CN108160022A - The application of particulate form SiSb sorbent preparation methods and product and its removal radioactivity Sr, Co and Ag - Google Patents
The application of particulate form SiSb sorbent preparation methods and product and its removal radioactivity Sr, Co and Ag Download PDFInfo
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- CN108160022A CN108160022A CN201810007803.8A CN201810007803A CN108160022A CN 108160022 A CN108160022 A CN 108160022A CN 201810007803 A CN201810007803 A CN 201810007803A CN 108160022 A CN108160022 A CN 108160022A
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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
- B01J20/02—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
- B01J20/0259—Compounds of N, P, As, Sb, Bi
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- 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
- B01J20/28016—Particle form
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- 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
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- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
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Abstract
The present invention relates to the applications of particulate form SiSb sorbent preparation methods and product and its removal radioactivity Sr, Co and Ag.In particular it relates to a kind of particulate form SiSb composite oxides adsorbents, it includes：Particle containing SiSb composite oxides；And the polymer material layer of the cladding particle.The adsorbent has high crush strength and low ion leaching rate.The invention further relates to the preparation method of the adsorbent and its in removal radioactivity90Sr and110mThe application of Ag.
Description
Technical field
The present invention relates to field of inorganic materials, more particularly to a kind of particulate form SiSb composite oxides adsorbent and its preparation
Method and application, the adsorbent is to radioactivity89Sr and90Sr、110mAg has good absorption property, and is suitably applied work
Industry scale can be loaded into the efficient removal that radionuclide is realized in fixed bed reactors.
Background technology
According to the Chinese Nuclear Power Long-and Medium-term Development object of planning, to the year two thousand twenty, China's Mainland operation nuclear power installed capacity will reach
To 58,000,000 kilowatts, 30,000,000 kilowatts or so are being built；It to be realized comprehensively to the year two thousand thirty and build nuclear power power target.In face of nuclear energy thing
Industry develops new situations new challenge, and there is an urgent need in Radwastes treatment, nuclear emergency technology, radioactive effluent discharge mark for China
Standard etc. is greatly developed.
In the radioactive liquid waste generated in nuclear power plant's day-to-day operation, the main source of radionuclide is activation products and corruption
Product is lost, the generation of these products is mainly related with the activation of metal material, burn into precipitation and release behavior, and part is radiated
Property nucleic is including Ag, Co, Cr, Mn, Fe etc..The major radiation substance occurred simultaneously in the radioactive liquid waste of nuclear power station not only wraps
Include the long-lived fission product with beta activity134Cs/137Cs and90Sr is further included110mAg。
90Sr is235One of fission product of U, yield 5.90%, half-life period are 28 years, have beta activity, via food
Or after water is absorbed by the body, 70%~80% dosage is excluded in vitro, remaining90Sr is largely deposited on bone and marrow
In, osteocarcinoma, soft tissue canceration and leukaemia can be caused.Due to90Sr is easy to accumulate in bone, and many countries are right90The discharge of Sr
Limit value ratio137Cs is lower.Therefore, it effectively removes present in radioactive liquid waste90Sr nucleic is a urgent problem to be solved.
110mMainly there are two approach in the source of Ag：First, since control rod Ag-In-Cd alloys absorb neutron, Ag therein
Isomeric transistion occurs, is formed metastable110mAg；Secondly the sealing material of argentiferous is formed under neutron activation110mAg。
More of China nuclear power station observes that its liquid relief liquor still includes significant quantity110mAg.The existing radioactive liquid waste processing in power station
Technology pair110mThe removal effect of Ag is bad.
Ion exchange resin is compared to, inorganic ions adsorbent has high selectivity, can be from the radioactivity of amount with high salt
Target species ion is efficiently removed in waste water, the radioactive activity of waste liquid can quickly be greatly lowered, on-radiation is coexisted
The advantages of influence of ion is small, therefore long with service life, and quantity of solid waste is small.In addition, the application of inorganic ions adsorbent
A large amount of radionuclide can be caused to be enriched in the adsorbent of small size, so as to which the solid waste generated is easy to be radiated
Protection.Compared to ion exchange resin, inorganic adsorbent technology generate radioactive waste thermal stability and chemical stability it is good,
Radiation-resistant property is strong, is not easy by RADIATION DECOMPOSITION or biological decomposition, disposes convenient for the processing in later stage, is stored in underground disposal head's phase
In the process, more long-term safety.Further, the waste liquid device for deep cleaning based on inorganic adsorbent technology has simple knot
Structure has the technical characterstic that effective, selectivity is strong, miniaturization, modularization, mobility are strong, low to the requirement of Site Service condition,
It is very suitable for the particular/special requirement that nuclear power plant's radioactive liquid waste ingredient is complex and site layout project space is limited.
At present, using the nucleic of inorganic ions adsorbent removal mainly for Cs, Sr, Co.Except Sr adsorbents mainly include
Two major class of zeolite and hydrated metal oxide, wherein hydrated metal oxide are because with adsorption capacity height, select specific ion
The characteristics of selecting property is strong and be considered having good development prospect.Common hydrated metal oxide type removes Sr adsorbent packets in research
Include hydrated manganese dioxide, hydrated zirconium dioxide, hydration stannic oxide, hydrated titanium dioxide etc. and metal composite oxide such as
Titanium-silicon compound, zirconium manganese compound, titanium manganese compound, zirconium titanium compound etc..The seminar of Tsinghua University succeeds in developing a few days ago
To Sr, Co ion have excellent absorption property metal stibate type adsorbent, as ZL201410132237.5,
Disclosed in ZL201410130939.X, ZL201410131091.2 and ZL201410132212.5.However, in more than patent
The adsorbent of acquisition is powder, is not suitable for being applied to the commercial plants such as fixed bed reactors, adsorption column.In addition, for being applied to
It is removed in radioactive liquid waste110mThe inorganic ions adsorbent research of Ag is less.It is only so far for micro in drinking water
Ag+The adsorbent of removal respectively includes：Hydroxyapatite, montmorillonite, chitosan, amido modified SiO2And contain sulfydryl
Organic polymer etc..
In view of the above circumstances, radioactive liquid waste processing industry needs one kind that can effectively remove90Sr and100mAg and be applicable in
In the inorganic ions adsorbent of the commercial Application of the commercial plants such as fixed bed reactors, adsorption column.
Invention content
The purpose of the present invention is to provide one kind effectively to remove90Sr and100mAg and suitable for fixed bed reactors,
The inorganic ions adsorbent of the commercial Applications such as adsorption column.
The present inventor through many experiments, it was unexpectedly found that, SiSb composite oxides adsorbent can be effective
Ground removes radioactivity90Sr and100mAg, and removed by washing and pine is combined on the surface of the particle containing SiSb composite oxides
After soluble ion in scattered solid phase particles and the particle, coated high molecular material layer, can obtain with reason on it
The mechanical stability thought and low ion leaching rate except the adsorbent of Sr and Ag, so as to be handled suitable for nuclear power station radioactive liquid waste
Practical Project.
On the one hand, the present invention provides one kind for removing radioactivity90Sr and100mThe particulate form SiSb composite oxides of Ag
Adsorbent, it includes：Particle containing SiSb composite oxides；With the polymer material layer for coating the particle.
Preferably, adsorbent according to the present invention has at least particle size of 0.2mm, the preferably at least particle of 0.5mm
Size.Further, the particle size of adsorbent according to the present invention is less than or equal to 10mm, preferably smaller than equal to 5mm.
Preferably, adsorbent according to the present invention has the crushing strength of 2-100N/particle.
Preferably, adsorbent according to the present invention has such ion leaching characteristic, so that the adsorbent is 10
Liquid-solid ratio under impregnate 24 hours after, the turbidity of acquired solution is 50mg/L or lower.
Preferably, adsorbent according to the present invention has such ion leaching characteristic, so that the adsorbent is 10
Liquid-solid ratio under impregnate 24 hours after, the conductivity of acquired solution is 50 μ s/cm or lower.
Preferably, in adsorbent according to the present invention, the polymer material layer includes sodium alginate, chitosan, number
Polyethylene glycol, polyvinyl alcohol, sucrose or its arbitrary combination of average molecular weight between 2000-6000.
Above-mentioned adsorbent can not only adsorb to quick high-selectivity90Sr and100mAg radionuclide ions, and with a scale
Very little particulate form, stable structure, and longtime running and the fast flush of flow can be stood, thus can be loaded into
Fixed bed reactors use for Practical Project.
On the other hand, the invention further relates to the preparation method of standby particulate form SiSb composite oxides adsorbents, the methods
Including：
1) particle containing SiSb composite oxides is provided；
2) particle of step 1) is washed with deionized, the Cl until not measuring cleaning solution with silver nitrate solution inspection-Ion；
3) washed particle is coated with high molecular material, it is preferably in the presence of acids and bases, coated so as to obtain
Particle；And
4) the coated particle of step 3) optionally, is washed with deionized, until the conductivity of cleaning solution is 50.0 μ
S/cm or lower and turbidity are 50mg/L or lower,
So as to obtain the particulate form SiSb composite oxides adsorbents.
Preferably, according to embodiment of the present invention, it provides the particle containing SiSb composite oxides to include, a) exist
Silicic acid C is supported on particulate form inorganic oxide carrier or particulate form absorbent charcoal carrier1-4Arrcostab and SbCl3Mixture, so
B) the obtained particles of step a) are aoxidized with hydrogen peroxide afterwards, are then hydrolyzed, so as to be formed containing SiSb composite oxides
Particle.Preferably, the particulate form inorganic oxide carrier is pellets, usually has the granularity of 0.5-3mm.
In the specific embodiment of the present invention, particulate form SiSb composite oxides adsorbents are as follows
It prepares：
1) carrier preparation and charging process：Particulate form inorganic oxide or particulate form activated carbon are selected as carrier, and
It is loaded into reaction kettle, reaction kettle is then mounted and sealed；
2) Sb-Si solution is prepared：Weigh a certain amount of antimony trichloride SbCl3With the silicic acid C of certain volume1-4Arrcostab, will
The two is dissolved in anhydrous solvent forms stock solution together, and feed liquid is added to and is added dropwise in bottle；
3) Sb-Si solution is added dropwise：Opening reaction kettle makes its rotation, while the solution of Sb-Si is slowly added dropwise into reaction kettle,
Make Sb (III) in material and Si (IV) by inorganic oxide or absorbent charcoal carrier uniform adsorption；
4) recycling design is evaporated：Solvent is made to volatilize using the method for vacuum distillation, and condensed recycling, make Sb (III) and
Si (IV) is equably supported on particulate form inorganic oxide or activated carbon supporting agent surface；
5) hydrogen peroxide oxidation process：The hydrogen peroxide of sufficient amount is added to and is added dropwise in bottle, Open valve is slow by hydrogen peroxide
It is added dropwise and enters reaction system, be Sb (V) by Sb (III) oxidation transformation；
6) complete hydrolysis process：The pure water of sufficient amount is added to and is added dropwise in bottle, valve is opened, pure water is added dropwise to reaction
Kettle makes Sb (V) and Si (IV) complete hydrolysis, and dispersed SiSb composite oxides microcrystals are formed in carrier surface；
7) adsorbent cleaning and filtering：After reaction, reaction kettle is opened, material therein is poured into Buchner funnel and was carried out
Filter, clean the absorbent particles containing SiSb composite oxides with pure water later, preferably progress 10 hours or longer, until with nitre
Sour silver inspection does not measure Cl-Until ion exists, then material is dried；
8) cladding of particle：Pass through the particle surface coated high molecular material layer obtained as follows in step (7)：To have viscous
The high molecular material of knot effect, which is dissolved in pure water, is configured to certain density solution；The particle that step (7) obtains is added to
In solution system；Preferably, according to the difference of high molecular material, acid or aqueous slkali are added dropwise during stirring；By mixture
After stirring 1-10h, Solid-Liquid Separation is carried out, so as to obtain particulate form SiSb composite oxides adsorbents；With
9) cleaning and drying of adsorbent：Using deionized water to the particulate form SiSb combined oxidations of acquisition in step (8)
Object adsorbent is cleaned, and is preferably carried out 10 hours or longer, until the conductivity of cleaning solution is 50.0 μ s/cm or lower and turbid
It spends for 50mg/L or lower, carries out Solid-Liquid Separation later, and adsorbent is dried, it is preferred to use constant temperature oven or vacuum drying oven
It is dried under 60-120 DEG C of drying temperature.
Further, in the step (1), particulate form inorganic oxide carrier has the granularity and 2-80N/ of 0.5-3mm
The crushing strength of particle.
Further, in the step (1), particulate form inorganic oxide carrier includes alumina globule, titanium oxide bead, oxygen
Change zirconium bead, silica gel bead；Particulate form absorbent charcoal carrier includes coconut husk charcoal or coal-based carbon.
Further, it is dried over anhydrous state in the step (1), in reaction kettle.
Further, in the step (2), silicic acid C1-4Arrcostab includes methyl silicate, silester, silicic acid propyl ester, silicic acid
Butyl ester or combination.
Further, in the step (2), antimony trichloride SbCl3With silicic acid C1-4The mixture of Arrcostab is in anhydrous solvent
The concentration for forming solution is controlled in 50~500g/L ranges.
Further, in the step (2), the molar ratio of Sb (III) and Si (IV) are 1:2~1:6.
Further, in the step (2), available anhydrous solvent includes：Ethyl alcohol, propyl alcohol, isopropanol and ethylene glycol.
Further, in the step (3), after control is added dropwise, the volume of Sb-Si- alcoholic solutions just flooded solid
Particle.
Further, in the step (4), solvent, the heating that reaction kettle uses are separated and recovered from using vacuum distillation method
Mode can be water-bath or oil bath, and temperature control is 30-70 DEG C, and until solvent, all volatilization finishes, and stops the process.
Further, in the step (5), the hydrogen peroxide concentration used is 30~50wt%；Hydrogen peroxide rubs with Sb (III's)
You are than being 1:1~5:1.
Further, in the step (5), controlling reaction temperature is 5-40 DEG C；Stop that the reaction time after hydrogen peroxide is added dropwise
For 1-5h.
Further, in the step (5), chlorine can be generated in reaction, needs to be evacuated reaction kettle using air pump, discharge
Chlorine enter and fill the Meng Shi drexel bottles of hypo solution and absorbed, drexel bottle discharges gas through silica dehydrator heel row
Enter outside atmosphere.
Further, in the step (6), antimony trichloride SbCl in the water and material of addition3Mass ratio be 1:1~5:1；
Hydrolysising reacting temperature control is 20~80 DEG C, and the reaction time is 2~8h.
Further, in the step (7), particle is dried in 60~120 DEG C of constant temperature oven.
Further, in the step (8), the high molecular material with cementation of use is sodium alginate, shell respectively
Glycan, polyethylene glycol (2000-6000), polyvinyl alcohol, sucrose etc.；Solution concentration is 1%~20wt%；High molecular material is with inhaling
Attached dose of mass ratio is 5%~30%.
Further, in the step (8), the acid of dropwise addition is hydrochloric acid, sulfuric acid, acetic acid or its arbitrary combination.Preferably, it is sour
A concentration of 0.01~1mol/L.
Further, in the step (8), the alkali of dropwise addition is sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium hydroxide or it is arbitrary
Combination.Preferably, a concentration of 0.01~1mol/L of alkali.
Present inventors have realized that carrying out water-washing process to the particle containing SiSb composite oxides, can remove
Loose partial solid phase particle is combined on the surface of particle, and the soluble ion in particle is made fully to discharge, is made washed
Particle have good mechanical strength and relatively low ion leaching characteristic.Further, it is carried out in washed particle surface
Macromolecule layer coats, and can further improve the mechanical strength of granule adsorbent, preferably has 2-100N/ so as to obtain
The adsorbent of the crushing strength of particle and extremely low ion leaching characteristic.
Specific embodiment
The present invention is further elaborated With reference to embodiment, but the present invention is not limited to following embodiments.
The method is conventional method unless otherwise instructed, and standardizing chemical reagent used in the raw material and detection is unless otherwise instructed
It can be obtained from open commercial sources.
Below in an example, adsorbent has carried out Static Adsorption respectively and ADSORPTION IN A FIXED BED reaction column performance test is surveyed
It is fixed, Sr before and after absorption2+And Ag+The concentration using plasma mass spectrum (ICP-MS) of ion measures, performance of the adsorbent using point
Distribution coefficient KdIt is represented with decontamination factor DF.
During Static Adsorption measures, a certain amount of adsorbent is added in the centrifuge tube of 50mL, is placed on constant-temperature table and is shaken
48h~72h measures the front and rear Sr of absorption2+And Ag+Ion concentration, performance of the adsorbent use distribution coefficient KdWith decontamination factor DF
To represent.Adsorption isothermequation Kd (mL/g) is as shown in following formula 1, wherein C0And CtRespectively the initial concentration of adion with
And reaching concentration after adsorption equilibrium, F is by the ratio between processing solution volume (mL) and adsorbent mass (mg).Decontamination factor such as following formula
Shown in 2, for adion influent concentration and reach the ratio of the aqueous concentration after adsorption equilibrium.General adsorption isothermequation
Illustrate the characteristic of sorbing material in itself, KdValue is 105Above illustrates the functional of adsorbent；The size of decontamination factor is not
Only related to the characterization of adsorption of material in itself, also related to the dosage of adsorbent, the value is bigger to illustrate that pollutant removal must be more dry
Only.
Kd=(Co-Ct) × F × 1000/Ct (1)
Dynamic adsorption is carried out using ADSORPTION IN A FIXED BED reaction column, test pole height 10cm, diameter 1.5cm, water flow
For 20BV/h.
The crushing strength of adsorbent according to the present invention is determined by：The crushing strength of adsorbent is using domestic
Crushing strength instrument be measured, instrument model is：YHKC-2A type detector for strength of particles.In measure, 60-100 is randomly selected
Particle is placed on center immediately below hammer by absorbent particles, when measure one by one, rotates handle, hammer is made to fall, when connecing
During nearly particle, slowly rotate, hammer is made slowly to contact, when the sound for hearing Particle Breakage, provided on instrument crushing the moment add
The power being loaded on particle is how much newton.
The ion Leaching Characteristics of adsorbent according to the present invention are determined by：Adsorbent is immersed in 10 first
In the pure water of times volume, it is stirred using blender or is shaken using shaking table, after a certain period of time, HACH is respectively adopted
2100N types nephelometer and DDSJ-308A conductivity meters measure the turbidity and conductivity of immersion liquid.The precision that nephelometer uses for
0.001mg/L, the precision that conductivity meter uses is 0.01 μ s/cm.
Embodiment 1：Particulate form SiSb/Al2O3The preparation of adsorbent
1) selective oxidation aluminium bead is carrier, choose in advance grain size 0.5~1mm with the carrier being tested, measure its pressure
Broken intensity is 3~10N/particle.500g alumina particles are weighed, are loaded into reaction kettle, reaction kettle is installed.
2) the antimony trichloride SbCl of 663.6g is weighed3, it is dissolved in the absolute ethyl alcohol of 2L and forms stock solution, molten
The silester TEOS of 1860mL is added in liquid, after mixed dissolution is uniform, material Sb-Si- ethanol solutions are utilized into vacuum suck
Bottle for material I after all sucking, closes vacuum pump, bottle for material is made to be separated with vacuum system.
3) reaction kettle Rotation Controllers is opened, adjusting rotating speed is 25 turns/min, and material Sb-Si- ethanol solutions are slowly dripped
It adds into reaction kettle, material is by alumina particle uniform adsorption, and it is more than solid material to keep liquid level.Treat that all solution is added dropwise
After, reaction kettle 1h is rotated further, makes dipping of the solution on alumina particle uniform.
4) cooling water machine is opened, cooling water is made to enter condenser, and condensation temperature is made to reach less than 5 DEG C.In reaction kettle
Deionized water is added in water-bath, opens electrical heating, set temperature is 80 DEG C.It opens vacuum pump to be evaporated under reduced pressure, Zhi Daoquan
Portion's ethanol evaporation is clean.
5) by 400mL hydrogen peroxide (30wt%) using vacuum suck bottle for material II, in reaction by hydrogen peroxide be slowly added dropwise into
Enter reaction kettle and by solid uniform adsorption.Negative pressure is caused to reaction system pumping using a small size air air pump in the process, generation
Chlorine is taken out of and is absorbed through hypo solution in drexel bottle.After hydrogen peroxide is added dropwise, in 5 DEG C of bath temperature and keep
2h is reacted under aeration status.
6) electrical heating is opened, it is 30 DEG C to adjust bath temperature.2L pure water is added in into bottle for material II, in the reaction drips pure water
It adds into reaction kettle, and 5h is reacted under the conditions of being 30 DEG C in bath temperature, make Sb (V) complete hydrolysis.
7) after reacting, reaction kettle is opened, material therein is poured into funnel and is filtered, is cleaned later with pure water, directly
Cl is not measured to silver nitrate solution inspection-Ion finally dries adsorbent at 100 DEG C.
8) using polyethylene glycol (6000) polyethylene glycol is dissolved in pure water and is configured to solution as covering material, it is dense
Spend is 5~30%.The adsorbent that step 7) obtains is added in solution system, liquid-solid ratio 10:1；Continue to stir and react
After 2-10h, Solid-Liquid Separation.
9) granule adsorbent that step 8) obtains further is cleaned using deionized water, every time cleaning water used
Volume is 10 times of adsorbent volume, until the conductivity of cleaning solution is less than 50 μ s/cm, later Solid-Liquid Separation, and will absorption
Agent obtains final SiSb/Al using vacuum drying2O3Adsorbent.
After measured, the crushing strength of obtained adsorbent is 3-15N/particle, under conditions of liquid-solid ratio is 10
After impregnating for 24 hours, turbidity is 10.3mg/L in liquid, and conductivity is 6.9 μ s/cm, a concentration of 0.87mg/L of COD in solution.Using
Static adsorption method is tested the Adsorption performance of the Ag and Sr ions of obtained adsorbent, a concentration of in initial ion
Under conditions of 10mg/L, the adsorption isothermequation K of Ag ionsdIt is 4.7 × 104ML/g, adsorption capacity 38mg/g；Sr ions
Adsorption isothermequation KdIt is 5.8 × 104ML/g, adsorption capacity 36mg/g.
As can be seen from the above results, SiSb composite oxides adsorbent of the invention can simultaneously effective remove Sr from
Son and Ag ions.Moreover, the present invention SiSb composite oxides due to having certain granularity and mechanical stability, because
And longtime running and the fast flush of flow can be stood, fixed bed reactors can be loaded into, for Practical Project
It uses.
The preparation of embodiment 2.SiSb/ active carbon particle adsorbents
1) the antimony trichloride SbCl of 663.6g is weighed3, it is dissolved in the absolute ethyl alcohol of 2L and forms stock solution, molten
The silester TEOS of 1860mL is added in liquid, after mixed dissolution is uniform, material Sb-Si- ethanol solutions are utilized into vacuum suck
Bottle for material I after all sucking, closes vacuum pump, bottle for material is made to be separated with vacuum system.
2) the active carbon particle 2000g that preferred granularity is 0.5~3mm is added in a kettle, and control reaction kettle turns
Speed is 20 turns/min.Bottle for material I control valves are opened, solution is instilled into reaction kettle, and adsorbed by granular activated carbon.Band solution is complete
Portion it is complete after, reaction kettle is heated at 30 DEG C~40 DEG C heating stirring and is flowed back, 1~3h is reacted, makes the material containing Si and Sb
By uniform adsorption on the surface of active carbon particle.
3) cooling water machine is opened, cooling water is made to enter condenser, and condensation temperature is made to reach less than 5 DEG C.In reaction kettle
Deionized water is added in water-bath, opens electrical heating, set temperature is 80 DEG C.It opens vacuum pump to be evaporated under reduced pressure, Zhi Daoquan
Portion's ethanol evaporation is clean.
4) by 250mL hydrogen peroxide (30wt%) using vacuum suck bottle for material II, in reaction by hydrogen peroxide be slowly added dropwise into
Enter reaction kettle and by solid uniform adsorption.Negative pressure is caused to reaction system pumping using a small size air air pump in the process, generation
Chlorine is taken out of and is absorbed through hypo solution in drexel bottle.After hydrogen peroxide is added dropwise, in 5 DEG C of bath temperature and keep
2h is reacted under aeration status；
4) ultra-pure water is added in the reaction system of step 3), reaction temperature is adjusted to 30 DEG C~50 DEG C, continues to stir
2~6h of reaction is hydrolyzed, later filters sediment, and sediment is cleaned with deionized water, until can not be detected in filtrate
To Cl-Ion；By the drying precipitate of acquisition, obtaining deposition has the SiSb/ activated carbon adsorptions of SiSb composite oxides microcrystals
Agent particle；
5) polyvinyl alcohol is used to dissolve polyvinyl alcohol in for covering material and be configured to solution in pure water, a concentration of 1~
5wt%.The adsorbent that step 4) obtains is added in solution system, liquid-solid ratio 10:1；Continue to stir and react 2-10h
Afterwards, Solid-Liquid Separation.
6) granule adsorbent that step 5) obtains further is cleaned using deionized water, every time cleaning water used
Volume is 10 times of adsorbent volume, until the conductivity of cleaning solution is less than 50 μ s/cm, later Solid-Liquid Separation, and will absorption
Agent obtains final graininess SiSb/ active carbon type adsorbents using vacuum drying.
The average crush strength of SiSb/ active carbon type adsorbents is determined, is 5~20N/particle.It is in liquid-solid ratio
After being impregnated for 24 hours under conditions of 10, turbidity is in liquid<15mg/L, conductivity<20 μ s/cm, COD is a concentration of in solution<1.2mg/
L.Adsorbent is determined to Ag+、Sr2+And Co2+The Static Adsorption removal capacity of ion, in the item of a concentration of 10mg/L of initial ion
Under part, the adsorption isothermequation K of Ag ionsdIt is 5.3 × 106ML/g, adsorption capacity 52mg/g；The absorption distribution system of Co ions
Number KdIt is 2.6 × 106ML/g, adsorption capacity 41mg/g；The distribution coefficient K of Sr ionsdIt is 9.7 × 106ML/g, adsorption capacity
For 49mg/g.
It is explained to various aspects of the present invention above with the mode of specific embodiment, but people in the art
Member is appreciated that：The present invention is not limited in specific embodiment described above, and those skilled in the art are public to institute herein
The equivalence replacement and and various technological means, raw material, work that the various particular technique means opened, raw material, processing step etc. are done
The combination of skill step etc. is within the scope of the present invention.
In order to which certain aspects of the invention are further illustrated, the present invention also specifically provides the non-limit of some following
Property embodiment processed：
1. one kind is used to remove radioactivity90Sr and110mThe particulate form SiSb composite oxides adsorbents of Ag, it includes：Contain
There is the particle of SiSb composite oxides；With the polymer material layer for coating the particle.
2. particulate form SiSb composite oxides adsorbents as tdescribed in embodiment 1 have the particle ruler of at least 0.2mm
It is very little.
3. the particulate form SiSb composite oxides adsorbents as described in embodiment 2, the particle ruler with 0.5-5mm
It is very little.
4. the particulate form SiSb composite oxides adsorbents as described in embodiment 1 or 2, with 2-100N/
The crushing strength of particle.
5. the particulate form SiSb composite oxides adsorbents as described in embodiment 1 or 2 are leached with such ion
Characteristic, so that after the adsorbent impregnates 24 hours under 10 liquid-solid ratio, the turbidity of gained liquid is 50mg/L or lower.
6. the particulate form SiSb composite oxides adsorbents as described in embodiment 1 or 2 are leached with such ion
Characteristic, so that after the adsorbent impregnates 24 hours under 10 liquid-solid ratio, the conductivity of gained liquid is for 50 μ s/cm or more
It is low.
7. the particulate form SiSb composite oxides adsorbents as described in embodiment 1 or 2, wherein, the high molecular material
Layer include polyethylene glycol between 2000-6000 of sodium alginate, chitosan, number-average molecular weight, polyvinyl alcohol, sucrose or its
Arbitrary combination.
8. for removing radioactivity90Sr and110mThe preparation method of the particulate form SiSb composite oxides adsorbents of Ag, it is described
Method includes：
1) particle containing SiSb composite oxides is provided；
2) particle of step 1) is washed with deionized, the Cl until not measuring cleaning solution with silver nitrate solution inspection-Ion；
3) washed particle is coated with high molecular material, so as to obtain coated particle；And
4) the coated particle of step 3) optionally, is washed with deionized, until the conductivity of cleaning solution is 50.0 μ
S/cm or lower, and turbidity is 50mg/L or lower,
So as to obtain the particulate form SiSb composite oxides adsorbents.
9. the method described in 8 according to embodiment, wherein, the step of providing the particle containing SiSb composite oxides, wraps
It includes,
A) by alkyl silicate and SbCl3Mixture be supported on particulate form inorganic oxide or particulate form absorbent charcoal carrier
On, then
B) the obtained particles of step a) are aoxidized with hydrogen peroxide, then hydrolyzed, so as to be formed containing SiSb composite oxygens
The particle of compound.
10. the method as described in embodiment 8, wherein, it is equal that the high molecular material includes sodium alginate, chitosan, number
Polyethylene glycol, polyvinyl alcohol, sucrose or its arbitrary combination of molecular weight between 2000-6000.
11. the method as described in embodiment 8, wherein, the step of coating washed particle with high molecular material, is in acid
Or it is carried out in the presence of alkali.
12. the method described in 11 according to embodiment, wherein, the acid is selected from by hydrochloric acid, sulfuric acid, acetic acid or combination group
Into group, the preferred concentration with 0.01-1mol/L.
13. the method described in 11 according to embodiment, wherein, the alkali is selected from by sodium hydroxide, sodium carbonate, bicarbonate
The group of sodium, ammonium hydroxide or combinations thereof, the preferably concentration with 0.01-1mol/L.
14. the method in 8-9 described in any one according to embodiment, wherein, the particulate form inorganic oxide carrier
Including silica gel bead, alumina globule, titanium oxide bead, zirconia ball, molecular sieve beads or combination, preferably with 0.3
To the granularity of 5mm and/or the crushing strength of 2-150N/particle.Particulate form activated carbon includes coconut husk charcoal and coal-based carbon,
It is preferred that with 0.3 to 5mm granularity and/or the crushing strength of 2-150N/particle.
15. a kind of particulate form SiSb composite oxides that gained is prepared by any one of claim 8-14 the methods are inhaled
Attached dose.
16. as any one in claim 1-7 or as the particulate form SiSb composite oxides described in claim 15
Adsorbent is used to remove radioactivity90The purposes of Sr.
17. as any one in claim 1-7 or as the particulate form SiSb composite oxides described in claim 14
Adsorbent is used to remove radioactivity100mThe purposes of Ag.
18. as any one in claim 1-7 or as the particulate form SiSb composite oxides described in claim 14
Adsorbent is used to remove radioactivity90Sr and100mThe purposes of Ag.
Claims (10)
1. one kind is used to remove radioactivity90Sr and110mThe particulate form SiSb composite oxides adsorbents of Ag, it includes：Contain
The particle of SiSb composite oxides；With the polymer material layer for coating the particle.
2. particulate form SiSb composite oxides adsorbents as described in claim 1 have at least particle size of 0.2mm.
3. particulate form SiSb composite oxides adsorbents as claimed in claim 1 or 2, with 2-100N/particle's
Crushing strength.
4. particulate form SiSb composite oxides adsorbents as claimed in claim 1 or 2 leach special with such ion
Property, so that after the adsorbent impregnates 24 hours under 10 liquid-solid ratio, the turbidity of gained liquid is 50mg/L or lower.
5. particulate form SiSb composite oxides adsorbents as claimed in claim 1 or 2 leach special with such ion
Property, so that after the adsorbent impregnates 24 hours under 10 liquid-solid ratio, the conductivity of gained liquid is for 50 μ s/cm or more
It is low.
6. particulate form SiSb composite oxides adsorbents as claimed in claim 1 or 2, wherein, the polymer material layer packet
It includes polyethylene glycol between 2000-6000 of sodium alginate, chitosan, number-average molecular weight, polyvinyl alcohol, sucrose or it is arbitrary
Combination.
7. for removing radioactivity90Sr and110mThe preparation method of the particulate form SiSb composite oxides adsorbents of Ag, the method
Including：
1) particle containing SiSb composite oxides is provided；
2) particle of step 1) is washed with deionized, the Cl until not measuring cleaning solution with silver nitrate solution inspection-Ion；
3) washed particle is coated with high molecular material, preferably in the presence of acids and bases, so as to obtain coated particle；
And
4) the coated particle of step 3) optionally, is washed with deionized, until the conductivity of cleaning solution is 50.0 μ s/cm
Or it is lower, and turbidity is 50mg/L or lower,
So as to obtain the particulate form SiSb composite oxides adsorbents.
8. according to the method described in claim 7, wherein, the step of providing the particle containing SiSb composite oxides, includes,
A) silicic acid C1-4 Arrcostabs and SbCl are supported on particulate form inorganic oxide carrier or particulate form absorbent charcoal carrier3, then
B) the obtained particles of step a) are aoxidized with hydrogen peroxide, then hydrolyzed, so as to be formed containing SiSb composite oxides
Particle.
9. a kind of particulate form SiSb composite oxides adsorbents that gained is prepared by any one of claim 7-8 the methods.
10. as any one in claim 1-6 or as the particulate form SiSb composite oxides adsorbents described in claim 9
For removing radioactivity90Sr and110mThe purposes of Ag.
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