WO2017114354A1 - 一种颗粒态除铯无机离子吸附剂的制备方法及产品与应用 - Google Patents

一种颗粒态除铯无机离子吸附剂的制备方法及产品与应用 Download PDF

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WO2017114354A1
WO2017114354A1 PCT/CN2016/112082 CN2016112082W WO2017114354A1 WO 2017114354 A1 WO2017114354 A1 WO 2017114354A1 CN 2016112082 W CN2016112082 W CN 2016112082W WO 2017114354 A1 WO2017114354 A1 WO 2017114354A1
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silica gel
salt
ferrocyanide
adsorbent
metal ion
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PCT/CN2016/112082
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French (fr)
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赵璇
尉继英
成徐州
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清华大学
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Priority to EP16881143.8A priority Critical patent/EP3412361A4/en
Priority to JP2017560545A priority patent/JP2018524149A/ja
Publication of WO2017114354A1 publication Critical patent/WO2017114354A1/zh

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    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/12—Processing by absorption; by adsorption; by ion-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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 invention relates to a particulate inorganic ion adsorbent for removing 134 Cs/ 137 Cs ions in a radioactive waste liquid treatment and an industrial preparation method thereof, in particular to a preparation method of a composite adsorbent material.
  • the material is supported by silica gel as a carrier, and a series of metal ion-stabilized ferrocyanide active components are supported by surface monolayer dispersion technology, wherein the stable metal ions include Fe 3+ , Co 2+ , Cu 2+ , Zn 2+ and Zr 4+ and so on.
  • the formed particulate adsorbent is suitable for filling in a fixed bed adsorption reactor and is applied to a waste liquid treatment process of a nuclear power plant and other nuclear facilities.
  • the invention belongs to the technical field of material preparation and radioactive wastewater treatment.
  • Low-level waste liquids are complex in water quality and usually contain fission products (I, Cs, Sr, Te, Ru, Mo, Ag, and rare earth elements), structural material activation products (Cr, Mn, Fe, Co, Ni), and radioactivity. Lanthanides (U, Pu, Am, Cm, etc.).
  • fission product 134 Cs/ 137 Cs is the main nuclides released under nuclear accident and is regarded as a pointer to monitor nuclear fuel damage.
  • helium is the main source of radiation in the large amount of radioactive waste leaking from the reactor (Hi ikata et.al., 2014; Tsukada et.al., 2014).
  • the final effective treatment process includes the following technical segments: First, pre-filtration And oil-water separation technology to remove the main solid residues in the waste liquid and the organic substances contained in the water; followed by the inorganic ion adsorption technology, focusing on the removal of 134 Cs/ 137 Cs and 129 I/ 131 I by selective inorganic adsorbents.
  • the radionuclide is rapidly enriched to the surface of the solid adsorbent, effectively reducing the level of radioactivity in the waste liquid; followed by the membrane technology finishing unit, which concentrates and separates various nuclide and other non-radioactive metal ions to discharge The activity in the water is further reduced and the emission requirements are met.
  • the membrane technology finishing unit which concentrates and separates various nuclide and other non-radioactive metal ions to discharge The activity in the water is further reduced and the emission requirements are met.
  • this nuclear accident emergency process in addition to the bismuth adsorbent played an important role.
  • the "ion exchange + evaporation concentration" process is generally used for the treatment of radioactive waste liquid, and the organic ion exchange resin is a conventional application material.
  • the metal ions in the waste liquid have the possibility of exchange with cations or anions on the resin, so the resin is a broad-spectrum treatment technology with low selectivity to nuclide ions. Due to the high salt content in low-level liquid waste, the concentration of nuclide is extremely low, and the amount of resin required to achieve a higher nuclide removal rate is large, which will eventually form a large amount of solid radioactive waste.
  • inorganic ion adsorbents have good thermal and chemical stability and strong radiation resistance.
  • the saturated saturated inorganic materials have high stability in long-term geological storage, and are easy to be used for on-site radiation protection and waste termination. Treatment and disposal; more importantly, the inorganic ion adsorbent has high selectivity to major nuclide such as 134 Cs/ 137 Cs, 90 Sr and 60 Co, and is suitable for treating high-salt, strong acid/alkaline low-level liquid waste. It can quickly and greatly reduce the radioactivity of waste liquid, reduce the amount of solid waste, and meet the principle of nuclear waste reduction. In addition, the inorganic ion adsorbent can be conveniently made into a portable small-scale purification device, and is particularly suitable for flexible handling of different forms of dispersive pollution sources under nuclear emergency accidents.
  • ferrocyanide-type adsorbents can maintain the antimony ions in a wide pH range. Good adsorption.
  • the ferrocyanide-based adsorbent Cs-treat developed by the University of Helsinki can treat about 10 tons of low-level liquid waste (240g/L) of a nuclear power plant per kilogram of material, and the decontamination coefficient of Cs reaches 2000. It is twice the traditional evaporation-ion exchange method, which is the best international research result except Cs.
  • ferrocyanide generally has small particle size and poor hydraulic properties, and can not be operated on the column, and the separation of solid and liquid phases is very difficult; in addition, the internal mass transfer conditions of ferrocyanide particles are poor, and the inner layer is adsorbed.
  • the first one is to prepare hybrid materials of potassium ferrocyanide and porous SiO 2 by silica sol in situ immobilization technology.
  • the adsorption capacity of Cs + can reach 0.335 meqCs/gadsorbent (Chinese patent CN 200710064453.0);
  • the formed silica gel pellet is reacted with tetrabutyl titanate to form a composite carrier coated with TiO 2 on the surface, and the carrier is immersed in a hydrochloric acid solution of potassium ferrocyanide to obtain a spherical potassium ferrocyanide/small Ball silica hybrid material (Chinese Patent 200710122085.0).
  • SiO 2 is used as a binder, and it is easy to wrap the active adsorbent ferrocyanide in the inner layer, which is not easy to exert its adsorption effect; coating the adsorbent on the outer surface of the silica gel ball can make the adsorbent easy Contact with Cs + , but due to the larger particle size (3-4mm) of the silica gel, it affects the adsorption efficiency and adsorption capacity of the adsorbent for Cs + ions.
  • the adsorbent prepared by this method has a disadvantage that the surface active component is easily lost in use and the adsorption efficiency and the adsorption capacity are limited.
  • the invention selects a large-porosity silica gel with a small particle size as a carrier, and uses a single layer dispersion principle to load a single layer of ferrocyanide on the surface of the silica gel, and is made stable by a plurality of transition metal ions Mn +.
  • a particulate ferrocyanide adsorbent, wherein M n+ Fe 3+ , Co 2+ , Cu 2+ , Zn 2+ and Zr 4+ .
  • the invention develops a particulate ferrocyanide adsorbent stabilized by a plurality of transition metal ions Mn + , and provides a method for industrially preparing a supported ferrocyanide composite adsorbent material, comprising the following specific steps:
  • a series of different concentrations of salt solution containing Mn + ions were immersed on the surface of the silica gel by an equal volume impregnation method, and the impregnated solid material was dried in an oven to obtain a silica gel intermediate M/SiO 2 having a different amount of M salt on the surface.
  • the single layer dispersion threshold of different species of Mn + ion salt on the surface of the silica gel is determined by X-ray diffraction method, and the value is the single layer loading of the different species of salt on the surface of the silica support.
  • silica gel is dispensed in a stainless steel tray in the blast oven equipment, and the Mn + ion salt is heated and dissolved in the dissolution tank, and the solute is completely dissolved by stirring to form a solution A of a certain concentration.
  • the potassium ferrocyanide is dissolved and dissolved in a dissolution tank to form a uniform solution B.
  • the adsorbent obtained in the third step is sieved, and the adsorbent having a complete particle size is selected and washed with tap water to remove the soluble substance and fine powder adhering to the surface of the particle until the cleaning liquid becomes clear.
  • the washed adsorbent is once again dried to obtain a silica-supported ferrocyanide-type adsorbent K 2 M[Fe(CN) 6 ]/SiO 2 which can be used as it is.
  • the present invention provides a silica-supported metal ion-stabilized ferrocyanide adsorbent, which is mainly characterized in that the specific surface area of the silica gel as a carrier is in the range of 900 to 1200 m 2 /g; The metal ion-stabilized ferrocyanide is supported on the silica gel as a monolayer dispersion.
  • the silica gel has a pore size of 10-15 nm and a particle size of 0.4-2 mm.
  • the metal ion is selected from the group consisting of Fe 3+ , Co 2+ , Cu 2+ , Zn 2+ and Zr 4+ , and these metal ions can be derived, for example, from salts of metal ions: FeCl 3 , Fe ( NO 3 ) 3 , Co(NO 3 ) 2 , CoCl 2 , Cu(NO 3 ) 2 , CuSO 4 , Zn(NO 3 ) 2 , ZnCl 2 , Zn(AC) 2 , ZrOCl 2 and ZrO(NO 3 ) 2 .
  • the ferrocyanide is selected from the group consisting of sodium ferrocyanide, potassium ferrocyanide, or a combination thereof, more preferably potassium ferrocyanide.
  • the macroporous silica gel is selected as a carrier, the average pore diameter is 10-15 nm, the specific surface area is 900-1200 m 2 /g, and the silica gel particle size is 0.4-2 mm.
  • the selected salts are: the Fe 3+ salt is FeCl 3 or Fe(NO 3 ) 3 ; containing Co 2+ salt Co(NO 3 ) 2 or CoCl 2 ; Cu 2+ salt Cu(NO 3 ) 2 or CuSO 4 ; Zn 2+ salt is Zn (NO 3 2 , ZnCl 2 or Zn(AC) 2 ; the salt containing Zr 4+ is ZrOCl 2 or ZrO(NO 3 ) 2 .
  • a single layer dispersion threshold of the Mn + ion salt on the surface of the silica gel needs to be determined, and the specific method is: applying a series of different contents of Mn + ion salt to the surface of the silica gel by solution dipping, and baking After drying, the sample to be tested is obtained.
  • the mass of the silica gel is 5-10 g, and the loading of the Mn + ion salt on the silica gel is 0.02 g, 0.05 g, 0.1 g, 0.5 g, 1.0 g, 2.0 g, 3.0 g, 4.0 g, 5.0 g per gram of silica gel. 6.0 g; Mn + ion solution volume to silica volume ratio of 0.5-2.
  • the obtained series of samples were subjected to X-ray diffraction (XRD) measurement, and the strongest diffraction peak intensity (y-axis) was used to make a linear relationship with the corresponding Mn + ion salt loading (x-axis), and the intercept on the x-axis in the figure. This is the single layer dispersion threshold.
  • the impregnation process is carried out in a water bath at a temperature of 90 ° C, and the process is continuously stirred until the liquid is completely evaporated, and the solute Mn + ion salt is all loaded onto the surface of the silica gel.
  • the silica gel intermediate M/SiO 2 was dried in an oven for 10 h at a temperature of 120 °C.
  • the monolayer dispersion threshold of different Mn + ion salts on silica gel was determined by the X-ray diffraction method described in the step (1).
  • the monolayer dispersion threshold of Co(NO 3 ) 2 is 0.4-0.7 g/g on silica gel ;
  • the monolayer dispersion threshold of CuSO 4 is 0.6-0.9 g/g;
  • a single layer of Zn(AC) 2 The dispersion threshold is 0.1-0.4 g/g;
  • the single-layer dispersion threshold of ZrO(NO 3 ) 2 is 0.9-1.2 g/g; and the single-layer dispersion threshold of FeCl 3 is 0.3-0.5 g/g.
  • the monolayer dispersion threshold of the Mn + ion salt on the silica gel is, for example, a Zn(AC) 2 threshold of 0.18 g/g; a Co(NO 3 ) 2 threshold of 0.63 g/g; and a CuSO 4 threshold. 0.79 g/g; ZrO(NO 3 ) 2 threshold 1.02 g/g; FeCl 3 threshold 0.43 g/g.
  • 1-2 kg of silica gel particles are added to each tray, and the volume ratio of the impregnation solution to the silica gel particles is 1-4, and the corresponding solute quality is obtained according to the monolayer dispersion threshold of the Mn + ion salt.
  • the corresponding A solution concentration can be calculated and the dissolution temperature is 30-60 °C.
  • the molar ratio of the potassium ferrocyanide to the Mn + ion salt is 0.5-1.5, and the volume ratio of the impregnation solution to the silica intermediate M/SiO 2 particles is 1-4, the dissolution temperature.
  • potassium ferrocyanide is used as the ferrocyanide to provide an adsorbent active component.
  • ferrocyanides which are readily available in the industry, such as sodium ferrocyanide, are also suitable for use in the present invention due to their similar chemical properties to potassium ferrocyanide.
  • the solution immersion time is 3-5 hours, and then dried in a blast oven at 120 ° C for 5-10 h.
  • the resulting ferrocyanide-containing K 2 M[Fe(CN) 6 ]-containing adsorbent prepared by the above preparation method is also within the scope of the present invention.
  • the inventors of the present invention have surprisingly found that the silica-supported metal ion-stabilized ferrocyanide adsorbent according to the present invention is characterized by structural stability and high adsorption performance. Since the adsorbent can adsorb the radioisotope Cs ions and adsorb the stable isotope Cs ions, it has broad application prospects. For example, adsorption can be used to effect separation and/or removal or extraction of radioisotope Cs ions, as well as for separation and/or removal or extraction of stable isotope Cs ions.
  • the silica-supported adsorbent containing ferrocyanide K 2 M[Fe(CN) 6 ] adsorbs (including removing or separating or extracting) radioisotope Cs ions and adsorption (including removal or separation or extraction)
  • the use of stable isotope Cs ions is also within the scope of the present invention.
  • the invention provides an effective method for industrially preparing a silica-supported ferrocyanide K 2 M[Fe(CN) 6 ] adsorbent, which can be applied to the efficient removal of Cs ions in a radioactive waste liquid of a nuclear power plant, and can also be applied. Under all conditions of removal or extraction or separation of stable isotope Cs.
  • the invention uses a macroporous silica gel as a carrier, and uses a Mn + ion salt and potassium ferrocyanide as raw materials to prepare a silica-supported ferrocyanide K 2 M[Fe(CN) 6 ] adsorbent by a two-step impregnation method.
  • the Mn + ion salt is first dispersed on the surface of the silica gel to form a dense monolayer, and the dispersion threshold of the Mn + ion salt is obtained by the method described in the present invention, that is, the optimal loading of the Mn + ion salt;
  • the surface reaction method was used to deposit ferrocyanide K 2 M[Fe(CN) 6 ] on the surface of silica gel to obtain a cerium-removing adsorbent with stable structure and high adsorption performance.
  • Example 1 is a photograph of five kinds of silica-supported ferrocyanide adsorbents obtained in Example 1;
  • Example 2 is an XRD pattern of five kinds of silica-supported ferrocyanide adsorbents obtained in Example 1;
  • Example 3 is an FT-IR diagram of five kinds of silica-supported ferrocyanide adsorbents obtained in Example 1;
  • Figure 4 (a-e) is an SEM image of five kinds of silica gel supported ferrocyanide adsorbents obtained in Example 1;
  • Figure 5 embodiment is obtained five kinds of silica gel adsorbent supported ferrocyanide ions of Cs + equilibrium adsorption isotherm of embodiment 1;
  • Figure 6 is a solid-state packed column penetration curve of the adsorbents KZnHCF-S and KCuHCF-S obtained in Example 1 for Cs + ions;
  • Example 7 is a relationship between a decontamination coefficient of a fixed bed Cs + adsorption cold experiment and a water treatment amount of the adsorbent KZnHCF-S obtained in Example 3;
  • Table 1 shows the results of specific surface area measurement and static Cs + adsorption capacity of five kinds of silica gel-supported ferrocyanide adsorbents obtained in Example 1.
  • the present invention will be further described below in conjunction with specific embodiments, but the invention is not limited to the following examples.
  • the method is a conventional method unless otherwise specified, and the raw materials and standard chemical reagents used for the detection can be obtained from public commercial sources unless otherwise specified.
  • the experiment using the stable isotope Cs is called the cold experiment, in which the performance of the adsorbent adopts the static adsorption method and the dynamic adsorption method of the fixed bed reactor, respectively, and the concentration of Cs + ions before and after adsorption. It was measured by plasma mass spectrometry (ICP-MS).
  • the experiment using radioisotope 137 Cs is called isotope tracing experiment, also known as thermal experiment.
  • the adsorbent is packed in a fixed bed reactor to determine its dynamic adsorption performance.
  • the activity of tracer 137 Cs before and after adsorption is adopted. ⁇ energy spectrum analysis.
  • the adsorption partition coefficient K d (mL/g) is shown in the following formula (1), where C 0 and C t are the initial concentration of the adsorbed ions and the concentration after reaching the adsorption equilibrium, respectively, F is the volume of the treated solution (mL) and adsorption. The ratio of the mass of the agent (mg).
  • the decontamination coefficient is as shown in the following formula (2), which is the ratio of the initial concentration of the adsorbed ions to the concentration after reaching the adsorption equilibrium.
  • the general adsorption partition coefficient indicates the characteristics of the adsorbent material itself.
  • the K d value above 10 5 indicates that the performance of the adsorbent is good; the size of the decontamination coefficient is not only related to the adsorption characteristics of the material itself, but also related to the amount of the adsorbent. A larger value indicates a cleaner removal of contaminants.
  • K d (C o –C t ) ⁇ F ⁇ 1000/C t (1)
  • the adsorbent In the dynamic adsorption performance measurement of fixed bed reactor, the adsorbent is packed in the first or two-stage adsorption column, and the Cs + solution is flowed through the adsorption bed at a fixed flow rate to determine the mass concentration of Cs + in the effluent (cold experiment). Or the activity (thermal test), the flow rate is set to 8 bed volumes per hour, that is, 8 BV/h, and the performance of the adsorption reactor is represented by a decontamination coefficient DF as shown in Formula 2.
  • 0.1 g, 0.5 g, 1.0 g, 2.0 g, 3.0 g, 4.0 g, 5.0 g, 6.0 g of cobalt nitrate Co(NO 3 ) 2 ⁇ 6H 2 O were added to 8 small beakers, and 20 mL of water was added thereto. completely dissolved. Thereafter, 1 g of silica gel particles were added to each beaker, and the beaker was placed in a water bath at a temperature of 90 °C. The glass rod is stirred evenly during the evaporation of water until the water is completely evaporated and the particles are substantially dry.
  • the beaker was transferred to an oven at 120 ° C for 10 h, and then 1 g of pink cobalt oxide-loaded silica gel particles were mixed with 0.2 g of sodium chloride (NaCl), and the diffraction peak was measured by XRD, and the XRD diffraction peak intensity was extrapolated.
  • the method was used to determine the monolayer dispersion threshold of cobalt nitrate on the surface of silica gel, and the measured value was 0.63 g/g.
  • 0.1 g, 0.5 g, 1.0 g, 2.0 g, 3.0 g, 4.0 g, 5.0 g, 6.0 g of copper sulfate (CuSO 4 ⁇ 5H 2 O) were added to 8 small beakers, and 20 mL of water was added to completely dissolve them. . Thereafter, 1 g of silica gel particles were added to each beaker, and the beaker was placed in a water bath at a temperature of 90 °C. The glass rod is stirred evenly during the evaporation of water until the water is completely evaporated and the particles are substantially dry.
  • the beaker was transferred to a 120 ° C oven for 10 h, after which 1 g of blue copper sulfate-loaded silica gel particles were mixed with 0.2 g of sodium chloride (NaCl), and the diffraction peak was measured by XRD, and the XRD diffraction peak intensity was extrapolated.
  • the method was used to determine the monolayer dispersion threshold of copper sulfate on the surface of silica gel, and the measured value was 0.79 g/g.
  • 0.1 g, 0.5 g, 1.0 g, 2.0 g, 3.0 g, 4.0 g, 5.0 g, 6.0 g of zinc acetate ((CH 3 COO) 2 Zn ⁇ 2H 2 O) were added to 8 small beakers, and 20 mL was added. Water completely dissolves it. Thereafter, 1 g of silica gel particles were added to each beaker, and the beaker was placed in a water bath at a temperature of 90 °C. The glass rod is stirred evenly during the evaporation of water until the water is completely evaporated and the particles are substantially dry.
  • the beaker was transferred to an oven at 120 ° C for 10 h, and then 1 g of white zinc oxide-loaded silica gel particles were mixed with 0.2 g of sodium chloride (NaCl), and the diffraction peak was measured by XRD, and extrapolated by XRD diffraction peak intensity.
  • the method was to determine the monolayer dispersion threshold of zinc acetate on the surface of silica gel, and the measured value was 0.18 g/g.
  • 0.1 g, 0.5 g, 1.0 g, 2.0 g, 3.0 g, 4.0 g, 5.0 g, 6.0 g of zirconyl nitrate (ZrO(NO 3 ) 2 ) were added to 8 small beakers, and 20 mL of water was added to make it complete. Dissolved. Thereafter, 1 g of silica gel particles were added to each beaker, and the beaker was placed in a water bath at a temperature of 90 °C. The glass rod is stirred evenly during the evaporation of water until the water is completely evaporated and the particles are substantially dry.
  • the beaker was transferred to an oven at 120 ° C for 10 h, and then 1 g of white silica particles loaded with ZrO(NO 3 ) 2 and 0.2 g of sodium chloride (NaCl) were mixed and ground, and the diffraction peak was measured by XRD, and XRD diffraction peak was used.
  • the strength extrapolation method was used to determine the monolayer dispersion threshold of zirconyl nitrate on the surface of the silica gel, and the measured value was 1.02 g/g.
  • 0.1 g, 0.5 g, 1.0 g, 2.0 g, 3.0 g, 4.0 g, 5.0 g, 6.0 g of ferric chloride (FeCl 3 ⁇ 6H 2 O) were added to 8 small beakers, and 20 mL of water was added thereto. completely dissolved. Thereafter, 1 g of silica gel particles were added to each beaker, and the beaker was placed in a water bath at a temperature of 90 °C. The glass rod is stirred evenly during the evaporation of water until the water is completely evaporated and the particles are substantially dry.
  • the beaker was transferred to an oven at 120 ° C for 10 h, and then 1 g of yellow silica gel particles loaded with FeCl 3 were mixed with 0.2 g of sodium chloride (NaCl), and the diffraction peak was measured by XRD, and extrapolated by XRD diffraction peak intensity.
  • the method was to determine the monolayer dispersion threshold of ferric chloride on the surface of silica gel, and the measured value was 0.43 g/g.
  • Example 1 Laboratory preparation of five silica-supported adsorbents
  • KMHCF-S silica-loaded ferrocyanide-type adsorbents
  • Figure 1 shows the appearance of five adsorbents.
  • Figures 2 and 3 show the XRD patterns and Fourier transform infrared (FT-IR) spectra of five adsorbents, respectively.
  • Figure 4 shows five adsorptions. Scanning electron micrograph of the agent. It can be seen from Fig. 1 and Fig. 4 that different adsorbents prepared by different metal ions have different colors, which are spherical under scanning electron microscopy and have different surface roughness; visible from XRD patterns and FT-IR spectra.
  • the adsorption equilibrium isotherms of five adsorbents for Cs ions were determined by static adsorption method. See Figure 4, it can be seen that KCoHCF-S, KCuHCF-S and KZnHCF-S have better adsorption properties for Cs, while KZrHCF-S and KFeHCF-S is poor.
  • the adsorption capacity of the material for Cs was obtained by Langmuir fitting and is listed in the attached Table 1.
  • Figure 6 shows the results of dynamic breakthrough curves of KCuHCF-S and KZnHCF-S filled in a single-stage fixed-bed reactor.
  • the adsorption column has a diameter of 1.5 cm and a filling height of 10 cm.
  • the breakthrough curve can be well matched with the Thomas model, and the maximum adsorption capacities of the beds obtained by fitting KCuHCF-S and KZnHCF-S are 0.022 mg/mg and 0.023 mg/mg, respectively.
  • the dried material is once again added to the reaction chamber, and the first impregnation process and operating conditions are repeated until the solution is substantially adsorbed.
  • the material was placed in a tray again and dried in an electric blast oven at 120 ° C for 24 h to obtain a Cu/SiO 2 adsorbent intermediate.
  • the filtrate was poured back into the reaction chamber, and the water was replenished so that the volume of the solution was equal to the first amount of water absorption.
  • the dried material is added to the reaction tank a second time, and the first impregnation reaction process and operating conditions are repeated until the solution is substantially adsorbed.
  • the material was placed in a tray again and dried in an electric blast oven at 120 ° C for 24 h to obtain a KCuHCF-S adsorbent.
  • the material was sieved and washed with water until the solution was clear.
  • the wet material was packed in a two-stage series fixed bed adsorption reactor with a column height of 1 m and a diameter of 100 cm.
  • the initial concentration of Cs solution was 1.5 mg/L, and the flow rate was 100 L/h (8 BV/h).
  • the sampling points were set at the inlet, the first-stage outlet and the second-stage outlet of the adsorption bed respectively, and the sample was filtered by a 0.22 ⁇ m microporous filter.
  • the measurement results show that the decontamination coefficient is still greater than 1000 when the treated water reaches 7000 bed volume.
  • Example 3 Trial production of a single batch of 500 kg KZnHCF-S
  • the filtrate was poured back into the reaction chamber, and the water was replenished so that the volume of the solution was equal to the first amount of water absorption.
  • the dried material is once again added to the reaction chamber, and the first impregnation process and operating conditions are repeated until the solution is substantially adsorbed.
  • the material was placed in a tray again and dried in an electric blast oven at 120 ° C for 24 h to obtain a Zn/SiO 2 adsorbent intermediate.
  • the filtrate was poured back into the reaction chamber, and the water was replenished so that the volume of the solution was equal to the first amount of water absorption.
  • the dried material is added to the reaction tank a second time, and the first impregnation reaction process and operating conditions are repeated until the solution is substantially adsorbed.
  • the material was placed in a tray again and dried in an electric blast oven at 120 ° C for 24 h to obtain a KZnHCF-S adsorbent.
  • the material was sieved and washed with water until the solution was clear.
  • the wet material was packed in a two-stage series fixed bed adsorption reactor with a column height of 1 m and a diameter of 100 cm.
  • the initial concentration of Cs solution is about 1.5mg/L, and the flow rate is 100L/h (8BV/h).
  • FIG. 7 is a graph showing the relationship between the logarithmic value of the adsorption reactor decontamination coefficient and the liquid treatment amount. It can be seen that the adsorbent has a good removal effect on Cs, the decontamination coefficient is high, the adsorption capacity is large, and the performance is stable for a long time. Under the premise of ensuring the decontamination coefficient is 1000, the ratio of the waste liquid treatment amount to the adsorbent dosage amount reaches 7000. .
  • Dispense 1-5kg of silica gel in a stainless steel tray in the blast oven equipment dissolve zinc acetate (CH 3 COO) 2 Zn ⁇ 2H 2 O in a dissolution tank, stir to completely dissolve the solute, and form a solution concentration of 5- 15wt%.
  • the solution was added to each tray at a volume ratio of 1-4 to the silica gel so that the solution was immersed in all of the silica gel particles. Place the tray on the material cart, shake for 20-30min, then push it into the blast drying room, let stand for 4-5 hours, then dry at 100-120 °C to obtain batch of silica gel intermediate Zn/SiO 2 .
  • the potassium ferrocyanide is dissolved and dissolved in a dissolution tank to form a homogeneous solution.
  • the molar ratio of potassium ferrocyanide to zinc acetate is 0.8-1.2.
  • a solution was added to each tray, and the volume ratio of the solution to the silica gel was 1-4, so that the solution was immersed in the entire silica gel intermediate Zn/SiO 2 .
  • the obtained adsorbent is sieved, and a granule-complete adsorbent is selected and washed with tap water to remove the soluble substance and fine powder adhering to the surface of the particle until the washing liquid becomes clear.
  • the washed adsorbent is once again dried to obtain a silica-supported ferrocyanide-type adsorbent KZnHCF-S which can be used directly.
  • the adsorbent was loaded into a two-stage series fixed bed adsorption reactor by a wet method.
  • the internal diameter of the single fixed bed reactor was 36 cm, and the adsorbent loading height was 80 cm.
  • a 137 Cs tracer experiment was used, in which the required treatment volume was 1.2 t/h, the influent concentration was 1.7 mg/L, and the initial activity of 137 Cs was 5.7 ⁇ 10 3 Bq/L.
  • the sampling points are set at the inlet of the adsorption bed, the first-stage outlet and the second-stage outlet respectively, and the decontamination coefficient of the adsorption reactor is determined by the ⁇ -ray spectrometer, and the effluent is required to satisfy the decontamination factor of more than 1000.
  • the actual measured decontamination coefficient was 1.2 ⁇ 10 4 .
  • the potassium ferrocyanide is dissolved and dissolved in a dissolution tank to form a homogeneous solution.
  • the molar ratio of potassium ferrocyanide to copper sulfate is from 0.8 to 1.2.
  • a solution was added to each tray, and the volume ratio of the solution to the silica gel was 1-4, so that the solution was immersed in all of the silica intermediate Cu/SiO 2 . Place the tray on the material cart, shake for 20-30min, then push it into the blast drying room, let it stand for 4-5 hours, then dry it to obtain batch of silica-supported ferrocyanide-type adsorbent KCuHCF-S. .
  • the obtained adsorbent is sieved, and a granule-complete adsorbent is selected and washed with tap water to remove the soluble substance adhered to the surface of the particle and the brown-red fine powder until the washing liquid becomes clear.
  • the washed adsorbent is once again dried to obtain a silica-supported ferrocyanide-type adsorbent KCuHCF-S which can be used directly.
  • Dispense 1-5kg of silica gel in a stainless steel tray in the blast oven equipment dissolve the cobalt nitrate Co(NO 3 ) 2 ⁇ 6H 2 O in a dissolution tank, stir to completely dissolve the solute, and form a solution concentration of 15-30. %.
  • the solution was added to each tray at a volume ratio of 1-4 to the silica gel so that the solution was immersed in all of the silica gel particles. Place the tray on the material cart, shake for 20-30min, then push it into the blast drying room, let stand for 4-5 hours, then dry at 100-120 °C to obtain batch of silica gel intermediate Co/SiO 2 .
  • the potassium ferrocyanide is dissolved and dissolved in a dissolution tank to form a homogeneous solution.
  • the molar ratio of potassium ferrocyanide to zinc acetate is 0.8-1.2.
  • a solution was added to each tray, and the volume ratio of the solution to the silica gel was 1-4, so that the solution was immersed in the entire silica gel intermediate Co/SiO 2 .
  • the obtained adsorbent is sieved, and a granule-sized adsorbent is selected and washed with tap water to remove the soluble substance adhered to the surface of the particle and the dark gray fine powder until the washing liquid becomes clear.
  • the washed adsorbent is once again dried to obtain a silica-supported ferrous cyanide-based adsorbent KCoHCF-S which can be used directly.
  • the invention also specifically provides some non-limiting embodiments as follows:
  • a silica-supported metal ion-stabilized ferrocyanide adsorbent characterized in that the specific surface area of the silica gel is in the range of 900 to 1200 m 2 /g; and the metal ion-stabilized ferrocyanide Loaded on the silica gel in a single layer dispersion.
  • metal ion is derived from a salt of a metal ion: FeCl 3 , Fe(NO 3 ) 3 , Co(NO 3 ) 2 , CoCl 2 , Cu ( NO 3 ) 2 , CuSO 4 , Zn(NO 3 ) 2 , ZnCl 2 , Zn(AC) 2 , ZrOCl 2 and ZrO(NO 3 ) 2 .
  • ferrocyanide is selected from the group consisting of sodium ferrocyanide, potassium ferrocyanide, or a combination thereof, preferably potassium ferrocyanide.
  • adsorbent is an adsorbent for adsorbing radioisotope Cs ions or adsorbing stable isotope Cs ions.
  • a method of preparing a silica-supported metal ion-stabilized ferrocyanide adsorbent includes:
  • the salt of the metal ion is selected from the group consisting of FeCl 3 , Fe(NO 3 ) 3 , Co(NO 3 ) 2 , CoCl 2 , Cu(NO 3 ) 2 , a group consisting of CuSO 4 , Zn(NO 3 ) 2 , ZnCl 2 , Zn(AC) 2 , ZrOCl 2 and ZrO(NO 3 ) 2 .
  • loading the salt of the metal ion in a monolayer dispersion onto the surface of the silica gel comprises: (a) extrapolating by XRD diffraction peak intensity a method for determining a monolayer dispersion threshold of a salt of the metal ion on the surface of the silica gel; and (b) a method of immersing the silica gel particle with a salt solution of a metal ion according to the single layer dispersion threshold The salt is loaded onto the surface of the silica to form a single layer.
  • adsorbent is an adsorbent for adsorbing radioisotope Cs ions or adsorbing stable isotope Cs ions.
  • ferrocyanide is selected from the group consisting of A group consisting of sodium ferrocyanide, potassium ferrocyanide, or a combination thereof.
  • a silica-supported metal ion-stabilized ferrocyanide adsorbent prepared by the method of any one of embodiments 11-20.
  • silica-supported ferrocyanide adsorbent according to any one of embodiments 1 to 10 or the embodiment 21 for adsorbing radioisotope Cs ions or adsorbing stable isotope Cs ions.

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Abstract

一种颗粒态除铯无机离子吸附剂的制备方法及产品与应用。具体地，首先依据盐类在氧化物载体表面单层分散原理，采用X射线衍射方法测定M n+离子盐在硅胶表面的单层分散阈值，以该值为最优的M n+离子盐负载量。在吸附剂制备中，先用一定浓度的M n+离子盐充分浸渍硅胶颗粒，使M n+离子负载在硅胶表面形成分散单层，并使M n+离子与硅胶之间有较强的结合力；之后用亚铁氰化钾溶液充分浸泡中间体M/SiO 2，使亚铁氰化钾与表面的M n+离子反应，在硅胶表面生成一层结合力较强的M离子稳定的亚铁氰化物。经过静态Cs +吸附性能测定、固定床反应器冷实验测定以及固定床反应器 137Cs放射性示踪试验的验证，以该法制备的硅胶负载型亚铁氰化物吸附剂对Cs +具有良好的吸附性能。

Description

一种颗粒态除铯无机离子吸附剂的制备方法及产品与应用 技术领域
本发明涉及一种用于放射性废液处理中去除134Cs/137Cs离子的颗粒态无机离子吸附剂及其工业化制备方法，特别涉及一种复合吸附材料的制备方法。该材料以硅胶为载体，利用表面单层分散技术负载了一系列金属离子稳定型亚铁氰化物活性组分，其中稳定金属离子包括Fe3+、Co2+、Cu2+、Zn2+和Zr4+等。形成的颗粒态吸附剂适合填装于固定床吸附反应器，应用于核电站及其他核设施的废液处理工艺。本发明属于材料制备及放射性废水处理技术领域。
背景技术
核电作为一种重要的清洁能源，正在逐渐成为我国能源结构中的重要组成部分。日本福岛核事故后，核安全已经成为核能发展中需要重点关注的问题，建立核电站事故应急机制、开展应急技术研究，是非常重要和紧迫的。而放射性废液能否快速高效及时处理，是核电站事故中需要重点关注的问题。在这方面，日本福岛核事故是一个严重的警示，核事故条件下大量的放射性废液排入海域，造成污染。
低放废液水质复杂，并且通常含有裂变产物(I、Cs、Sr、Te、Ru、Mo、Ag及稀土元素等)，结构材料活化产物(Cr、Mn、Fe、Co、Ni)，以及放射性锕系元素(U、Pu、Am、Cm等)。其中裂变产物134Cs/137Cs是核事故下释放的主要核素，被视为监测核燃料破损的指针。在福岛核事故中，从反应堆泄漏出来的大量放射性废水中，铯就是主要的辐射来源(Hi ikata et.al.,2014；Tsukada et.al.,2014)。有研究表明，一次放射性铯的污染能够在生物系统中循环很多年(Avery,1996)。由于含量高、半衰期长、高溶解性和生物相容性等特点，134Cs/137Cs是低放废液中需要去除的主要目标。
核电站事故应急条件下，低放废液处理技术必须满足快速、高效、可 靠的要求。福岛事故的处理也是集世界多个国家之力，对核应急条件下放射性废液处理技术进行了一次实践优选和评估，最终形成的有效处理工艺包括了以下几个技术段：首先是预过滤和油水分离技术，去除废液中主要的固体残留物和水中含有的柴油等有机物；其次是无机离子吸附技术，重点是采用选择性无机吸附剂去除134Cs/137Cs和129I/131I，使核素快速富集到固体吸附剂表面，有效地降低废液中的放射性活度水平；接下来是膜技术精处理单元，将多种核素和其他非放射性金属离子进行浓缩分离，使排放出的水中放射性活度进一步降低并达到排放的要求。在这套核事故应急工艺中，除铯吸附剂起到了重要的作用。
核电站正常运行中，普遍采用“离子交换+蒸发浓缩”工艺进行放射性废液处理，有机离子交换树脂是常规的应用材料。从原理上说，废液中的金属离子都具有与树脂上的阳离子或阴离子进行交换的可能性，因此树脂是一种广谱性的处理技术，对核素离子的选择性低。由于低放废液中一般含盐量高，核素浓度极低，要达到较高的核素去除率所需的树脂量很大，这将最终形成大量的固体放射性废弃物。与有机树脂材料相比，无机离子吸附剂的热稳定性和化学稳定性好、耐辐照性能强，吸附饱和的无机材料在长期地质储存中具有高度的稳定性，易于现场辐射防护以及废物终端处理处置；更重要的是无机离子吸附剂对主要核素如134Cs/137Cs、90Sr和60Co的选择性高，适用于处理高盐量、强酸性/碱性的低放废液，能快速大幅度降低废液的放射性活度，降低固体废物量，满足核废物减量化的原则。此外无机离子吸附剂可以方便地制成可移动式小型净化设备，尤其适合于在核应急事故下灵活处理不同形式的分散性污染源。
在过去的几十年间，用无机吸附剂去除溶液中铯离子的研究有很多，吸附剂的种类也各异，其中亚铁氰化物型吸附剂在很宽的pH范围内皆能保持对铯离子良好的吸附效果。例如，赫尔辛基大学研制的亚铁氰化物型吸附剂Cs-treat，每千克材料可处理某核电站低放废液(含盐量240g/L)10吨左右，对Cs的去污系数达到了2000，是传统的蒸发-离子交换方法的2倍，这是除Cs方面国际上的最好研究成果。
金属离子Ti、Co、Cu、Zn、Ni和Zr等稳定的亚铁氰化物可以从pH＝ 1～13范围的高盐度低放废液中高效吸附Cs+，Cs+的分配系数可以达到104～106，在Na+存在下Cs的选择性系数KCs/Na可达1500000(Nuclear Science and Engineering,137,206-214,2001)。但在实际应用中，亚铁氰化物一般颗粒度小、水力学特性差，不能进行柱上操作，且固液相的分离非常困难；此外亚铁氰化物颗粒内部传质条件差，内层吸附剂往往不能完全利用(核化学与放射化学,23,108-113,2001)。针对此问题，国内外同行通常采用固载化技术，一种是将亚铁氰化物负载到二氧化硅等载体表面(Separation and Purification Technology 16,147–158,1999)，其缺点在于：活性组分的负载量低；利用过渡金属离子固定亚铁氰化物的过程很难完全进行，活性亚铁氰化物组分在使用中容易流失。另一种是将吸附剂与PAN结合制成无机/有机杂化小球(中国专利CN1319849A)，存在的问题是粘结剂易于堵塞吸附剂表面积孔道，降低吸附剂性能。
本研究组前期针对除铯吸附剂的固载化，采用了两种技术路线，有效地避免了单独使用亚铁氰化物粒子导致的床层水阻过大的问题。第一种是采用硅溶胶原位固定技术制备了亚铁氰化钴钾与多孔SiO2的杂化材料，对Cs+的吸附容量可达0.335meqCs/gadsorbent(中国专利CN 200710064453.0)；第二种是以成型的硅胶小球与钛酸四丁酯反应形成表面包覆TiO2的复合载体，再将该载体浸泡于亚铁氰化钾的盐酸溶液中，获得球形亚铁氰化钛钾/小球硅胶杂化材料(中国专利200710122085.0)。在原位固定技术中，SiO2作为粘结剂，易于将活性吸附剂亚铁氰化物包裹在内层，不易发挥其吸附作用；将吸附剂包覆在硅胶球的外表面可以使吸附剂易于与Cs+接触，但由于硅胶球的颗粒度较大(3-4mm)，影响了吸附剂对Cs+离子的吸附效率和吸附容量。
从生产实践出发，通过在成型的硅胶球表面引入吸附剂来实现吸附剂的固载化是令人期望的方法。然而，如上所述，通过这种方法制备的吸附剂具有表面活性组分在使用中容易流失而且吸附效率和吸附容量有限的不足。为了制备具有高吸附效率和吸附容量的硅胶担载型吸附剂，通常的做法是，在硅胶球表面引入大量金属盐，从而使得尽可能多的吸附活性组分能够通过表面反应而被担载在硅胶球上。然而，过多的金属盐堆积导致载 体表面的活性成分在使用中容易大量流失，从而降低了吸附剂的使用寿命，并且带来了二次污染问题。因此，实践中，在制备具有理想吸附效率和吸附容量的硅胶球负载型吸附剂时，减少甚至消除这种载体表面的活性组分在使用中的流失是一项具有挑战性的任务。
发明内容
本发明在前期工作的基础上，选择以颗粒度较小的大孔硅胶为载体，采用单层分散原理在硅胶表面上负载单层亚铁氰化物，制成由多种过渡金属离子Mn+稳定的颗粒态亚铁氰化物吸附剂，其中Mn+＝Fe3+、Co2+、Cu2+、Zn2+和Zr4+等。
本发明研制开发一种由多种过渡金属离子Mn+稳定的颗粒态亚铁氰化物吸附剂，并提供一种工业化制备负载型亚铁氰化物复合吸附材料的方法，包括如下的具体步骤：
(1)确定Mn+盐在硅胶表面的单层分散阈值
采用等体积浸渍法将一系列浓度不同的含有Mn+离子的盐溶液浸渍在硅胶表面，浸渍后的固体物料在烘箱内干燥，获得表面负载有不同量M盐的硅胶中间体M/SiO2。依据金属盐在载体表面单层分散的原理，采用X射线衍射方法确定不同种Mn+离子盐在硅胶表面的单层分散阈值，该值为不同种盐在硅胶载体表面的单层负载量。
(2)在硅胶表面负载单层Mn+离子盐
在鼓风烘房设备内的不锈钢托盘中分装等量硅胶，在溶解罐中加热溶解Mn+离子盐，搅拌使溶质完全溶解，形成一定浓度的溶液A。将一定体积的溶液A加入每个托盘中，浸没全部的硅胶颗粒，将托盘放置在物料车上，摇动20-30min，之后推入鼓风烘房内，先静置4-5小时，之后烘干，获得批量的硅胶中间体M/SiO2。
(3)利用表面反应制备亚铁氰化物吸附剂
在溶解罐中加热溶解亚铁氰化钾，使之形成均匀的溶液B。将一定体积的溶液B加入每个托盘中，浸没全部的硅胶中间体M/SiO2，摇动20-30min，之后推入鼓风烘房内，先静置4-5小时，之后烘干，获得批量的硅 胶负载型亚铁氰化物型吸附剂K2M[Fe(CN)6]/SiO2。
(4)吸附剂的清洗
将第3)步获得的吸附剂过筛，选取颗粒度完整的吸附剂，并用自来水清洗，去掉颗粒表面粘附的可溶性物质和细粉末，直到清洗液变得澄清。将清洗后的吸附剂再一次烘干，获得可以直接使用的硅胶负载型亚铁氰化物型吸附剂K2M[Fe(CN)6]/SiO2。
本发明的发明人惊讶地发现，可通过本发明的方法制备这样的硅胶负载型金属离子稳定的亚铁氰化物吸附剂，该吸附剂具有理想的初始吸附效率和吸附容量，同时在使用中活性组分的流失大大减少了，保持长时间的性能稳定。具体而言本发明提供了一种硅胶负载型金属离子稳定的亚铁氰化物吸附剂，其主要特征在于，作为载体的所述硅胶的比表面积在900-1200m2/g的范围内；并且所述金属离子稳定的亚铁氰化物以单层分散形式负载在所述硅胶上。优选地，所述硅胶具有10-15nm的孔径和0.4-2mm的颗粒度。优选地，所述金属离子选自由Fe3+、Co2+、Cu2+、Zn2+和Zr4+组成的组，这些金属离子例如可以衍生自如下金属离子的盐：FeCl3、Fe(NO3)3、Co(NO3)2、CoCl2、Cu(NO3)2、CuSO4、Zn(NO3)2、ZnCl2、Zn(AC)2、ZrOCl2和ZrO(NO3)2。优选地，所述亚铁氰化物选自由亚铁氰化钠、亚铁氰化钾、或其组合组成的组，更优选亚铁氰化钾。
进一步，所述所有步骤(1)—(4)中，选择大孔硅胶为载体，平均孔径在10-15nm，比表面积在900-1200m2/g，硅胶颗粒度在0.4-2mm。
进一步，所述步骤(1)—(2)中，Mn+＝Fe3+、Co2+、Cu2+、Zn2+或Zr4+等，选择的盐分别为：含Fe3+盐为FeCl3或Fe(NO3)3；含Co2+盐Co(NO3)2或CoCl2；含Cu2+盐Cu(NO3)2或CuSO4；含Zn2+盐为Zn(NO3)2、ZnCl2或Zn(AC)2；含Zr4+的盐为ZrOCl2或ZrO(NO3)2。
进一步，所述步骤(1)中，首先需要测定Mn+离子盐在硅胶表面的单层分散阈值，具体方法为：采用溶液浸渍法将一系列不同含量的Mn+离子盐负载到硅胶表面，烘干后得到待测样品。
硅胶质量为5-10g，Mn+离子盐在硅胶上的负载量为每克硅胶分别负载0.02g、0.05g、0.1g、0.5g、1.0g、2.0g、3.0g、4.0g、5.0g、6.0g；Mn+离子 溶液体积与硅胶体积比为0.5-2。
将获得的系列样品进行X射线衍射(XRD)测定，采用最强的衍射峰强度(y轴)与对应Mn+离子盐负载量(x轴)做线性关系图，图中x轴上的截距即为单层分散阈值。
进一步，所述步骤(1)中，浸渍过程在温度为90℃的水浴锅中进行，过程中不断搅拌，直到液体全部蒸发，溶质Mn+离子盐全部负载到硅胶表面。
进一步，所述步骤(1)中，硅胶中间体M/SiO2在烘箱内干燥10h，温度为120℃。
进一步，采用步骤(1)中所述的X射线衍射方法测定出不同Mn+离子盐在硅胶上的单层分散阈值。根据本发明，在硅胶上，Co(NO3)2的单层分散阈值为0.4-0.7g/g；CuSO4的单层分散阈值为0.6-0.9g/g；Zn(AC)2的单层分散阈值为0.1-0.4g/g；ZrO(NO3)2的单层分散阈值为0.9-1.2g/g；FeCl3的单层分散阈值为0.3-0.5g/g。在本发明的各个实施例中，Mn+离子盐在硅胶上的单层分散阈值例如为：Zn(AC)2阈值0.18g/g；Co(NO3)2阈值0.63g/g；CuSO4阈值0.79g/g；ZrO(NO3)2阈值1.02g/g；FeCl3阈值0.43g/g。进一步，所述步骤(2)中，每个托盘中加入1-2kg的硅胶颗粒，浸渍溶液体积与硅胶颗粒体积比为1-4，依据Mn+离子盐的单层分散阈值获得相应的溶质质量，可计算获得对应的A溶液浓度，溶解温度在30-60℃。
进一步，所述步骤(3)中，亚铁氰化钾与Mn+离子盐的摩尔数比为0.5-1.5，浸渍溶液体积与硅胶中间体M/SiO2颗粒体积比为1-4，溶解温度为在30-60℃。根据本发明的一个优选实施例，使用亚铁氰化钾作为亚铁氰化物以提供吸附活性组分。然而，本领域技术人员可以理解，工业上容易得到的其他亚铁氰化物，诸如亚铁氰化钠，由于其与亚铁氰化钾相似的化学性质，同样也适用于本发明。
进一步，所述步骤(2)和(3)中，溶液浸渍时间为3-5小时，之后在120℃的鼓风烘房内干燥5-10h。
由上述制备方法制备所得的含有亚铁氰化物K2M[Fe(CN)6]的吸附剂，也在本发明的保护范围之内。
本发明的发明人惊讶地发现，根据本发明的硅胶负载型金属离子稳定的亚铁氰化物吸附剂具有结构稳定、吸附性能高的特点。这种吸附剂由于可以吸附放射性同位素Cs离子，也可以吸附稳定性同位素Cs离子，因此具有广阔的应用前景。例如，可以通过吸附作用用于实现分离和/或去除或提取放射性同位素Cs离子，也可以用于分离和/或去除或提取稳定性同位素Cs离子的应用。因此，根据本发明的含有亚铁氰化物K2M[Fe(CN)6]的硅胶负载型吸附剂在吸附(包括去除或分离或提取)放射性同位素Cs离子和吸附(包括去除或分离或提取)稳定同位素Cs离子的应用，也在本发明的保护范围之内。
本发明提供了一种工业化制备硅胶负载型亚铁氰化物K2M[Fe(CN)6]吸附剂的有效方法，该材料可以应用于核电站放射性废液中Cs离子的高效去除，也可以应用于所有去除或提取或分离稳定同位素Cs的工况下。本发明以大孔硅胶为载体，以Mn+离子盐和亚铁氰化钾为原料，采用两步浸渍法制备硅胶负载型的亚铁氰化物K2M[Fe(CN)6]吸附剂。过程中首先将Mn+离子盐分散在硅胶表面，形成密致单层，并通过本发明中所述的方法获得Mn+离子盐的分散阈值，也就是Mn+离子盐的最优负载量；其次采用表面反应方法，使亚铁氰化物K2M[Fe(CN)6]在硅胶表面沉积，获得结构稳定、吸附性能高的除铯吸附剂。
附图说明
附图1为实施例1中所得五种硅胶负载型亚铁氰化物吸附剂的照片；
附图2为实施例1中所得五种硅胶负载型亚铁氰化物吸附剂的XRD图；
附图3为实施例1中所得五种硅胶负载型亚铁氰化物吸附剂的FT-IR图；
附图4(a-e)为实施例1中所得五种硅胶负载型亚铁氰化物吸附剂的SEM图；
附图5为实施例1中所得五种硅胶负载型亚铁氰化物吸附剂对Cs+离子的平衡吸附等温线；
附图6为实施例1中所得吸附剂KZnHCF-S和KCuHCF-S对Cs+离子的固 定床填充柱穿透曲线；
附图7为实施例3中所得的吸附剂KZnHCF-S的固定床Cs+吸附冷实验去污系数与水处理量关系；
附表1为实施例1中所得五种硅胶负载型亚铁氰化物吸附剂的比表面积测定结果以及静态Cs+吸附容量。
具体实施方式
下面结合具体实施方式对本发明作进一步阐述，但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法，所述原材料及检测所用标准化学试剂如无特别说明均能从公开商业途径获得。
在所述的实施例中，采用稳定同位素Cs进行测定的实验称为冷实验，其中吸附剂的性能分别采用了静态吸附法和固定床反应器动态吸附两种方法，吸附前后Cs+离子的浓度采用等离子体质谱(ICP-MS)来测定。采用放射性同位素137Cs进行测定的实验称为同位素示踪实验，也称为热实验，吸附剂装填于固定床反应器中测定其动态吸附性能，其中吸附前后示踪剂137Cs的放射性活度采用γ能谱分析。
静态吸附测定中，一定量的吸附剂加入到50mL的离心管中，置于恒温摇床上摇动48h-72h，测定吸附前后的Cs+离子浓度，吸附剂性能采用分配系数Kd和去污系数DF来表示。吸附分配系数Kd(mL/g)如下式(1)所示，其中C0和Ct分别为被吸附离子的初始浓度以及达到吸附平衡后浓度，F为被处理溶液体积(mL)与吸附剂质量(mg)之比。去污系数如下式(2)所示，为被吸附离子的初始浓度与达到吸附平衡后浓度的比值。一般吸附分配系数说明了吸附材料本身的特性，Kd值在105以上的说明吸附剂的性能良好；去污系数的大小不仅与材料本身的吸附特性相关，也与吸附剂的用量相关，该值越大说明污染物去除得越干净。
Kd＝(Co–Ct)×F×1000/Ct         (1)
DF＝Co/Ct             (2)
固定床反应器动态吸附性能测定中，吸附剂装填于一级或两级吸附柱中，含Cs+溶液以固定流速流过吸附床层，测定其流出液中Cs+的质量浓度 (冷实验)或放射性活度(热试验)，流量设定为每小时8个床体积，即8BV/h，吸附反应器的性能采用如2式所示的去污系数DF来表示。
对比例1
在8个小烧杯中分别加入0.1g、0.5g、1.0g、2.0g、3.0g、4.0g、5.0g、6.0g的硝酸钴Co(NO3)2·6H2O，加入20mL水使之完全溶解。之后在每个烧杯中加入1g的硅胶颗粒，将烧杯放入水浴锅内，温度为90℃。在水分挥发的过程中一直用玻璃棒搅拌均匀，直到水分全部蒸发，颗粒基本上干燥。将烧杯转入120℃烘箱内干燥10h，之后将1g粉红色的负载有硝酸钴的硅胶颗粒与0.2g氯化钠(NaCl)混合研磨，用XRD测定其衍射峰，利用XRD衍射峰强度外推的方法测定硝酸钴在硅胶表面的单层分散阈值，测定值为0.63g/g。
对比例2
在8个小烧杯中分别加入0.1g、0.5g、1.0g、2.0g、3.0g、4.0g、5.0g、6.0g的硫酸铜(CuSO4·5H2O)，加入20mL水使之完全溶解。之后在每个烧杯中加入1g的硅胶颗粒，将烧杯放入水浴锅内，温度为90℃。在水分挥发的过程中一直用玻璃棒搅拌均匀，直到水分全部蒸发，颗粒基本上干燥。将烧杯转入120℃烘箱内干燥10h，之后将1g蓝色的负载有硫酸铜的硅胶颗粒与0.2g氯化钠(NaCl)混合研磨，用XRD测定其衍射峰，利用XRD衍射峰强度外推的方法测定硫酸铜在硅胶表面的单层分散阈值，测定值为0.79g/g。
对比例3
在8个小烧杯中分别加入0.1g、0.5g、1.0g、2.0g、3.0g、4.0g、5.0g、6.0g的醋酸锌((CH3COO)2Zn·2H2O)，加入20mL水使之完全溶解。之后在每个烧杯中加入1g的硅胶颗粒，将烧杯放入水浴锅内，温度为90℃。在水分挥发的过程中一直用玻璃棒搅拌均匀，直到水分全部蒸发，颗粒基本上干燥。将烧杯转入120℃烘箱内干燥10h，之后将1g白色的负载有醋酸锌的硅胶颗粒与0.2g氯化钠(NaCl)混合研磨，用XRD测定其衍射峰，利用XRD衍射峰强度外推的方法测定醋酸锌在硅胶表面的单层分散阈值，测定值为0.18g/g。
对比例4
在8个小烧杯中分别加入0.1g、0.5g、1.0g、2.0g、3.0g、4.0g、5.0g、6.0g的硝酸氧锆(ZrO(NO3)2)，加入20mL水使之完全溶解。之后在每个烧杯中加入1g的硅胶颗粒，将烧杯放入水浴锅内，温度为90℃。在水分挥发的过程中一直用玻璃棒搅拌均匀，直到水分全部蒸发，颗粒基本上干燥。将烧杯转入120℃烘箱内干燥10h，之后将1g白色的负载有ZrO(NO3)2的硅胶颗粒与0.2g氯化钠(NaCl)混合研磨，用XRD测定其衍射峰，利用XRD衍射峰强度外推的方法测定硝酸氧锆在硅胶表面的单层分散阈值，测定值为1.02g/g。
对比例5
在8个小烧杯中分别加入0.1g、0.5g、1.0g、2.0g、3.0g、4.0g、5.0g、6.0g的三氯化铁(FeCl3·6H2O)，加入20mL水使之完全溶解。之后在每个烧杯中加入1g的硅胶颗粒，将烧杯放入水浴锅内，温度为90℃。在水分挥发的过程中一直用玻璃棒搅拌均匀，直到水分全部蒸发，颗粒基本上干燥。将烧杯转入120℃烘箱内干燥10h，之后将1g黄色的负载有FeCl3的硅胶颗粒与0.2g氯化钠(NaCl)混合研磨，用XRD测定其衍射峰，利用XRD衍射峰强度外推的方法测定三氯化铁在硅胶表面的单层分散阈值，测定值为0.43g/g。
实施例1：五种硅胶负载型吸附剂的实验室制备
两步浸渍法制备硅胶负载型吸附剂：
1)在5个10L的大烧杯中分别加入4L去离子水，分别加入：A—630g的Co(NO3)2·6H2O；B—790g的CuSO4·5H2O；C—180g的(CH3COO)2Zn·2H2O；D—1020g的ZrO(NO3)2；E—430g的FeCl3·6H2O。加热搅拌至完全溶解，之后将五种溶液分别倒入五个均盛有1kg硅胶颗粒的搪瓷托盘中，溶液基本上浸没全部的硅胶，静置3h，过程中经常搅拌使颗粒浸渍均匀。之后将5个托盘放置在恒温烘箱内，120℃下烘干10h，之后取出自然降温，获得浸渍不同离子的硅胶中间体。
2)在A、B、C、D、E这5个10L的大烧杯中各加入5L去离子水，分别加入一定量的亚铁氰化钾，加热至60-80℃下使之全部溶解。每个烧杯中加入的亚铁氰化钾与所对应的Co(A)、Cu(B)、Zn(C)、Zr(D)、Fe(E)离子的摩 尔数比为1.05。将准备好的溶液分别加入上一步中对应的托盘内，使溶液没过固体颗粒，静置3h，过程中经常搅拌使浸渍过程和表面反应均匀。之后将5个托盘放置在恒温烘箱内，120℃下烘干10h，之后取出自然降温，获得五种硅胶负载型亚铁氰化物型吸附剂，命名为KMHCF-S，其中M＝Co、Cu、Zn、Fe、Zr。
附图1给出五种吸附剂的外观照片，图2和图3分别给出五种吸附剂的XRD图谱和傅里叶变换红外(FT-IR)光谱，附图4给出了五种吸附剂的扫描电子显微镜照片。从附图1和附图4中可见，不同的金属离子制备获得的吸附剂具有不同的颜色，扫描电镜下可见均为球形，表面的粗糙度不同；从XRD图和FT-IR谱图中可见属于亚铁氰化物的特征衍射峰和特征红外吸收峰(2080cm-1处)，说明在硅胶表面确实形成了金属离子M稳定的亚铁氰化物活性组份。附表1中给出了采用氮气低温吸附法测定的物种吸附剂的比表面积值。
采用静态吸附方法测定了五种吸附剂对Cs离子的吸附平衡等温线，参见附图4，从中可见KCoHCF-S、KCuHCF-S和KZnHCF-S对Cs的吸附性能较好，而KZrHCF-S和KFeHCF-S较差。利用Langmuir拟合获得材料对Cs的吸附容量，列于附表1中。
附表1：五种硅胶负载型亚铁氰化物吸附剂比表面积分析结果
样品 比表面积(m2/g) 吸附容量(mg/mg)
KFeHCF-S 137.947  
KCoHCF-S 66.537 0.022
KCuHCF-S 389.429 0.061
KZnHCF-S 49.627 0.059
KZrHCF-S 90.728  
附图6给出了KCuHCF-S和KZnHCF-S两种材料装填于单级固定床反应器中进行的动态穿透曲线测定结果。吸附柱直径1.5cm，装填高度10cm。穿透曲线能够较好地符合Thomas模型，拟合所得KCuHCF-S和KZnHCF-S的床层最大吸附容量分别为0.022mg/mg和0.023mg/mg。
实施例2：单批次500kg量级KCuHCF-S试制
在1吨的反应箱内加入500L水，加入395kg的CuSO4·5H2O，加热至80℃条件下连续搅拌使之完全溶解。之后加入500kg硅胶载体，在80℃条件下浸渍12h，过程中经常搅拌使吸附过程均匀。之后将物料过滤，放置在托盘中，置于120℃的电热鼓风烘房内烘干24h。收集滤出液，通过体积测定第一次浸渍的吸水量。将滤出液重新倒入反应箱内，并在其中补水，使溶液体积等于第一次吸水量。将烘干的物料再一次加入反应箱内，重复第一次的浸渍过程和操作条件，直到溶液基本上吸附干净。再一次将物料放置在托盘中，置于120℃的电热鼓风烘房内烘干24h，获得Cu/SiO2吸附剂中间体。
在1吨的反应箱内加入500L水，加入与CuSO4·5H2O等摩尔数的亚铁氰化钾，加热至60℃条件下连续搅拌使之完全溶解。之后加入上一步获得的Cu/SiO2吸附剂中间体，在60℃条件下浸渍反应12h，过程中经常搅拌使吸附与反应过程均匀。之后将物料过滤，放置在托盘中，置于120℃的电热鼓风烘房内烘干24h。收集滤出液，测定首次浸渍的吸水量。将滤出液重新倒入反应箱内，补水使溶液体积等于第一次吸水量。将烘干的物料第二次加入反应箱内，重复第一次的浸渍反应过程和操作条件，直到溶液基本上吸附干净。再一次将物料放置在托盘中，置于120℃的电热鼓风烘房内烘干24h，获得KCuHCF-S吸附剂。
将材料过筛，用清水洗涤，直到溶液澄清。将湿物料装填于两级串联固定床吸附反应器中，柱子高度为1m，直径为100cm。实验中Cs溶液初始浓度为1.5mg/L，流量为100L/h(8BV/h)，分别在吸附床入口、一级出口和二级出口设置采样点，用0.22μm的微孔过滤器过滤采样，测定吸附反应器的去污系数。测定结果表明，当处理水量达到7000床体积时去污系数仍然大于1000。
实施例3：单批次500kg量级KZnHCF-S试制
在1吨的反应箱内加入500L水，加入92kg的(CH3COO)2Zn·2H2O，加热至40℃条件下连续搅拌使之完全溶解。之后加入500kg硅胶载体，在40℃条件下浸渍12h，过程中经常搅拌使吸附过程均匀。之后将物料过滤，放置在托盘中，置于120℃的电热鼓风烘房内烘干24h。收集滤出液，通过体 积减少量测定第一次浸渍的吸水量。将滤出液重新倒入反应箱内，补水使溶液体积等于第一次吸水量。将烘干的物料再一次加入反应箱内，重复第一次的浸渍过程和操作条件，直到溶液基本上吸附干净。再一次将物料放置在托盘中，置于120℃的电热鼓风烘房内烘干24h，获得Zn/SiO2吸附剂中间体。
在1吨的反应箱内加入500L水，加入与(CH3COO)2Zn·2H2O等摩尔数的亚铁氰化钾，加热至50℃条件下连续搅拌使之完全溶解。之后加入上一步获得的Zn/SiO2吸附剂中间体，在60℃条件下浸渍反应12h，过程中经常搅拌使吸附与反应过程均匀。之后将物料过滤，放置在托盘中，置于120℃的电热鼓风烘房内烘干24h。收集滤出液，测定首次浸渍的吸水量。将滤出液重新倒入反应箱内，补水使溶液体积等于第一次吸水量。将烘干的物料第二次加入反应箱内，重复第一次的浸渍反应过程和操作条件，直到溶液基本上吸附干净。再一次将物料放置在托盘中，置于120℃的电热鼓风烘房内烘干24h，获得KZnHCF-S吸附剂。将材料过筛，用清水洗涤，直到溶液澄清。将湿物料装填于两级串联固定床吸附反应器中，柱子高度为1m，直径为100cm。实验中Cs溶液初始浓度约为1.5mg/L，流量为100L/h(8BV/h)，分别在吸附床入口、一级出口和二级出口设置采样点，用0.22μm的微孔过滤器过滤采样，测定吸附反应器的去污系数。采用固定床吸附实验，附图7为吸附反应器去污系数对数值与液体处理量关系曲线。可见，吸附剂对Cs具有很好的去除效果，去污系数高、吸附容量大、性能稳定时间长，在保证去污系数为1000的前提下，废液处理量与吸附剂用量的比达到7000。
实施例4：KZnHCF-S吸附剂的稳定工业化制备
在鼓风烘房设备内的不锈钢托盘中分装1-5kg硅胶，在溶解罐中加热溶解醋酸锌(CH3COO)2Zn·2H2O，搅拌使溶质完全溶解，形成溶液浓度为5-15wt％。在每个托盘中加入溶液，溶液与硅胶的体积比为1-4，使溶液浸没全部的硅胶颗粒。将托盘放置在物料车上，摇动20-30min，之后推入鼓风烘房内，先静置4-5小时，之后在100-120℃下烘干，获得批量的硅胶中间体Zn/SiO2。
在溶解罐中加热溶解亚铁氰化钾，使之形成均匀的溶液。亚铁氰化钾与醋酸锌的摩尔比为0.8-1.2。在每个托盘中加入溶液，溶液与硅胶的体积比为1-4，使溶液浸没全部的硅胶中间体Zn/SiO2。将托盘放置在物料车上，摇动20-30min，之后推入鼓风烘房内，先静置4-5小时，之后烘干，获得批量的硅胶负载型亚铁氰化物型吸附剂KZnHCF-S。
将获得的吸附剂过筛，选取颗粒度完整的吸附剂，并用自来水清洗，去掉颗粒表面粘附的可溶性物质和细粉末，直到清洗液变得澄清。将清洗后的吸附剂再一次烘干，获得可以直接使用的硅胶负载型亚铁氰化物型吸附剂KZnHCF-S。
将吸附剂用湿法装入两级串联固定床吸附反应器中，单个固定床反应器的内径为36cm，吸附剂装填高度为80cm。采用137Cs示踪实验，其中要求的处理量为1.2t/h，进水浓度为1.7mg/L，137Cs的初始活度为5.7×103Bq/L。分别在吸附床入口、一级出口和二级出口设置采样点，用γ能谱仪测定吸附反应器的去污系数，要求出水满足去污因子大于1000。实际测定去污系数为1.2×104。
实施例5：KCuHCF-S吸附剂的稳定工业化制备
在鼓风烘房设备内的不锈钢托盘中分装1-5kg硅胶，在溶解罐中加热溶解硫酸铜CuSO4·5H2O，搅拌使溶质完全溶解，形成溶液浓度为15-40wt％。在每个托盘中加入溶液，溶液与硅胶的体积比为1-4，使溶液浸没全部的硅胶颗粒。将托盘放置在物料车上，摇动20-30min，之后推入鼓风烘房内，先静置4-5小时，之后在100-120℃下烘干，获得批量的硅胶中间体Cu/SiO2。
在溶解罐中加热溶解亚铁氰化钾，使之形成均匀的溶液。亚铁氰化钾与硫酸铜的摩尔比为0.8-1.2。在每个托盘中加入溶液，溶液与硅胶的体积比为1-4，使溶液浸没全部的硅胶中间体Cu/SiO2。将托盘放置在物料车上，摇动20-30min，之后推入鼓风烘房内，先静置4-5小时，之后烘干，获得批量的硅胶负载型亚铁氰化物型吸附剂KCuHCF-S。
将获得的吸附剂过筛，选取颗粒度完整的吸附剂，并用自来水清洗，去掉颗粒表面粘附的可溶性物质和棕红色细粉末，直到清洗液变得澄清。 将清洗后的吸附剂再一次烘干，获得可以直接使用的硅胶负载型亚铁氰化物型吸附剂KCuHCF-S。
实施例6：KCoHCF-S吸附剂的稳定工业化制备
在鼓风烘房设备内的不锈钢托盘中分装1-5kg硅胶，在溶解罐中加热溶解硝酸钴Co(NO3)2·6H2O，搅拌使溶质完全溶解，形成溶液浓度为15-30％。在每个托盘中加入溶液，溶液与硅胶的体积比为1-4，使溶液浸没全部的硅胶颗粒。将托盘放置在物料车上，摇动20-30min，之后推入鼓风烘房内，先静置4-5小时，之后在100-120℃下烘干，获得批量的硅胶中间体Co/SiO2。
在溶解罐中加热溶解亚铁氰化钾，使之形成均匀的溶液。亚铁氰化钾与醋酸锌的摩尔比为0.8-1.2。在每个托盘中加入溶液，溶液与硅胶的体积比为1-4，使溶液浸没全部的硅胶中间体Co/SiO2。将托盘放置在物料车上，摇动20-30min，之后推入鼓风烘房内，先静置4-5小时，之后烘干，获得批量的硅胶负载型亚铁氰化物型吸附剂KCoHCF-S。
将获得的吸附剂过筛，选取颗粒度完整的吸附剂，并用自来水清洗，去掉颗粒表面粘附的可溶性物质和深灰色细粉末，直到清洗液变得澄清。将清洗后的吸附剂再一次烘干，获得可以直接使用的硅胶负载型亚铁氰化物型吸附剂KCoHCF-S。
上面通过具体实施例的方式对本发明的各个方面进行了解释，但是本领域技术人员可以理解：本发明并不仅限于上面所描述的具体实施方式，本领域技术人员对本文所公开的各种具体技术手段、原料、工艺步骤等所做的等效替换和以及各种技术手段、原料、工艺步骤等的组合都在本发明的范围之内。
为了进一步举例说明本发明的某些方面，本发明还具体地提供了如下的一些非限制性实施方式：
1.一种硅胶负载型金属离子稳定的亚铁氰化物吸附剂，其特征在于，所述硅胶的比表面积在900-1200m2/g的范围内；并且所述金属离子稳定的亚铁氰化物以单层分散形式负载在所述硅胶上。
2.如实施方式1所述的吸附剂，其特征在于，所述硅胶具有10-15nm的 孔径和0.4-2mm的颗粒度。
3.如实施方式1所述的吸附剂，其特征在于，所述金属离子选自由Fe3+、Co2+、Cu2+、Zn2+和Zr4+组成的组。
4.如实施方式3所述的吸附剂，其特征在于，所述金属离子衍生自如下金属离子的盐：FeCl3、Fe(NO3)3、Co(NO3)2、CoCl2、Cu(NO3)2、CuSO4、Zn(NO3)2、ZnCl2、Zn(AC)2、ZrOCl2和ZrO(NO3)2。
5.如实施方式1所述的吸附剂，其特征在于，所述亚铁氰化物选自由亚铁氰化钠、亚铁氰化钾、或其组合组成的组，优选亚铁氰化钾。
6.如实施方式4至5中任一项所述的吸附剂，其特征在于，以单层分散形式负载在所述硅胶上的所述金属离子稳定的亚铁氰化物是通过如下步骤形成的：
(i)将所述金属离子的盐以单层分散形式负载到所述硅胶的表面；
(ii)使所述亚铁氰化物的溶液与负载在所述硅胶的表面上的所述金属离子的盐以0.5-1.5:1的摩尔比进行表面反应，从而形成以单层分散形式负载在所述硅胶上的所述金属离子稳定的亚铁氰化物。
7.如实施方式6所述的吸附剂，其特征在于，所述亚铁氰化物与所述金属离子的盐的摩尔比为0.8-1.2:1。
8.如实施方式6所述的吸附剂，其特征在于，将所述金属离子的盐以单层分散形式负载到所述硅胶的表面包括：(a)利用XRD衍射峰强度外推的方法确定所述金属离子的盐在所述硅胶的表面的单层分散阈值；然后(b)依据所述单层分散阈值，通过用金属离子的盐溶液浸泡硅胶颗粒的方法，将所述金属离子的盐以单层分散形式负载到所述硅胶的表面。
9.如实施方式8所述的吸附剂，其特征在于，在所述硅胶上，Co(NO3)2的单层分散阈值为0.4-0.7g/g；CuSO4的单层分散阈值为0.6-0.9g/g；Zn(AC)2的单层分散阈值为0.1-0.4g/g；ZrO(NO3)2的单层分散阈值为0.9-1.2g/g；FeCl3的单层分散阈值为0.3-0.5g/g。
10.如实施方式1所述的吸附剂，其特征在于，所述吸附剂是用于吸附放射性同位素Cs离子或吸附稳定同位素Cs离子的吸附剂。
11.一种制备硅胶负载型金属离子稳定的亚铁氰化物吸附剂的方法， 所述方法包括：
(i)选择比表面积在900-1200m2/g的范围内的硅胶作为载体；
(ii)将金属离子的盐以单层分散形式负载到所述硅胶的表面；
(iii)使所述亚铁氰化物的溶液与负载在所述硅胶表面上的所述金属离子的盐以0.5-1.5:1的摩尔比进行表面反应，从而在所述硅胶上形成金属离子稳定的亚铁氰化物。
12.如实施方式11所述的方法，其特征在于，所述硅胶具有10-15nm的孔径和0.4-2mm的颗粒度。
13.如实施方式11所述的方法，其特征在于，所述金属离子的盐选自由FeCl3、Fe(NO3)3、Co(NO3)2、CoCl2、Cu(NO3)2、CuSO4、Zn(NO3)2、ZnCl2、Zn(AC)2、ZrOCl2和ZrO(NO3)2组成的组。
14.如实施方式11-13中任一项所述的方法，其特征在于，将金属离子的盐以单层分散形式负载到所述硅胶的表面包括：(a)利用XRD衍射峰强度外推的方法确定所述金属离子的盐在所述硅胶表面的单层分散阈值；以及(b)依据所述单层分散阈值，通过用金属离子的盐溶液浸泡硅胶颗粒的方法，将所述金属离子的盐负载到所述硅胶表面形成单层。
15.如实施方式14所述的方法，其特征在于，在所述硅胶上，Co(NO3)2的单层分散阈值为0.4-0.7g/g；CuSO4的单层分散阈值为0.6-0.9g/g；Zn(AC)2的单层分散阈值为0.1-0.4g/g；ZrO(NO3)2的单层分散阈值为0.9-1.2g/g；FeCl3的单层分散阈值为0.3-0.5g/g。
16.如实施方式11所述的方法，其特征在于，所述吸附剂是用于吸附放射性同位素Cs离子或吸附稳定同位素Cs离子的吸附剂。
17.如实施方式14所述的方法，其特征在于，所述金属离子的盐的溶液与所述硅胶的体积比为1-4：1。
18.如实施方式14所述的方法，其特征在于，将所述硅胶在所述金属离子的盐的水溶液中浸渍3-5小时，并且在120℃下干燥5-10h。
19.如实施方式11所述的方法，其特征在于，所述亚铁氰化物与所述金属离子的盐的摩尔比为0.8-1.2：1。
20.如实施方式11所述的方法，其特征在于，所述亚铁氰化物选自由 亚铁氰化钠、亚铁氰化钾、或其组合组成的组。
21.一种由实施方式11-20任一项所述方法制备所得的硅胶负载型金属离子稳定的亚铁氰化物吸附剂。
22.由实施方式1-10中任意一项或者由实施方式21所述的硅胶负载型亚铁氰化物吸附剂用于吸附放射性同位素Cs离子或吸附稳定同位素Cs离子的用途。
23.如实施方式22所述的用途，用于去除或分离或提取放射性同位素Cs离子或用于去除或分离或提取稳定同位素Cs离子。

Claims (33)

  1. 一种颗粒态除铯无机离子吸附剂的制备方法，其特征在于，所述方法包括以下步骤：
    (1)选择采用大孔硅胶为载体；
    (2)依据单层分散原理，采用X射线衍射方法测定不同的金属离子Mn+离子盐在硅胶表面的单层分散阈值，获得最优的Mn+离子盐负载量；
    (3)用Mn+离子盐溶液浸泡硅胶颗粒，之后烘干，获得中间体M/SiO2；
    (4)将中间体M/SiO2浸泡在亚铁氰化钾溶液中，在SiO2表面生成Mn+离子稳定的亚铁氰化物，静置一定时间后烘干，所获材料经过筛和清洗，获得硅胶负载型亚铁氰化物吸附剂。
  2. 如权利要求1所述的制备方法，其特征在于，所述步骤(1)中，硅胶孔径10-15nm，比表面积在900-1200m2/g，硅胶颗粒度在0.4-2mm。
  3. 如权利要求1所述的制备方法，其特征在于，所述步骤(2)和(3)中，金属离子Mn+＝Fe3+、Co2+、Cu2+、Zn2+或Zr4+；选择的盐分别为：含Fe3+盐为FeCl3或Fe(NO3)3；含Co2+盐为Co(NO3)2或CoCl2；含Cu2+盐为Cu(NO3)2或CuSO4；含Zn2+盐为Zn(NO3)2、ZnCl2或Zn(AC)2；含Zr4+盐为ZrOCl2或ZrO(NO3)2。
  4. 如权利要求1所述的制备方法，其特征在于，首先需要测定Mn+离子盐在硅胶表面的单层分散阈值，具体方法为：采用溶液浸渍法将一系列不同含量的Mn+离子盐负载到硅胶表面，烘干后得到待测样品；
    硅胶质量为5-10g，Mn+离子盐在硅胶上的负载量为每克硅胶分别负载0.02g、0.05g、0.1g、0.5g、1.0g、2.0g、3.0g、4.0g、5.0g、6.0g；
    Mn+离子溶液体积与硅胶体积比为0.5-2；
    将获得的系列样品进行X射线衍射测定，获得单层分散阈值。
  5. 如权利要求3所述的制备方法，其特征在于，所述步骤(2)所测定的硅胶表面不同盐的单层分散阈值为：Co(NO3)2为0.4-0.7g/g；CuSO4为0.6-0.9g/g；Zn(AC)2为0.1-0.4g/g；ZrO(NO3)2为0.9-1.2g/g；FeCl3为0.3-0.5g/g。
  6. 如权利要求1所述的制备方法，其特征在于，所述步骤(3)和(4)中，浸渍溶液与硅胶颗粒的体积比为1-4，溶解温度为30-60℃。
  7. 如权利要求1所述的制备方法，其特征在于，所述步骤(4)中，亚铁氰化钾与Mn+离子盐的摩尔比为0.5-1.5。
  8. 如权利要求1所述的制备方法，其特征在于，所述步骤(3)和(4)中，溶液浸渍时间为3-5小时，之后在120℃的鼓风烘房内干燥5-10h。
  9. 一种由权利要求1-8任一项所述制备方法制备所得的硅胶负载型亚铁氰化物吸附剂。
  10. 权利要求8所述的硅胶负载型亚铁氰化物吸附剂在吸附去除放射性同位素Cs离子及吸附稳定同位素Cs离子的应用。
  11. 一种硅胶负载型金属离子稳定的亚铁氰化物吸附剂，其特征在于，所述硅胶的比表面积在900-1200m2/g的范围内；并且所述金属离子稳定的亚铁氰化物以单层分散形式负载在所述硅胶上。
  12. 如权利要求11所述的吸附剂，其特征在于，所述硅胶具有10-15nm的孔径和0.4-2mm的颗粒度。
  13. 如权利要求11所述的吸附剂，其特征在于，所述金属离子选自由Fe3+、Co2+、Cu2+、Zn2+和Zr4+组成的组。
  14. 如权利要求13所述的吸附剂，其特征在于，所述金属离子衍生自如下金属离子的盐：FeCl3、Fe(NO3)3、Co(NO3)2、CoCl2、Cu(NO3)2、CuSO4、Zn(NO3)2、ZnCl2、Zn(AC)2、ZrOCl2和ZrO(NO3)2。
  15. 如权利要求11所述的吸附剂，其特征在于，所述亚铁氰化物选自由亚铁氰化钠、亚铁氰化钾、或其组合组成的组，优选亚铁氰化钾。
  16. 如权利要求14至15中任一项所述的吸附剂，其特征在于，以单层分散形式负载在所述硅胶上的所述金属离子稳定的亚铁氰化物是通过如下步骤形成的：
    (i)将所述金属离子的盐以单层分散形式负载到所述硅胶的表面；
    (ii)使所述亚铁氰化物的溶液与负载在所述硅胶的表面上的所述金属离子的盐以0.5-1.5:1的摩尔比进行表面反应，从而形成以单层分散形式 负载在所述硅胶上的所述金属离子稳定的亚铁氰化物。
  17. 如权利要求16所述的吸附剂，其特征在于，所述亚铁氰化物与所述金属离子的盐的摩尔比为0.8-1.2:1。
  18. 如权利要求16所述的吸附剂，其特征在于，将所述金属离子的盐以单层分散形式负载到所述硅胶的表面包括：(a)利用XRD衍射峰强度外推的方法确定所述金属离子的盐在所述硅胶的表面的单层分散阈值；然后(b)依据所述单层分散阈值，通过用金属离子的盐溶液浸泡硅胶颗粒的方法，将所述金属离子的盐以单层分散形式负载到所述硅胶的表面。
  19. 如权利要求18所述的吸附剂，其特征在于，在所述硅胶上，Co(NO3)2的单层分散阈值为0.4-0.7g/g；CuSO4的单层分散阈值为0.6-0.9g/g；Zn(AC)2的单层分散阈值为0.1-0.4g/g；ZrO(NO3)2的单层分散阈值为0.9-1.2g/g；FeCl3的单层分散阈值为0.3-0.5g/g。
  20. 如权利要求11所述的吸附剂，其特征在于，所述吸附剂是用于吸附放射性同位素Cs离子或吸附稳定同位素Cs离子的吸附剂。
  21. 一种制备硅胶负载型金属离子稳定的亚铁氰化物吸附剂的方法，所述方法包括：
    (i)选择比表面积在900-1200m2/g的范围内的硅胶作为载体；
    (ii)将金属离子的盐以单层分散形式负载到所述硅胶的表面；
    (iii)使所述亚铁氰化物的溶液与负载在所述硅胶表面上的所述金属离子的盐以0.5-1.5:1的摩尔比进行表面反应，从而在所述硅胶上形成金属离子稳定的亚铁氰化物。
  22. 如权利要求21所述的方法，其特征在于，所述硅胶具有10-15nm的孔径和0.4-2mm的颗粒度。
  23. 如权利要求21所述的方法，其特征在于，所述金属离子的盐选自由FeCl3、Fe(NO3)3、Co(NO3)2、CoCl2、Cu(NO3)2、CuSO4、Zn(NO3)2、ZnCl2、Zn(AC)2、ZrOCl2和ZrO(NO3)2组成的组。
  24. 如权利要求21-23中任一项所述的方法，其特征在于，将金属离子的盐以单层分散形式负载到所述硅胶的表面包括：(a)利用XRD衍射峰强度外推的方法确定所述金属离子的盐在所述硅胶表面的单层分散阈值； 以及(b)依据所述单层分散阈值，通过用金属离子的盐溶液浸泡硅胶颗粒的方法，将所述金属离子的盐负载到所述硅胶表面形成单层。
  25. 如权利要求24所述的方法，其特征在于，在所述硅胶上，Co(NO3)2的单层分散阈值为0.4-0.7g/g；CuSO4的单层分散阈值为0.6-0.9g/g；Zn(AC)2的单层分散阈值为0.1-0.4g/g；ZrO(NO3)2的单层分散阈值为0.9-1.2g/g；FeCl3的单层分散阈值为0.3-0.5g/g。
  26. 如权利要求21所述的方法，其特征在于，所述吸附剂是用于吸附放射性同位素Cs离子或吸附稳定同位素Cs离子的吸附剂。
  27. 如权利要求24所述的方法，其特征在于，所述金属离子的盐的溶液与所述硅胶的体积比为1-4：1。
  28. 如权利要求24所述的方法，其特征在于，将所述硅胶在所述金属离子的盐的水溶液中浸渍3-5小时，并且在120℃下干燥5-10h。
  29. 如权利要求21所述的方法，其特征在于，所述亚铁氰化物与所述金属离子的盐的摩尔比为0.8-1.2：1。
  30. 如权利要求21所述的方法，其特征在于，所述亚铁氰化物选自由亚铁氰化钠、亚铁氰化钾、或其组合组成的组。
  31. 一种由权利要求21-30任一项所述方法制备所得的硅胶负载型金属离子稳定的亚铁氰化物吸附剂。
  32. 由权利要求11-20中任意一项或者由权利要求31所述的硅胶负载型亚铁氰化物吸附剂用于吸附放射性同位素Cs离子或吸附稳定同位素Cs离子的用途。
  33. 如权利要求32所述的用途，用于去除或分离或提取放射性同位素Cs离子或用于去除或分离或提取稳定同位素Cs离子。
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