CN115672286A - Material for simultaneously adsorbing and separating cesium and strontium, preparation method and adsorption and separation method - Google Patents
Material for simultaneously adsorbing and separating cesium and strontium, preparation method and adsorption and separation method Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 99
- 229910052792 caesium Inorganic materials 0.000 title claims abstract description 97
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 96
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 238000000926 separation method Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 title abstract description 53
- 239000000243 solution Substances 0.000 claims abstract description 67
- 102000008186 Collagen Human genes 0.000 claims abstract description 33
- 108010035532 Collagen Proteins 0.000 claims abstract description 33
- 229920001436 collagen Polymers 0.000 claims abstract description 33
- 239000000835 fiber Substances 0.000 claims abstract description 32
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- -1 potassium zirconium pyrophosphate Chemical compound 0.000 claims abstract description 18
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 9
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 6
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical class [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims description 36
- 239000012266 salt solution Substances 0.000 claims description 31
- 239000011259 mixed solution Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000012153 distilled water Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 230000000274 adsorptive effect Effects 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 14
- SGGPVBOWEPPPEH-UHFFFAOYSA-N [K].[Zr] Chemical compound [K].[Zr] SGGPVBOWEPPPEH-UHFFFAOYSA-N 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- 238000011069 regeneration method Methods 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 230000008929 regeneration Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 235000011180 diphosphates Nutrition 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 7
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 6
- 239000003929 acidic solution Substances 0.000 abstract description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 abstract description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 abstract description 2
- 229910001427 strontium ion Inorganic materials 0.000 abstract description 2
- 238000010828 elution Methods 0.000 description 24
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 8
- 235000015393 sodium molybdate Nutrition 0.000 description 8
- 239000011684 sodium molybdate Substances 0.000 description 8
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 8
- 229940048084 pyrophosphate Drugs 0.000 description 7
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
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- CWUWQESOUGLIBQ-UHFFFAOYSA-N [K+].[K+].[K+].[O-][Sb]([O-])([O-])=S Chemical compound [K+].[K+].[K+].[O-][Sb]([O-])([O-])=S CWUWQESOUGLIBQ-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000003100 immobilizing effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention belongs to the technical field of nuclide adsorption, and discloses a material for simultaneously adsorbing and separating cesium and strontium, a preparation method and an adsorption and separation method. The collagen fiber is used as a base material to load the potassium zirconium pyrophosphate molybdate, is used for simultaneously adsorbing cesium and strontium ions, is used as a filler to be arranged in a chromatographic column, and has a good adsorption effect on the cesium and strontium. After adsorption, cesium is eluted by using an alkaline dipotassium phosphate solution, strontium is eluted by using an acidic solution, separation and recovery of cesium and strontium can be realized, and a material can be regenerated by using a potassium ion solution.
Description
Technical Field
The invention relates to the technical field of nuclide adsorption, in particular to a material for simultaneously adsorbing and separating cesium and strontium, a preparation method and an adsorption and separation method.
Background
Cesium and strontium are both highly harmful contaminants of uranium fission products, both of which are water soluble, often exist in an ionic state and are highly mobile in the environment of release. Cancellation of 137 Cs and 90 sr is important for the post-treatment of spent nuclear fuel and has important significance for strengthening the emergency response of nuclear accidents; on the other hand, recovery 137 Cs and 90 sr is used as a heat source and a radiation source, and is also desirable for industrial, agricultural and medical applications. Some of the current processing techniques are to adsorb radioactive cesium and strontium simultaneously and cure them to prevent them from being leaked and harmed, but the utilization value of cesium and strontium is lost; the other part is to carry out adsorption and then elution recovery or solidification treatment on one element, so that a plurality of treatment systems are required to be combined for practical application, thereby increasing the equipment cost, complicating the operation and increasing the accumulated waste. Paper pH-Controlled Switch over Coadsorption and Separation for Mixed Cs + and Sr 2+ by an Acid-Resistant Potassium Thioantimonate, zhao et al synthesized an Acid-Resistant Potassium Thioantimonate, which was capable of adsorbing strontium and cesium at pH =6 and having an adsorption function only for cesium at pH =2, so that adsorption and separation were achieved by controlling ion exchange by adjusting the pH of the solution. However, in practical application, the amount of wastewater generated is large, and repeated adjustment of the pH value is uneconomical, practical and complicated.
The current research shows that potassium zirconium pyrophosphoryl molybdate (ZMPP) has good adsorption effect on cesium and strontium, but the potassium zirconium pyrophosphoryl molybdate (ZMPP) is granular, is difficult to settle and filter, is not suitable for column separation, and limits the application of the potassium zirconium pyrophosphoryl molybdate (ZMPP), and only co-adsorption of cesium and strontium is reported so far, and separation and recovery of the cesium and the strontium are not realized.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention provides a material for simultaneously adsorbing and separating cesium and strontium, a preparation method and an adsorption and separation method, which can be used for adsorbing and simultaneously adsorbing cesium and strontium elements in radioactive wastewater by a column and realizing separation and recovery of the cesium and the strontium elements.
In order to achieve the above purpose, the first technical scheme adopted by the invention is as follows:
meanwhile, the cesium and strontium materials are adsorbed and separated, and the collagen fibers are loaded with potassium zirconium pyrophosphate molybdate.
The second technical scheme adopted by the invention is as follows:
a method for preparing a material for simultaneous adsorptive separation of cesium and strontium, comprising the steps of:
performing a cross-linking reaction on the first zirconium ion salt solution and the collagen fibers to obtain an intermediate material; and
reacting the first mixed solution with the intermediate material and zirconium in the second zirconium ion salt solution under an acidic condition to obtain potassium zirconium pyrophosphorymolybdate, and washing and drying to obtain a material for simultaneously adsorbing and separating cesium and strontium;
wherein the first mixed solution is a mixed solution of molybdate and pyrophosphate.
Preferably, the crosslinking reaction comprises mixing the collagen fibers with the solution of the first zirconium ion salt, reacting at 25 ℃ for 3-6 h, adjusting the pH to 3.5-4.0, reacting at 35-40 ℃ for 4-6 h, standing for 8-12h, and washing with water.
Preferably, the method further comprises the step of soaking the collagen fibers with distilled water for 8-12h before mixing the collagen fibers with the solution of the first zirconium ion salt.
Preferably, the first zirconium ion salt solution comprises a zirconium sulfate solution and a zirconium nitrate solution.
Preferably, the molar ratio of the molybdate to the pyrophosphate is 1:10-15 parts of;
the concentration of the molybdate is 0.001-0.200 mol/L.
Preferably, the reacting the first mixed solution with zirconium in the intermediate material and the second zirconium ion salt solution under acidic conditions to obtain the potassium zirconium pyrophosphorylybdate comprises: soaking the intermediate material in the second zirconium ion salt solution, oscillating and stirring for 10-30 min, adding the first mixed solution, stirring and oscillating for 10-30 min at pH of 2.0-4.0, and standing for 12-24 h.
Preferably, the molar concentration of the second zirconium ion salt solution is 0.001-0.4 mol/L.
Preferably, the second zirconium ion salt solution comprises a zirconium sulfate solution, a zirconium nitrate solution and a zirconium oxychloride solution.
Preferably, the cesium and strontium simultaneously adsorbed and separated material is obtained after 3-5 times of washing with distilled water and drying at 50 ℃ for 12-24 hours.
The third technical scheme adopted by the invention is as follows:
an adsorptive separation process for the simultaneous adsorptive separation of cesium and strontium materials comprising the steps of:
contacting a material that simultaneously adsorbs and separates cesium and strontium with an aqueous solution comprising cesium and strontium such that cesium and strontium adsorb to the material;
mixing the cesium and strontium adsorbed material with a dipotassium hydrogenphosphate solution at a pH of 7.0-11.0 to elute cesium;
and mixing the cesium eluted material with acid solution with the pH of 2.0-5.0 to elute strontium.
Preferably, after the cesium-eluted material is mixed with acid solution with pH of 2.0-5.0 to elute strontium, regeneration is further carried out for 0.5h-24h by using potassium ion solution with pH of 2.0-11.0;
when the acid solution with the pH value of 2.0-5.0 contains potassium ions, the regeneration of the material is also included after the strontium is eluted.
Compared with the prior art, the invention has the following beneficial effects:
the collagen fiber is used as a base material to load the potassium zirconium pyrophosphate molybdate, has a good adsorption effect on cesium and strontium, and is used as a filler to be arranged in a chromatographic column for adsorbing cesium and strontium ions simultaneously. Cesium is eluted by using an alkaline dipotassium hydrogen phosphate solution after adsorption, strontium is eluted by using an acidic solution, and separation and recovery of cesium and strontium can be realized. In addition, after the potassium ion solution is adopted to regenerate the material, the material has better adsorption performance, which indicates that the material has better reutilization property. The method can greatly reduce the equipment cost, is simple and convenient to operate, and has great significance in practical application.
Drawings
FIG. 1 is a graph of the adsorption rate of cesium for the material prepared in example 1;
FIG. 2 is an adsorption isotherm for cesium for the material prepared in example 1;
FIG. 3 is a graph of the strontium adsorption rate for the material prepared in example 1;
FIG. 4 is an adsorption isotherm for strontium for the material prepared in example 1;
FIG. 5 is a graph showing the elution rate of cesium eluted from the material prepared in example 1 at various pH's with a 40 mmol/L dipotassium hydrogenphosphate solution;
FIG. 6 shows the elution rate of strontium eluted from the material prepared in example 1 at different pH values with a 40 mmol/L solution of dipotassium hydrogen phosphate;
fig. 7 (a) is a simultaneous adsorption cesium and strontium breakthrough curves for new columns of the material prepared in example 1; (b) Elution profile after saturation for new column adsorption of material prepared in example 1; (c) A regenerated column of material prepared for example 1 simultaneously adsorbed cesium and strontium breakthrough curves; (d) Elution profile after saturation of the regenerated column for the material prepared in example 1;
fig. 8 (a) is a simultaneous cesium and strontium adsorption breakthrough curve for a new column of example 2 prepared material; (b) Elution profile after saturation of new column adsorption for the material prepared in example 2; (c) A regeneration column of the material prepared for example 2 simultaneously adsorbs cesium and strontium breakthrough curves; (d) The elution profile after saturation of the adsorption of the regenerated column for the material prepared in example 2.
Detailed Description
In order to better understand the technical solution of the present invention, the technical solution of the present invention will be further described with reference to the accompanying drawings and examples. The mode for carrying out the present invention includes, but is not limited to, the following examples, which are provided for illustrating the present invention and are not intended to limit the scope of the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The test methods in the following examples are conventional methods unless otherwise specified.
In a first embodiment of the present invention, a collagen fiber-supported potassium zirconium pyrophosphomolybdate is provided as a material for simultaneous adsorptive separation of cesium and strontium.
The Collagen Fibers (CFs) have a multi-level structure, have low mass transfer resistance to flowing liquid, and are very suitable for column adsorption. In addition, the side chain of the collagen fiber has numerous groups such as amino, carboxyl and the like, and can coordinate with various metal ions, thereby providing a potential anchor point for the fixation of the pyrophosphate zirconium potassium molybdate. Therefore, the material (ZMPP-CFs) obtained by immobilizing the zirconium potassium pyrophosphate molybdate by using the collagen fibers as the carrier can be used for common column adsorption of cesium and strontium, and has better application value. More importantly, separation of cesium and strontium can be achieved after adsorption, eluting with different eluents.
The supporting rate of the supporting amount of potassium zirconium pyrophosphoromolybdate is not particularly limited, and theoretically, the higher the supporting amount of potassium zirconium pyrophosphoromolybdate, the better the adsorption-separation performance of cesium and strontium.
A second embodiment of the present invention provides a method for preparing a cesium and strontium adsorptive separation material simultaneously, comprising the steps of:
a method for preparing a material for the simultaneous adsorptive separation of cesium and strontium comprising the steps of:
performing a cross-linking reaction on the first zirconium ion salt solution and the collagen fiber to obtain an intermediate material; and
reacting the first mixed solution with zirconium in the intermediate material and the second zirconium ion salt solution under an acidic condition to obtain potassium zirconium pyrophosphate molybdate, and washing and drying to obtain a material for simultaneously adsorbing and separating cesium and strontium;
wherein the first mixed solution is a mixed solution of molybdate and pyrophosphate.
Under acidic conditions, molybdate and pyrophosphate and zirconium ions are precipitated together to generate the pyrophosphoric acid zirconium potassium molybdate.
In the reaction process of the first zirconium ion salt solution and the collagen fibers, the zirconium ions and the amino and carboxyl of the collagen fibers are subjected to full cross-linking reaction, so that the collagen fibers are fully dispersed and become metal sites for fixing the zirconium potassium pyrophosphate molybdate. And uniformly mixing the crosslinked intermediate material and a second zirconium ion salt solution to ensure that zirconium ions in the crosslinked intermediate material are fully diffused in the intermediate material, then adding a mixed solution of molybdate and pyrophosphate for mixing again, reacting with zirconium on the intermediate material and in the second zirconium ion salt solution together to obtain pyrophosphoric zirconium potassium molybdate, and washing and drying the mixture to obtain the material for simultaneously adsorbing and separating cesium and strontium. Wherein the addition of zirconium ions in the second zirconium ion salt solution is to provide more zirconium ions to form more precipitates.
In the embodiment of the present invention, the first zirconium ion salt solution and the second zirconium ion salt solution are zirconium ion salt solutions commonly used in the art, and the first zirconium ion salt solution preferably includes a zirconium sulfate solution and a zirconium nitrate solution; the second zirconium ion salt solution preferably comprises a zirconium sulfate solution, a zirconium nitrate solution, a zirconium oxychloride solution.
In order to fully diffuse zirconium ions in the collagen fibers, the first zirconium ion salt solution is firstly reacted with the collagen fibers for 3-6 h at 25 ℃. In order to make the zirconium ion and the amino and carboxyl of the collagen fiber to generate crosslinking reaction more fully, the collagen fiber is fully dispersed, the pH of the solution after the reaction is adjusted to 3.5-4.0, and the temperature is raised to 35-40 ℃. After reacting for 4-6 h, standing for 8-12h, and washing with distilled water to obtain the intermediate material.
The pH of the above reaction solution may be adjusted using a sodium bicarbonate solution, and it is preferable to adjust the pH of the solution using a sodium bicarbonate solution of 8 to 10% (w/w).
In order to make the collagen fiber fully soaked by water and facilitate the subsequent metal ions to diffuse in the fiber, the method also comprises the step of soaking the collagen fiber for 8-12h by using distilled water before mixing the collagen fiber with the first zirconium ion salt solution.
The reaction of the first mixed solution with zirconium in the intermediate material and the second zirconium ion salt solution to obtain the pyrophosphoric zirconium potassium molybdate comprises the following steps: firstly, soaking the intermediate material in a second zirconium ion salt solution, oscillating and stirring for 10-30 min, adding the first mixed solution, oscillating and stirring for 10-30 min under an acidic condition, standing for 24h, washing and drying to obtain the material for simultaneously adsorbing and separating cesium and strontium.
The preparation method of the first mixed solution comprises the steps of mixing sodium molybdate and potassium pyrophosphate to prepare a solution, and adjusting the pH of the mixed solution to 2.0-4.0. The molar ratio of molybdate to pyrophosphate is preferably 1:10-15 parts of; the molybdate concentration is preferably 0.001 to 0.200 mol/L.
In fact, in the above production method, the amount of each raw material used is not particularly limited as long as metal sites for immobilizing zirconium potassium pyrophosphate molybdate are formed on the collagen fibers.
As some embodiments, a method for preparing a material for simultaneous adsorptive separation of cesium and strontium can be:
a. soaking collagen fiber 3.0-7.0 g in distilled water for 8-12 hr; filtering to remove water, and dispersing in 60-140 ml distilled water; adding 30-70 mL of first zirconium ion salt solution, firstly reacting for 3-6 h at 25 ℃, then adjusting the pH to 3.5-4.0 by using 8-10% (w/w) sodium bicarbonate solution, raising the temperature to 35-40 ℃, and reacting for 4-6 h; standing for 8-12h; the intermediate material was obtained by washing three times with 1000ml of distilled water.
b. Using pure water to mix certain amount of sodium molybdate and potassium pyrophosphate according to the mol ratio of 1:10-15, mixing to prepare a first mixed solution, wherein the concentration of sodium molybdate is 0.001-0.200 mol/L, and adjusting the pH of the mixed solution to 2.0-4.0 to obtain the mixed solution.
c. Soaking the intermediate material in 30-100 mL of 0.1-0.4 mol/L second zirconium ion salt solution, oscillating and stirring for 10-30 min, adding 30-100 mL of the mixed solution obtained in the step b, stirring and oscillating for 10-30 min, and standing for 12-24 h to obtain a mixture;
d. and c, washing the mixture obtained in the step c with distilled water for 3-5 times, and drying at 50 ℃ for 12-24 h to obtain the material for simultaneously adsorbing and separating cesium and strontium.
A third embodiment of the present invention is an adsorptive separation method for simultaneously adsorptive separation of cesium and strontium materials, comprising the steps of:
contacting a material that simultaneously adsorbs and separates cesium and strontium with an aqueous solution comprising cesium and strontium such that cesium and strontium adsorb to the material;
mixing the cesium and strontium adsorbed material with a dipotassium hydrogenphosphate solution at a pH of 7.0-11.0 to elute cesium;
mixing the cesium-eluted material with an acid solution with a pH of 2.0-5.0 to elute strontium, and then regenerating with a potassium ion solution with a pH of 2.0-11.0 for 0.5-24h.
Since the first mixed solution is a mixed solution obtained by mixing sodium molybdate and potassium pyrophosphate and adjusting the pH to 2.0 to 4.0, strontium can be eluted using the first mixed solution and the material can be regenerated.
In the above separation process, cesium is first eluted using an alkaline dipotassium hydrogen phosphate solution (preferably having a pH of 7.0 to 11.0), under which condition the dipotassium hydrogen phosphate solution can elute cesium but not strontium, which is an important factor for achieving separation of the two.
For the present embodiment, only the separation of cesium and then strontium can be achieved by eluting the cesium first and then the strontium. The elution method of strontium comprises the following steps: eluting strontium with acid solution (preferably pH of 2.0-5.0), which can be various solutions with acidic pH, but contains no K as much as possible + 、Na + Other metal ions; then regenerating for 0.5-24h by using potassium ion solution with pH of 2.0-11.0. When the used acid liquor contains potassium ions, the material can be regenerated at the same time.
The elution method of the present invention is only applicable to the collagen fiber-supported zirconium potassium pyrophosphate molybdate material provided in the embodiment of the present invention.
The materials, the production method, the adsorptive separation method, the regeneration method, and the performance for simultaneous adsorptive separation of cesium and strontium of the present invention will be described in detail below with reference to a plurality of embodiments.
Example 1 preparation of a material for simultaneous adsorptive separation of cesium and strontium and Performance testing
Soaking collagen fiber 4.0 g in distilled water for 12 hr; filtering to remove water, and adding 80 ml of distilled water; dissolving 4.0 g of zirconium sulfate in 40 mL of distilled water, adding the solution, reacting at 25 ℃ for 4h, adjusting the pH to 3.5 by using 10% (w/w) sodium bicarbonate solution, raising the temperature to 40 ℃, reacting for 4h, standing for 12h, and washing with 1000mL of distilled water for three times; soaking the washed material in 40 mL of 0.1 mol/L zirconyl chloride solution, shaking and stirring for 30 min, adding 40 mL of 0.01 mol/L sodium molybdate and 0.1 mol/L potassium pyrophosphate mixed solution B with pH =3.0, stirring and shaking for 30 min, standing for 24h, then washing with 1000mL of distilled water for three times, and drying at 50 ℃ for 12h to obtain the material for simultaneously adsorbing and separating cesium and strontium.
The adsorption rate and the adsorption isotherm of the cesium and strontium simultaneous adsorption-separation material prepared in this example on cesium are shown in fig. 1 and fig. 2, the adsorption rate is fast, the cesium can reach equilibrium in 10 min, and the maximum adsorption capacity can reach 1.047 mmol/g; the adsorption rate and the adsorption isotherm of strontium are shown in fig. 3 and fig. 4, the adsorption rate is also high, the equilibrium is reached in 20 min, and the maximum adsorption capacity can reach 0.445 mmol/g; in addition, the elution rates of cesium and strontium eluted from a 40 mmol/L dipotassium hydrogen phosphate solution at different pH values are shown in FIGS. 5 and 6, respectively, and the results show that a dipotassium hydrogen phosphate solution at a pH value in the range of 7.0 to 11.0 can elute cesium from a material while taking away only a small amount of strontium element, thereby achieving separation of the two elements.
1.000 g of the material prepared in this example was weighed and packed in a packed column with a diameter of 1 cm, a column height of about 5.9 cm and a bed volume of about 4.71 cm 3 (ii) a The complex value contains 0.05 mmol/L Sr 2+ And 0.05 mmol/L Cs + The solution was passed through a packed column at a flow rate of 1.0 mL/min, and the adsorption effect thereof was as shown in FIG. 7 (a); after saturation of adsorption, cesium 44BV is eluted by using 30 mmol/L dipotassium hydrogen phosphate solution with the pH of 8.0, strontium 55BV is eluted by switching to nitric acid solution with the pH of 3.0, and finally 33BV is regenerated by using 0.01 mol/L sodium molybdate and 0.1 mol/L potassium pyrophosphate mixed solution B with the pH =3.0, and the elution curve is shown in fig. 7 (B); the regenerated column was again subjected to adsorption and elution experiments, and the adsorption curve and elution curve are shown in fig. 7 (c) and fig. 7 (d), respectively. The new column has a penetration point for adsorbing cesium of 200BV and a penetration point for adsorbing strontium of 244BV, after adsorption is completed, cesium can be completely eluted by a dipotassium hydrogen phosphate solution of about 25BV, strontium can be eluted between 70 and 90BV of the whole elution curve, and the elution method has a good separation effect on cesium and strontium as can be seen from the elution curve; the breakthrough point of the regeneration column for adsorbing cesium is 267BV, and the breakthrough point for adsorbing strontium is 332BV, so that the adsorption performance of the material is improved to a certain extent after regeneration, and the good adsorption performance and reutilization property of the material are illustrated; compared with the new column elution curve, the higher cesium concentration and strontium concentration of the desorption curve of the regeneration column further prove the better adsorption performance of the regeneration column. The whole experiment shows that the collagen fiber-based loaded zirconium potassium pyrophosphate molybdate adsorbing material prepared by the invention can adsorb cesium and strontium simultaneously, has good adsorption performance and reusability, andhas better separation effect.
Example 2 preparation of a material for simultaneous adsorptive separation of cesium and strontium and Performance testing
Soaking 5.0 g of collagen fiber in distilled water for 8 h; filtering to remove water, and adding 100 ml of distilled water; then 5.0 g of zirconium nitrate was dissolved in 50 mL of distilled water and added, and the mixture was reacted at 25 ℃ for 5 hours and then 10% (w/w) Adjusting the pH value of the sodium bicarbonate solution to 4.0, raising the temperature to 40 ℃, reacting for 6 hours, standing for 8 hours, and washing with 1000ml of distilled water for three times; soaking the washed material in 50 mL of 0.1 mol/L zirconium sulfate solution, shaking and stirring for 20 min, adding 50 mL of 0.01 mol/L sodium molybdate and 0.1 mol/L potassium pyrophosphate mixed solution B with pH =3.0, stirring and shaking for 30 min, standing for 24h, then washing with 1000mL of distilled water for three times, and drying at 50 ℃ for 12h to obtain the material for simultaneously adsorbing and separating cesium and strontium.
Weighing 1.000 g of the prepared material, and filling the material into a packed column with the diameter of 1 cm, the height of the column is about 5.9 cm, and the volume of a column bed is about 4.71 cm 3 (ii) a The coordination limit contains 0.05 mmol/L Sr 2+ And 0.05 mmol/L Cs + The solution was passed through a packed column at a flow rate of 1.0 mL/min, and the adsorption effect thereof was as shown in FIG. 8 (a); after saturation of adsorption, cesium 39BV was eluted with 30 mmol/L dipotassium hydrogen phosphate solution at pH 8.0, followed by switching to mixed solution B of 0.01 mol/L sodium molybdate and 0.1 mol/L potassium pyrophosphate at pH =3.0 to elute strontium and regenerate 80 BV, the elution curve of which is shown in fig. 8 (B); the regenerated column was again subjected to adsorption and elution experiments, and the adsorption curve and elution curve are shown in fig. 8 (c) and fig. 8 (d), respectively. The new column has a penetration point for adsorbing cesium at 241BV and a penetration point for adsorbing strontium at 361BV, after adsorption is completed, cesium can be eluted cleanly by dipotassium phosphate solution with 25BV, strontium can be eluted between 55 and 100BV of the whole elution curve, and the elution method has a good separation effect on cesium and strontium as can be seen from the elution curve; after regeneration, the breakthrough point of the regeneration column for adsorbing cesium is 311BV, and the breakthrough point for adsorbing strontium is 431BV, so that the adsorption performance of the material is improved to a certain extent after elution and regeneration by adopting the method, and the material has good adsorption performance, reusability and good separation effect.
In summary, any combination of the various embodiments of the present invention without departing from the spirit of the present invention should be considered as the disclosure of the present invention; within the scope of the technical idea of the invention, any combination of various simple modifications and different embodiments of the technical solution without departing from the inventive idea of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. The material for simultaneously adsorbing and separating cesium and strontium is characterized in that collagen fibers are loaded with potassium zirconium pyrophosphate molybdate.
2. The method for the preparation of a material for the simultaneous adsorptive separation of cesium and strontium according to claim 1, comprising the steps of:
performing a cross-linking reaction on the first zirconium ion salt solution and the collagen fibers to obtain an intermediate material; and
reacting the first mixed solution with zirconium in the intermediate material and the second zirconium ion salt solution under an acidic condition to obtain potassium zirconium pyrophosphate molybdate, and washing and drying to obtain a material for simultaneously adsorbing and separating cesium and strontium;
wherein the first mixed solution is a mixed solution of molybdate and pyrophosphate.
3. The method of claim 2, wherein the cross-linking reaction comprises mixing collagen fibers with a solution of zirconium ion salt, reacting at 25 ℃ for 3-6 hours, adjusting the pH to 3.5-4.0, increasing the temperature to 35-40 ℃ for 4-6 hours, standing for 8-12 hours, and washing with water.
4. The method of claim 3, wherein the step of soaking collagen fibers with distilled water for 8-12 hours before mixing the collagen fibers with the solution of the first zirconium ion salt;
preferably, the first zirconium ion salt solution comprises a zirconium sulfate solution and a zirconium nitrate solution.
5. The method of claim 2, wherein the molar ratio of molybdate to pyrophosphate is 1;
the concentration of the molybdate is 0.001-0.200 mol/L.
6. The method of claim 2, wherein reacting the first mixed solution with zirconium in the intermediate material and the second zirconium ion salt solution under acidic conditions to obtain potassium zirconium pyrophosphoromolybdate comprises: soaking the intermediate material in the second zirconium ion salt solution, oscillating and stirring for 10-30 min, adding the first mixed solution, stirring and oscillating for 10-30 min at the pH of 2.0-4.0, and standing for 12-24 h;
preferably, the molar concentration of the second zirconium ion salt solution is 0.001-0.4 mol/L;
preferably, the second zirconium ion salt solution comprises a zirconium sulfate solution, a zirconium nitrate solution and a zirconium oxychloride solution.
7. The method according to claim 2, wherein the cesium and strontium are simultaneously adsorbed and separated after washing with distilled water 3 to 5 times and drying at 50 ℃ for 12 to 24 hours.
8. A material for simultaneous adsorptive separation of cesium and strontium obtained by the production method according to any one of claims 2 to 7.
9. The adsorptive separation method for the simultaneous adsorptive separation of cesium and strontium according to claim 1 or 8, comprising the steps of:
contacting the cesium and strontium simultaneously adsorbed and separated material with an aqueous solution containing cesium and strontium so that cesium and strontium are adsorbed to the material;
mixing the cesium and strontium adsorbed material with a dipotassium hydrogenphosphate solution at a pH of 7.0-11.0 to elute cesium;
and mixing the cesium eluted material with acid liquor with the pH value of 2.0-5.0 to elute strontium.
10. The adsorptive separation process according to claim 9, wherein said mixing the cesium eluted material with an acid solution having a pH of 2.0 to 5.0 to elute strontium further comprises regenerating with a potassium ion solution having a pH of 2.0 to 11.0 for 0.5h to 24h;
when the acid solution with the pH value of 2.0-5.0 contains potassium ions, the regeneration of the material is also included after the strontium is eluted.
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| CN114749157A (en) * | 2022-05-11 | 2022-07-15 | 四川大学 | Cesium adsorption material with prussian blue compounds loaded on collagen fibers, and preparation method and application thereof |
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| CN114749157A (en) * | 2022-05-11 | 2022-07-15 | 四川大学 | Cesium adsorption material with prussian blue compounds loaded on collagen fibers, and preparation method and application thereof |
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