CN100469435C - Method for preparing high-loading iron cyanide complex/silicon dioxide hybrid materials - Google Patents
Method for preparing high-loading iron cyanide complex/silicon dioxide hybrid materials Download PDFInfo
- Publication number
- CN100469435C CN100469435C CNB2007100644530A CN200710064453A CN100469435C CN 100469435 C CN100469435 C CN 100469435C CN B2007100644530 A CNB2007100644530 A CN B2007100644530A CN 200710064453 A CN200710064453 A CN 200710064453A CN 100469435 C CN100469435 C CN 100469435C
- Authority
- CN
- China
- Prior art keywords
- ferrocyanide
- silicon dioxide
- silica
- hybrid materials
- dioxide hybrid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to a preparing method for ferrocyanide with high load/silica hybrid material, belonging to a preparing method for radionuclide ion absorbing material. The method uses the salt solution with metal ion such as Mn, Sn, Ti, Fe, and Ni so on to react with potassium (sodium) ferrocyanide so as to obtain nanometer particle of ferrocyannide. The particle is fixed by silica solution in water system or is fixed by polymerization siloxane in organic solvent and proper inorganic acid, organic amine or amine water is added to obtain hybrid gel. The hybrid gel is dried, rubbed and screened to obtain ferrocyanide with high load/silica hybrid material. The high load of the material is high and the absorption to nuclide ion is strong. In addition, the material intensity can satisfy the demand of packed bed. The particle diameter can be controlled so as to avoid the problem that the water resistance of bed layer generated by ferrocyanide used alone is overlarge.
Description
Technical field
The present invention relates to a kind of preparation method of radionuclide ion absorbing material, particularly a kind of preparation method of ferrocyanide/silicon dioxide hybrid materials of high capacity amount belongs to material preparation and radioactive wastewater processing technology field.
Background technology
The energy policy of China changes " develop actively nuclear power " into from " optimum development nuclear power ".To the year two thousand twenty, domestic nuclear power installed capacity will be risen to by 8,000,000 present kW about 4,000 ten thousand kW.The year two thousand twenty also has bigger development later on.Can the radioactive wastewater that nuclear industry produced properly be disposed is one of key link that is related to nuclear safety.Research and development are efficient, the radioactive wastewater treatment technology of high selectivity, realize the refuse small quantization to the full extent, are the very significant work in nuclear industry field.The processing of radioactive wastewater method commonly used has following several:
1) evaporation concentration method: radioactive wastewater steams raffinate and solidifies the back disposal after evaporation and concentration is handled, and distillate discharges after ion exchange resin treatment.This method energy consumption is big, and because radioactive wastewater salt content height is very serious to the corrosion of vaporising device.
2) natural aluminosilicate hydrochlorate facture, this method is that the natural aluminosilicate hydrochlorate that adopts kaolin, rectorite, vermiculite etc. to have certain ion-exchange capacity is handled radioactive wastewater, in the hope of the radionuclide ion is fixed on these material internals, finish processing to waste water.Yet these material ion-exchange capacities are limited, and poor to the nucleic ion selectivity, produce a large amount of radwastes, need further to handle to dispose.
3) zeolite process: natural zeolite or artificial synthetic zeolite have suitable rule space structure, can the adsorption treatment radionuclide.Zeolite can reach 2meq/g to the exchange capacity of Cs in theory, but other ion such as potassium ion in the reality, can the strong removal of disturbing Cs, cause the adsorption capacity of zeolite very low, the per kilogram zeolite only can be handled 10 kilograms of waste water.Because adsorbent can not be regenerated during radioactive wastewater was handled, therefore a large amount of radwaste that produces needs further to handle to dispose.
4) ion exchange resin treatment method; At present China's nuclear facilities ion exchange resin of being used for handling low radioactive waste liquid mostly is the strong acid and strong base type that SDEB styrene diethylenebenzene is a matrix.Generally, the adsorption capacity utilization rate less than 30% of resin.Radionuclide in the resin centering low radioactive waste liquid lacks enough selectivity, and the disposable use of resin is not regenerated, so the radioactive spent resin generation is big, and the later stage disposal costs is quite surprising.In addition, resin is an organic material, and radiation-resistant property is poor, and irradiation decomposes may produce hydrogen, becomes the major hidden danger of radioactive spent resin long-term storage.
5) ammonium phosphomolybdate facture: ammonium phosphomolybdate is to Cs
+Selectivity with height, however ammonium phosphomolybdate is tiny crystallite, can't carry out the packed bed operation, and this has seriously limited its commercial Application.People such as Sun Zhaoxiang have prepared ammonium phosphomolybdate and tetravalent metal phosphate (as Ti, Zr, Sb etc.) hybrid material, granulating (ion-exchange and absorption, 12,44-49,1996 of having realized ammonium phosphomolybdate; Nuclear chemistry and radiochemistry, 21,76-82,1999; Beijing Normal University's journal: natural science edition, 27,339-343,1991), but introduces comparatively expensive tetravalent metal, increased cost.From the technical report that the radwaste of International Atomic Energy Agency's issue in 2002 is handled, the ammonium phosphomolybdate series material does not also obtain large-scale practical application in radioactive wastewater is handled.
6) ferrocyanide facture: the ferrocyanide of being fixed by transition metal is to radioactive Cs
+, Sr
2+Ion has good selectivity absorbability.At Na
+Under the situation of concentration 5mol/L, such material is for Cs
+Selectivity factor (at Na
+) reach 1500000 (Nuclear Science and Engineering, 137,206-214,2001).Yet ferrocyanide granule interior mass transfer condition is poor, and adsorption capacity often can not be utilized (nuclear chemistry and radiochemistry, 23,108-113,2001) fully.Ferrocyanide loaded on the porous material carrier can improve the mass transfer dynamics condition.Mardan has studied the employing solvent evaporated method, and the porous silica that adopts moulding is as carrier, fixedly K
2[CoFe (CN)
6] (Separation andPurification Technology 16,147-158,1999), its high capacity amount has only 1.36g-K
2[CoFe (CN)
6]/g-SiO
2, and need be with solvent evaporation step repeated multiple times, complex steps needs to consume a large amount of organic solvents, the possibility of practical application little (Talanta, 17-23,955,1970).Wang Qiuping etc. adopt the method for co-precipitation to prepare multiple materials such as calcium ferrocyanide potassium, zinc ferrocyanide potassium, manganous ferrocyanide potassium under acid condition, all has Cs ion adsorption capacity preferably, but all owing to the stability of particle is not good, breaking and Dusting in practical operation easily, can't be used to radiate processing (ion-exchange and the absorption of waste water, 16 (3), 225～233,2000).(Talanta 1970,17,955-963) and Konecny (Radioanal.Chem. for Terada, 1973,14,255-266) all reported potassium ferrocyanide has been fixed on earlier in the silica dioxide gel, be translated into the method for ferrocyanide absorbent again with transition metal ions.Yet, because conversion reaction is carried out in the hole of silica, so its speed is extremely slow, need to use excessive greatly metal ion, and the product component of conversion reaction is difficult to control, in addition because conversion reaction is difficult to carry out fully, can not prevent in the silica dioxide gel that the part potassium ferrocyanide is leached and runs off in the ion absorption process.
Summary of the invention
The objective of the invention is to overcome that the ferrocyanide load capacity is low in the prior art, granulation is difficult, granule strength is not high, the fixing inadequate shortcoming of potassium ferrocyanide (sodium), thereby a kind of method for preparing the ferrocyanide/silicon dioxide hybrid materials of high capacity amount is provided, guarantees that simultaneously material has high adsorption capacity and selectivity.
The objective of the invention is to realize by the following technical solutions: a kind of preparation method of ferrocyanide/silicon dioxide hybrid materials of high capacity amount is characterized in that this method carries out as follows:
1) preformed precipitate: potassium ferrocyanide or sodium ferrocyanide are dissolved in the deionized water, under vigorous stirring to the soluble-salt solution that wherein adds Mn, Sn, Ti, Fe, Ni, Co, Cr, Zr, Cu, Pb, Zn transition metal, the mol ratio of Hexacyanoferrate root and metal ion is 1:1～1:6, sediment through centrifuge washing repeatedly, is obtained the ferrocyanide nano particle;
2) gel sets: adopt and in aqueous systems, fix or in organic solvent, fix with the polymeric alkanones radical siloxane with Ludox:
2.1) in aqueous systems, fix with Ludox
Under vigorous stirring, add the alkaline silica sol aqueous solution to gained ferrocyanide nano particle, the mass ratio of the silica in ferrocyanide nano particle and the Ludox is 0.2:1 ~ 7:1, in water-bath, system is heated to 40～80 ℃ again, add inorganic acid, be selected from any or its several mixture of hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid; The pH of system is adjusted to 2～7, places constant temperature oven to dry the gained gel, obtain ferrocyanide/silicon dioxide hybrid materials to constant weight;
2.2) in organic solvent, fix with the polymeric alkanones radical siloxane
Alkoxy silane is dissolved in the organic solvent, and alkoxy silane is selected from 1～3 kind mixture in tetramethoxy-silicane, tetraethoxysilane and the tetrapropoxysilane, and organic solvent is selected from 1～3 kind of mixture in methyl alcohol, ethanol and the acetone; Stir and to add deionized water and concentrated hydrochloric acid down, form mixed liquor, the addition of organic solvent is 1～2 times of alkoxy silane volume, and the addition of HCl and H2O is respectively 0.01～0.1 times and 0.4～1.8 times of mole of alkoxy silane; Mixed-liquor return is heated to 60～90 ℃, keeps 2～8hr, obtain the solution of poly-alkylsiloxane; The ferrocyanide nano particle for preparing in the step 1) is washed with ethanol, be scattered in again in the poly-alkylsiloxane solution, and the mass ratio of the silica in ferrocyanide and the system is 0.2:1 ~ 7:1; Fully after the dispersed with stirring, 1～4 kind mixture in dropping ammonia, methylamine, ethamine and the ethylenediamine under agitation, addition is 1/20 ~ 1/10 of a former alkoxy silane volume, form gel, the gained gel is dried in constant temperature oven to constant weight, obtain ferrocyanide/silicon dioxide hybrid materials.
Technical characterictic of the present invention also is; The Hexacyanoferrate root in the described step 1) and the preferred molar ratio of metal ion are 1:1.5～1:3.Described step 2.1) and 2.2) in the preferred mass of ferrocyanide nano particle and silica than 0.5; 1～4:1.Described step 2.1) the preferred temperature that in water-bath system is heated in is 70～80 ℃.Described step 2.2) polymerisation is carried out under the temperature that is higher than 5～10 ℃ of solvent boiling points in.
Step 2.1 of the present invention) dioxide-containing silica in the alkaline silica sol aqueous solution in is 10～35wt%, and wherein the silicon dioxide granule particle diameter is 10～40nm, density 1.1 ~ 1.3g/mL.
This method has avoided adopting the porous silica of moulding as carrier, but adopt the liquid precursor (Ludox or polysiloxanes) of silica and ferrocyanide to mix back initiated gel reaction, thereby obtained the very high hybrid material of ferrocyanide load capacity.Have the following advantages: (a) the ferrocyanide load capacity is big: the load capacity of its ferrocyanide of material that this method obtains can reach more than 80%.(b) ferrocyanide in the material is dispersed in the hybrid material with the form of molecule, and silica has played the effect of ferrocyanide carrier, can satisfy requirement of strength.(c) prepared ferrocyanide/silicon dioxide hybrid materials has loose structure, can improve the adsorption dynamics adsorption kinetics condition, improves the rate of adsorption.(d) the prepared material of the present invention had both been brought into play nanoscale ferrocyanide absorption property efficiently, had satisfied the particle size and the intensity of packed bed action need again.
The prepared sorbing material of this method can be the Na of 0.5mol/L in concentration
+With concentration be the H of 0.5mol/L
+Interference under with Cs in the water
+Concentration is reduced to below the 8 μ g/L from 1000 μ g/L, and the adsorbent consumption only is 2g/L.
The specific embodiment
The preparation method of the ferrocyanide/silicon dioxide hybrid materials of a kind of high capacity amount provided by the invention, its concrete processing step is as follows:
1) preformed precipitate: potassium ferrocyanide or sodium ferrocyanide are dissolved in the deionized water, to the soluble-salt solution that wherein adds Mn, Sn, Ti, Fe, Ni, Co, Cr, Zr, Cu, Pb, Zn transition metal, the mol ratio of Hexacyanoferrate root and metal ion is 1:1～1 under vigorous stirring; 6, be preferably 1:1.5～1:3; Sediment through centrifuge washing repeatedly, is obtained the ferrocyanide nano particle;
2) gel sets: adopt and in aqueous systems, fix or in organic solvent, fix with the polymeric alkanones radical siloxane with Ludox:
2.1) in aqueous systems, fix with Ludox
Add the alkaline silica sol aqueous solution to gained ferrocyanide nano particle under vigorous stirring, the dioxide-containing silica in the alkaline silica sol aqueous solution is 10～35wt%, and wherein the silicon dioxide granule particle diameter is 10～40nm, density 1.1～1.3g/mL.The mass ratio of the silica in ferrocyanide nano particle and the Ludox is 0.2:1～7:1, and preferred mass is than being 0.5:1～4:1; In water-bath, system is heated to 40～80 ℃ again, is preferably 70～80 ℃, add inorganic acid, be selected from any or its several mixture of hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid; The pH of system is adjusted to 2～7, preferred 4～6; Place constant temperature oven to dry the gained gel, obtain ferrocyanide/silicon dioxide hybrid materials to constant weight;
2.2) in organic solvent, fix with the polymeric alkanones radical siloxane
Alkoxy silane is dissolved in the organic solvent, and alkoxy silane is selected from 1～3 kind mixture in tetramethoxy-silicane, tetraethoxysilane and the tetrapropoxysilane, and organic solvent is selected from 1～3 kind of mixture in methyl alcohol, ethanol and the acetone; Stir adding deionized water and concentrated hydrochloric acid down, form mixed liquor, the addition of organic solvent is 1～2 times of alkoxy silane volume, HCl and H
2The addition of O is respectively 0.01～0.1 times and 0.4～1.8 times of mole of alkoxy silane; Mixed-liquor return is heated to 60～90 ℃, preferably is higher than the temperature of 5～10 ℃ of solvent boiling points; Keep 2～8hr, obtain the solution of poly-alkylsiloxane; The ferrocyanide nano particle for preparing in the step 1) is washed with ethanol, be scattered in again in the poly-alkylsiloxane solution, and the mass ratio of the silica in ferrocyanide nano particle and the system is 0.2:1～7:1; Fully after the dispersed with stirring, 1～4 kind mixture in dropping ammonia, methylamine, ethamine and the ethylenediamine under agitation, addition is 1/20～1/10 of a former alkoxy silane volume, form gel, the gained gel is dried in constant temperature oven to constant weight, obtain ferrocyanide/silicon dioxide hybrid materials.
Enumerate several specific embodiments below, understand the present invention with further.
Embodiment 1:
The 9g potassium ferrocyanide is dissolved in the 50mL deionized water, slowly adds 50mL Co (NO under the vigorous stirring
3)
2Solution, K
4[Fe (CN)
6]) and the mol ratio=1:1.5 of Co ion, then system being stirred 30min, ageing 24hr filters, washing.With gained nanoscale K
2[CoFe (CN)
6] particle is dispersed in the 50mL deionized water, adding dioxide-containing silica is the alkaline silica sol 115mL of 30% (wt), K in the system
2[CoFe (CN)
6] and the mass ratio of silica be 0.2/1.Fully stir and mix the back and be heated to 80 ℃ in water-bath, add 35% concentrated hydrochloric acid again under vigorous stirring, regulating pH is 5, and system is left standstill, and gel behind the 1min is dried gel to constant weight under 100 ℃, grinds, and crosses 60 mesh sieves.Get radionuclide ion absorbing material, its active component is K
2[CoFe (CN)
6].
Embodiment 2:
The 15g sodium ferrocyanide is dissolved in the 80mL deionized water, slowly adds 80mL Zn (NO under the vigorous stirring
3)
2Solution, Na
4[Fe (CN)
6] and the mol ratio=1:2 of Zn ion, then system being stirred 60min, ageing 12hr filters, washing.With gained Na
2[CoFe (CN)
6] particle is dispersed in the 80mL deionized water, then adding dioxide-containing silica is the alkaline silica sol 50mL of 25% (wt), Na in the system
2[ZnFe (CN)
6] and the mass ratio of silica be 0.9/1.Fully stir and mix the back and be heated to 40 ℃ in water-bath, add 65% red fuming nitric acid (RFNA) again under vigorous stirring, regulating pH is 4, the gained gel rubber system is left standstill, gel is dried to constant weight under 120 ℃, grind, cross 60 mesh sieves, get radionuclide ion absorbing material, its active component is Na
2[ZnFe (CN)
6].
Embodiment 3:
The 1Kg potassium ferrocyanide is dissolved in the 5.6L deionized water, slowly adds 5L Mn (NO under the vigorous stirring
3)
2Solution, K
4[Fe (CN)
6] and the mol ratio=1:1 of Mn ion, then system being stirred 20min, ageing 48hr filters, washing.With gained K
2[MnFe (CN)
6] nano particle is scattered in the 4L deionized water, then adds the alkaline silica sol that the 315mL dioxide-containing silica is 30% (wt), K in the system
2[MnFe (CN)
6] and the mass ratio of silica be 7/1.Fully stir and mix the back and be heated to 80 ℃ in water-bath, add sulfuric acid (1:1) again under vigorous stirring, regulating pH is 5, the gained gel is left standstill, under 100 ℃, dry, grind to constant weight, cross 50 mesh sieves, get radionuclide ion absorbing material, its active component is K
2[MnFe (CN)
6].
Embodiment 4:
The 15g potassium ferrocyanide is dissolved in the 80mL water, slowly adds 100mL Cu (NO under the vigorous stirring
3)
2Solution, K
4[Fe (CN)
6] and the mol ratio=1:6 of Cu ion, stirring 45min, ageing 12hr filters, washing.The gained precipitation is scattered in the 50mL deionized water, then adds the alkaline silica sol that the 20mL dioxide-containing silica is 30% (wt), Cu in the system
2[Fe (CN)
6] and the mass ratio of silica be 1.6/1.Fully stir and mix the back and be heated to 70 ℃ in water-bath, add sulfuric acid (1:1) again under vigorous stirring, regulating pH is 5, and system is supergrip very, the gained gel is left standstill, under 110 ℃, dry, grind to constant weight, cross 50 mesh sieves, get radionuclide ion absorbing material, its active component is Cu
2[Fe (CN)
6].
Embodiment 5:
The 50g potassium ferrocyanide is dissolved in the 250mL deionized water, slowly adds 250mL Ni (NO under the vigorous stirring
3)
2Solution, K
4[Fe (CN)
6] and the mol ratio=1:5 of Ni ion, stirring 30min, ageing 24hr filters, washing.The gained precipitation is scattered in the 200mL deionized water, then adds the alkaline silica sol that the 60mL dioxide-containing silica is 25% (wt), Ni in the system
2[Fe (CN)
6] and the mass ratio of silica be 2.16/1.Mix the back water-bath and be heated to 80 ℃, add 60% red fuming nitric acid (RFNA) and regulate pH to 6, system loses flowability in 30s and gel.The gained gel is dried to constant weight under 80 ℃, grind, cross 100 mesh sieves, get radionuclide ion absorbing material, its active component is Ni
2[Fe (CN)
6].
Embodiment 6:
The 100g potassium ferrocyanide is dissolved in the 700mL water, adds 500mL Cu (NO under the vigorous stirring
3)
2Solution, K
4[Fe (CN)
6] and the mol ratio=1:4 of Cu ion, stirring 40min, ageing 48hr filters, washing.The gained precipitation is scattered in the 500mL deionized water, then adds the alkaline silica sol that the 35mL dioxide-containing silica is 30% (wt), Cu in the system
2[Fe (CN)
6] and the mass ratio of silica be 6.3/1.Mix the back water-bath and be heated to 80 ℃, add 60% red fuming nitric acid (RFNA) and regulate pH to 4, system loses flowability in 10min and gel.The gained gel is dried to constant weight under 100 ℃, grind, cross 50 mesh sieves, get radionuclide ion absorbing material, its active component is Cu
2[Fe (CN)
6].
Embodiment 7:
The 40g potassium ferrocyanide is dissolved in the 220mL water, adds 250mL Sn (NO under the vigorous stirring
3)
2Solution, K
4[Fe (CN)
6] and the mol ratio=1:1.6 of Sn ion, stirring 20min, ageing 24hr filters, washing.The gained precipitation is scattered in the 200mL deionized water, then adds the alkaline silica sol that the 60mL dioxide-containing silica is 20% (wt), K in the system
2[SnFe (CN)
6] and the mass ratio of silica be 2.7/1.Mix the back water-bath and be heated to 80 ℃, then add phosphoric acid and regulate pH to 5, system gel.The gained gel is dried to constant weight under 100 ℃, grind, cross 100 mesh sieves, get radionuclide ion absorbing material, its active component is K
2[SnFe (CN)
6].
Embodiment 8:
The 20g potassium ferrocyanide is dissolved in the 100mL water, adds 120mL Pb (NO under the vigorous stirring
3)
2Solution, K
4[Fe (CN)
6] and the mol ratio=1:2 of Pb ion, stirring 45min, ageing 36hr filters, deionized water washing three times.Be scattered in that (dioxide-containing silica is 15g in the acetone soln of the poly-tetraethoxysilane of 100mL, its preparation method is as follows: get the 52g tetraethoxysilane and be dissolved in the 100mL acetone, reflux to stir down and be heated to 60 ℃, keep 4hr, 110mL gathers the acetone soln of tetraethoxysilane) K in the system
2[PbFe (CN)
6] and the mass ratio of silica be 1.57/1.Stirring adds 6.5mL30wt% ammoniacal liquor down in this solution, system is supergrip very, and the gained gel is dried under 120 ℃ to constant weight, grinds, and crosses 100 mesh sieves, gets radionuclide ion absorbing material, and its active component is K
2[PbFe (CN)
6].
Embodiment 9:
The 10g potassium ferrocyanide is dissolved in the 100mL water, adds 120mL CrCl under the vigorous stirring
3Solution K
4[Fe (CN)
6] and the mol ratio=1:1.5 of Cr ion, stirring 70min, ageing 10hr filters, deionized water washing three times.Be scattered in that (wherein dioxide-containing silica is 6g in the ethanolic solution of the poly-tetrapropoxysilane of 40mL, its preparation method is as follows: get the 27g tetrapropoxysilane and be dissolved in the 50mL ethanol, backflow is heated to 90 ℃ under stirring, keep 8hr, the ethanolic solution of the poly-tetrapropoxysilane of 53mL) K[CrFe (CN) in the system
6] and the mass ratio of silica be 1.2/1.Stirring adds the 2mL ethylenediamine down in this solution, the gained gel is dried under 110 ℃ to constant weight, grinds, and crosses 100 mesh sieves, gets radionuclide ion absorbing material, and its active component is K[CrFe (CN)
6].
Embodiment 10:
The 18g potassium ferrocyanide is dissolved in the 100mL deionized water, slowly adds 110mL Co (NO under the vigorous stirring
3)
2Solution, K
4[Fe (CN)
6]) and the mol ratio=1:1.5 of Co ion, then system being stirred 30min, ageing 24hr filters, deionized water washing three times.Be scattered in that (wherein dioxide-containing silica is 15g in the methanol solution of the poly-tetramethoxy-silicane of 85mL, its preparation method is as follows: get the 38g tetramethoxy-silicane and be dissolved in the 47mL methyl alcohol, reflux to stir down and be heated to 70 ℃, keep 2hr, 85mL gathers the methanol solution of tetramethoxy-silicane) K in the system
2[CoFe (CN)
6] and the mass ratio of silica be 1/1.Stirring adds the 2.4mL methylamine down in this solution, the gained gel is dried under 90 ℃ to constant weight, grinds, and crosses 100 mesh sieves, gets radionuclide ion absorbing material, and its active component is K
2[CoFe (CN)
6].
Claims (6)
1, a kind of preparation method of ferrocyanide/silicon dioxide hybrid materials of high capacity amount is characterized in that this method carries out as follows:
1) preformed precipitate: potassium ferrocyanide or sodium ferrocyanide are dissolved in the deionized water, under vigorous stirring to the soluble-salt solution that wherein adds Mn, Ti, Fe, Ni, Co, Cr, Zr, Cu, Zn transition metal, the mol ratio of Hexacyanoferrate root and metal ion is 1:1～1:6, sediment through centrifuge washing repeatedly, is obtained the ferrocyanide nano particle;
2) gel sets: adopt and in aqueous systems, fix or in organic solvent, fix with polyalkoxysilane with Ludox:
2.1) in aqueous systems, fix with Ludox
Under vigorous stirring, add the alkaline silica sol aqueous solution to gained ferrocyanide nano particle, the mass ratio of the silica in ferrocyanide nano particle and the Ludox is 0.2:1～7:1, in water-bath, system is heated to 40～80 ℃ again, add inorganic acid, be selected from any or its several mixture of hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid; The pH of system is adjusted to 2～7, places constant temperature oven to dry the gained gel, obtain ferrocyanide/silicon dioxide hybrid materials to constant weight;
2.2) in organic solvent, fix with polyalkoxysilane
Alkoxy silane is dissolved in the organic solvent, and alkoxy silane is selected from 1～3 kind mixture in tetramethoxy-silicane, tetraethoxysilane and the tetrapropoxysilane, and organic solvent is selected from 1～3 kind of mixture in methyl alcohol, ethanol and the acetone; Stir adding deionized water and concentrated hydrochloric acid down, form mixed liquor, the addition of organic solvent is 1～2 times of alkoxy silane volume, HCl and H
2The addition of O is respectively 0.01～0.1 times and 0.4～1.8 times of mole of alkoxy silane; Mixed-liquor return is heated to 60～90 ℃, keeps 2～8hr, obtain the solution of polyalkoxysilane; The ferrocyanide nano particle for preparing in the step 1) is washed with ethanol, be scattered in again in the polyalkoxysilane solution, and the mass ratio of the silica in ferrocyanide nano particle and the system is 0.2:1～7:1; Fully after the dispersed with stirring, 1～4 kind mixture in dropping ammonia, methylamine, ethamine and the ethylenediamine under agitation, addition is 1/20～1/10 of a former alkoxy silane volume, form gel, the gained gel is dried in constant temperature oven to constant weight, obtain ferrocyanide/silicon dioxide hybrid materials.
2, the preparation method of the ferrocyanide/silicon dioxide hybrid materials of high capacity amount as claimed in claim 1 is characterized in that: the Hexacyanoferrate root in the described step 1) and the mol ratio of metal ion are 1:1.5～1:3.
3, the preparation method of the ferrocyanide/silicon dioxide hybrid materials of high capacity amount as claimed in claim 1 or 2, it is characterized in that: the dioxide-containing silica in the alkaline silica sol aqueous solution described step 2.1) is 10～35wt%, wherein the silicon dioxide granule particle diameter is 10～40nm, density 1.1～1.3g/mL.
4, the preparation method of the ferrocyanide/silicon dioxide hybrid materials of high capacity amount as claimed in claim 1 or 2 is characterized in that: described step 2.1) and 2.2) in the mass ratio 0.5:1～4:1 of ferrocyanide nano particle and silica.
5, the preparation method of the ferrocyanide/silicon dioxide hybrid materials of high capacity amount as claimed in claim 1 is characterized in that: described step 2.1) system is heated to 70～80 ℃.
6, the preparation method of the ferrocyanide/silicon dioxide hybrid materials of high capacity amount as claimed in claim 1 is characterized in that: described step 2.2) polymerisation is carried out under the temperature that is higher than 5～10 ℃ of solvent boiling points.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100644530A CN100469435C (en) | 2007-03-16 | 2007-03-16 | Method for preparing high-loading iron cyanide complex/silicon dioxide hybrid materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100644530A CN100469435C (en) | 2007-03-16 | 2007-03-16 | Method for preparing high-loading iron cyanide complex/silicon dioxide hybrid materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101041123A CN101041123A (en) | 2007-09-26 |
| CN100469435C true CN100469435C (en) | 2009-03-18 |
Family
ID=38807052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100644530A Active CN100469435C (en) | 2007-03-16 | 2007-03-16 | Method for preparing high-loading iron cyanide complex/silicon dioxide hybrid materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100469435C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102217654A (en) * | 2011-04-15 | 2011-10-19 | 中国科学院过程工程研究所 | Method for preparing nano zinc/potassium ferrocyanide antibacterial material |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279249B (en) * | 2008-05-23 | 2010-04-07 | 清华大学 | Preparation of potassium zirconium hexacyanoferrate using pellet silica-gel as carrier |
| FR2945756B1 (en) * | 2009-05-20 | 2011-08-05 | Commissariat Energie Atomique | NANOCOMPOSITE SOLID MATERIAL BASED ON HEXA AND OCTACYANOMETALLATES, PROCESS FOR PREPARING THE SAME, AND METHOD FOR FIXING MINERAL POLLUTANTS USING THE SAME |
| US9745202B2 (en) * | 2012-03-28 | 2017-08-29 | Board of Regents, U of Texas System | Metal cyanometallate synthesis method |
| FR2996149B1 (en) | 2012-09-28 | 2014-10-31 | Commissariat Energie Atomique | SUPPORTED HEXA- AND OCTACYANOMETALLATE MEMBRANE-SUPPORTED MEMBRANE, PROCESS FOR PREPARING THE SAME, AND SEPARATION METHOD USING THE SAME |
| CN103274757B (en) * | 2013-06-07 | 2014-06-25 | 苏磊 | Function ceramic material for efficiently filtering radioactive iodine and cesium, and preparation method thereof |
| CN103695205B (en) * | 2013-12-03 | 2016-01-20 | 中国人民解放军总参谋部工程兵科研三所 | A kind of Self-broken decontamination liquid |
| CN105651816B (en) * | 2014-11-12 | 2019-01-25 | 长沙理工大学 | A kind of novel ammonia gas sensor and preparation method thereof |
| CN104923167B (en) * | 2015-07-10 | 2017-01-04 | 山东大学 | A kind of stable Nano-meter SiO_22the preparation method of/tributyl phosphate composite adsorbing material |
| CN105381780B (en) * | 2015-12-07 | 2017-10-31 | 中国科学院生态环境研究中心 | A kind of magnetic adsorbent for adsorbing superconduction Magneto separate arsenic removal antimony and preparation method thereof |
| CN105741897B (en) * | 2016-03-30 | 2018-03-13 | 中国科学院上海应用物理研究所 | A kind of halide radwaste glass solidified body and preparation method thereof |
| FR3055558B1 (en) | 2016-09-08 | 2022-01-14 | Commissariat Energie Atomique | SOLID NANOCOMPOSITE MATERIAL BASED ON HEXA- OR OCTACYANOMETALLATES OF ALKALINE METALS, METHOD FOR PREPARING IT, AND METHOD FOR EXTRACTION OF METALLIC CATIONS. |
| CN117019109A (en) * | 2018-01-04 | 2023-11-10 | 清华大学 | Large-scale preparation method of high-stability cesium removal adsorbent, and product and application thereof |
| CN111111621A (en) * | 2018-11-01 | 2020-05-08 | 四川德天合盛环保科技有限公司 | Method for fixing copper ferrocyanide on PVDF hollow fiber membrane |
| CN109967048A (en) * | 2019-02-19 | 2019-07-05 | 江苏海普功能材料有限公司 | The resin-base nano compound adsorbent and preparation method thereof of caesium is mentioned for brine |
| CN109911914B (en) * | 2019-04-25 | 2020-06-12 | 江西省科学院应用物理研究所 | Preparation method of core-shell structure silver aluminum ferrocyanide nanomaterial |
| CN111167517B (en) * | 2019-12-31 | 2021-09-10 | 青岛科技大学 | Au-GSH@TiO2@ PDMS composite material and preparation method and application thereof |
| CN114516960B (en) * | 2022-01-19 | 2023-03-24 | 山东共聚有机硅技术研究院有限公司 | Iron cyano silicone resin heat-resistant liquid filler and preparation method thereof |
| CN115522068B (en) * | 2022-09-16 | 2023-08-01 | 河北远大中正生物科技有限公司 | Method for separating rubidium and cesium from high-salt mother solution |
-
2007
- 2007-03-16 CN CNB2007100644530A patent/CN100469435C/en active Active
Non-Patent Citations (6)
| Title |
|---|
| Silica gel as a support for inorganic ionexchangersfor the determination of caesium-137 in natural waters. Kikuo Terada, et al.Talanta,Vol.17 . 1970 |
| Silica gel as a support for inorganic ionexchangersfor the determination of caesium-137 in natural waters. Kikuo Terada, et al.Talanta,Vol.17 . 1970 * |
| Sorption of cesium on copperhexacyanoferrate/polymer/silica composites in batchanddynamic conditions. S.Milonjic, et al.Journal of Radioanalytical and Nuclear Chemistry,Vol.252 No.3. 2002 |
| Sorption of cesium on copperhexacyanoferrate/polymer/silica composites in batchanddynamic conditions. S.Milonjic, et al.Journal of Radioanalytical and Nuclear Chemistry,Vol.252 No.3. 2002 * |
| 亚铁氰化铜-硅胶对钴、锌、铯和铈吸附性能的研究. 秦学祥等.海洋环境科学，第12卷第1期. 1993 |
| 亚铁氰化铜-硅胶对钴、锌、铯和铈吸附性能的研究. 秦学祥等.海洋环境科学，第12卷第1期. 1993 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102217654A (en) * | 2011-04-15 | 2011-10-19 | 中国科学院过程工程研究所 | Method for preparing nano zinc/potassium ferrocyanide antibacterial material |
| CN102217654B (en) * | 2011-04-15 | 2013-05-01 | 中国科学院过程工程研究所 | Method for preparing nano zinc/potassium ferrocyanide antibacterial material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101041123A (en) | 2007-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100469435C (en) | Method for preparing high-loading iron cyanide complex/silicon dioxide hybrid materials | |
| CN104014316B (en) | The method of tannic acid in the preparation of chitosan magnetic and adsorbed water | |
| CN102942239B (en) | Preparation method of composite material | |
| Liang et al. | Synthesis of a novel three-dimensional porous carbon material and its highly selective Cr (VI) removal in wastewater | |
| CN100551519C (en) | With bead silica gel is the preparation method of the ferrocyanide titanium potassium of carrier | |
| CN101279249B (en) | Preparation of potassium zirconium hexacyanoferrate using pellet silica-gel as carrier | |
| CN106552602A (en) | A kind of preparation method for adsorbing the composite adsorbing material of rubidium cesium ion | |
| CN106732481B (en) | A kind of pertechnetate adsorbent and its synthetic method and the application in processing radioactive wastewater | |
| Bi et al. | Growth of a mesoporous Zr-MOF on functionalized graphene oxide as an efficient adsorbent for recovering uranium (VI) from wastewater | |
| CN107262071A (en) | A kind of industrial production process of iron oxide resin compounded adsorbent | |
| Liu et al. | Adsorption performance of U (VI) by amidoxime-based activated carbon | |
| Wei et al. | Interaction of U (VI) with amine-modified peanut shell studied by macroscopic and microscopic spectroscopy analysis | |
| CN106824071A (en) | C@SiO of the one kind for Cr (VI) Adsorption2The preparation method of hollow ball | |
| Wang et al. | Application of polypyrrole-based adsorbents in the removal of fluoride: a review | |
| Huang et al. | Efficient and selective capture of uranium by polyethyleneimine-modified chitosan composite microspheres from radioactive nuclear waste | |
| CN105148835B (en) | Granular pattern 13X molecular sieves/attapulgite loaded Nanoscale Iron nickel material and preparation method thereof | |
| CN107876006A (en) | A kind of preparation method and applications of carbon nano-fiber hydrotalcite composite material adsorbent | |
| CN104923167B (en) | A kind of stable Nano-meter SiO_22the preparation method of/tributyl phosphate composite adsorbing material | |
| Dong et al. | A comparative study of immobilizing ammonium molybdophosphate onto cellulose microsphere by radiation post-grafting and hybrid grafting for cesium removal | |
| CN106824272A (en) | A kind of nuclear grade ion-exchange resins based composites and preparation method thereof | |
| Tao et al. | Copper hexacyanoferrate nanoparticle-decorated biochar produced from pomelo peel for cesium removal from aqueous solution | |
| Wu et al. | Efficient removal of Sr2+ and Cs+ from aqueous solutions using a sulfonic acid-functionalized Zr-based metal–organic framework | |
| Liu et al. | Pellet silica-based titanate adsorbents with high selectivity for strontium removal from synthetic radioactive solutions | |
| CN101708464B (en) | Cation resin matrix CdS-loaded composite material and preparation method thereof | |
| Ma et al. | Novel one-pot solvothermal synthesis of high-performance copper hexacyanoferrate for Cs+ removal from wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |