WO2015129941A1 - Vanadosilicate contenant des ions cs+ hexadéca-coordonnés et utilisation - Google Patents

Vanadosilicate contenant des ions cs+ hexadéca-coordonnés et utilisation Download PDF

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WO2015129941A1
WO2015129941A1 PCT/KR2014/001659 KR2014001659W WO2015129941A1 WO 2015129941 A1 WO2015129941 A1 WO 2015129941A1 KR 2014001659 W KR2014001659 W KR 2014001659W WO 2015129941 A1 WO2015129941 A1 WO 2015129941A1
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sgu
ion adsorbent
water
silicate
ions
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윤경병
다타슈보짓
문원경
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ZEOEN Co Ltd
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ZEOEN Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2805—Sorbents inside a permeable or porous casing, e.g. inside a container, bag or membrane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0214—Compounds of V, Nb, Ta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/685—Devices for dosing the additives
    • C02F1/687—Devices for dosing solid compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/006—Radioactive compounds

Definitions

  • the present invention relates to vanadosilicates having 16 coordinating Cs + ; And use thereof, specifically Cs + ion adsorbent; Drinking water purification tea bags; Contaminated water treatment method; And Cs + removal methods.
  • 137 Cs is the most dangerous radionucleotide because of its high fission yield (6.09%), medium half-life (30.17 years), and water-soluble properties. Thus, once released into the environment, it easily spreads to nature and enters the food chain, creating a serious threat to human and animal health. In this respect, even traces of 137 Cs must be removed from contaminated groundwater, seawater and stored nuclear waste solutions. To this end, strong, mineral resistant adsorbents have to be developed for the safety of the public and for the continued operation of spent fuel regenerative and nuclear power plants.
  • 137 Cs + there are three main target solutions for which 137 Cs + should be removed.
  • Groundwater pH varies from 1 to 12, depending on the region.
  • Cs + inorganic adsorbents have been developed in the past. These are porous three-dimensional (3D) materials, layered two-dimensional (2D) materials and one-dimensional (1D) materials.
  • the partition coefficient is the ratio of the amount of Cs + adsorbed per gram of adsorbent to the amount of Cs + not adsorbed per mL of solution (Equation 1).
  • V is the solution volume (mL) and m is the weight of the adsorbent (g).
  • KMS-1 has a very low K d value at Na + / Cs + > 50 and Ca 2+ / Cs + > 10 and therefore cannot be applied to remove Cs + from contaminated groundwater and seawater.
  • V vanadosilicates with mixed 4 + and 5 + oxidation numbers of V have very good Cs + removal performance, which is known in terms of speed and capacity even at very low Cs + concentrations. It was found to outperform materials. It has also been found that the present invention can produce vanadosilicates with 16 coordinating Cs + . The present invention is based on this finding.
  • a first aspect of the invention provides a Cs + ion adsorbent comprising a vanadosilicate having 16 coordinating Cs + .
  • a second aspect of the present invention provides a Cs + ion adsorbent comprising vanadium silicate mixed with vanadium (V) having oxidation numbers of 4 + and 5 + .
  • a third aspect of the present invention provides a Cs + ion adsorbent comprising cesium vanado silicate represented by the following formula (1):
  • a fourth aspect of the present invention provides a tea bag for drinking water purification having a container containing the Cs + ion adsorbent of the first, second or third aspect and the ion adsorbent, wherein the ions are passable.
  • a fifth aspect of the present invention is a method of treating contaminated water such that the concentration of Cs + is 1 ppm or less, wherein the contaminated water is characterized by using the Cs + ion adsorbent of the first, second or third aspect.
  • a sixth aspect of the present invention is a method for removing Cs + ions from water having a pH of 1 to 5 or pH 9 to 14, wherein the Cs + ion adsorbent of the first, second or third aspect is used. Provides a way to remove Cs + .
  • a seventh aspect of the present invention provides a method of removing Cs + from water containing 0.1-10 ppb levels of Cs + and containing at least 100 ppm of other competing metal ions, wherein the first, second, or second aspects of the invention Provided is a Cs + removal method characterized by using three Cs + ion adsorbents.
  • Eighth aspect of the present invention provides the first aspect, the second aspect or is characterized by a Cs + removal method using a Cs + ion adsorbent of the third aspect In the method of removing the 137 Cs + from basic nuclear waste solution do.
  • a ninth aspect of the invention is a process for the preparation of vanasilicates having 16 coordinating Cs + , comprising a V 5+ -containing compound, a reducing agent, a Cs + containing salt as a silicon source, base, vanadium source. It provides a manufacturing method characterized in that it comprises the step of hydrothermally reacting the reaction mixture containing (salt) and water to produce the vanado silicate.
  • a tenth aspect of the present invention provides cesium vanado silicate represented by the following formula:
  • Me is K alone or a combination of Na and K
  • the invention was found to unprecedented 16 coordinated Cs +, the present invention provides a bar of the new I very high Cs + over K-silicate SGU-45 and run existing ones - provides the release properties.
  • a to E are SEM images of Na x Cs y -SGU-4 crystals synthesized from gels containing different molar ratios of CsCl (0.43, 1.30, 1.95, 2.60 and 4.55 relative to V), F to J above Superimposed images of low-resolution transmission electron microscopy (TEM) and corresponding electron diffraction patterns for each crystal shown, where K through O are ⁇ 100 ⁇ , ⁇ 010 ⁇ , ⁇ 01'0 ⁇ , ⁇ 011 ⁇ , ⁇ 011 ' ⁇ Is a schematic diagram of Na x Cs y -SGU-4 showing various percentages of the planes ⁇ , ⁇ 101 ⁇ , ⁇ 101 ' ⁇ and ⁇ 011 ⁇ .
  • TEM transmission electron microscopy
  • SBU framework and secondary growth units
  • FIG. 4 is a graph showing Cs + capture in actual seawater and similar nuclear waste solutions.
  • Degree of Cs + removal of K-SGU-45 and the best reported Cs + trapping substance at conditions of V / m 250 mL / g and 0.01 ppm ⁇ C i ⁇ 10 ppm in real seawater after equilibration for 24 hours (A ) And corresponding logK d values (B).
  • Critical C i values (C) from four sorbents capable of 50 and 90% removal of Cs + from seawater, respectively, at conditions of V / m 250 mL / g and 0.01 ppm ⁇ C i ⁇ 12 ppm.
  • FIG. 5 shows SEM images and X- of SGU-4-A, SGU-4-B, SGU-4-C, SGU-4-D, SGU-4-D1, SGU-4-D2 and SGU-4-E.
  • FIG. 6 is a graph showing the susceptibility ( ⁇ ) and the inverse of the susceptibility (1 / ⁇ ) with respect to (A) T.
  • the measured magnetic moment values of the atoms are 1.70 and 1.09 BM for native Na 7 -SGU-4 and partially oxidized Na 4.6 -SGU-45, respectively.
  • multipurpose porous banadosilicate materials have been found whose K d values are much higher than Na-CST, Na-PMica and GaSbS, regardless of C i from 10 ppb to 100 ppm.
  • the vanadate silicate was vanasilicate with 16 coordinating Cs + and vanadium (V) with valent valences (IV and V) or vanadium silicate with 4+ and 5+ oxides.
  • Cesium vanado silicate that can be used as an example of the Cs + ion adsorbent in the present invention may be represented by the following formula (1):
  • Me is at least one alkali metal except Cs,
  • alkali metal examples include Na, K, Rb, Fr and the like.
  • the cesium vanado silicate of Formula 1 is preferably Me is K alone or a combination of Na and K.
  • n + m 4
  • x + y 2n + m.
  • cesium vanado silicate of Formula 1 may be obtained by oxidizing cesium vanado silicate of Formula 2:
  • Vanasilicates with Cs + coordinating according to the invention contain V 5+ -containing compounds, reducing agents, Cs + containing salts and water as silicon sources, bases, vanadium sources.
  • the reaction mixture can be prepared by hydrothermal reaction.
  • a process for preparing vanadosilicate having 16 coordinating Cs + comprises preparing a first solution containing the silicon source, the base and water: a V 5+ -containing compound, the reducing agent, and the vanadium source; Second step of preparing a second solution containing water: third step of preparing the reaction mixture by mixing the first solution, the second solution and a Cs + containing salt ; and the reaction mixture is subjected to hydrothermal reaction. It is preferred to include a fourth step of forming the nasi silicate.
  • V 5+ contained in the V 5+ -containing compound as the vanadium source may be reduced to V 4+ by the reducing agent, and thus, the vanadium silicate prepared by the manufacturing method may contain V 5+ ions. Although it may be pure V IV vanasilicate that is substantially free. It is not limited to this.
  • V 4+ in the vanasilicate with 16 coordinating Cs + is oxidized to V 5+ to give vanadium (V) mixed valences (IV and V) or vanasilicates with oxidation numbers 4+ and 5+. It can manufacture.
  • Banadosilicates having 16 coordinating Cs + prepared according to the present invention, may have O-rings of 12 oxygens in the U-shape, Cs + ions and 4 coordinating water molecules.
  • Non-limiting examples of the silicon source may be a silicate salt, a silicon oxide, or a silicon compound represented by the following general formula (3):
  • R 1 to R 4 are each independently hydrogen, hydroxyl group, carboxyl group, halogen group element, C1 to C22 alkyl group or alkoxy group, aralkyl or aryl group, R 1 to R 4 are each one or more It may include, but is not limited to, oxygen, nitrogen, sulfur or metal atoms.
  • the alkyl group included in the group may include a linear or branched alkyl group of C1 to C22, but is not limited thereto.
  • non-limiting examples of the silicon source include silicate salts of alkali metals or alkaline earth metals, colloidal silica, silica hydrogels, silicic acid, fumed silica, tetraalkylorthosilicates, silicon hydroxides and There is a combination of these.
  • Non-limiting examples of the V 5 + -containing compounds include V 2 O 5 , VOCl 3 , VOBr 3 , VOF 3 , VOI 3 , VOCl 3 , VOSO 4 , NaVO 3 , Na 3 VO 4 , NH 4 VO 3 and these There is a combination.
  • Non-limiting examples of the base may include a compound containing an alkali metal or alkaline earth metal.
  • the Cs + -containing salt may be selected from the group consisting of halogen salts, ammonium salts, carbonates, sulfates, nitrates, phosphates, and combinations thereof, but is not limited thereto.
  • Non-limiting examples of the reducing agent may be an organic reducing agent, an inorganic reducing agent, or a combination thereof.
  • the organic reducing agent is a carboxyl group, a hydroxyl group, an aldehyde group, an amine group, a sulfite group, a bisulfite group, a carbonate group, a bicarbonate group, a phosphorous acid group, a hypophosphite group, a thiol group, a cyan group, a thiocyanate group, an ammonium group, a hydra
  • It may include one or more organic reducing agents having a functional group selected from the group consisting of a genyl, borohydride group, amide group, silane group, amino group, carbamoyl group, urea group and combinations thereof.
  • Non-limiting examples of the inorganic reducing agent include inorganic acids, halogen salts of metals, thiosulfate salts of metals, sulfite salts of metals, bisulfite salts of metals, ferrous salts, sulfites of metals, metal hydrides, metal borohydrides , Ammonium salts of metals, persulfates of metals, periodic salts of metals, hypophosphites, ammonium hypophosphites, hypophosphites of metals, ethylenediaminetetraacetic acid salts of metals, and combinations thereof It may be.
  • the reaction mixture may be aged before hydrothermal reaction.
  • the aging process can be carried out, for example, by stirring the reaction mixture at room temperature or higher, and by this aging process the reaction mixture can be formed in a gel state.
  • the hydrothermal reaction may be performed at room temperature or above room temperature, for example, but may be performed at 100 ° C. or higher, but is not limited thereto.
  • the hydrothermal reaction may be carried out by introducing the reaction mixture into a high pressure reactor such as an autoclave and heating to a constant temperature in a closed state.
  • the V 4+ ions may be oxidized to V 5+ ions by an oxidant including an organic oxidant, an inorganic oxidant, or a combination thereof, but non-limiting examples of the oxidant include hydrogen peroxide, peroxides, oxygen acids, and halogens.
  • the parent vanadium silicate named 3 ⁇ x ⁇ 7, 0 ⁇ y ⁇ 4) (FIG. 1, A to E), was synthesized for the first time (see Preparation Example 1).
  • the molar ratio of CsCl in the gel sensitively affected the shape of the Na x Cs y -SGU-4 crystals.
  • Their electron diffraction patterns are shown in J in Figs. 1, F, and schematics of these forms and corresponding crystal axes are shown in Figs.
  • the corresponding powder diffraction pattern is shown in FIG. 5. Therefore, as the Cs + content increased, crystals grew instantly and longer along the c axis.
  • FIGS. 1A and 1E were obtained using an emission light diffractometer (FIGS. 5 and 8, Table 1 and Table 2).
  • Na 7 -SGU-4 and Na 4 Cs 3 -SGU-4 Sogang University-4
  • FIG. 2 shows the crystal structures of Na 7 -SGU-4 and Na 4 Cs 3 -SGU-4, their secondary building units, interconnection patterns and unit cell structures.
  • the color labels of the atoms are shown in FIG. 2A.
  • the 12 member O ring is part of the basic secondary building unit (SBU) for SGU-4.
  • the 12 membered ring is folded in a U shape, and one Cs + ion is present in the center of the 12 membered O ring.
  • the van der Waals distance between Cs + and eight O (2) atoms is 3.383 ⁇
  • the Van der Waals distance between Cs + and four O (5) atoms is 3.590 ⁇ .
  • the unit cell formula is Na 7 ⁇ [(V IV O) 2 H 2 O] 2 ⁇ ⁇ Si 12 O 32 [Cs (H 2 O) 4 ] ⁇ ⁇ xH 2 O and Na 4 Cs 3 ⁇ [(V IV O) 2 H 2 O] 2 ⁇ ⁇ Si 12 O 32 [Cs (H 2 O) 4 ] ⁇ .
  • XH 2 O expressed as Si 12 O 32 [Cs (H 2 O) 4 ] Is represented by SBU-A.
  • FIG. 2D The observation surface of the silica tube along the c axis is shown in FIG. 2E, which is shown to be a square silica tube. The corresponding projection surface is shown in FIG. 2F.
  • the observation planes of Na 7 -SGU-4 along the c and b axes are shown in FIGS. 2I and J, respectively.
  • SBU-B does not exist in polyhedral form and shows the positions of Na + and water molecules more clearly.
  • Another eight member ring is in the center of the four square silica tubes, and a six member ring is present between the two square silica tubes.
  • I, II and III FIG. 2K
  • Cs + ion adsorbents include vanadosilicates having 16 coordinating Cs + ; Or vanadium (V) the I bar silicate having a mixed valence (IV and V) or the oxidation number + 4 and + 5; Or while having a 16-coordinated Cs + I bar having a vanadium (V) in a mixed valence (IV and V) or the oxidation number + 4 + 5 and silicates; is characterized comprising a.
  • Cs + ion adsorbents according to the invention can be used to remove radioactive Cs.
  • Na 7 -SGU-4 did not ion exchange with Cs + in which its 7 Na + ions were dissolved in aqueous solution. Interestingly, however, when some V IV ions are oxidized to V V , good Cs + ion exchange capacity is conferred. It is presumed that this is caused by reducing the traffic congestions by reducing the number of charge-balancing Na + ions. Thus, Na 7 -SGU-4 was treated with an appropriate amount of Br 2 to give Na 4.6 ⁇ [(V IV O) 0.8 (V V O) 1.2 H 2 O] 2 ⁇ in a partially oxidized (60%) form. ⁇ Si 12 O 32 [Cs (H 2 O) 4 ] ⁇ . XH 2 O was prepared (Example 1, FIGS.
  • Na 4.6 -SGU-45 Na 4.6 -SGU-45 was completely ion exchanged with K + to produce a complete K 4.6 -SGU-45 (simply referred to as K-SGU-45). This is because the K + -form was more active in terms of Cs + removal.
  • the Cs + ion adsorbent according to the present invention may be in the form of a powder, a foam, a film, or a fixed bed column filled with the adsorbent, and may be in the form of a molding to which the Cs + ion adsorbent is attached.
  • the molding may be a garment.
  • the present invention provides a tea bag for drinking water purification, comprising a Cs + ion adsorbent according to the present invention and a container for receiving the ion adsorbent, but the ions pass through.
  • a tea bag for drinking water purification comprising a Cs + ion adsorbent according to the present invention and a container for receiving the ion adsorbent, but the ions pass through.
  • drinking water purifying tea bags according to the present invention can be used.
  • the container may be in the form of a nonwoven and may be in the form of a plastic.
  • one equivalent condition is to adjust the added volume ( ⁇ 850 mL) of the ⁇ 1 ppm solution for a fixed amount of adsorbent (2.5 mg each), so that the total number of Cs + ions in the ⁇ 1 ppm solution is the amount of adsorbent added.
  • I mean it corresponds to the total number of exchangeable sites.
  • the exchange time was 8 hours.
  • the results are shown in Figure 3A.
  • the degree of ion exchange was 25, 21, 7.6, 3 and 1%, respectively.
  • the corresponding K d (logK d) values were respectively 112,000 (5.05) 102 008 (5.01) 29 876 (4.48), 5332 (3.73) 4108 (3.61).
  • the invention is another feature that the contaminated water can be treated so that the concentration of Cs + is 1 ppm or less using the Cs + ion adsorbent according to the present invention.
  • the contaminated water may be groundwater, seawater or nuclear waste solution.
  • the present invention is characterized by a Cs + ion can be removed using the Cs + ion adsorbent according to the invention in water of pH 1 ⁇ 5 or pH 9 ⁇ 14.
  • the present invention is characterized in that Cs + can be removed using Cs + ion adsorbent according to the present invention even in water containing 0.1-10 ppb Cs + and other competitive metal ions of 100 ppm or more.
  • the pH of the water to be removed Cs + may be out of 6 ⁇ 8.
  • the competitive metal ion may be selected from the group consisting of Na + , Ca 2+ , Mg 2+ , K + .
  • K-SGU-45 and Na-CST, Na-PMica, CHA, HEU, MOR, GaSbS is shown in real sea water and similarly prepared nuclear waste solution conditions.
  • HEU and MOR are natural zeolites called clinoptiolite and mordenite, respectively.
  • the seawater used here comes from the waters off the island called Anmyeondo, located on the west coast of Korea.
  • the compositions of Na + , Mg + , K + and Ca 2+ were 11,000, 1,200, 600 and 300 ppm, respectively.
  • C i between 10 ppb and 10.9 ppm the degree of Cs + removal from the real seawater and the corresponding logK d -C i under 250 mL / g are shown in Figures 4A and 4B, respectively, for various adsorbents.
  • Cs + removal is 100, 99, 89, 81, 35, 29 and 6 for K-SGU-45, Na-CST, Na-PMica, CHA, HEU, MOR and GaSbS, respectively.
  • % (FIG. 4A, Table 4 and Table 5).
  • the corresponding K d (logK d) value was 132,152 (5.12), 19,277 (4.29 ), 1,966 (3.29), 1,033 (3.01), 136 (2.13), mL / g 100 (2.00) , and 16 (1.21) ( 4B).
  • the degree of Cs + removal rapidly decreased with decreasing C i (FIG. 4A). However, the reduction rate of K-SGU-45 is much lower than in other cases.
  • K-SGU-45 is the best 137 Cs + -remover for the improvement of contaminated seawater.
  • concentration of Cs + in which the adsorbents can remove 50% and 90% of Cs + ions, respectively, from real seawater under 250 mL / g conditions is shown in FIG. 4C.
  • concentrations of Cs + that can be removed by 50% by K-SGU-45 and Na-CST are 8 and 113 ppb respectively and the corresponding Cs + concentrations by which 90% can be removed are 93 ppb and 1.5 ppm, respectively. to be.
  • the corresponding seawater volumes for Na-CST (10.01 ppm), GaSbS (10.71 ppm) and Na-PMica (12.86 ppm) are 42, 18, and 31 L, respectively.
  • the competition between Cs + and M n + is much more severe under 1 equivalent conditions than 250 mL / g conditions.
  • the 1 equivalent condition is the best condition to compare the intrinsic affinity of the adsorbent for Cs + .
  • K-SGU-45 removes 28% of Cs + from seawater, while Na-CST, GaSbS and Na-PMica only remove 5,4 and 3% of Cs + , This supports that K-SGU-45 has 6-9 times higher affinity for Cs + than other adsorbents.
  • K-SGU -45 still removes Cs + by 7%, which is still higher than the performance of other adsorbents under ⁇ 10 ppm and under 42L sea water conditions (3-5%). This indicates that K-SGU-45 has a much higher intrinsic affinity for Cs + than other adsorbents.
  • the present invention is characterized in that 137 Cs + can be removed from the basic nuclear waste solution by using the Cs + ion adsorbent according to the present invention.
  • the total M n + concentration in seawater is 13,100 ppm, whereas the concentration of Na + ions in stored nuclear waste solutions is typically about 133,000 ppm (5.7M), which is about 10 times higher than seawater. In this respect, removal of 137 Cs + from stored high basic nuclear waste solutions is much more challenging.
  • Silicate Sodium Na 2 SiO 3 , 17-19% Na 2 O and 35-38% SiO 2 , Canto
  • Tetraethyl Orthosilicate Si (OC 2 H 5 ) 4 , 98% Across
  • Vanadium Oxide V ) (V 2 O 5 , 99%, Aldrich)
  • titanium isopropoxide Ti (OC 3 H 7 ) 4 , 98%, Junsei
  • oxalic acid H 2 O 4 C 2 , 99%, Sigma-Aldrich
  • Sodium hydroxide NaOH, 93%, three thousand
  • sodium chloride NaCl, 99%, three thousand
  • sodium tetraphenylborate NaTPB, 99.5%, across
  • ethylenediaminetetracetic acid disodium salt dihydrate EDTA, 99- 101%, Sigma-Aldrich
  • Potassium chloride KCl, 99%, Three thousand
  • Cesium chloride CsCl, 99.9%, Sigma-Aldrich
  • V feed solution mixed with oxalic acid (6.3 g) and V 2 O 5 (2.5 g) was added dropwise to sodium silicate solution.
  • Ethanol (15 ml) was added to the vanadium and silicon feed mixture and the mixture was stirred for 1 hour.
  • CsCl solutions SGU-4-A, SGU-4-B, SGU-4-C, SGU-4-D, SGU-4-D1, SGU-4-D2 and SGU-4-E, respectively
  • 1, 3, 4.5, 6, 7.5, 9 and 10.5 g of CsCl and 10 g of DDW were added to the mixture.
  • the mixture was aged for 6 hours at room temperature, the gel was transferred to 50 ml of Teflonized high pressure reactor, and then reacted in an oven preheated to 200-210 ° C. for 10 hours.
  • the precipitated pale green crystals (powder sample) were collected, washed, dried at 100 ° C. for 1 hour and analyzed by X-ray powder diffraction. Single crystals (dark green) were stored as mother liquor for single crystal X-ray diffraction.
  • Na 7 -SGU-45 powder (0.6 g) was dispersed in 35 ml of toluene and 2 ⁇ l of Br 2 was added. The mixture was stirred for 1 hour, recovered with a filter and dried at 70 ° C. An oxidized powder sample (Na 4.6 -SGU-45) was degassed at 150 ° C. vacuum to remove residual Br 2 inside the crystals. Na 4.6 -SGU-45 was washed with distilled deionized water to remove NaBr formed during V IV oxidation.
  • Na 4.6 -SGU-45 powder (0.5 g) was dispersed in KCl solution (50 mL, 2.5 M) and stirred at 80 ° C for 6 h. Samples were collected by centrifugation and washed with distilled deionized water. The same process was repeated four times to give K 4.6 -SGU-45.

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Abstract

La présente invention concerne un vanadosilicate contenant des ions Cs+hexadéca-coordonnés et une utilisation de celui-ci, et en particulier un adsorbant pour des ions Cs+, un sachet de thé pour purifier l'eau potable, un procédé de traitement d'eau polluée radioactive et un procédé d'extraction de Cs+.
PCT/KR2014/001659 2014-02-28 2014-02-28 Vanadosilicate contenant des ions cs+ hexadéca-coordonnés et utilisation Ceased WO2015129941A1 (fr)

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