CN106179181A - The preparation method of magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent and product and application - Google Patents

The preparation method of magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent and product and application Download PDF

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CN106179181A
CN106179181A CN201610531712.5A CN201610531712A CN106179181A CN 106179181 A CN106179181 A CN 106179181A CN 201610531712 A CN201610531712 A CN 201610531712A CN 106179181 A CN106179181 A CN 106179181A
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adsorbent
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magnetic core
magnetic powder
potassium
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尉继英
赵璇
成徐州
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Tsinghua University
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Abstract

The present invention relates to the preparation method of magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent and product and application.Specifically, at Fe3O4Magnetic powder surface is coated with complete SiO initially with two-step reaction method2Protective layer, makes Fe3O4It is difficult to dissolution in an acidic solution；Then use butyl titanate/alcoholic solution dipping and the method for vapor phase hydrolysis, under high-temperature high-pressure steam effect, prepare transition clad TiO2, overcome at the mutually incidental Ti of solution4+Homogeneous hydrolysis effect, improves TiO2Load capacity and bond strength；Finally use the method for solution phase surface reaction by potassium ferrocyanide and TiO2Layer reaction, makes the active ferrous iron titanium cyanide potassium absorbent component of generation be grown in magnetic core surface securely, makes the magnetic magnetic core cladded type Potassium titanium hexacyanoferrate of tool except caesium adsorbent.This adsorbent through test determination to Cs +There is good Adsorption characteristic, be suitable for using batch-type dynamic adsorption reactor pattern, be applied to the removal of the radioactive liquid waste that nuclear power station scale is less and dispersibility is strong.

Description

The preparation method of magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent and product and application
Technical field
The present invention relates to field of inorganic materials, particularly to the industry of a kind of magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent Change preparation method and products thereof and application.
Background technology
Nuclear power, as a kind of important clean energy resource, is being increasingly becoming the important component part in China's energy resource structure. In Fukushima, Japan nuclear accident, rapidly and efficiently removing of radioactive liquid waste becomes the key issue of accident post processing.With Fukushima accident For warning, set up Nuclear Power Station Accident Emergency mechanism in China, carry out radioactive liquid waste urgent technique research, be extremely important With urgent.
As a example by the process technique of Fukushima, radioactive liquid waste due to the reactor fuel element damaged and other is contaminated Component touch, pollution level is different, and total amount reaches 110000 tons, and radioactive contamination level reaches the magnitude of 1Ci/L, its In134/137Cs be main source radiation (Hijikata et.al., 2014；Tsukada et.Al., 2014).
In Fukushima, Japan accident, Liquid Radwaste Treatment used can be divided into four parts (Gay et.al., 2012): 1) using oil-water separation technique to remove the oily substance in waste water, to ensure the properly functioning of subsequent technique, segregation apparatus comes From Toshiba Corp；2) inorganic adsorbent using Kurion company of the U.S. to provide removes Cs；3) Avera company of France is used The chemical coprecipitation process provided removes Cs and Sr further；4) reverse osmosis unit and evaporating and concentrating process is used to carry out desalination essence Processing, device is from using Hitachi, Ltd, Avera company and Toshiba.In the process by the absorption of Kurion and The co-precipitation two-step process of Avera,134Cs and137The decontamination factor of Cs is 105～106(Fournel et.al., 2012), wherein Have employed chabasie is except caesium adsorbent (Rhodes et.al., 2012), have employed ferrocyanide in chemical coprecipitation process Thing (Denton et.al., 2012), Cs+Final with Cs2NiFe(CN)6Form precipitate.This this system of processing system Main advantage is: inorganic adsorbent is strong to the selectivity of trace level activity radionuclide ion, is applicable to the sea water of high salinity Cooling water；Inorganic adsorbent has been greatly reduced the radioactivity of waste liquid, has effectively ensured operation and the radiation of subsequent film technique Protection；In addition inorganic adsorbent is compared to resin, and radwaste generation amount is little, and post processing is more simple and safe.But in this technique The chabasie adsorbent speed used is fast not, is still difficult to meet a large amount of radioactive liquid wastes under emergency conditions and quickly processes Requirement.
The stable ferrocyanide of transition metal ions is a class High-rate sedimentation and the inorganic material of fixing Cs ion (Ambashta et.al., 2003；Mimura et.al., 1997；Vrtoch et.al., 2011；Zhang et.al., 2009), to Cs+Selectivity factor up to 1500000 (Pickett et.al., 2002), and in the widest pH value range In can keep Cs+Efficient absorption.Such as, caesium is remained to keep 21.7mg/ in the case of pH is 1.1 by cupric potassium ferrocyanide The adsorption capacity (Sangvanich et.al., 2010) of g.But ferrocyanide grain diameter is little, easily form colloid, nothing Method directly applies in common packed bed operation, it is also difficult to carry out Solid-Liquid Separation.And utilize the methods such as heating, ageing by it Being prepared as the material that particle diameter is bigger, make again material internal resistance to mass tranfer big, the rate of adsorption is little, ultimately results in adsorption capacity low. Then there is researcher sol-gal process to be carried on porous carrier by ferrocyanide, form compound adsorbent (Chang Et.al., 2008；Hu et.al., 2012；Liu et.al., 2009).The compound iron cobalt potassium cyanide adsorption capacity energy to caesium Reach 46.6mg/g (Lehto et.al., 1987).With TiCl4For raw material, use and be usually used in preparative high-performance liquid chromatographic filler Method, TiO 2 sol is joined in carbamide and hexamethylenetetramine solution, adds containing surfactant after mixing In kerosene, prepare hydrated titania gels granule；Then the titanium dioxide granule obtained is soaked in potassium ferrocyanide and salt In acid mixed solution, Potassium titanium hexacyanoferrate spheroidal particle (the flat et.al. of generation slowly, 1997) can be prepared.This solves Ferrocyanide is difficult to the problem of spheroidization, but the material specific surface area of synthesis is less, and still remains in material and substantial amounts of have Machine thing, is susceptible to blast processing the calcining cure stage carried out after radioactive liquid waste.
This seminar does a lot of work in terms of the immobilized molding of ferrocyanide, such as: the first is to use silicon Colloidal sol technique for fixing in situ is prepared for cobaltous ferrocyanide potassium and porous SiO2Hybrid material, to Cs+Adsorption capacity up to 0.335meq Cs/g-adsorbent (Chinese patent CN200710064453.0)；The second be the silica gel bead with molding with Butyl titanate reaction forms Surface coating TiO2Complex carrier, then this carrier is soaked in the hydrochloric acid solution of potassium ferrocyanide In, it is thus achieved that spherical Potassium titanium hexacyanoferrate/bead silica gel hybridization material (Chinese patent 200710122085.0)；The third is to use Magnetic core coating technology, at the submicron order Fe prepared with water chemical method3O4Surface coating protective layer SiO2, lead to the most thereon Cross sol-gel technique or the deposition sedimentation technology different metal ions M transition zone of load (M=Ti, Zr, Zn, Fe, Cu, Co, Ni etc.), finally magnetic carrier be impregnated in the hydrochloric acid solution of potassium ferrocyanide, it is thus achieved that micron order magnetic ferrocyanide adsorbs Agent (Chinese patent ZL 2,012 1 0347269.8).This adsorbent has outside the ability of efficient absorption Cs ion, it is also possible to logical Cross externally-applied magnetic field and realize the separation of solid liquid phase.
In the immobilized method of above-mentioned numerous ferrocyanides, use the magnetic ferrocyanide that magnetic core coating technology prepares Thing adsorbent can realize the characteristic of Solid-Liquid Separation and particularly interesting by externally-applied magnetic field due to it.But, so far Magnetic ferrocyanide adsorbent prepared by till is all the Fe with high surface using synthetic3O4Indoor rice Particle is as core, thus obtained adsorbent is generally of the particle size of several microns.Such as, at Chinese patent In CN102836693, obtained magnetic ferrocyanide adsorbent particle diameter is 0.2 to 5 micron.So particle size size Adsorbent being limited in scope in commercial Application, it is difficult to promote.
Industry magnetic powder has low cost, obtains easy feature.From industrial point of view, as core with above-mentioned magnetic It is interesting that core coating technology prepares magnetic ferrocyanide adsorbent.Additionally industry magnetic powder from settling property Good, it is relatively more suitable for commercial Application.But, this industry magnetic powder have particle diameter compared with big, surface compact, specific surface area are little, surface The feature that activity hydroxy functional group is few, thus it is carried out superficial growth and/or Surface coating exists certain difficulty technically Degree；Also cannot prepare according to the method for prior art with the industry magnetic powder magnetic ferrocyanide adsorbent as core.
Summary of the invention
The present invention develops and on the basis of enlarged experiment preparation at early stage magnetic adsorbent, it is provided that a kind of industrial scale Prepare method of magnetic core cladded type Potassium titanium hexacyanoferrate and products thereof, gained adsorbent can be used for removing in radioactive liquid waste Cs from Stable Cs isotope in son, or other liquid environments.
A kind of industrial scale of the present invention is prepared in the preparation method of magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent used The production line arrived, capital equipment includes: reactor, centrifuge, automatic sample handling system, vacuum drying oven, electric heating steaming tank, air blast drying room Deng.Centrifuge is arranged on below reactor, and reactor is provided with automatic sample handling system, and automatic sample handling system can use wriggling Pump.Automatic sample handling system is also referred to as auto-feeding system.
A kind of industrial scale of the present invention prepares the preparation method of magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent, the method Comprise the following steps:
Selecting to use industry magnetic powder or self-control magnetic powder is carrier；
(1) bag silicon for the first time: be first sequentially added into dehydrated alcohol and tetraethyl orthosilicate (TEOS) in No. 1 reactor, open Opening stirring paddle 20min makes TEOS be uniformly dissolved, and adds magnetic powder from solid feed inlet with continuous stirring, opens oil bath heating system Make temperature reach 30 DEG C, and continue to stir 2h；Then pass through auto-feeding system and add strong aqua ammonia, and by pH automatic linkage control System, makes reaction system react 1h under conditions of pH is not less than 11.5；Pure water is added afterwards, in stirring by auto-feeding system Lower reaction 5～10h.The discharge valve of Polycondensation Reactor and Esterification Reactor is opened in reaction after terminating, the centrifuge that material enters below reactor is carried out Solid-liquid separation, solid material clear water rinses, until centrifuge water outlet pH is reduced to 9.Obtained solid material is designated as FeSi1.
(2) bag silicon for the second time: prepare the sulfuric acid solution of 1mol/L in advance and concentration be 5～20% sodium silicate solution standby With.In No. 2 reactors, add pure water, add the solid material FeSi1 that step (1) is obtained under agitation, open oil bath Heating system makes temperature reach 90 DEG C, uses auto-feeding system two-way to drip sodium silicate solution and sulfuric acid solution the most respectively, Control to make system pH=9.5 during whole dropping with automatic pH, until the dropping of whole sodium silicate solutions is complete, stop dropping sulfur Acid solution, makes system react 5～10h under agitation.The discharge valve of Polycondensation Reactor and Esterification Reactor is opened in reaction after terminating, material enters Centrifuge below reactor carries out solid-liquid separation, and solid material clear water rinses, until centrifuge water outlet pH is reduced to 7～8. Solid material being put into air blast drying room be dried to thoroughly be dried, obtained solid material is designated as FeSi2.
(3) absorption bag titanium process: add ethanol or isopropanol in being dried anhydrous No. 3 reactors, is further continued for adding titanium Acid four butyl esters, turn on agitator makes to be uniformly dissolved.Dry solid material FeSi2 is joined in reactor, after stirring 1h, stops Only stirring stands 3h.Opening the discharging opening valve of Polycondensation Reactor and Esterification Reactor afterwards, the centrifuge that material enters below reactor carries out solid-liquid Separating, the liquid of the discharge bucket being dried is collected.The solid material obtained is placed in vacuum drying oven, evacuation at 50 DEG C, Desolvation ethanol or isopropanol.The solid material obtained is designated as FeSiTi1.
(4) vapor phase hydrolysis bag titanium process: the solid material FeSiTi1 that step (3) obtains is divided equally and puts into electric heating steaming tank Multiple pallets in, open steam box, make under high temperature and certain pressure steam and butyl titanate generation hydrolysis 2～ 4h, generates TiO at material surface2Clad.Use the method can suppress easily to occur in solution phase (such as aqueous phase) is reacted Titanium source homogeneous hydrolysis phenomenon, improve TiO2Load capacity and the structural stability of protective layer.Air blast put into by reacted material Thoroughly dry at 120 DEG C in baking oven.The solid material obtained is designated as FeSiTi2.
(5) adsorbent cladding process: add pure water in No. 4 reactors, uses auto-feeding system under conditions of stirring System adds concentrated hydrochloric acid, and the concentration making hydrochloric acid is 0.5～1.0mol/L；Continuously add potassium ferrocyanide, after stirring, make it dense Degree reaches 15wt%～40wt%.In reactor, add solid material FeSiTi2, and immersion carries out 24h, period at 30 DEG C 30min is stirred every 3～4h.After question response terminates, open the discharge valve of Polycondensation Reactor and Esterification Reactor, material enter below reactor from Scheming carries out solid-liquid separation, and solution is collected in a clean liquid storing barrel.The solid material clear water obtained rinses, until Centrifuge water outlet is light green color or colourless.Solid material being put into air blast drying room be dried to thoroughly be dried, obtained solid material is i.e. Magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent for target.
Further, in described step (1)～(5), magnetic powder uses Fe3O4Or other any ferrous magnetic materials, granularity≤ 80 mesh (i.e. 180 microns).Technical grade Fe can be used3O4Magnetic powder, granularity preferably 80～120 mesh (120 microns-180 microns).? In the context of the present invention, " technical grade magnetic powder " refers to, is directly ground by Ore, sieves the magnetic powder of tool obtained Grain, it is generally of 120 microns or the particle size of bigger (i.e. having 120 mesh or more low mesh number).This industry magnetic powder has The feature that surface compact, specific surface area are little, surface activity hydroxy functional group is few, thus it is carried out superficial growth and/or surface It is coated on and technically there is certain difficulty.The present inventor surprisingly it has been found that, use the two step bag silicon process can be in industry Magnetic powder surface, such as granule have the industrial Fe of 80-120 mesh particle size3O4Magnetic powder surface, forms the SiO that cladding is complete2Protect Sheath, thus protect Fe3O4It is difficult to dissolution in an acidic solution.
Further, in described step (1), organic solvent can be ethanol, propanol or isopropanol etc.；Silicon source can be positive silicon Acid methyl ester or tetraethyl orthosilicate.
Further, in described step (1), the amount in organosilicon source is relevant to quality of magnetic iron powder, Si:Fe3O4=5wt%～ 10wt%；Organosilicon source is 1:5～1:10 with the volume ratio of alcohol, and the pure water of addition and the volume ratio of alcohol are 1:5～1:10；
Further, in described step (1), the alkali liquor of addition can be strong aqua ammonia, NaOH solution, Na2CO3Solution etc..Alkali liquor Addition total amount and rate of addition controlled by reaction system pH, it is ensured that in whole course of reaction, pH is not less than 11.5.
Further, in described step (1), reaction temperature is 20～50 DEG C, and the response time is 5～10h.Described step (1) In, leach waste liquid rectifier unit and carry out water/alcohol separation, it is thus achieved that the recovery alcohol repeated application of 95%.
Further, in described step (2), it is 1: 1～1 that the addition of initial pure water and magnetic powder meets solid liquid phase mass ratio: 5, the amount of sodium silicate is relevant to magnetic powder quality, for Si:Fe3O4=5wt%～10wt%, the concentration of sodium silicate solution be formulated as 5～ 20wt%, uses between dilute acid soln regulation pH=9～10, and dilute acid soln uses concentration to be 0.2～1mol/L dilute sulfuric acid or dilute Hydrochloric acid, the response time is 5～10h.
Further, in described step (2), the concentration of preparation sulfuric acid solution is 1mol/L；The addition of sulphuric acid is by reactant It is pH control, it is ensured that pH=9.5 in whole course of reaction.Step can also use hydrochloric acid solution in (2).
Further, in described step (2), reaction temperature is 80～90 DEG C, and the response time is 5～10h.
Further, obtained in described step (2), intermediate FeSi2 needs thoroughly to dry.
Further, in described step (3), the industrial magnetic powder of silicon dioxide layer will be coated with under anhydrous conditions in titanium source Impregnate.In the context of the present invention, " titanium source " refers to provide the material of element ti into adsorbent, and it includes, but does not limits In tetralkyl titanate and titanium tetrachloride, it is preferably selected from by metatitanic acid tetramethyl ester, metatitanic acid tetraethyl ester, metatitanic acid tetrapropyl ester, titanium The group of acid tetrabutyl ester or combinations thereof, is more preferably selected from butyl tetra titanate.In an embodiment of the invention, will Butyl titanate impregnates under anhydrous conditions as titanium source.
Further, in described step (3), using butyl titanate is titanium source, Ti:Fe3O4=5wt%～10wt%；Use Solvent is dehydrated alcohol, anhydrous isopropyl alcohol or anhydrous propanol；The two volume ratio is 1: 2～1: 4.
Further, in described step (3), obtained solid product needs to remove substantial amounts of organic solvent under cryogenic vacuum, Temperature is 40～50 DEG C.
Further, in described step (4), vapor phase hydrolysis temperature is 100 DEG C～120 DEG C, and pressure is 0.05～0.08MPa； Material after hydrolysis is dried in the convection oven of normal pressure 120 DEG C.
Further, for improving TiO2Load capacity, repeating said steps (3) and (4) 2～3 times so that adsorbent surface Ti Content reach Ti/ magnetic powder more than 5wt%.
Further, in described step (5), Fe3O4Being 1: 3～1: 5 with pure water mass ratio, in reactant liquor, the concentration of hydrochloric acid is 0.5～1.0mol/L；Ferrocyanide potassium concn is 15wt%～40wt%.According to a preferred embodiment of the present invention, use Potassium ferrocyanide as ferrocyanide to provide adsorption activity component.But, it will be understood by those skilled in the art that industrial Other ferrocyanides being readily obtained, such as sodium ferrocyanide, due to the chemical property that it is similar to potassium ferrocyanide, equally It is also applied for the present invention.
The present inventor surprisingly it has been found that, in the step (5) of the present invention, surface reaction can be inorganic in small amount Implement with higher solid-liquid phase mass ratio in the presence of acid, and reaction effect is not had a negative impact.With Chinese patent The preparation process of the magnetic core cladded type ferrocyanide adsorbent disclosed in CN102836693A is compared, and the method for the present invention makes Post-processing step subsequently is more prone to, and decreases discharge of wastewater, beneficially environment.
Further, in described step (5), concretely comprising the following steps of described post processing: after reaction, the precipitate of gained is by centrifugation After machine separates, by clean water, until centrifuge outlet liquid is light green color or colourless, precipitate is dried through 120 DEG C, it is thus achieved that mesh Mark magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent.
The magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent of gained is prepared, also in the protection of the present invention by above-mentioned preparation method Within the scope of.The kernel of this magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent is that (preferably smaller than 120 mesh, are i.e. more than magnetic powder particle 120 microns), it is respectively arranged with silicon dioxide coating layer from inside to outside and Potassium titanium hexacyanoferrate covers at described magnetic powder particle outer surface Film layer.This big particle diameter magnetic powder particle is novel as the magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent of core.
The present inventor has further surprisingly found that, has according to the magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent of the present invention There is the feature that Stability Analysis of Structures, absorption property are high.This adsorbent is due to can be with Adsorption of Radioactive isotope Cs ion, it is also possible to inhale Attached stable isotope Cs ion, therefore has broad application prospects.For example, it is possible to be used for realizing separating by adsorption And/or remove and/or extract radiosiotope Cs ion, it is also possible to for separate and/or remove and/or extract stability with The application of position element Cs ion.Therefore, (include removing in absorption according to the magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent of the present invention Or separate or extract) radiosiotope Cs ion and absorption (including removing or separating or extract) stable isotope Cs ion Application, also within protection scope of the present invention.
Above-mentioned magnetic core cladded type Potassium titanium hexacyanoferrate is being removed radiosiotope Cs ion except caesium adsorbent and is being removed steady Determine the application process of isotope Cs ion, use batch-type dynamic adsorption reactor pattern to carry out liquid waste processing.Described reactor Being designed as two-way in parallel, each road is divided into two-stage.
The present invention is at the industrial Fe of 80～120 mesh3O4Magnetic powder surface is coated with complete SiO initially with two-step reaction method2Protect Sheath, makes Fe3O4It is difficult to dissolution in an acidic solution；Then butyl titanate/alcoholic solution dipping and the side of vapor phase hydrolysis are used Method, prepares transition clad TiO under high-temperature high-pressure steam effect2, overcome at the mutually incidental Ti of solution4+Homogeneous water Solution effect, improves TiO2Load capacity and bond strength；Finally use the method for solution phase surface reaction by potassium ferrocyanide With TiO2Layer reaction, makes the active ferrous iron titanium cyanide potassium absorbent component of generation be grown in magnetic core surface securely, makes and have Magnetic except caesium adsorbent.
Accompanying drawing explanation
Fig. 1 is the production line structural representation that magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent is prepared in scale；
Fig. 2 is that embodiment 1 obtained magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent is to Cs+Adsorption isotherm；
Fig. 3 is acidity M-PTH obtained to embodiment 1 (english abbreviation of magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent) Zeta current potential and except the impact of caesium performance；
Fig. 4 is that anions in solution (0.01mol/L) M-PTH obtained to embodiment 1 adsorbs Cs+The impact of performance；
Fig. 5 is embodiment 1 obtained M-PTH material Cs under different dosages+Curve of adsorption kinetics；
Fig. 6 is sequencing batch reactor operation principle schematic diagram；
Fig. 7 is two-way two-stage sequencing batch type dynamic adsorption structure of reactor schematic diagram；
Fig. 8 is that the obtained M-PTH of embodiment 1 each decontamination factor processing batch in two-way two-stage sequencing batch type reactor becomes Change；
Fig. 9 is embodiment 2 obtained Potassium titanium hexacyanoferrate adsorbent infrared spectrum；
Figure 10 is that the obtained M-PTH of embodiment 2 is each in two-stage sequencing batch type reactor processes the change of batch decontamination factor.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further elaborated, but the present invention is not limited to following example. Described method is conventional method, described raw material and detection standardizing chemical reagent used if no special instructions if no special instructions All can be either commercially available from open.
Below in an example, adsorbent has carried out static adsorption respectively and batch-type adsorptive reactor performance test is surveyed Fixed, Cs before and after absorption+Concentration using plasma mass spectrum (ICP-MS) of ion measures, and performance of the adsorbent uses partition coefficient KdRepresent with decontamination factor DF.
During static adsorption measures, a certain amount of adsorbent joins in the centrifuge tube of 50mL, is placed on constant-temperature table shake 48h～72h, measures the Cs before and after absorption+Ion concentration, performance of the adsorbent uses partition coefficient KdRepresent with decontamination factor DF. Adsorption isothermequation Kd(mL/g) as shown in following formula (1), wherein C0And CtIt is respectively the initial concentration of adion and reaches Concentration after adsorption equilibrium, F is the ratio of processed liquor capacity (mL) and adsorbent mass (mg).Decontamination factor such as following formula (2) institute Show, for influent concentration and the ratio reaching the aqueous concentration after adsorption equilibrium of adion.General adsorption isothermequation is said Understand the characteristic of adsorbing material itself, KdValue is 105Above illustrates the functional of adsorbent；The size of decontamination factor is not only Relevant to the characterization of adsorption of material itself, also relevant to the consumption of adsorbent, this value the biggest explanation pollutant removal must be the cleanest.
Kd=(Co-Ct) × F × 1000/Ct (1)
D F = C i n C o u t - - - ( 2 )
Dynamic adsorption uses sequencing batch reactor to carry out, and its work process is divided into four-stage as shown in Figure 6, respectively For intaking, adsorb, precipitating, water outlet.Assuming that treating capacity is 1t/h, influent concentration is 1.5mg/L, and decontamination factor is more than 1000, enters Water, adsorb, precipitate, water outlet stage each 2.5min, then a processing cycle needs 10min, can process 6 circulations per hour, then The effective volume of single reactor needs 167L.It is in parallel that reactor is designed as two-way, and each road is divided into two-stage, as it is shown in fig. 7, work as In reactor, adsorbent needs to be replaced when exhausting.Decontamination factor DF is used to represent the Cs of two-stage+Clean effect.
Embodiment 1: prepared by the laboratory of feather weight adsorbent
The preparation of feather weight magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent has been carried out, step in experimental glass reactor Rapid as follows:
Selecting to use industry magnetic powder or self-control magnetic powder is carrier；
(1) being sequentially added into 8L dehydrated alcohol and 1L tetraethyl orthosilicate (TEOS) in a kettle., continuous stirring 20min makes TEOS is uniformly dissolved, and adding 4kg granularity afterwards is the magnetic iron powder about 100 mesh, and heating in water bath makes temperature be always held at 30 DEG C Lower continuation stirs 2h；Then it is slowly added dropwise strong aqua ammonia about 2L, hydrolyzes to form SiO by base catalysis induction TEOS2, along with reaction Carry out there will be the reduction of pH.During use pH meter on-line determination, by dropping ammonia control reaction be not less than all the time at pH 2h is reacted, until observing pH to occur without reduction phenomenon under conditions of 11.5.Dropping pure water 2L, under agitation reacts 5 afterwards ～10h.React from Polycondensation Reactor and Esterification Reactor discharging after terminating, use magnetic field to carry out solid-liquid separation, and solid material clear water is rinsed, directly It is reduced to 9 to water outlet pH.Obtained solid material is designated as FeSi1.
(2) sulfuric acid solution and the sodium silicate solution that 4L concentration is 5wt% of preparation 2L concentration 1mol/L are standby in advance.Instead Answer addition pure water 8L in still, add solid material FeSi1 under agitation, open water bath heating system and make temperature reach 90 ℃；Use bifilar and flow method and be simultaneously added dropwise sodium silicate solution and sulfuric acid solution, using pH meter on-line determination, control whole dropping System pH=9.5 in journey, until the dropping of whole sodium silicate solutions is complete, stops dropping sulfuric acid solution, makes system at stirring condition Lower reaction 5～10h.Reaction carries out solid-liquid separation from Polycondensation Reactor and Esterification Reactor discharging, employing magnetic field after terminating, and by solid material clear water Rinse, until water outlet pH is reduced to 7～8.Solid material is put into and is thoroughly dried at convection oven 120 DEG C, obtained solid Material is designated as FeSi2.
(3) in being dried anhydrous large beaker, add 1.5L isopropanol and 1L butyl titanate, stir with bench mixer Make to be uniformly dissolved.Drying solid material FeSi2 is added in large beaker, after stirring 1h, stop stirring and stand 3h.Afterwards with being dried Suction filtration device carry out solid-liquid separation, leach liquid and be collected in drying bottle sealing, amount volume is about 0.8L.Solid material is placed In vacuum drying oven, evacuation at 50 DEG C, remove isopropanol.The solid material obtained is designated as FeSiTi1.
(4) solid material FeSiTi1 is put into pressure cooker, under high-temperature steam effect, carry out vapor phase hydrolysis 2～4h, at material Material Surface Creation TiO2Clad.Convection oven put into by reacted material thoroughly dries at 120 DEG C.The solids obtained Material is designated as FeSiTi2.
(5) above (3) and (4) step 2 time is repeated, to improve material surface TiO2Covering amount, the 2nd time and the 3rd time inhale Attached mixed liquor volume is about 2L.
(6) add 5L pure water in a kettle. and 10L concentration is the hydrochloric acid of 1mol/L, under agitation add potassium ferrocyanide 5kg, is stirred to dissolve uniformly.Adding solid material FeSiTi2 in reactor, and immersion carries out 48h at 30 DEG C, period is every 30min is stirred every 3～4h.Reaction carries out solid-liquid separation by Suction filtration device after terminating, and filtrate collection is in clean reagent bottle.Institute Obtain solid material clear water to rinse until water outlet is light green color or colourless, put into convection oven afterwards and be dried thoroughly in 120 DEG C, Sample is designated as M-PTH.
Fig. 2 is that sample M-PTH is to Cs+The adsorption isotherm of ion, result shows: M-PTH is to Cs+Absorption than tiltedly sending out boiling Stone and modenite are more favourable, as Cs in solution+Equilibrium concentration when 0.006mg/L increases to 1.959mg/L, M-PTH pair Cs+Equilibrium adsorption capacities increased to 0.070mg/mg from 0.014mg/mg；And in same scope, two kinds of zeolitic materials To Cs+Equilibrium adsorption capacities only increase to 0.044mg/mg from 0.004mg/mg.
Fig. 3 is that three kinds of materials are to Cs+Clearance and the zeta current potential of the M-PTH situation of change under different pH, MPTH (pH=1～11) in the widest pH value range can keep Cs+There is the clearance of more than 90%, especially at meta-acid Property pH value range in (pH=1～5), the clearance of M-PTH will be apparently higher than two kinds of zeolitic materials.And pH value higher than 11 it After, three kinds of materials are to Cs+Removal efficiency the most substantially reduce.The zeta potential diagram of M-PTH shows in the pH value range measured (pH=2～10) adsorbent surface is electronegative, thus promotes Cs+Diffusion in adsorbent surface electric double layer and and H+'s Exchange；M-PTH material in strong basicity (pH ＞ 11) solution is it may happen that decompose, thus causes it to Cs+Adsorption effect Decline.
Embodiment 1 is obtained M-PTH by the non-cation (0.01mol/L) of putting coexisted in pending radioactive liquid waste by Fig. 4 Absorption Cs+The impact of performance, therefrom the cation of visible identical valence state is essentially identical on the impact of maximum adsorption capacity；Monovalence from Son is the most essentially identical on the impact of adsorption capacity with divalent ion, all reduces to about 0.058mg/mg；Compared to monovalent ion and Divalent ion, trivalent ion is slightly larger on the impact of adsorption capacity, is down to about 0.035mg/mg.
Fig. 5 is embodiment 1 obtained M-PTH material Cs under different dosages+Curve of adsorption kinetics, therefrom visible phase With M-PTH under adsorbent dosage to Cs+The rate of adsorption be significantly greater than zeolite, this also means that at Adsorption Cs+Process In, M-PTH adapts to less solid liquid phase time of contact and bigger water treating capacity.
Fig. 8 is that the M-PTH using two-way two-stage sequencing batch type reactor to measure dynamically removes caesium performance, visible just from result In stage beginning, the decontamination factor of the first order is more than 1000, and along with the increase of process batch, the decontamination factor of the first order is gradually reduced, Meaning that primary effluent concentration is gradually increased, the effect that now second level reactor plays is more and more obvious, therefore, and the second level Decontamination factor increases along with the increase processing batch；The overall removal of soils factor of two-stage reactor is processing after 70 batches of former water still 1000 can be remained above.Meet decontamination factor more than under conditions of 1000, process the enrichment Cs that the former water of 70L produces+Discarded Adsorbent only 40g (about 10mL), treating capacity is 7000 with the volume ratio of refuse generation amount.
Embodiment 2: the preparation of industrialization of magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent
Prepared by the amplification carrying out magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent on a production line.
Selecting to use industry magnetic powder or self-control magnetic powder is carrier；
(1) bag silicon for the first time: be first sequentially added into dehydrated alcohol and tetraethyl orthosilicate (TEOS) in No. 1 reactor, two Person's volume ratio is 8:1, opens stirring paddle 20min and makes TEOS be uniformly dissolved, adds Magnet from solid feed inlet with continuous stirring Powder, opens oil bath heating system and makes temperature reach 30 DEG C, and continues to stir 2h；Then passing through auto-feeding system addition concentration is The NaOH solution of 1mol/L, and controlled by pH automatic linkage, make reaction system react 1h under conditions of pH is not less than 11.5； Adding pure water by auto-feeding system afterwards, water/ethanol volume ratio is 1: 8, under agitation reaction 5～10h.After reaction terminates Opening the discharge valve of Polycondensation Reactor and Esterification Reactor, the centrifuge that material enters below reactor carries out solid-liquid separation, solid material clear water Rinse, until centrifuge water outlet pH is reduced to 9.Obtained solid material is designated as FeSi1；Leach waste liquid rectifier unit to carry out Water/separation of ethanol, it is thus achieved that the recovery ethanol of 95% can be with repeated application.
(2) bag silicon for the second time: sulfuric acid solution and the sodium silicate solution that concentration is 5wt% of preparing 1mol/L in advance are standby. In No. 2 reactors, add pure water, add the solid material FeSi1 that step (1) is obtained under agitation, make solid liquid phase quality Ratio is 1: 2.Opening oil bath heating system makes temperature reach 90 DEG C, uses auto-feeding system two-way to drip sodium silicate the most respectively Solution and sulfuric acid solution, control to make system pH=9.5 during whole dropping with automatic pH, until whole sodium silicate solutions drip Complete, stop dropping sulfuric acid solution, make system react 5～10h under agitation.Reaction opens going out of Polycondensation Reactor and Esterification Reactor after terminating Material valve, the centrifuge that material enters below reactor carries out solid-liquid separation, and solid material clear water rinses, until centrifuge goes out Water pH is reduced to 7～8, leaches alkaline waste liquor bucket and collects.Solid material is put into air blast drying room be dried to thoroughly be dried, obtained Solid material is designated as FeSi2.
(3) absorption bag titanium process: add ethanol and butyl titanate strict being dried in anhydrous No. 3 reactors, the two Volume ratio is 1.5:1, and turn on agitator makes to be uniformly dissolved.Dry solid material FeSi2 is joined in reactor, stirs 1h After, stop stirring and stand 3h.Opening the discharging opening valve of Polycondensation Reactor and Esterification Reactor afterwards, the centrifuge that material enters below reactor is carried out Solid-liquid separation, the liquid of the discharge bucket being dried is collected.The solid material obtained is placed in vacuum drying oven, takes out true at 50 DEG C Sky, desolvation ethanol.The solid material obtained is designated as FeSiTi1.
(4) vapor phase hydrolysis bag titanium process: the solid material FeSiTi1 that step (3) obtains is divided equally and puts into electric heating steaming tank Multiple pallets in, open steam box, make under high temperature and certain pressure steam and butyl titanate generation hydrolysis 2～ 4h, generates TiO at material surface2Clad.Convection oven put into by reacted material thoroughly dries at 120 DEG C.Obtain Solid material be designated as FeSiTi2.
(5) above (3) and (4) step 2 time is repeated, to improve material surface TiO2Covering amount.
(6) adsorbent cladding process: add pure water in No. 4 reactors, uses auto-feeding system under conditions of stirring System adds concentrated hydrochloric acid, and the concentration making hydrochloric acid is 0.5～1.0mol/L；Continuously add potassium ferrocyanide, after stirring, make it dense Degree reaches 30wt%.In reactor add solid material FeSiTi2, and at 30 DEG C soak carry out 24～48h, period every 3～4h stirring 30min.After question response terminates, opening the discharge valve of Polycondensation Reactor and Esterification Reactor, material enters the centrifuge below reactor Carrying out solid-liquid separation, solution is collected in a clean liquid storing barrel.The solid material clear water obtained rinses, until centrifugal Machine water outlet is light green color or colourless.Solid material being put into air blast drying room be dried to thoroughly be dried, obtained solid material is mesh Target magnetic core cladded type Potassium titanium hexacyanoferrate adsorbent.
Obtained adsorbent understands through x-ray fluorescence analysis, and the covering amount of Si is that the covering amount of 6.4wt%, Ti is 6.2wt%, is fourier transformed infrared spectrum detection (seeing Fig. 9), and material surface defines good ferrocyanide activity Structure.
Figure 10 is to use two-way two-stage sequencing batch type reactor to measure the adsorbent removal capacity to Cs+.Each batch processed 20 liters of former water, treating capacity is 100L/h.From result, along with the increase of process batch, the decontamination factor of the first order is gradually Reducing, the decontamination factor of the second level is gradually increased, and the overall removal of soils factor of two-stage reactor is gradually lowered, and is processing about 30 batches Reduce to 1000 after secondary former water, after processing about 70 former water of batch, reduce to 100.Meeting the decontamination factor condition more than 1000 Under, calculate by processing 30 batches, process the enrichment Cs that the former water of 600L produces+Discarded adsorbent be 800g (A reactor Middle adsorbent dosage, about 200mL), treating capacity is 3000 with the volume ratio of refuse generation amount.It is more than meeting decontamination factor Under conditions of 100, respective volume ratio is 7000.
Mode above with specific embodiment is explained to various aspects of the present invention, but people in the art Member is understood that the present invention is not limited in detailed description of the invention described above, and those skilled in the art are public to institute herein The equivalence that the various concrete technological means opened, raw material, processing step etc. are done is replaced and and various technological means, raw material, work The combination of skill step etc. is within the scope of the present invention.
In order to be further illustrated by certain aspects of the invention, the present invention also specifically provides the non-limit of following some Property embodiment processed:
1. the method being used for preparing magnetic core cladded type ferrocyanide adsorbent, it is characterised in that described method bag Include following steps:
(1) in the presence of magnetic powder, the alcoholic solution in organosilicon source is made to carry out liquid-phase hydrolysis under the pH being not less than 11.5, from And at described magnetic powder Surface coating SiO2, thus obtain intermediate FeSi1；
(2) in the presence of described FeSi1, silicate is made to carry out liquid-phase hydrolysis, thus further on described FeSi1 surface Coated Si O2, so obtain intermediate FeSi2；
(3) in anhydrous conditions, by the method for absorption in FeSi2 area load titanium source, thus obtain area load and have The intermediate FeSiTi1 in titanium source；
(4) under high-temperature and high-pressure conditions, make the titanium source in described FeSiTi1 react with steam and carry out vapor phase hydrolysis, from And obtain Surface coating and have TiO2The intermediate FeSiTi2 of layer；
(5) make described in ferrocyanide is coated with by intermediate FeSiTi2 contact with acid ferrocyanide solution FeSiTi2, more post-treated obtain described magnetic core cladded type ferrocyanide adsorbent.
Preparation method the most as tdescribed in embodiment 1, it is characterised in that described magnetic powder has less than 120 mesh (more than 120 Micron) particle size, preferably there is the particle size in the range of 80-120 mesh (120 microns-180 microns).
Preparation method the most as tdescribed in embodiment 1, it is characterised in that in described step (1), introduces alkali, it is preferable that Described alkali choosing free ammonia, NaOH, Na2CO3And combinations thereof composition group.
Preparation method the most as tdescribed in embodiment 1, it is characterised in that in described step (1), described organosilicon source is selected The group of free silane methyl ester, silane ethyl ester and combinations thereof composition.
Preparation method the most as tdescribed in embodiment 1, it is characterised in that in described step (1), relative to described magnetic powder Weight, the consumption in described organosilicon source is in the range of 5wt% to 10wt%.
Preparation method the most as tdescribed in embodiment 1, it is characterised in that in described step (1), described organosilicon source with The volume ratio of described alcohol is in the range of 1:5 to 1:10.
Preparation method the most as tdescribed in embodiment 1, it is characterised in that in described step (1), described alcohol selects free second The group of alcohol, isopropanol, propanol and combinations thereof composition.
Preparation method the most as tdescribed in embodiment 1, it is characterised in that in described step (2), introduces mineral acid, excellent Selection of land, the group of described mineral acid choosing free hydrochloric acid, sulphuric acid or combinations thereof.
Preparation method the most as tdescribed in embodiment 1, it is characterised in that in described step (2), described silicate is selected from By the group of alkali silicate, alkaline-earth-metal silicate or combinations thereof, preferably sodium silicate.
10. the preparation method as described in embodiment 8, it is characterised in that in described step (2), described silicate and Described mineral acid is simultaneously added dropwise.
11. preparation methoies as tdescribed in embodiment 1, it is characterised in that in described step (3), described titanium source includes Tetralkyl titanate and titanium tetrachloride, be preferably selected from by metatitanic acid tetramethyl ester, metatitanic acid tetraethyl ester, metatitanic acid tetrapropyl ester, metatitanic acid The group of tetrabutyl ester or combinations thereof, more preferably butyl tetra titanate.
12. preparation methoies as tdescribed in embodiment 1, it is characterised in that in described step (3), relative to described magnetic The weight of powder, the consumption in described titanium source is in the range of 5wt% to 10wt%.
13. preparation methoies as tdescribed in embodiment 1, it is characterised in that described step (3) includes soaking described FeSi2 Stain is in the alcoholic solution in titanium source.
14. preparation methoies as described in embodiment 13, it is characterised in that in described step (3), described titanium source and institute State the volume ratio of alcohol 1:2 to 1: 4 in the range of.
15. preparation methoies as described in embodiment 14, it is characterised in that in described step (3), the choosing of described alcohol is freely The group of ethanol, isopropanol, propanol and combinations thereof composition.
16. preparation methoies as tdescribed in embodiment 1, it is characterised in that in described step (4), vapor phase hydrolysis is 100 DEG C～the temperature of 120 DEG C and 0.05～0.08MPa pressure under implement.
17. preparation methoies as tdescribed in embodiment 1, it is characterised in that in described step (5), make ferrocyanide It is coated with described FeSiTi2 to include, in the presence of a mineral acid, intermediate FeSiTi2 is immersed in acid ferrocyanide solution Middle certain time, ferrocyanide and TiO2Layer carries out surface reaction and generates the ferrocyanide that titanium ion is stable.
18. preparation methoies as described in embodiment 17, it is characterised in that in step (5), the concentration of described mineral acid Between 0.5～1.0mol/L.
19. preparation methoies as described in embodiment 17, it is characterised in that in step (5), ferrocyanide aqueous solution Concentration between 15wt% to 40wt%.
20. preparation methoies as described in embodiment 17, it is characterised in that in step (5), described magnetic powder and pure water Mass ratio is between 1:3 to 1:5.
21. preparation methoies as described in embodiment 17, it is characterised in that in step (5), the choosing of described mineral acid is freely The group of hydrochloric acid, sulphuric acid or combinations thereof.
22. preparation methoies as described in embodiment 1 or 17, it is characterised in that in step (5), described ferrocyanide Thing select free sodium ferrocyanide, potassium ferrocyanide, or combinations thereof group, preferably potassium ferrocyanide.
23. preparation methoies as described in embodiment 2, it is characterised in that described magnetic powder is the work in the range of 80-120 mesh Industry level Fe3O4Magnetic powder.
The ferrous iron that magnetic core cladded type titanium ion that in 24. embodiments 1 to 23, method described in any one obtains is stable Cyanide adsorbent.
The ferrocyanide adsorbent that 25. 1 kinds of magnetic core cladded type titanium ions are stable, it comprises:
Particle size as kernel is less than the magnetic powder particle of 120 mesh (more than 120 microns)；
It is coated with the silicon dioxide layer of described magnetic powder particle；And
It is coated with the ferrocyanide nitride layer that the titanium ion of described silicon dioxide layer is stable.
The ferrocyanide adsorbent that the 26. magnetic core cladded type titanium ions as described in embodiment 25 are stable, its feature exists In, described magnetic powder particle has the particle size of 80-120 mesh (120 microns-180 microns).
The ferrocyanide adsorbent that the 27. magnetic core cladded type titanium ions as described in embodiment 26 are stable, its feature exists In, described magnetic powder is the technical grade Fe in the range of 80-120 mesh3O4Magnetic powder.
The ferrocyanide adsorbent that the 28. magnetic core cladded type titanium ions as described in embodiment 25 are stable, its feature exists Make the described magnetic powder in an acidic solution will not dissolution in, the consistency of described silicon dioxide layer.
The ferrocyanide suction that the 29. magnetic core cladded type titanium ions as described in any one in embodiment 25-28 are stable Attached dose, it is characterised in that relative to the weight of described magnetic powder, the content of Ti is more than 5wt%.
The ferrocyanide suction that the 30. magnetic core cladded type titanium ions as described in any one in embodiment 25-28 are stable Attached dose, it is characterised in that described ferrocyanide select free sodium ferrocyanide, potassium ferrocyanide, or combinations thereof group, excellent Select potassium ferrocyanide.
The 31. magnetic core cladded type titanium ions as described in any one in embodiment 24 or embodiment 25-30 are stable Ferrocyanide adsorbent for Adsorption of Radioactive isotope Cs ion and/or the use of absorption stability isotope Cs ion On the way.
32. purposes as described in embodiment 31, for remove separate or extract radiosiotope Cs ion and/or Remove or segregational stability isotope Cs ion.
33. purposes as described in embodiment 31 or 32, it is characterised in that described radiosiotope Cs ion and/or Stable isotope Cs ion is present in pH water-based system in the range of 1-11.
34. purposes as described in embodiment 31 or 32, it is characterised in that described radiosiotope Cs ion and/or Stable isotope Cs ion is present in pH water-based system in the range of 1-5.
35. 1 kinds of process units producing the stable ferrocyanide adsorbent of magnetic core cladded type titanium ion, its feature exists In, described process units includes reactor, centrifuge, vacuum drying oven, electric heating steaming tank and air blast drying room.
36. process units as described in embodiment 35, it is characterised in that described centrifuge is arranged under described reactor Side.
37. process units as described in embodiment 35 or 36, it is characterised in that described reactor is provided with online pH control System processed and automatic sample handling system, be set with certain chain control planning between the two system.

Claims (10)

1. the preparation method of magnetic core cladded type ferrocyanide adsorbent, it is characterised in that said method comprising the steps of:
(1) selecting magnetic powder is carrier, uses base catalysis hydrolysis of alkoxide method coated Si O on magnetic powder surface2Layer, solid liquid phase is centrifuged Separate and rinse to water outlet pH value less than 9 with clear water, it is thus achieved that intermediate is designated as FeSi1；
(2) sodium silicate method for hydrolysis is used to be evenly coated on FeSi1 surface further and the SiO of densification2Film, prepared material The most thoroughly it is dried, it is thus achieved that intermediate is designated as FeSi2；
(3) use the method for butyl titanate/alcohol non-aqueous solution absorption in FeSi2 area load titanium source, vacuum dried remove Solvent, it is thus achieved that area load has the intermediate of butyl titanate, is designated as FeSiTi1；
(4) FeSiTi1 is put into electric heating steaming tank or other high-temperature high-pressure steam environment, the method using vapor phase hydrolysis, make titanium Acid four butyl esters and steam react formation TiO on magnetic nuclear material surface2Transition zone, the intermediate so obtained is designated as FeSiTi2；
(5) intermediate FeSiTi2 is immersed in acid potassium ferrocyanide solution certain time, makes potassium ferrocyanide and TiO2Protect Sheath reaction generates Potassium titanium hexacyanoferrate, and is carried on magnetic material surface, and the material prepared after completion of the reaction is performing centrifugal separation on, And use clear water rinse to water outlet be light green, afterwards prepare material be the most thoroughly dried, it is thus achieved that target product magnetic core Cladded type Potassium titanium hexacyanoferrate removes caesium adsorbent.
2. preparation method as claimed in claim 1, it is characterised in that the operating process of described step (1) is: first in reaction Still adds anhydrous organic solvent and Shi Gui source, organosilicon source is uniformly dissolved, add magnetic powder with continuous stirring and continue stirring 2h；Be subsequently added into base catalyst, and control ph be not less than 11.5 under the conditions of react 1h；Add pure water afterwards and make hydrolysis Completely.
3. preparation method as claimed in claim 2, it is characterised in that in described step (1), the anhydrous organic solvent used For ethanol, propanol or isopropanol；The organosilicon source used is methyl silicate or silester, and the base catalyst of use is ammonia Water, NaOH or Na2CO3Solution；The addition total amount of alkali liquor and rate of addition are controlled by reaction system pH, it is ensured that whole course of reaction Middle pH is not less than 11.5, and reaction temperature is 20～50 DEG C, and the response time is not less than 2h.
4. preparation method as claimed in claim 3, it is characterised in that in described step (1), the amount in organosilicon source and magnetic powder matter Amount is relevant, and Si: magnetic powder=5wt%～10wt%；The volume ratio of organosilicon source and alcohol is 1: 5～1: 10, the pure water of addition with The volume ratio of alcohol is 1: 5～1: 10.
5. preparation method as claimed in claim 1, it is characterised in that the operating process of described step (2) is: in a kettle. Add pure water and step (1) obtained intermediate FeSi1, at 90 DEG C, be simultaneously added dropwise sodium silicate solution and dilute acid soln, control volume Be pH=9.5, whole sodium silicate solutions dropping complete while stop dropping dilute acid soln, system under agitation react 5～ 1Oh。
6. preparation method as claimed in claim 1, it is characterised in that using butyl titanate in described step (3) is titanium source, Ti: magnetic powder=5wt%～10wt%；Employing solvent is dehydrated alcohol, anhydrous isopropyl alcohol or anhydrous propanol, butyl titanate with Both solvents volume ratio is 1: 2～1: 4, and vacuum drying temperature is 40～50 DEG C.
7. preparation method as claimed in claim 1, it is characterised in that in described step (5), add dense under conditions of stirring Hydrochloric acid, adds potassium ferrocyanide, and magnetic powder is 1: 3～1: 5 with pure water mass ratio in reactant liquor, and in reactant liquor, the concentration of hydrochloric acid is 0.5～1.0mol/L；Ferrocyanide potassium concn is 15wt%～40wt%, after gained precipitate machine by centrifugation separates, uses clear water Cleaning, until centrifuge outlet liquid is light green color or colourless, precipitate is dried at 120 DEG C and i.e. obtains target product magnetic core bag Cover type Potassium titanium hexacyanoferrate except caesium adsorbent.
8. the magnetic core cladded type Potassium titanium hexacyanoferrate prepared in preparation method described in any one of claim 1-7 removes caesium adsorbent, It is characterized in that, kernel is magnetic powder particle, is respectively arranged with silicon dioxide overlay film from inside to outside at described magnetic powder particle outer surface Layer and Potassium titanium hexacyanoferrate coating layer.
9. magnetic core cladded type Potassium titanium hexacyanoferrate described in claim 8 except caesium adsorbent at Adsorption of Radioactive isotope Cs ion and The application process of absorption stable isotope Cs ion, it is characterised in that use batch-type dynamic adsorption reactor pattern to give up Liquid processes.
10. the process units used in preparation method described in any one of claim 1-7, it is characterised in that described process units Including reactor, centrifuge, vacuum drying oven, electric heating steaming tank and air blast drying room.
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