CN101279249B - Preparation of potassium zirconium hexacyanoferrate using pellet silica-gel as carrier - Google Patents
Preparation of potassium zirconium hexacyanoferrate using pellet silica-gel as carrier Download PDFInfo
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- CN101279249B CN101279249B CN2008101126232A CN200810112623A CN101279249B CN 101279249 B CN101279249 B CN 101279249B CN 2008101126232 A CN2008101126232 A CN 2008101126232A CN 200810112623 A CN200810112623 A CN 200810112623A CN 101279249 B CN101279249 B CN 101279249B
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- silica gel
- ferrocyanide
- zirconium
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000000741 silica gel Substances 0.000 title claims abstract description 77
- 229910002027 silica gel Inorganic materials 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- SGGPVBOWEPPPEH-UHFFFAOYSA-N [K].[Zr] Chemical compound [K].[Zr] SGGPVBOWEPPPEH-UHFFFAOYSA-N 0.000 title claims description 38
- 229960001866 silicon dioxide Drugs 0.000 title abstract description 64
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 title 1
- 239000008188 pellet Substances 0.000 title 1
- 239000011324 bead Substances 0.000 claims abstract description 82
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000276 potassium ferrocyanide Substances 0.000 claims abstract description 20
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims abstract description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 16
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 229910003849 O-Si Inorganic materials 0.000 abstract 1
- 229910003872 O—Si Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 239000002354 radioactive wastewater Substances 0.000 description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- YVBOZGOAVJZITM-UHFFFAOYSA-P ammonium phosphomolybdate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])=O.[O-][Mo]([O-])(=O)=O YVBOZGOAVJZITM-UHFFFAOYSA-P 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 3
- 238000006253 efflorescence Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000002285 radioactive effect Effects 0.000 description 3
- 206010037844 rash Diseases 0.000 description 3
- 229910003321 CoFe Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- KYNKUCOQLYEJPH-UHFFFAOYSA-N [K][Ti] Chemical compound [K][Ti] KYNKUCOQLYEJPH-UHFFFAOYSA-N 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 229910001417 caesium ion Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002901 radioactive waste Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- KQMCGGGTJKNIMC-UHFFFAOYSA-N 2-hydroxy-3-propyl-2h-furan-5-one Chemical compound CCCC1=CC(=O)OC1O KQMCGGGTJKNIMC-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000000279 calcium ferrocyanide Substances 0.000 description 1
- 235000012251 calcium ferrocyanide Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000013139 quantization Methods 0.000 description 1
- -1 rectorite Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
A preparation method for ferrocyanide zirconium Kalium taking bead silica gel as carrier relates to the preparation method for ferrocyanide zirconium Kalium with high specific surface and taking the bead silica gel as the carrier. In the method, fashioned porous bead silica gel react with the solution of zirconium oxychloride under the condition of heating and refluxing, acquired bead silica gel loaded with amorphous zirconium dioxide is dried and then dipped in the hydrochloric acid solution of yellow potassium ferrocyanide for reaction under stirring for 12-24 hours, thus the hybrid material of ferrocyanide zirconium Kalium with high specific surface and taking bead silica gel as the carrier is obtained. The load of ferrocyanide of the material can be adjusted and the material has strong adsorption capability for nuclide ion, high specific surface, good particle degree of sphericity, and being uneasy to break, which avoids the problem of oversized bed water resistance caused by using ferrocyanide zirconium Kalium particles separately; besides, owing to the existence of Zr-O-Si covalent bond, nano ferrocyanide zirconium Kalium particles can closely combine with the bead silica-gel, thus being uneasy to run away in the process of waste water treatment.
Description
Technical field
The present invention relates to a kind of preparation method of radionuclide ion absorbing material, particularly a kind of is the preparation method of the ferrocyanide zirconium potassium of carrier with bead silica gel, 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 and PurificationTechnology 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.
(nuclear chemistry and radiochemistry 1995,17 (2) 99-104) wait the method for the creationary employing urea of people-hexamethylenetetramine condensation with TiCl for Jiang Changyin, Song Chongli
4Be made as TiO
2Bead is then with this TiO
2Bead is immersed in the mixture of potassium ferrocyanide (0.7M) and hydrochloric acid (1M), thereby obtains spherical ferrocyanide titanium potassium absorbing material, and preamble is addressed: the not high (14m of this material specific surface
2/ g), inner duct seldom, so the absorption of caesium is only concentrated in the thin layer of particle surface; In addition, this material particle size is not too even, in use has part and takes place broken.Moreover this material internal can not solidify with the method for heat-agglomerating commonly used after cesium ion absorption is saturated owing to have an organic polymer, because common NO in the radioactive wastewater
3 -Ion can oxidation under heating condition wherein polymer and blast, the material that as seen is used to handle the actual radiation wastewater must avoid its inside to contain too much organic matter.
People such as Wang Qiuping, Song Chongli (ion-exchange and absorption 2000,16 (3), 225-233) sediment of multiple metal ion and potassium ferrocyanide is discovered, ferrocyanide zirconium potassium has very high static adsorbance for the Cs ion, yet it is same because its particle size is small, it is easy to efflorescence fragmentation under the immersion of water, causes great bed pressure drop, so can't be used for fixing the bed operation.Therefore exploitation is that the high-ratio surface ferrocyanide zirconium potassium material of carrier is very necessary with the porous material.
The present inventor once utilized bead silica gel successfully to prepare the ferrocyanide titanium potassium sorbing material of high-ratio surface for carrier, and its titanium source is a butyl titanate, and reaction system is an organic solvent.It is the preparation of the high-ratio surface ferrocyanide zirconium potassium of carrier that yet its method can not be directly used in bead silica gel; Reason has three: one, and organic zirconium source hydrolytic process is violent far beyond butyl titanate; Its two, the organic zirconium source costs an arm and a leg, and is unfavorable economically; Its three: inorganic zirconium source zirconium oxychloride price is lower, but its hydrolytic process is difficult for carrying out under organic solvent, therefore needs the new preparation method of research.
Summary of the invention
The objective of the invention is to overcome ferrocyanide granulation difficulty in the prior art, granule strength is not high, specific surface is low shortcoming, utilize ready-made high-ratio surface bead silica gel to be carrier, develop the method that a kind of preparation does not contain organic matter and has the ferrocyanide zirconium potassium material of high-ratio surface, guarantee that simultaneously material has good sphericity, also has high adsorption capacity and selectivity.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of is the method for ferrocyanide zirconium potassium material of the high-ratio surface of carrier with bead silica gel, comprises following step:
With bead silica gel is the preparation method of the ferrocyanide zirconium potassium of carrier, it is characterized in that this method carries out as follows:
1) the bead silica gel of the unformed zirconium dioxide of preparation load
Zirconium oxychloride is dissolved in the water, its concentration is 0.01～0.1mol/L, bead silica gel is added in the zirconyl chloride solution water, under stirring and condensing reflux, be heated to 60～100 ℃, reaction leaches bead silica gel behind 2～24h, is washed with water in the cleaning solution not chloride ion-containing, dries in air atmosphere to constant weight, prepare the bead silica gel of the unformed zirconium dioxide of load, the zirconia-supported amount is between 2%～20%; The quality of bead silica gel and the mass ratio of zirconium oxychloride are 1: 0.3～1: 3;
2) the bead silica gel of preparation load ferrocyanide zirconium potassium
The bead silica gel of the unformed zirconium dioxide of load of gained in the step 1) is immersed in the hydrochloric acid solution of potassium ferrocyanide, the ferrocyanide potassium concn is between 0.5M～1.0M, concentration of hydrochloric acid is between 0.5M～1.5M, stir reaction 12～24h down, then fully wash this bead silica gel with deionized water, to flushing liquor be colourless till, obtaining with bead silica gel is the ferrocyanide zirconium potassium hybrid material of carrier, the load capacity of its ferrocyanide zirconium potassium is between 4%～35%.
Above-mentioned steps 1) the bead silica gel described in is silica bead silica gel, and specific surface is at 180～700m
2Between/the g, aperture 2nm～15nm, pore volume 0.29ml/g～0.76ml/g, granularity is between 1mm～6mm.
Technical characterictic of the present invention also is: heating-up temperature is at 75-90 ℃ under the condensing reflux in the described step 1).
It is carrier that this method adopts particle good sphericity, intensity height, bead silica gel cheap and easy to get, that acid resistance is high; Products obtained therefrom has uniform grain sizes and good ball degree, and the intensity height, is difficult for the efflorescence fragmentation.For the report of other load ferrocyanides in the middle of porous material, the innovation part of this research is to adopt ZrO
2+Ion is potassium ferrocyanide fixedly: the first, along with the hydrolysis of zirconium oxychloride, can in the duct of bead silica gel, form layer of even ZrO
2On silica-gel carrier, this ferrocyanide zirconium potassium that can avoid for second step generated is washed away when handling radioactive wastewater to come off by comparatively firm Si-O-Zr covalent bonds for film, this film.The second, this zirconium dioxide film can utilize on it as yet the not active ZrO of complete hydrolysis condensation
2+Obtain ferrocyanide zirconium potassium with the ferrocyanide nak response.
The bead silica gel that this method obtained is that the ferrocyanide zirconium potassium hybrid material of carrier has the following advantages: (a) the potassium ferrocyanide load capacity is adjustable: 4%～30%.(b) the ferrocyanide zirconium potassium in the material forms a thin layer with the form of fine particle on the wall in the duct, inside of bead silica gel, very big reaction surface is provided for the reaction that absorbs cesium ion.Can improve the adsorption dynamics adsorption kinetics condition, improve the rate of adsorption.(c) prepared bead silica gel is that the ferrocyanide zirconium potassium hybrid material of carrier has good sphericity and very high intensity, and the phenomenon of broken and efflorescence even loss can not take place in the packed bed the inside.(d) the prepared material of the present invention had both been brought into play nanoscale ferrocyanide zirconium potassium absorption property efficiently, had satisfied the particle size and the intensity of packed bed action need again.
Description of drawings
Fig. 1: preparation bead silica gel is the process chart of the ferrocyanide zirconium potassium hybrid material of carrier.
The specific embodiment
Provided by the invention a kind of be the preparation method of the ferrocyanide zirconium potassium of carrier with bead silica gel, its concrete preparation process is as follows:
1) at first prepares the bead silica gel of the unformed zirconium dioxide of load
Zirconium oxychloride is dissolved in the water, and its concentration is 0.01～0.1mol/L, and bead silica gel is added in the zirconyl chloride solution water, is heated to 60～100 ℃ under stirring and condensing reflux, is preferably 75-90 ℃; Reaction leaches bead silica gel behind 2～24h, is washed with water in the cleaning solution not chloride ion-containing, dries in air atmosphere to constant weight, prepares the bead silica gel of the unformed zirconium dioxide of load, and the zirconia-supported amount is between 2%～20%; The quality of bead silica gel and the mass ratio of zirconium oxychloride are 1: 0.3～1: 3; Described bead silica gel is silica bead silica gel, and specific surface is at 180～700m
2Between/the g, aperture 2nm～15nm, pore volume 0.29ml/g～0.76ml/g, granularity is between 1mm～6mm.
2) the bead silica gel of preparation load ferrocyanide zirconium potassium
The bead silica gel of the unformed zirconium dioxide of load of gained in the step 1) is immersed in the hydrochloric acid solution of potassium ferrocyanide, the ferrocyanide potassium concn is between 0.5M～1.0M, concentration of hydrochloric acid is between 0.5M～1.5M, stir reaction 12～24h down, then fully wash this bead silica gel with deionized water, to flushing liquor be colourless till, obtaining with bead silica gel is the ferrocyanide zirconium potassium hybrid material of carrier, the load capacity of its ferrocyanide zirconium potassium is between 4%～35%.
Further understand the present invention below by several specific embodiments
Embodiment 1:
With 10g bead silica gel, its specific surface is 184.9m
2/ g, pore volume are 0.565mL/g, and average pore size is 12.23nm.This bead silica gel is eluriated in water totally, 90 ℃ of oven dry 10h, drop into concentration and be in the aqueous solution of zirconium oxychloride of 0.01mol/L, wherein be dissolved with the 3g zirconium oxychloride, add hot reflux under 90 ℃, reaction leaches bead behind the 2h, washs to the cleaning solution not chloride ion-containing, dry in air atmosphere to constant weight, its zirconia-supported amount is 2% (quality).Again this Zirconium dioxide loaded bead silica gel is immersed in the hydrochloric acid solution of 100mL potassium ferrocyanide, the concentration of potassium ferrocyanide is 1M, concentration of hydrochloric acid is 1M, stir reaction 24hr down, fully wash with deionized water again, get ferrocyanide zirconium potassium/bead silica gel hybrid material, the load capacity of its ferrocyanide zirconium potassium is about 4% (quality).
Embodiment 2:
With 10g bead silica gel, its specific surface is 184.9m
2/ g, pore volume are 0.565mL/g, and average pore size is 12.23nm.This bead silica gel is eluriated in water totally, 90 ℃ of oven dry 10h, drop into concentration and be in the aqueous solution of zirconium oxychloride of 0.05mol/L, wherein be dissolved with the 10g zirconium oxychloride, add hot reflux under 60 ℃, reaction leaches bead behind the 12h, washs to the cleaning solution not chloride ion-containing, dry in air atmosphere to constant weight, its zirconia-supported amount is 9.5% (quality).Again this Zirconium dioxide loaded bead silica gel is immersed in the hydrochloric acid solution of 150mL potassium ferrocyanide, the concentration of potassium ferrocyanide is 0.5M, concentration of hydrochloric acid is 1.5M, stir reaction 18hr down, fully wash with deionized water again, get ferrocyanide zirconium potassium/bead silica gel hybrid material, the load capacity of its ferrocyanide zirconium potassium is in 18% (quality).
Embodiment 3:
With 10g bead silica gel, its specific surface is 700m
2/ g, pore volume are 0.35mL/g, and average pore size is 2nm.This bead silica gel is eluriated in water totally, 90 ℃ of oven dry 10h, drop into concentration and be in the aqueous solution of zirconium oxychloride of 0.1mol/L, wherein be dissolved with the 20g zirconium oxychloride, add hot reflux under 75 ℃, reaction leaches bead behind the 12h, washs to the cleaning solution not chloride ion-containing, dry in the air atmosphere to constant weight, its zirconia-supported amount is 15% (quality).Again this Zirconium dioxide loaded bead silica gel is immersed in the hydrochloric acid solution of 150mL potassium ferrocyanide, the concentration of potassium ferrocyanide is 0.5M, concentration of hydrochloric acid is 0.5M, stir reaction 20hr down, fully wash with deionized water again, obtain ferrocyanide zirconium potassium/bead silica gel hybrid material, the load capacity of its ferrocyanide zirconium potassium is in 22% (quality).
Embodiment 4:
With 10g bead silica gel, its specific surface is 700m
2/ g, pore volume are 0.35mL/g, and average pore size is 2nm.This bead silica gel is eluriated in water totally, 90 ℃ of oven dry 10h, drop into concentration and be in the aqueous solution of zirconium oxychloride of 0.1mol/L, wherein be dissolved with the 30g zirconium oxychloride, add hot reflux under 100 ℃, reaction leaches bead behind the 24h, washs to the cleaning solution not chloride ion-containing, dry in air atmosphere to constant weight, its zirconia-supported amount is 20% (quality).Again this Zirconium dioxide loaded bead silica gel is immersed in the hydrochloric acid solution of 250mL potassium ferrocyanide, the concentration of potassium ferrocyanide is 1M, concentration of hydrochloric acid is 1M, stir reaction 24hr down, fully wash with deionized water again, obtain ferrocyanide zirconium potassium/bead silica gel hybrid material, the load capacity of its ferrocyanide zirconium potassium is in 35% (quality).
Embodiment 5:
With 50g bead silica gel, its specific surface is 202m
2/ g, pore volume are 0.76mL/g, and average pore size is 15nm.This bead silica gel is eluriated in water totally, 90 ℃ of oven dry 10h, drop into concentration and be in the aqueous solution of zirconium oxychloride of 0.1mol/L, wherein be dissolved with the 100g zirconium oxychloride, add hot reflux under 80 ℃, reaction leaches bead behind the 8h, washs to the cleaning solution not chloride ion-containing, dry in the air atmosphere to constant weight, its zirconia-supported amount is 13.5% (quality).Again this Zirconium dioxide loaded bead silica gel is immersed in the hydrochloric acid solution of 500mL potassium ferrocyanide, the concentration of potassium ferrocyanide is 0.5M, concentration of hydrochloric acid is 1M, stir reaction 12hr down, fully wash with deionized water again, obtain ferrocyanide zirconium potassium/bead silica gel hybrid material, the load capacity of its ferrocyanide zirconium potassium is in 20% (quality).
Claims (2)
1. be the preparation method of the ferrocyanide zirconium potassium of carrier with bead silica gel, it is characterized in that this method carries out as follows:
1) the bead silica gel of the unformed zirconium dioxide of preparation load
Zirconium oxychloride is dissolved in the water, its concentration is 0.01～0.1mol/L, bead silica gel is added in the zirconyl chloride solution water, under stirring and condensing reflux, be heated to 60～100 ℃, reaction leaches bead silica gel behind 2～24h, is washed with water in the cleaning solution not chloride ion-containing, dries in air atmosphere to constant weight, prepare the bead silica gel of the unformed zirconium dioxide of load, the quality percentage composition of zirconia-supported is between 2%～20%; The quality of bead silica gel and the mass ratio of zirconium oxychloride are 1: 0.3～1: 3; Described bead silica gel is silica bead silica gel, and specific surface is at 180～700m
2Between/the g, aperture 2nm～15nm, pore volume 0.29ml/g～0.76ml/g, granularity is between 1mm～6mm;
2) the bead silica gel of preparation load ferrocyanide zirconium potassium
The bead silica gel of the unformed zirconium dioxide of load of gained in the step 1) is immersed in the hydrochloric acid solution of potassium ferrocyanide, the ferrocyanide potassium concn is between 0.5M～1.0M, concentration of hydrochloric acid is between 0.5M～1.5M, stir reaction 12～24h down, then fully wash this bead silica gel with deionized water, to flushing liquor be colourless till, obtaining with bead silica gel is the ferrocyanide zirconium potassium hybrid material of carrier, the quality percentage composition of its ferrocyanide zirconium potassium load is between 4%～35%.
2. as claimed in claim 1 is the preparation method of the ferrocyanide zirconium potassium of carrier with bead silica gel, and it is characterized in that: heating-up temperature is at 75-90 ℃ under the condensing reflux in the described step 1).
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| CN102774924A (en) * | 2012-07-12 | 2012-11-14 | 清华大学 | Method for removing radiocesium 137 with titanium potassium ferrocyanide spherical particles |
| CN102773067B (en) * | 2012-08-22 | 2014-09-24 | 中国原子能科学研究院 | Preparation method of selective adsorbent for magnetic cesium |
| CN104226278B (en) * | 2014-09-05 | 2016-05-25 | 桂林奥尼斯特节能环保科技有限责任公司 | A kind of preparation method of thallium adsorbent and purposes |
| CN105597660A (en) * | 2015-12-30 | 2016-05-25 | 清华大学 | Preparing method of particle caesium removing inorganic ion adsorbent and product and application |
| CN108160040A (en) * | 2017-12-29 | 2018-06-15 | 北京大学 | Load the mesoporous silica gel of Prussian blue and the like nano-particle and its preparation and application |
| CN108160048B (en) * | 2018-01-04 | 2023-07-14 | 清华大学 | Large-scale preparation method of high-stability cesium removal adsorbent, and product and application thereof |
| JP7300173B2 (en) * | 2019-10-16 | 2023-06-29 | 国立研究開発法人産業技術総合研究所 | Prussian Blue Derivative-Containing Composite Using Silicon Oxide as Substrate, Ammonia Adsorption/Desorption Method Using the Composite, and Ammonia Recovery Device |
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