniform particle size), PA306S, PA308, PA312, PA316, PA318L, HPA25, HPA25 , 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. In addition, an amphoteric ion exchange resin described in paragraph [0018] of JP-A-2014-184391 can be suitably applied.

Other specific adsorbents that can be used include Duolite ^™ A109D, A113LF, A113MA, A113MB, A113OH, A116, A116LF, A134LF, A161JCL, A162LF, A368MS, A375LF, A378D, A561 manufactured by Sumika Chemtex Co., Ltd. , A568, C20J, C20JH, C20LF, C20LFH, C255LFH, C26A, C26CH, C26H/2095, C26TRH, C433LF, C467, C476, C548, C747UPS, ES371N, PWA7, PWA7, S4LF, S874, S876, S877, S878 , SC200, SC300, SC400, SC500, SC600, UP5000, UP6000, UP7000, XAD761, etc., Imac ^TM HP1220Na, HP333, HP555, etc., Sumikaion ^TM MB77, S8TR, etc., DuoJet ^TM A1130CL, A1160CL, C2255H, etc., Sumikirate ^TM MC250, MC600H, MC700, MC760, MC760CA, MC770, MC850, MC900, MC960, etc. Kiles Pearl ^TM CH112, CH351, CH400, SA110, SB130, SB230, WB150, etc. manufactured by Chelest Co., Ltd. Chelest Fiber ^TM GRY-L, GRY-LW, GRY-HW, IRY, IRY-L, IRY-LW, IRY-HW, A100, A103S, A110, A111S, A133S, A170/4675, A200, A300, A400, A500, A501P, A502PS, manufactured by Purolite Co., Ltd. A503, A510, A520E, A532E, A600, A830W, A845, A847, A850, A860, A870, Bromide ^PlusTM , C100, C100E, C100EAg, C100x10, C100x12, C100x16MBH, C104, C106, C115E, C115E, C115E, C115E, C160, FerrIXTM ^A33E , MB400, MB378LT, MB478LT, MN102, MN150, MN170, MN202, MN250, MN270, MN500, MN502, NRW1000, NRW1600, NRW2400, NRW600, NRW5010, NRW1600/NRW600, NRW1600L i7/NRW600, PAD300, PAD350, PAD400, PAD500, PAD550, PAD600, PAD610, PAD700, PAD900, PAD910, PAD950, ^PurogoldTM A193, S106, S108, S910, S914, S920, S930/4922, S950, S950, S950, S950 SGC650, SSTC60, SSTC60H, SSTC80DL, SSTC104, SSTA63, SSTA64, etc. Amberlight ^TM 200CT, 252, FPC3500, FPX66, IR120B, IR124, IRA67, IRA96SB, IRA98, IRA400J, IRA402BL, IRA404J, IRAAIR410J, manufactured by Organo Corporation , IRA458RF, IRA478RF, IRA743, IRC76, IRC747, IRC747UPS, IRC748, IRA900J, IRA904, IRA910CT, IRA958, XAD-2, XAD4, XAD7HP, XAD1180N, XAD2000, XE583, Ambar-Jet ^TM 1020, 1024, 2024, 1024 4400, 4010, AmberlystTM ^15DRY , 15JWET, 16WET, 31WET, 35WET, A21, MB-1, MB-2, MB-4, EG-4A-HG, EG-5A-HG, ESP-1, ESP- 2nd class, Kyoward ^TM 200, 500, 600, 700, etc. manufactured by Kyowa Chemical Industry Co., Ltd., KW-2000 ^TM , etc., READ-As, READ-B, READ-B (MC), READ manufactured by Nihonkaisui Co., Ltd. -B(LC), READ-Cs(Co), READ-Cs(Fe), READ-F, READ-F(HG), READ-F(PG), READ-Sb, READ-Sr1, READ-Sr2, READ-Sr3, A-19S, AC-1, CAMZ, CAMZ-S, CAMZ-W, CAPA-CT, MB4, TKS105, Ash Claw A, Ash Claw S, etc. of Amron Co., Ltd., Astec Co., Ltd. MP-C, MP-CC, MP-HC, MP-S, etc. Catenatio AB, AB-c, AB-e, AB-L, etc. manufactured by Nippon Safety Co., Ltd. Nova, etc. manufactured by Mizoguchi Business Co., Ltd. I can give an example.

In addition, the adsorbent disclosed in JP-A-2016-7601 can also be suitably used. Moreover, as a suitable adsorbent for rare metal recovery, the adsorbents described in the following documents can be exemplified. In other words, "development of in-factory recycling technology for nickel-plated wastewater", 2010-2011, Fukuoka Industry and Science and Technology Promotion Foundation Industry-Academia-Government Joint Research and Development Project Research Result Report, [January 30, 2018 Japan search], Internet <URL: http://www.ist.or.jp/randd/seikahoukokusyo/H23-2.pdf>, Tetsuo Katsura, “Separation analysis of copper, nickel and cobalt by ion exchange resin Utilization of exchange resin" (2nd report) Analytical Chemistry, Vol. In addition, Sumichelate MC960 (manufactured by Sumika Chemtex Co., Ltd.) as a chelate for adsorbing indium, Sumichelate MC900 (manufactured by Sumika Chemtex Co., Ltd.) as a chelate for adsorbing gallium, and Sumichelate MC700 (manufactured by Sumika Chemtex Co., Ltd.) as an adsorbent for copper, nickel and zinc. (manufactured by Ka Chemtex Co., Ltd.) and the like are suitable. In addition, when chromium is the target substance, a method using an ion-exchange resin is suitable (reference: "Detoxification treatment of hexavalent chromium", [searched on January 30, 2018], Internet <URL: https ://jp.tech.misumi-ec.com/categories/surface_treatment_technology/st01/c0027.html> Regarding terbium adsorption chelate, Setsu Kobayashi, 5 others, "Waste by chelate resin containing diethylenetriamine-polycarboxylic acid Concentration and recovery of terbium in the medium "Journal of the Japan Ion Exchange Society/vol.3 (1992) No.2" can be exemplified.

Further, regarding adsorbed chelates of uranium, gallium, indium, germanium, molybdenum, vanadium, gold, platinum, palladium, silver, copper, trivalent chromium, hexavalent chromium, cobalt, cerium, plutonium, zinc and radium, Masahide Hirai, Reference can be made to "Chelate resin for recovering trace metals", Organic Synthetic Chemistry, Vol. 42, No. 11, 1984, p. 1005. For manganese and lanthanum, DIAION ^™ CR series manufactured by Mitsubishi Chemical Corporation is suitable as a chelate resin. As for tungsten, tantalum, and titanium, refer to Kakuzo Tada and one other person, "Determination of Cobalt, Titanium, and Tantalum in Ultra-high Humidity Alloys by Anion Exchange Separation", Analytical Chemistry, Vol. 12 (1963) No. 9. The described adsorbents can be applied.

Furthermore, niobium- and zirconium-adsorbing ion-exchange resins are suitable. In addition, the adsorbent described in Koichi Oguma and one other person, “Development of Iron and Steel Trace Component Analysis by Separation and Concentration”, Tetsu to Hagane, Vol. 100, 2014, No. 7, is suitable. As the rhodium adsorbent, the adsorbent described in JP-A-10-17953 can be preferably used.

As a 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 to exchange sodium ions for hydrogen ions, and Rb ₈ Nb ₂₂ O ₅₉ for acid-treating to exchange rubidium ions for hydrogen ions, followed by water A lithium-type adsorbent obtained by contacting a lithium oxide solution to exchange the hydrogen ions into lithium ions, a proton-type adsorbent obtained by acid-treating Rb ₁₀ Zr ₂ Nb ₂₀ O ₅₉ to exchange rubidium ions into hydrogen ions, and Rb ₁₃ Zr. A proton-type adsorbent obtained by acid-treating _{5Nb 17} O ₅₉ to exchange rubidium ions into hydrogen ions, a proton-type adsorbent obtained by acid-treating Rb ₁₀ Ti ₂ Nb ₂₀ O ₅₉ to exchange rubidium ions into hydrogen ions, or A proton-type adsorbent obtained by acid-treating Rb ₁₀ Sn ₂ Ta ₂₀ O ₅₉ to replace rubidium ions with hydrogen ions can be exemplified.

It should be noted that the specific examples of the above-mentioned adsorbents are examples, and the present invention is not limited to these. The adsorbent 4 may be in any form as long as it can be contained in the scavenger hydrogel, and is not particularly limited. For the purpose of increasing the surface area of the adsorbent 4, pulverization processing may be performed using a pulverizer X-TREME manufactured by Waring Co., Ltd., or the like. As the grinder, for example, various grinders manufactured by 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, about 0.005 to 0.5 times the mass of the scavenging hydrogel.

Spatial movement of the adsorbent 4 and/or the magnetic powder 3 is constrained 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 within a range that does not hinder the entrance and exit of the substance and ions to be adsorbed.

When the target substance is, for example, heavy metals (arsenic, selenium, lead, hexavalent chromium, cadmium, etc.), common iron powder or iron oxide having both functions of adsorbent and magnetic powder may be used. In the case of trapping these heavy metals, by using hydrotalcite in combination with iron powder and iron oxide, it is possible to further improve the accumulation efficiency. Moreover, by adding hydrotalcite to these heavy metals, there is also the advantage that fluorine and boron can be removed.

When iron powder is used, there is a problem that it is easily corroded when it gets wet and cannot be magnetically adsorbed, separated, and collected. Therefore, when iron powder is used as the magnetic powder 3, it is preferable to use it in an alkaline environment. From this point of view, a combination of an alkaline adsorbent and a magnetic powder is more preferable. A suitable example is a combination of hydrotalcite and iron powder. Since hydrotalcite uses a strong alkali such as calcium hydroxide in its manufacturing process, hydrotalcite exhibits alkalinity when dispersed in water. Therefore, the hydrogel containing hydrotalcite and iron powder has the effect of remarkably increasing the stability. As the hydrotalcite, natural hydrotalcite or commercially available hydrotalcites may be used.

Moreover, as a method of preventing iron powder from rusting, the hydrogel may be stored in an alkaline aqueous solution. Also suitable is a method in which the liquid for recovering the target substance is made into an alkaline environment.

The stability of the iron powder can be enhanced by using hydrotalcite, but when using an adsorbent that does not exhibit alkalinity, a pH adjuster is added to make the scavenging hydrogel alkaline. You may adjust it suitably. In addition to being effective in preventing iron powder from rusting, an alkaline environment is suitable for coagulating konjac, for example. However, since iron ions are not preferable for coagulation of konjac, it is preferable to remove iron ions in order to promote coagulation.

Specific examples of metal ferrocyanides include metal ferrocyanides 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 minerals, and pectin are particularly effective. In addition, polydextrose, sodium alginate, inulin, carrageenan, cellulose, hemicellulose, lignin, chitin, chitosan, etc. are also effective. Prussian blue is effective for removing thallium as well as cesium. The adsorbent may be appropriately selected according to the radioactive substance to be captured.

The adsorbent 4 may be subjected to a treatment such as heat treatment or pressure treatment, if necessary. For example, zeolite and the like can be improved in cesium adsorption capacity by heat treatment or pressure heat treatment. If it is desired to capture multiple types of radioactive substances, different types of adsorbents may be introduced into the coated magnetic nanoparticles, or multiple capturing hydrogels may be used. Titanium hydroxide is particularly effective when the target substance to be captured is strontium.

In the case of particles having both magnetic performance and adsorptivity, the magnetic powder 3 and the adsorbent 4 may be made of the same particles. Composites of magnetic powder and adsorbents, such as magnetic hydrotalcite composites, are also preferably used. The complexes may be bound to each other or unbound. As a bonding method, known bonding methods such as covalent bond, ionic bond, intermolecular force, hydrogen bond, and complex formation can be applied. By binding the magnetic powder 3 and the adsorbent 4 to each other, the magnetic powder 3 and the adsorbent 4 can be firmly held in the hydrogel due to the additive and synergistic effects of the indirect bonding of 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 contained within the sequestering hydrogel (within the network of the three-dimensional mesh structure), bound to the surface, or a combination thereof. A mode is also suitable in which the magnetic powder is incorporated inside the scavenger hydrogel and the adsorbent 4 is bound to the surface of the scavenger hydrogel. From the viewpoint of preventing the magnetic powder 3 and the adsorbent 4 from falling off from the captive hydrogel, it is preferable that they are incorporated inside. By preventing the magnetic powder 3 from flowing out of the hydrogel, the reliability of magnetic recovery can be enhanced. Alternatively, a hydrogel containing only a magnetic powder and a hydrogel containing only an adsorbent may be separately prepared, and a scavenging hydrogel may be used in which these are firmly bound together.

In addition, depending on the type of target substance, the magnetic powder alone and the scavenging hydrogel may be used together as appropriate. For example, in the case of wastewater with a high arsenic content and a small amount of fluorine and/or boron, a large amount of inexpensive iron powder is used to selectively remove arsenic, and fluorine and/or boron, which cannot be removed with iron powder, is removed. By using a small amount of scavenging hydrogel for boron and boron, it is possible to efficiently treat waste water at a low cost. By such a method, it is possible to efficiently recover the target substance at a low cost according to the characteristics of the target substance.

Next, the target substance to be captured is captured by the scavenging hydrogel 1 put into the liquid containing the target substance to be recovered (Step 2, see FIG. 4). If necessary, the liquid may be stirred, dispersed, heated, cooled, or the like. In addition, when recovering rare metals and the like, additives such as liquid pH adjusters can be appropriately added in order to promote ionization of the metals.

It is sufficient that the target substance can be adsorbed on the scavenging hydrogel, and any capture form is acceptable. Any of a mode in which the target substance is adsorbed on the surface of the scavenging hydrogel, a mode in which the target substance is adsorbed inside the scavenging hydrogel, and a combination thereof may be used. From the viewpoint of strong capture, it is preferable to incorporate the target substance into the three-dimensional network structure holding the adsorbent (for example, Shigen Ogasawara, Attempts of electrophoresis", Biophysical Chemistry, Vol.31, No.3, 1987 (No. 155-158), etc.).

After that, the captive hydrogel 1 is accumulated from the liquid by the magnetic force accumulation means. Next, after the magnetic force accumulating means is separated from the liquid, the magnetic field generation is turned off to recover the scavenging hydrogel to be captured (Step 3, see FIG. 5). That is, the trapping hydrogel 1 trapping the target substance to be trapped is accumulated and collected by the magnetic force of the magnetic force accumulation means. According to such a method, the target substance to be captured can be recovered simply and efficiently. The magnetic force accumulating means may be brought into contact with or close to the outer wall of the container without being immersed in the liquid, thereby accumulating, separating and recovering the captive hydrogel 1 .

From the viewpoint of improving the ion adsorption efficiency, it is advantageous to make the size of the adsorbent as small as possible because the reaction surface area per unit weight increases. Disadvantage is that processing takes time. According to the substance recovery method according to the present embodiment, since an adsorbent with a large specific surface area and a small size and a magnetic particle are supported on the scavenger hydrogel, high adsorption capacity and rapid recovery capacity can be achieved at the same time. .

A known technique can be appropriately used as the magnetic force accumulation means. Appropriate magnetic force accumulation means may be used depending on 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. Also, 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, it is possible to use a device having a magnetic force ON/OFF function and a moving mechanism. It is also possible to control ON/OFF of the magnetic force by the permanent magnet and the shield means. Furthermore, the scavenging hydrogel 1 is first recovered using a permanent magnet or the like, then the scavenging hydrogel 1 is recovered using a stronger electromagnet, superconducting magnet, or the like, and then the magnetic force of the electromagnet, superconducting magnet, or the like is turned off. Thus, it is also possible to separate the scavenging hydrogel 1 .

A compact magnetic separator is also suitably used. For example, MDK-4(-U), MDK-6(-U), MDK-8(-U), MDK-12(-U), MDK-18(-U), MDK-24(-U), As mentioned above, products manufactured by Noritake Co., Ltd., etc. can be suitably used. In addition, Diabar DB1, DB2, DB3 manufactured by Daika Co., Ltd., 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), Diarotor DRP-200, DRP-250, DRP-300, DRP-400, DRP-500, Dia Cannon 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 Magnetic separators such as -60, DSH-70, DSH-80 and DSH-100 are also preferably used.

When a permanent magnet is used, ferrite, Ne--Fe--B alloy, and samarium-cobalt alloy can be mentioned as examples, although not particularly limited. A Ne--Fe--B alloy is preferred when a strong magnetic force is required. Even when an electromagnet, a superconducting magnet, or the like is used as the magnetic force accumulating means, it is effective to provide a shielding means in order to impart directivity to the lines of magnetic force of the magnet. In order to properly protect the magnetic force accumulation means from corrosion due to seawater, the magnets and the like are sealed in the casing as required.

After that, the concentration of the target substance in the liquid 20 is measured again by a sensor, ICP-MS, Lanthanum Alizarin Complexone absorption photometry, or the like (Step 4). Then, when it is determined that recovery of the target substance to be captured is necessary, the above Steps 1 to 3 are repeated. If recovery of the target substance to be captured is determined to be unnecessary, the task of recovering the target substance to be captured is terminated. Note that the process of step 4 may be performed on the supernatant of the liquid after step 2, and then step 3 may be performed. In that case, steps 1 and 2 are repeated when recovery of the target substance is insufficient.

Since most of the scavenging hydrogel is water, it can be treated by incineration, filter press dehydrator ("filter press that pressurizes sludge in the filtration chamber", [searched on February 9, 2018] Internet <URL: https:/ /kcr.kurita.co.jp/wtschool/052.html>), belt press dehydrator ("Mechanism of belt press and screw press", [searched on February 9, 2018] Internet <URL: https://kcr .kurita.co.jp/wtschool/050.html>, screw press dehydrator, vacuum dehydrator ("Mechanism and usage of vacuum dehydrator", [searched on February 9, 2018] Internet <URL: https:/ /kcr.kurita.co.jp/wtschool/053.html>), Centrifugal dehydrator (“Centrifugal dehydrator that separates using centrifugal force”, [searched February 9, 2018], Internet <URL: https (http://kcr.kurita.co.jp/wtschool/051.html>) The incineration residue becomes magnetic powder such as iron oxide and adsorbents such as hydrotalcite. Since cattle rumen fluid, which is livestock waste generated during meat processing, contains cellulolytic enzymes, it can be decomposed when a scavenging hydrogel is produced from raw materials composed of components that decompose in the rumen fluid. An example of such a hydrogel is konjac, which can be reused because the hydrotalcite and iron powder can be separated from each other by magnetic force after these treatments.

Different types of magnetic powders 3 can be used in combination with the scavenging hydrogel 1 . Similarly, the adsorbents may be used singly or in combination of two or more. In addition to using one type of scavenging hydrogel, multiple types of scavenging hydrogels can be used in combination. A plurality of target substances can be collected at once by using a plurality of them together. Therefore, there is an advantage that it can be collected with high efficiency, especially in the case of contaminant removal.

When recovering the target substance to be captured from muddy water, turbid water, and contaminated soil (hereinafter referred to as muddy water, etc.), a scavenging hydrogel is added to the mixed liquid containing muddy water, etc. or contaminated soil. Prior to this, it is desirable to collect the magnetic material contained in the muddy water or the mixed liquid of the contaminated soil in advance by magnetic separation. As a result, it is possible to efficiently capture and recover the target substance to be captured by the scavenging hydrogel.

The material recovery system according to this embodiment is not limited to the example of this embodiment described above, and various modifications are possible. For example, a material recovery system may include a liquid inlet, a scavenging hydrogel and liquid mixing tank, a magnetic scavenging hydrogel recovery tank, and a filtration device. For example, as the liquid is injected from the liquid inlet, the captive hydrogel set in advance according to the amount of liquid to be injected, the degree of contamination, etc. is injected into the captive hydrogel mixing tank. Then, the liquid and the scavenging hydrogel are thoroughly mixed in the scavenging hydrogel mixing tank. After that, the liquid containing the scavenging hydrogel is moved to the scavenging hydrogel recovery tank by magnetic force, and the scavenging hydrogel is recovered by the magnetic accumulation means. After that, it is passed through a filtering device, if necessary depending on the application. Such a substance recovery system, which is an object to be captured, can be suitably used, for example, as a water purifier, a water and sewage treatment facility, a clean water treatment system such as an apartment building, or a wastewater treatment facility in a factory.

The amount of water may be reduced or removed during storage and transportation of the scavenging hydrogel. As a method for reducing or removing moisture, for example, by mixing sugars such as sucrose, glucose and maltose, salts such as sodium chloride and calcium chloride, alcohols such as ethanol and glycerin with the scavenging hydrogel, the permeation can be achieved. There is a method using the pressure difference. Alternatively, water may be removed by natural drying by standing, drying by hot air/low humidity air/low pressure/vacuum, freeze-drying, or forced drying by mixing a desiccant such as silica gel or powdery hydrotalcite. At the time of use, the scavenging hydrogel can be regenerated by soaking it in water to swell it.

The material recovery system according to the present embodiment is excellent in that it can directly magnetically separate harmful ions from turbid water such as wastewater or muddy water without separating liquid and solid content, even in an environment where suspended solids coexist. have the same effect. In addition, according to the system of this embodiment, the target substance to be captured can be collected by turning ON/OFF the magnetic force accumulating means, so that the operability and efficiency are high. Moreover, the magnetic force accumulating means has the excellent advantage that it can be used many times. It is also excellent in that there is no need to introduce special equipment or the like.

The scavenging hydrogel according to this embodiment can be suitably used in the substance recovery system described above, but is not limited to use in the system described above.

<Example>
EXAMPLES The present invention will be described in more detail below with reference to examples. However, the present invention is by no means limited to 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 thoroughly mixed in a polypropylene 15 mL centrifuge tube and allowed to stand for 1 hour. After that, it 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 this mixture and mixed well. After standing for 2 weeks and observing, no rust was observed visually.

(Example 2)
3 grams of KW-2000 and 30 mL of distilled water were thoroughly mixed in a polypropylene 50 mL centrifuge tube, and the supernatant was collected after standing for 24 hours.

(Example 3)
0.25 g of hydrotalcite KW-2000 (manufactured by Kyowa Chemical Industry Co., Ltd.) and 12.5 mL of distilled water were thoroughly mixed in a polypropylene 15 mL centrifuge tube and allowed to stand for 1 hour. After that, it was confirmed to be 11.8 by pH measurement. Then, 1.5 g of iron powder RK-200 (manufactured by DOWA IP Creation Co., Ltd.) was added and 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 gradually added to 15 mL of distilled water heated to 75° C. and thoroughly stirred 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. Attach the mixture to a 20 mL syringe with a luer cap, put it in a container that prevents hot water from entering, and heat it in a stainless steel beaker at 75 ° C. for 30 minutes to form a hard gel-like mass. got

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

(Example 7)
50 mL of distilled water was added to the gel-like mass obtained in Example 5, and crushing was performed for 1.5 seconds x 3 times using a mixer SKR-T250 (manufactured by Tiger Co., Ltd.). A piece of the size of . Moisture was removed by sieving through a 0.25 mm stainless steel mesh.

(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 the occurrence of rust.

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

(Example 10)
Selenium standard solution (manufactured by WAKO Pure Chemical Industries Co., Ltd.), fluoride ion standard solution (manufactured by Kishida Chemical Co., Ltd.), and boron standard solution (manufactured by Kishida Chemical Co., Ltd.) are added to and mixed with distilled water. Selenium concentration: 1.2 mg/L, fluorine: 3.2 mg/L, and boron: 3.2 mg/L were adjusted to prepare simulated contaminated water.

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

(Example 12)
For the simulated contaminated water after the above process, selenium and boron were quantified by ICP-MS, and fluorine was quantified by Lanthanum Alizarin Complexone spectrophotometry. Concentration: 0.1 mg/L, fluorine: 1.6 mg/L, boron: 1.9 mg/L, confirming high trapping efficiency.

(Example 13)
0.2 g of hydrotalcite KW-2000 (manufactured by Kyowa Chemical Industry Co., Ltd.) and 10 mL of distilled water were thoroughly mixed in a polypropylene 15 mL centrifuge tube and allowed to stand for 1 hour. After that, it 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 and mixed well, and left 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 Laboratory Co., Ltd.) was added little by little to 10 mL of distilled water heated to 75° C. and thoroughly stirred 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. Attach the mixture to a 20 mL syringe with a luer cap, put it in a container that prevents hot water from entering, and heat it in a stainless steel beaker at 75 ° C. for 30 minutes to form a hard gel-like mass. 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 the occurrence of rust.

(Example 17)
50 mL of distilled water was added to the gel-like mass obtained in Example 15, and crushing treatment was performed for 1.5 seconds x 3 times using a mixer SKR-T250 (manufactured by Tiger Co., Ltd.). A piece of the size of . Moisture was removed by sieving through a 0.25 mm stainless steel mesh.

(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 the occurrence of rust.

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

(Example 20)
To the washed gel from Example 17 was added 10 grams of glucose and mixed well. Some of the water in the gel came out of the gel, and the volume of the gel decreased. It was confirmed that no change in appearance including color tone such as rusting occurred even after 2 weeks of storage after removing the water that had come out.

(Example 21)
30 mL of water was added to the gel obtained in Example 20 and mixed for 24 hours to recover the reduced volume of the gel. It was confirmed that no change in appearance including color tone such as rust occurred, and that the particles 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, which may be advantageous for storage and transportation.

(Example 22)
0.75 g of odorless konjac powder (manufactured by Fuji Fine Research Institute) 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. A soft gel was obtained by stirring vigorously for a minute.

(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. Attach the mixture to a 20 mL syringe with a luer cap, put it in a container that prevents hot water from entering, and heat it in a stainless steel beaker at 75 ° C. for 30 minutes to form a hard gel-like mass. got

(Example 24)
50 mL of distilled water was added to the gel-like mass obtained in Example 23, and crushing was performed for 1.5 seconds x 3 times using a mixer SKR-T250 (manufactured by Tiger Co., Ltd.). A piece of the size of . Moisture was removed by sieving through a 0.25 mm stainless steel mesh.

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

(Example 26)
To 20 mL of the simulated water of Example 25, 3 grams of the washed, pulverized hydrotalcite/activated carbon/iron powder-dispersed scavenging hydrogel (konjac) gel obtained in Example 24 was added, and Stirring was performed for 3 hours at a speed of 15 rpm using a tube rotator TR-350. After magnetic separation, it was confirmed that it could be recovered within 2 seconds with a neodymium magnet of about 0.5 tesla. On the other hand, since the simulated polluted water after the treatment turned almost colorless and transparent, it was confirmed that methylene blue was removed from the simulated polluted water.

(Example 27)
A three-way stopcock was attached to a 10 mL syringe (A) with a luer lock tip made of polypropylene from which the piston was removed. After closing the three-way 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 pressing the piston so that the tip of the piston was positioned at the 10 mL scale. The hydrotalcite was dispersed in the water inside the syringe (A) by repeating inversion mixing while the position of the piston was fixed.

(Example 28)
A 10 mL syringe (B) with an empty polypropylene luer lock tip was connected to another part of the three-way stopcock to which the syringe (A) of Example 27 was connected. By gradually opening the three-way stopcock, the space between the syringe (A) and the syringe (B) was opened. While keeping the tip of the syringe (A) facing upward, pull out the piston of the empty syringe (B) to remove most of the air inside the syringe (A) while being careful not to suck in the hydrotalcite-dispersed water. After draining, the three-way stopcock on the side of the syringe (A) containing the hydrotalcite-dispersed water was closed. The air-sucked syringe (B) was removed.

(Example 29)
A three-way stopcock was attached to a 10 mL syringe (C) with a luer lock tip made of polypropylene from which the piston was removed. After closing the three-way stopcock, 0.021 g of activated carbon powder (manufactured by WAKO Pure Chemical Industries, Ltd.) and 1 mL of distilled water were put into the syringe (C). Powdered activated carbon was sealed inside the syringe (C) by pressing the piston so that the tip of the piston was positioned at the 10 mL mark. The powdered activated carbon was dispersed in water inside the syringe (C) by repeating inversion mixing while the position of the piston was fixed.

(Example 30)
A 10 mL syringe (D) with an empty polypropylene luer lock tip was connected to another part of the three-way stopcock to which the syringe (C) of Example 29 was connected. By gradually opening the three-way stopcock, the space between the syringe (C) and the syringe (D) was opened. With the tip of the syringe (C) pointing upwards, remove most of the air inside the syringe (C) by withdrawing the piston of the empty syringe (D), taking care not to suck in the water in which the powdered activated carbon is dispersed. After removing the water, the three-way stopcock on the side of the syringe (C) containing the water in which the powdered activated carbon was dispersed was closed. Remove the air aspirated syringe (D).

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

(Example 32)
A three-way stopcock 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 three-way 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 pressing the piston so that the tip of the piston was positioned at the 10 mL scale. With the tip of the syringe (E) facing upward, the three-way stopcock was opened, and most of the air inside the syringe (E) was removed by pushing the piston gradually while being careful not to stir up the iron powder. .

(Example 33)
A three-way stopcock was attached to a 10 mL syringe (F) with a luer lock tip made of polypropylene from which the piston was removed. After closing the three-way stopcock, 0.375 g of odorless konjac powder (manufactured by Fuji Fine Research Institute) was put into the syringe (F). Odorless konjac powder was sealed inside the syringe (F) by press-fitting and attaching the piston so that the tip of the piston was positioned at the 10 mL scale. With the tip of the syringe (F) facing upward, open the three-way stopcock, and while being careful not to stir up the odorless konjac powder, push the piston gradually to remove most of the air inside the syringe (F). rice field.

(Example 34)
A three-way stopcock was attached to a 10 mL syringe (G) with a luer lock tip made of polypropylene from which the piston was removed. After closing the three-way stopcock, 5 mL of distilled water heated to 75° C. was put into the syringe (G). Warmed distilled water was sealed inside the syringe (G) by press-fitting and attaching the piston so that the tip of the piston was positioned at the 10 mL scale. While fixing the position of the piston, turn the tip of the syringe (G) upward, open the three-way stopcock, and push the piston gradually so that the distilled water does not splash out, removing most of the air inside the syringe (G). pulled out.

(Example 35)
A syringe (G) filled with warm distilled water prepared in Example 34 was connected to another part of the three-way stopcock connected to the syringe (F) filled with odorless konjac powder prepared in Example 33. After opening the three-way stopcock between syringe (F) and syringe (G), alternately compress each piston and mix well the contents of syringe (F) and syringe (G) to produce 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 stopcock connected to the syringe (G) filled with gel-like konjac prepared in Example 35. After opening the three-way stopcock between syringe (G) and syringe (E), alternately compress each piston and mix the contents of syringe (G) and syringe (E) well to add iron powder 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 containing dispersed hydrotalcite/powder activated carbon prepared in Example 31 at another part of the three-way stopcock connected to the syringe (G) filled with gelatinous konjac in which iron powder was dispersed prepared in Example 36. (A) connected. After opening the three-way stopcock between syringe (G) and syringe (A), each piston was alternately compressed to mix the contents of syringe (G) and syringe (A) well. Eventually the entire contents of both syringes were transferred into syringe (A). It was confirmed that the alkali component of hydrotalcite reacted with konjac to increase the hardness of the gel. The syringe (G) and 3-way stopcock were removed.

(Example 38)
The hydrotalcite/activated carbon/iron powder-dispersed konjac gel prepared in Example 37 was cut into a circle with a diameter of 13 cm from the tip of the syringe (A), and the surface was silicon-coated aluminum foil (Cooker (registered trademark) manufactured by Asahi Kasei Home Products Co., Ltd. )), ejected and placed on top. At that time, the tip of the syringe was gradually moved on the aluminum foil so as to draw a line, and the piston was gradually pushed out. Specifically, the konjac gel was spread while adjusting the movement speed of the tip of the syringe and the extrusion speed of the piston so that the konjac gel would maintain continuity and be as smooth as possible without overlapping, forming a cylindrical shape with a diameter of about 1.5 mm. Placed on aluminum foil.

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

(Example 40)
By cutting the konjac gel prepared in Example 39 into small pieces with stainless steel scissors, cylindrical hydrotalcite/activated carbon/iron powder dispersed scavenging hydrogel ( Konjac gel) particles were obtained. The entrapping hydrogel (konjac gel) particles were transferred to a polypropylene 50 mL tube, capped and stored to prevent 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 the occurrence of rust.

(Example 42)
To 25 mL of the simulated water of Example 10, add 2.5 g of the hydrotalcite/activated carbon/iron powder-dispersed scavenging hydrogel (konnyaku) gel obtained in Example 40, and use a tube rotator TR-350 to Stirring was performed for 24 hours at a speed of 15 revolutions/minute. After magnetic separation, it was confirmed that it could be recovered within 2 seconds with a neodymium magnet of about 0.5 tesla.

(Example 43)
Selenium, boron and fluorine were quantified by the same method as in Example 12 for the simulated contaminated water after the above steps. Selenium concentration: 0.1 mg/L, fluorine: 1.2 mg/L, boron : 1.6 mg/L, confirming high capture efficiency.

(Example 44)
6 and 7 show 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 (vertical)×45 mm (horizontal)×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 put on top of the silicon rubber plate 50 without a hole, and the silicon rubber plate 40 and the silicon rubber plate 50 were brought into close contact with each other by pressing.

(Example 45)
A female luer fitting made of polypropylene (inner diameter 1.5 mm; VRF106, sold by Isis Co., Ltd.) was connected to the tip of the syringe (A) filled with konjac gel in which hydrotalcite/activated carbon/iron powder prepared in Example 37 was dispersed. Insert the tip of the female luer fitting into the hole of diameter 1.5 mm of the silicon rubber plate 40 prepared in Example 44 by about 0.5 mm, and slowly pour the konjac gel onto the bottom surface of the silicon rubber plate 40 (silicon rubber plate 50 The top surface of the tube) was filled to a height of 1.5 mm, ie, to the tip of the inserted luer fitting.

(Example 46)
After adding tap water to about 80% of the height of a steaming pot for a steamer with a diameter of 15 cm, the pot was placed on a gas range and heated over medium heat until boiling. The silicon rubber plate 40 and the silicon rubber plate 50 filled with hydrotalcite/activated carbon/iron powder-dispersed konjac gel prepared in Example 45 and placed in close contact with each other were transferred into a steamer with a diameter of 15 cm and covered with a lid. A steamer was set in a steaming pot, and boiling water was added to the steaming pot as needed to prevent empty heating, and boiling was continued for 15 minutes. After the fire was extinguished, the mixture was cooled as it was for 5 minutes.

(Example 47)
The silicon rubber plate 40 and the silicon rubber plate 50 prepared in Example 46 were taken out and separated by peeling off the silicon rubber plate 40 and the silicon rubber plate 50 . The end of a cylindrical resin rod with a diameter of about 1.5 mm is pressed against the scavenging hydrogel (konjac gel) in which heated hydrotalcite/activated carbon/iron powder is dispersed and remains in the hole of the silicon rubber plate 40. The gel was then extruded and collected in a polypropylene 50 mL tube to prevent drying. On the other hand, the heated gel adhering to the surface of the silicon rubber plate 50 was peeled off using tweezers and collected in a polypropylene 50 mL tube to prevent 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 the occurrence of rust.

(Example 49)
To 25 mL of the simulated water of Example 10, add 2.5 g of the hydrotalcite/activated carbon/iron powder-dispersed scavenging hydrogel (konnyaku) gel obtained in Example 47, and use a tube rotator TR-350 to Stirring was performed for 24 hours at a speed of 15 revolutions/minute. After magnetic separation, it was confirmed that it could be recovered within 2 seconds with a neodymium magnet of about 0.5 tesla.

(Example 50)
Selenium, boron and fluorine were quantified by the same method as in Example 12 for the simulated contaminated water after the above steps. Selenium concentration: 0.1 mg/L, fluorine: 1.1 mg/L, boron : 1.5 mg/L, confirming high capture efficiency.

(Example 51)
Put 4 grams of konjac powder (purchased from Kitamura liquor store) in a 50 mL polypropylene tube, add 20 mL of ethanol aqueous solution (50% v / v), tighten the cap, attach it to the tube rotator TR-350, and rotate 15 times / Stirring was carried out for 12 hours at a speed of 10 minutes.

(Example 52)
The tube of Example 51 was removed from the tube rotator TR-350, 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 ethanol aqueous solution (50% v/v) was added, the cap was tightened, the tube rotator TR-350 was mounted, and stirring was performed at a speed of 15 rpm 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, the cap was opened, and only the supernatant was carefully removed using a 5 mL pipette. Again, 20 mL of ethanol aqueous solution (75% v/v) was added, the cap was tightened, the tube rotator TR-350 was mounted, and the mixture was stirred at a speed of 15 rpm for 12 hours.

(Example 54)
The tube of Example 53 was removed from the tube rotator TR-350, allowed to stand for 15 minutes, the cap was opened, and only the supernatant was carefully removed using a 5 mL pipette. 8 mL of absolute ethanol was added again, the cap was tightened, the tube rotator TR-350 was mounted, and stirring was performed for 15 minutes at a speed of 15 revolutions/minute. This operation was repeated once more.

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

(Example 56)
Instead of the odorless konjac flour used in Example 33, the ethanol-treated konjac flour obtained in Example 55 was used. That is, a three-way stopcock was attached to a 10 mL syringe (H) with a luer lock tip made of polypropylene from which the piston was removed. After closing the three-way stopcock, 0.375 g of ethanol-treated konjac powder was put into the syringe (H). The ethanol-treated konjac powder was sealed inside the syringe (H) by press-fitting and attaching 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, the three-way stopcock is opened, and while being careful not to stir up the ethanol-treated konjac powder, push the piston gradually to remove most of the air inside the syringe (H). pulled out.

(Example 57)
A syringe (G) filled with warm distilled water prepared in Example 34 was connected to another part of the three-way stopcock connected to the syringe (H) filled with ethanol-treated konjac powder prepared in Example 56. After opening the three-way stopcock between syringe (H) and syringe (G), alternately compressing each piston and mixing the contents of syringe (H) and syringe (G) well to create a soft konjac gel. Finally, the entire contents of both syringes were transferred into 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 stopcock connected to the syringe (H) filled with gel-like konjac prepared in Example 57. After opening the three-way stopcock between the syringe (H) and the syringe (E), alternately compressing each piston and mixing the contents of the syringe (H) and the syringe (E) well to add iron powder to the konjac gel. was dispersed and finally the entire contents of both syringes were transferred into the syringe (H).

(Example 59)
A syringe filled with water in which hydrotalcite/activated carbon dispersed prepared in Example 31 was connected to another part of the three-way stopcock connected to the syringe (H) filled with gelatinous konjac in which iron powder was dispersed prepared in Example 58. (A) connected. After opening the three-way stopcock between syringe (H) and syringe (A), each piston was alternately compressed to mix the contents of syringe (H) and syringe (A) well. Finally, the entire contents of both syringes were transferred into syringe (H). It was confirmed that the alkali component of hydrotalcite reacted with konjac to increase the hardness of the gel. The syringe (A) and 3-way stopcock were removed.

(Example 60)
The hydrotalcite/activated carbon/iron powder-dispersed konjac gel prepared in Example 59 was cut into a circle with a diameter of 13 cm by the same method as in Example 38 from the tip of the syringe (H). , ejected and loaded.

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

(Example 62)
By cutting the konjac gel prepared in Example 61 into small pieces with stainless steel scissors, cylindrical hydrotalcite/activated carbon/iron powder dispersed scavenging hydrogel ( Konjac gel) particles were obtained. The entrapping hydrogel (konjac gel) particles were transferred to a polypropylene 50 mL tube, capped and stored to prevent 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 the occurrence of rust.

(Example 64)
To 25 mL of the simulated water of Example 10, add 2.5 g of the hydrotalcite/activated carbon/iron powder-dispersed scavenging hydrogel (konnyaku) gel obtained in Example 62, and use a tube rotator TR-350 to Stirring was performed for 24 hours at a speed of 15 revolutions/minute. After magnetic separation, it was confirmed that it could be recovered within 2 seconds with a neodymium magnet of about 0.5 tesla.

(Example 65)
Regarding the simulated contaminated water after the above steps, selenium, boron and fluorine were quantified by the same method as in Example 12. Selenium concentration: 0.1 mg / L, fluorine: 1.3 mg / L, boron : 1.7 mg/L, confirming high capture efficiency.

(Example 66)
A female luer fitting made of polypropylene (inner diameter 1.5 mm; VRF106, sold by Isis Co., Ltd.) was connected to the tip of the syringe (H) filled with konjac gel in which hydrotalcite/activated carbon/iron powder prepared in Example 59 was dispersed. The tip of the female luer fitting is inserted about 0.5 mm into a hole with a diameter of 1.5 mm in which the plate 40 and the plate 50 prepared in Example 44 are brought into close contact with each other, and the konjac gel is slowly applied to the bottom surface of the plate 40 (plate 50) to a height of 1.5 mm, ie, to the inserted luer fitting tip.

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

(Example 68)
The silicon rubber plate 40 and the silicon rubber plate 50 prepared in Example 67 were taken out and separated by peeling off the silicon rubber plate 40 and the silicon rubber plate 50 . The end of a cylindrical resin rod with a diameter of about 1.5 mm is pressed against the scavenging hydrogel (konjac gel) in which heated hydrotalcite/activated carbon/iron powder is dispersed and remains in the hole of the silicon rubber plate 40. The gel was then extruded and collected in a polypropylene 50 mL tube to prevent drying. On the other hand, the heated gel adhering to the surface of the silicon rubber plate 50 was peeled off using tweezers and collected in a polypropylene 50 mL tube to prevent 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 the occurrence of rust.

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

(Example 71)
Regarding the simulated contaminated water after the above steps, selenium, boron and fluorine were quantified by the same method as in Example 12. Selenium concentration: 0.1 mg / L, fluorine: 1.3 mg / L, boron : 1.6 mg/L, confirming high capture efficiency.

(Example 72)
A three-way stopcock was attached to a 10 mL syringe (I) with a luer lock tip made of polypropylene from which the piston was removed. After closing the three-way stopcock, 0.375 g of odorless konjac powder (manufactured by Fuji Fine Research Institute) and 0.067 g of Cherest Fiber GRY-HW (manufactured by Cherest Co., Ltd.) were put into the syringe (I). The odorless konjac powder was sealed inside the syringe (I) by press-fitting and attaching 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 stopcock is opened, and the piston is gradually pushed in while being careful not to stir up the odorless konjac powder and the crystal fiber GRY-HW. Removed most of the air.

(Example 73)
Syringe (G) filled with warm distilled water prepared in Example 34 was connected to another part of the three-way stopcock connected to syringe (I) filled with odorless konjac powder and chelest fiber GRY-HW prepared in Example 72. . After opening the three-way stopcock between the syringe (I) and the syringe (G), each piston was alternately compressed and the contents of the syringe (I) and the syringe (G) were well mixed to obtain the chelrest fiber GRY-HW. A soft konjac gel in which was dispersed was obtained, and finally the entire contents of both syringes were transferred into 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 stopcock connected to the syringe (I) filled with gel-like konjac with crystal fiber GRY-HW dispersed therein prepared in Example 73. did. After opening the three-way stopcock between syringe (I) and syringe (E), each piston was alternately compressed and the contents of syringe (I) and syringe (E) were well mixed to obtain Chelast Fiber GRY-HW. The 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 stopcock 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 three-way 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 pressing the piston so that the tip of the piston was positioned at the 10 mL scale. The hydrotalcite was dispersed in the water inside the syringe (J) by repeating inversion mixing while the position of the piston was fixed.

(Example 76)
A 10 mL syringe (K) with an empty polypropylene luer lock tip was connected to another part of the three-way stopcock to which the syringe (J) of Example 75 was connected. By gradually opening the three-way stopcock, the space between the syringe (J) and the syringe (K) was opened. With the tip of the syringe (J) facing upward, most of the air inside the syringe (J) is removed by pulling the piston of the empty syringe (K) while being careful not to suck the hydrotalcite-dispersed water. After draining, the three-way stopcock on the side of the syringe (J) containing the hydrotalcite-dispersed water was closed. Remove the syringe (K) from which the air was drawn.

(Example 77)
The hydrotalcite-dispersed water prepared in Example 76 was added to another part of the three-way stopcock connected to the syringe (I) filled with gel-like konjac in which chelest fiber GRY-HW/iron powder was dispersed prepared in Example 74. A filled syringe (J) was connected. After opening the three-way stopcock between syringe (I) and syringe (J), each piston was alternately compressed to mix the contents of syringe (I) and syringe (J) well. Eventually the entire contents of both syringes were transferred into syringe (I). It was confirmed that the alkali component of hydrotalcite reacted with konjac to increase the hardness of the gel. The syringe (J) and 3-way stopcock were removed.

(Example 78)
The hydrotalcite/chelest fiber GRY-HW/iron powder-dispersed konjac gel prepared in Example 77 was cut from the tip of syringe (I) into a circle with a diameter of 13 cm in the same manner as in Example 38, and the surface was silicon-coated. Drain and place on aluminum foil.

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

(Example 80)
By cutting the konjac gel prepared in Example 79 into small pieces with stainless steel scissors, cylindrical hydrotalcite/chelest fiber GRY-HW/iron powder-dispersed traps having a diameter of about 1.5 mm and a length of about 1.5 mm were obtained. Thus, soluble hydrogel (konjac gel) particles were obtained. The entrapping hydrogel (konjac gel) particles were transferred to a polypropylene 50 mL tube, capped and stored to prevent 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 the occurrence of rust.

(Example 82)
To 25 mL of the simulated water of Example 10, 2.5 g of the hydrotalcite/chelest fiber GRY-HW/iron powder-dispersed scavenging hydrogel (konnyaku) gel obtained in Example 80 was added, and the tube rotator-TR-350 was added. was used to stir at a speed of 15 revolutions/minute for 24 hours. After magnetic separation, it was confirmed that it could be recovered within 2 seconds with a neodymium magnet of about 0.5 tesla.

(Example 83)
Regarding the simulated contaminated water after the above steps, selenium, boron and fluorine were quantified by the same method as in Example 12. Selenium concentration: 0.1 mg / L, fluorine: 1.3 mg / L, boron : 1.5 mg/L, confirming high capture efficiency.

(Example 84)
The hydrotalcite/chelest fiber GRY-HW/iron powder-dispersed konjac gel prepared in Example 77 was connected to the tip of the syringe (I) with a female luer fitting made of polypropylene (inner diameter 1.5 mm; VRF106: sold by Isis Co., Ltd.). . The tip of the female luer fitting is inserted about 0.5 mm into a hole with a diameter of 1.5 mm in which the plate 40 and the plate 50 prepared in Example 44 are brought into close contact with each other, and the konjac gel is slowly applied to the bottom surface of the plate 40 (plate 50) to a height of 1.5 mm, ie, to the inserted luer fitting tip.

(Example 85)
After adding tap water to about 80% of the height of a steaming pot for a steamer with a diameter of 15 cm, the pot was placed on a gas range and heated over medium heat until boiling. The silicon rubber plate 40 and the silicon rubber plate 50 filled with the hydrotalcite/chelest fiber GRY-HW/iron powder-dispersed konjac gel prepared in Example 84 and in close contact with each other were transferred into a steamer with a diameter of 15 cm, covered. A steamer was set in a steaming pot, and boiling water was added to the steaming pot as needed to prevent empty heating, and boiling was continued for 15 minutes. After the fire was extinguished, the mixture was cooled as it was for 5 minutes.

(Example 86)
The silicon rubber plate 40 and the silicon rubber plate 50 prepared in Example 85 were 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 with a diameter of about 1.5 mm was applied to heated hydrotalcite remaining in the hole of the silicon rubber plate 40/Chelast fiber GRY-HW/Scavenging hydrogel in which iron powder was dispersed (Konnyaku The gel was extruded by pressing on the gel) and collected in a polypropylene 50 mL tube to prevent drying. On the other hand, the heated gel adhering to the surface of the silicon rubber plate 50 was peeled off using tweezers and collected in a polypropylene 50 mL tube to prevent 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 the occurrence of rust.

(Example 88)
To 25 mL of the simulated water of Example 10, 2.5 g of the hydrotalcite/chelest fiber GRY-HW/iron powder-dispersed scavenging hydrogel (konnyaku) gel obtained in Example 80 was added, and the tube rotator-TR-350 was added. was used to stir at a speed of 15 revolutions/minute for 24 hours. After magnetic separation, it was confirmed that it could be recovered within 2 seconds with a neodymium magnet of about 0.5 tesla.

(Example 89)
Regarding the simulated contaminated water after the above steps, selenium, boron and fluorine were quantified by the same method as in Example 12. Selenium concentration: 0.1 mg / L, fluorine: 1.3 mg / L, boron : 1.4 mg/L, confirming high capture efficiency.

(Example 90)
A three-way stopcock was attached to a 10 mL syringe (L) with a luer lock tip made of polypropylene from which the piston was removed. After closing the three-way stopcock, 0.375 g of odorless konjac powder (manufactured by Fuji Fine Research Institute) and 0.067 g of Cherest Fiber IRY-HW (manufactured by Cherest Co., Ltd.) were put into the syringe (L). Odorless konjac powder was sealed inside the syringe (L) by press-fitting and attaching 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 stopcock is opened and the piston is gradually pushed in while being careful not to stir up the odorless konjac powder and the crystal fiber IRY-HW. Removed most of the air.

(Example 91)
A syringe (G) filled with warm distilled water prepared in Example 34 was connected to another part of the three-way stopcock connected to the syringe (L) filled with odorless konjac powder and chelest fiber IRY-HW prepared in Example 90. . After opening the three-way stopcock between the syringe (L) and the syringe (G), each piston was alternately compressed and the contents of the syringe (L) and the syringe (G) were well mixed to obtain the crystal fiber IRY-HW. A soft konjac gel in which was dispersed 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 stopcock connected to the syringe (L) filled with gel-like konjac in which the crystal fiber IRY-HW was dispersed prepared in Example 91. did. After opening the three-way stopcock between the syringe (L) and the syringe (E), alternately compressing each piston and mixing the contents of the syringe (L) and the syringe (E) well, the crystal fiber IRY-HW was prepared. The 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 hydrotalcite-dispersed water prepared in Example 75 was added to another part of the three-way stopcock connected to the syringe (L) filled with the gel-like konjac in which the gel-like konjac in which the crystal fiber IRY-HW/iron powder dispersed was prepared in Example 92. A filled syringe (J) was connected. After opening the three-way stopcock between syringe (L) and syringe (J), each piston was alternately compressed to mix the contents of syringe (L) and syringe (J) well. Eventually the entire contents of both syringes were transferred into syringe (L). It was confirmed that the alkali component of hydrotalcite reacted with konjac to increase the hardness of the gel. The syringe (J) and 3-way stopcock were removed.

(Example 94)
The hydrotalcite/chelest fiber IRY-HW/iron powder-dispersed konjac gel prepared in Example 93 was cut from the tip of a syringe (L) into a circle with a diameter of 13 cm in the same manner as in Example 38, and the surface was silicon-coated. Drain and place on aluminum foil.

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

(Example 96)
By chopping the konjac gel prepared in Example 95 with stainless steel scissors, cylindrical hydrotalcite/chelest fiber IRY-HW/iron powder-dispersed traps having a diameter of about 1.5 mm and a length of about 1.5 mm were obtained. Thus, soluble hydrogel (konjac gel) particles were obtained. The entrapping hydrogel (konjac gel) particles were transferred to a polypropylene 50 mL tube, capped and stored to prevent 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 the occurrence of 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, thereby preparing simulated rare metal water.

(Example 99)
To 25 mL of the simulated water of Example 98, 2.5 g of the hydrotalcite/chelest fiber IRY-HW/iron powder-dispersed scavenging hydrogel (konnyaku) gel obtained in Example 95 was added, and a tube manufactured by AS ONE CORPORATION was added. Stirring was performed for 24 hours at a speed of 15 revolutions/minute using a rotator TR-350. After magnetic separation, it was confirmed that it could be recovered within 2 seconds with a neodymium magnet of about 0.5 tesla.

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

(Example 101)
The hydrotalcite/chelest fiber IRY-IW/iron powder-dispersed konjac gel prepared in Example 93 was connected to the tip of a syringe (L) with a female luer fitting made of polypropylene (inner diameter 1.5 mm; VRF106: sold by Isis Co., Ltd.). . The tip of the female luer fitting is inserted about 0.5 mm into a hole with a diameter of 1.5 mm in which the plate 40 and the plate 50 prepared in Example 44 are brought into close contact with each other, and the konjac gel is slowly applied to the bottom surface of the plate 40 (plate 50) to a height of 1.5 mm, ie, to the inserted luer fitting tip.

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

(Example 103)
The silicon rubber plate 40 and the silicon rubber plate 50 prepared in Example 102 were 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 with a diameter of about 1.5 mm was coated with heated hydrotalcite remaining in the hole of the silicon rubber plate 40/Chelast fiber IRY-HW/Capturing hydrogel in which iron powder is dispersed (Konnyaku The gel was extruded by pressing on the gel) and collected in a polypropylene 50 mL tube to prevent drying. On the other hand, the heated gel adhering to the surface of the silicon rubber plate 50 was peeled off using tweezers and collected in a polypropylene 50 mL tube to prevent 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 the occurrence of rust.

(Example 105)
To 25 mL of the simulated water of Example 98 was added 2.5 g of the hydrotalcite/chelest fiber IRY-HW/iron powder-dispersed scavenging hydrogel (konnyaku) gel obtained in Example 103, and the tube rotator-TR-350 was used to stir at a speed of 15 revolutions/minute for 24 hours. After magnetic separation, it was confirmed that it could be recovered within 2 seconds with a neodymium magnet of about 0.5 tesla.

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

From the above examples, it was confirmed that hydrotalcite, which has the property of adsorbing harmful ions, exhibits strong alkalinity when dispersed in water. In addition, it was confirmed that rusting of iron powder, which normally easily rusts, can be strongly prevented in a strong alkaline environment. Furthermore, by combining the fact that low-molecular-weight and water-transferable konnyaku is relatively easy even after being solidified with alkali, harmful heavy metals and useful rare metals can be removed from water containing various fine particles. It was confirmed that there are few, it can be integrated instantaneously and at low cost.

1: Scavenging hydrogel 2: Three-dimensional network structure 3: Magnetic powder 4: Adsorbent 5: Water 20: Liquid 21: Target substance 30: Magnetic force accumulation means 40: Perforated silicon rubber plate 41: Apertures 50: Holes No silicon rubber plate

Claims (8)

A method for producing a scavenging hydrogel having a three-dimensional network structure containing magnetic powder and an adsorbent,
Step A of mixing at least the magnetic powder, the adsorbent that captures the target substance, the gel component and water in an alkaline environment;
After the step A, including a step B of gelling,
A method for producing a scavenging hydrogel, wherein at least part of the magnetic powder is iron powder. The adsorbent includes hydrotalcite, activated carbon, calcite, montmorillonite, kaolinite, birnessite, zeolite, illite, vermiculite, pyrophyllite, perlite, bentonite, cobalt oxide, neodymium oxide, indium oxide, silver oxide, and 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, porous crystal inorganic ion exchanger with niobium oxide skeleton, zirconium phosphate, aluminum oxide, polydextrose, sodium alginate, inulin, carrageenan, cellulose, hemicellulose, lignin, chitin, 2. The method for producing a scavenging hydrogel according to claim 1, wherein the scavenging hydrogel is selected from the group consisting of chitosan and pectin. A scavenging hydrogel having a three-dimensional network structure,
Within the three-dimensional network structure,
magnetic powder;
an adsorbent that captures a target substance in a liquid;
containing water and
The magnetic powder is a combination of iron powder and magnetic powder different from the iron powder,
A scavenging hydrogel for material recovery that exhibits alkalinity and can be recovered by magnetic force. The entrapping hydrogel according to claim 3, which is bead-like. The adsorbent includes hydrotalcite, activated carbon, calcite, montmorillonite, kaolinite, birnessite, zeolite, illite, vermiculite, pyrophyllite, perlite, bentonite, cobalt oxide, neodymium oxide, indium oxide, silver oxide, and 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, porous crystal inorganic ion exchanger with niobium oxide skeleton, zirconium phosphate, aluminum oxide, polydextrose, sodium alginate, inulin, carrageenan, cellulose, hemicellulose, lignin, chitin, A scavenging hydrogel according to claim 3 or 4 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 enzymatic hydrolyzate, locust bean gum, polyampholite gel, protein gel using egg white, triblock copolymer, ring-shaped A scavenging hydrogel according to any one of claims 3 to 5, derived from a structure selected from gels, nanocomposite gels and double network gels. The scavenging hydrogel according to any one of claims 3 to 6, wherein the target substance is a decontamination substance or a rare metal. The scavenging hydrogel according to any one of claims 3 to 7, which captures a target substance in a liquid;
a magnetic force accumulation means for magnetically accumulating the scavenging hydrogel with the target substance adsorbed thereon.

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