CN115845807B - Adsorbent for selectively extracting palladium nuclide from high-level radioactive waste liquid and preparation method and application thereof - Google Patents
Adsorbent for selectively extracting palladium nuclide from high-level radioactive waste liquid and preparation method and application thereof Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 93
- 239000007788 liquid Substances 0.000 title claims abstract description 67
- 239000002927 high level radioactive waste Substances 0.000 title claims abstract description 62
- 239000003463 adsorbent Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- TXSOLYKLZBJHFF-UHFFFAOYSA-N 5-thiophen-2-yl-1h-pyrazol-3-amine Chemical compound N1N=C(N)C=C1C1=CC=CS1 TXSOLYKLZBJHFF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002079 double walled nanotube Substances 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000013538 functional additive Substances 0.000 claims abstract description 5
- 239000002699 waste material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 238000003795 desorption Methods 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 54
- -1 palladium ions Chemical class 0.000 abstract description 26
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- 239000002915 spent fuel radioactive waste Substances 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 238000009377 nuclear transmutation Methods 0.000 abstract description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000002041 carbon nanotube Substances 0.000 description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
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- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 4
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- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an adsorbent for selectively extracting palladium nuclide from high-level radioactive waste liquid, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing the aqueous solution of the double-walled carbon nanotube with 5-amino-3- (2-thienyl) pyrazole, carrying out hydrothermal reaction after the 5-amino-3- (2-thienyl) pyrazole is completely dissolved, finishing grafting of functional additive substance pyrazole, and separating, washing and drying after the reaction is finished to obtain the adsorbent for selectively extracting palladium nuclide from the high-level radioactive waste liquid. The adsorbent has specific high-selectivity adsorption on palladium ions in the high-level waste liquid, overcomes the limitations of low adsorption efficiency, small adsorption quantity and poor selectivity of the traditional solid-phase adsorption method, is favorable for recycling rare noble metal resource palladium in the high-level waste liquid, effectively reduces the total amount of radioactive waste, solves the main problems of radioactive nuclear waste liquid treatment in spent fuel post-treatment and the like, and provides a new idea for industrial utilization of palladium and future long-life palladium nuclide transmutation.
Description
Technical Field
The invention belongs to the technical field of high-level wastewater treatment, and particularly relates to an adsorbent for selectively extracting palladium nuclides from high-level waste liquid, and a preparation method and application thereof.
Background
Palladium plays an important role in many industrial applications because it has unique and useful properties such as excellent catalytic properties, good ductility, excellent electrical conductivity and high chemical inertness. However, the large scale and range of applications of palladium increases the demand for palladium due to its low abundance in the crust (about 10% -6%), thus putting pressure on scarce natural resources. One of the potential secondary sources of palladium is the high-level waste liquid generated by nuclear spent fuel, and the high-level waste liquid contains palladium ions and various metal ions. However, since the high-level waste liquid has the characteristics of high acidity, complex components and the like, the high-selectivity extraction of palladium ions from the high-level waste liquid is very challenging. In recent years, selective separation and extraction of palladium ions have certain limitations on carbon materials, silicon-based materials, metal Organic Frameworks (MOFs) and the like, and have the disadvantages of low extraction efficiency, poor element selectivity, unstable adsorbents and the like. Therefore, there is a need for developing a highly efficient adsorbent material capable of separating palladium ions from a high level of radioactive waste liquid with high selectivity.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide the adsorbent for selectively extracting palladium nuclides from the high-level waste liquid, and the preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
A preparation method of an adsorbent for selectively extracting palladium nuclide from high-level radioactive waste liquid comprises the following steps:
Mixing the aqueous solution of the double-walled carbon nanotube with 5-amino-3- (2-thienyl) pyrazole, carrying out hydrothermal reaction after the 5-amino-3- (2-thienyl) pyrazole is completely dissolved, finishing grafting of functional additive substance pyrazole, and separating, washing and drying after the reaction is finished to prepare the adsorbent for selectively extracting palladium nuclide from the high-level radioactive waste liquid.
Preferably, the mass ratio of the double-walled carbon nanotube to the 5-amino-3- (2-thienyl) pyrazole is (0.495-0.505): (0.995-1.005).
Preferably, in the aqueous solution of the double-walled carbon nanotubes, the mass ratio of the double-walled carbon nanotubes to deionized water is (0.495-0.505): 300.
Preferably, when the aqueous solution of the double-walled carbon nanotube and the 5-amino-3- (2-thienyl) pyrazole are subjected to hydrothermal reaction, the reaction temperature is 48-52 ℃.
Preferably, when washing and drying the product separated after the hydrothermal reaction is completed, washing is repeated for a plurality of times by washing with water, ethanol and tetrahydrofuran in sequence, and freeze drying is performed after the washing is completed.
The invention also provides an adsorbent for selectively extracting palladium nuclides from the high-level waste liquid, and the adsorbent for selectively extracting palladium nuclides from the high-level waste liquid is prepared by the preparation method disclosed by the invention.
The invention relates to application of the adsorbent for selectively extracting palladium nuclide from the high-level waste liquid, wherein the adsorbent for selectively extracting palladium nuclide from the high-level waste liquid is used for adsorbing palladium nuclide.
Preferably, when the adsorbent for selectively extracting palladium nuclide from the high-level radioactive waste liquid adsorbs palladium nuclide, a sufficient amount of adsorbent for selectively extracting palladium nuclide from the high-level radioactive waste liquid is added into the waste liquid containing palladium nuclide, and stirring reaction is carried out at room temperature.
The desorption method of the adsorbent for selectively extracting palladium nuclide from the high-level radioactive waste liquid comprises the following steps: drying an adsorbent for selectively extracting palladium nuclide from the high-level radioactive waste liquid for adsorbing palladium nuclide, performing hydrothermal reaction with the extract, and separating, washing and vacuum drying after the hydrothermal reaction is finished to obtain the adsorbent for selectively extracting palladium nuclide from the desorbed high-level radioactive waste liquid;
the extract is a mixed solution of thiourea and nitric acid.
Preferably: the extract is prepared by mixing 1M thiourea and 1M nitric acid with equal volume; the dosage of the adsorbent for selectively extracting palladium nuclide in the dried high-level radioactive waste liquid for adsorbing palladium nuclide in the extract is 3g/L;
when the adsorbent for selectively extracting palladium nuclide from the high-level waste liquid for adsorbing palladium nuclide is dried, the drying temperature is 58-62 ℃;
When the hydrothermal reaction is carried out, the reaction temperature is 48-52 ℃;
During washing, deionized water and absolute ethyl alcohol are used for washing for a plurality of times;
And in vacuum drying, the drying temperature is 58-62 ℃.
The invention has the following beneficial effects:
The PyCNT material prepared by the hydrothermal reaction method (namely the adsorbent for selectively extracting palladium nuclide from the high-level waste liquid) has the advantages of simple and feasible working procedure, easy operation in a laboratory and short time consumption, and optimizes the complicated working procedures of the preparation of the conventional adsorbent material; the PyCNT material prepared is resistant to strong acid environment, has excellent stability, can be reused, and meets the environmental protection requirement; the adsorbent PyCNT has specific high-selectivity adsorption on palladium ions in the simulated high-level waste liquid of the 3M nitric acid medium, overcomes the defects of low adsorption efficiency, small adsorption quantity and poor selectivity of the traditional solid-phase adsorption method, is beneficial to recycling of rare noble metal resource palladium in the high-level waste liquid, effectively reduces the total amount of radioactive waste, solves the main problems of treatment of radioactive nuclear waste liquid in spent fuel aftertreatment and the like, and provides a new idea for industrial utilization of palladium and transmutation of future long-life palladium nuclides.
Drawings
FIG. 1 is a microscopic schematic of a functional adsorbent PyCNT of the present invention;
FIG. 2 is an X-ray photoelectron spectrum of a functional adsorbent PyCNT of the present invention, wherein (a) is the peak of O1S for PyCNT material, (b) is the peak of N1S for PyCNT material, and (c) is the peak of S2p for PyCNT material;
FIG. 3 is a transmission electron microscope image of a functional adsorbent PyCNT of the present invention;
FIG. 4 is a graph showing the adsorption efficiency of sample PyCNT on each ion in a simulated high level waste solution in accordance with an embodiment of the present invention;
FIG. 5 is a graph showing the adsorption efficiency of sample CNTs for each ion in a simulated high level waste solution in an embodiment of the present invention;
FIG. 6 shows adsorption kinetics PyCNT in example 3 of the present invention;
FIG. 7 is an adsorption isotherm of sample PyCNT in example 4 of the present invention;
FIG. 8 is a cyclic suction chart of sample PyCNT in example 5 of the present invention.
Detailed Description
The invention will be further described with reference to the drawings and examples.
The preparation method of the adsorbent for selectively extracting palladium nuclide from the high-level radioactive waste liquid comprises the following steps:
step 1), firstly, dissolving 0.5+/-0.05 g of double-walled carbon nano-tube (CNT) in 300ml of deionized water and performing ultrasonic treatment to obtain a double-walled carbon nano-tube solution after the double-walled carbon nano-tube is completely dissolved;
Step 2) adding 1+/-0.05 g of 5-amino-3- (2-thienyl) pyrazole (Py) into the double-walled carbon nanotube solution in the step 1), and continuing to carry out ultrasonic treatment for 0.5-1h to completely dissolve the 5-amino-3- (2-thienyl) pyrazole (Py);
Step 3) transferring the solution obtained in the step 2) to a water bath constant temperature oscillator, and performing heating oscillation reaction for 24 hours at the temperature of 50+/-2 ℃ and the speed of 140+/-5 rpm to complete grafting of functional additive substance pyrazole;
Step 4) washing the hydrothermal product in the step 3 with water, ethanol and tetrahydrofuran for three times, centrifuging, and drying by using a freeze dryer, wherein a microscopic schematic diagram of the process is shown in fig. 1. The morphology of the transmission electron microscope analysis of the black powder of the obtained functional adsorbent PyCNT is shown in fig. 3, and the obtained functional adsorbent PyCNT has a hollow tubular structure. The X-ray photoelectron spectrum of fig. 2 analyzes the chemical state of element O, N, S in the obtained functional adsorbent PyCNT, wherein (a) is a peak of O1s, and the obtained three peaks are respectively assigned to c=o, O on phenol, and O in bound water; (b) Peak for N1s, the resulting N is assigned to N in the imidazolyl group and N in the amide; (c) For the peak separation of S2p, the two peaks obtained by the peak separation are assigned to S2p 1/2 and S2p 3/2, and the appearance of characteristic peak amide and the like indicates the successful synthesis of PyCNT.
The adsorbent (PyCNT) for selectively extracting palladium nuclide from the high-level radioactive waste liquid prepared by the invention is subjected to a simulated adsorption test, and comprises the following steps:
Step a) adding 10ml of the prepared simulated high level waste liquid in 3M nitric acid medium into 30mg PyCNT black powder, and reacting for 24 hours at room temperature of 25+/-0.5 ℃ on a water bath constant temperature oscillator at the oscillating speed of 140rpm to perform adsorption experiments.
Step b) equal amounts of CNTs were weighed according to the amount of step a) and subjected to adsorption and desorption experiments as well, as a blank.
Step c) measuring the concentration before and after the reaction of each ion in the mixed ion system in the reaction of step a) and step b), and monitoring the adsorption effect of each ion by the unmodified CNT and the functionalized PyCNT.
Step d) adding 30mg PyCNT powder into 10ml of simulated high level waste liquid under 3M nitric acid medium according to the reaction parameters on the water bath constant temperature oscillator in the step a), monitoring the adsorption degree of palladium ions in 0-24 hours with the time, and monitoring adsorption kinetics.
Step e) 30mg PyCNT powder was added to 10ml of the reaction solution with an initial palladium ion concentration in the range of 50-700 ppm M nitric acid medium, and the adsorption isotherm of PyCNT on palladium ions was evaluated according to the reaction parameters on the water bath thermostatted shaker in step a).
Step f) mixing PyCNT with 3M nitric acid medium to obtain a mixed waste liquid according to 3:1, and carrying out adsorption reaction on a water bath constant temperature oscillator at room temperature of 25+/-0.5 ℃ for 9 hours according to the rotating speed of 140 rpm.
Step g) measuring the concentration of palladium ions in the supernatant liquid after the reaction in the step f), collecting the PyCNT black solid adsorbed with palladium ions at the bottom layer in the reaction bottle to the maximum extent by a suction filtration mode, transferring the powder into an oven, and drying at the temperature of 60 ℃.
Step k) preparing an extract, namely adopting 1M thiourea: mixing uniformly with the volume dosage of 1M nitric acid=1:1 to obtain an extract; weighing completely dried black powder, adding the powder and the extract according to the dosage of 3g/L, reacting for 1 hour at the speed of 180rpm at 50 ℃ in a water bath constant temperature oscillator, performing a desorption experiment in the extract, and monitoring the concentration of palladium ions in supernatant after the reaction;
And step l) washing the black powder subjected to the desorption reaction in the step k) by deionized water and absolute ethyl alcohol, centrifuging, and drying the solid powder at 60 ℃ in a vacuum drying oven to obtain the desorbed PyCNT.
Step m) repeating steps f), g), k), l) for 5 cycles.
Example 1
The preparation method of the functional carbon nano tube adsorbent (PyCNT) and the application of the functional carbon nano tube adsorbent in adsorbing palladium ions in high-level radioactive waste liquid comprise the following steps:
Weighing 0.5 g+/-0.05 g of double-walled carbon nano-tube (CNT) to be dissolved in 300ml of deionized water, carrying out ultrasonic treatment, obtaining a carbon nano-tube solution after complete dissolution, adding 1+/-0.05 g of 5-amino-3- (2-thienyl) pyrazole (Py) into the solution, continuing ultrasonic treatment for 0.5h to completely dissolve the solution, transferring the solution to a water bath constant temperature oscillator after complete reaction, carrying out heating and oscillating reaction for 24h under the parameters of 50 ℃ and 140 rpm, and finishing grafting of functional additive substance pyrazole. Wherein + -0.05 is a weighing error of the weighing apparatus.
And washing the obtained hydrothermal product with water, ethanol and tetrahydrofuran for three times in sequence, centrifuging, and drying the hydrothermal product by a freeze dryer to obtain the functional adsorbent PyCNT black powder. 30mg PyCNT black powder is taken and added into 10ml of the prepared simulated high level radioactive waste liquid under the 3M nitric acid medium, and the mixture is kept on a water bath constant temperature oscillator at the room temperature of 25 ℃ at the oscillation speed of 140rpm, and reacted for 24 hours to carry out an adsorption experiment. And measuring the concentration of each ion before and after the reaction of the obtained mixed ion system, and quantitatively detecting the adsorption effect of the functionalized PyCNT on each ion. By the formulaAnd calculating PyCNT the adsorption efficiency of each ion in the simulated high-level radioactive waste liquid. Wherein C 0 is the ion concentration in the stock solution, and C e is the ion concentration in the solution in ppm under normal conditions. PyCNT shows that the adsorption condition of each ion in the simulated high-level radioactive waste liquid is shown in fig. 4, the adsorption efficiency of Pd (II) in the mixed system is as high as 96.85%, and the adsorption of other ions is not obvious, so that the high-selectivity and high-efficiency adsorption of palladium ions are shown.
Comparative example 1
0.5+/-0.05 G of CNT is weighed and directly added into 10ml of simulated high level radioactive waste liquid in 3M nitric acid medium, and the mixture is kept on a water bath constant temperature oscillator at the room temperature of 25 ℃ at the oscillation speed of 140rpm to react for 24 hours to perform adsorption experiments to serve as a blank control.
The concentration of each ion before and after the reaction of the mixed ion system is measured, and the adsorption effect of the unmodified CNT on each ion is quantitatively detected. By the formulaCalculating the adsorption efficiency of the CNT on each ion in the simulated high-level radioactive waste liquid, wherein/>Is the ion concentration in the stock solution,/>The concentration of ions in the solution is in ppm in the usual state. The adsorption of the CNT to each ion in the simulated high level waste liquid is shown in fig. 5, which shows that the CNT adsorbs Pd (ii) slightly with an adsorption efficiency of 23.07%.
Example 2
Adding 90 mg PyCNT black powder into 30ml of 3M nitric acid medium simulated high level waste liquid, performing adsorption reaction at 25deg.C on 140: 140 rpm vibration speed in water bath constant temperature vibrator, sampling at 0 time, 0.5h, 1h, 2h, 5h, 6h, 8h, and 24h, filtering supernatant with pinhole filter and 0.22 μm filter membrane, measuring palladium ion concentration ρe in supernatant with Inductively Coupled Plasma (ICP), and measuring palladium ion concentration ρe by formulaThe adsorption capacity qe is calculated, wherein qe is the adsorption capacity at the time t, ρ0 is the initial concentration, ρe is the concentration at the time t, V is the ion volume, m is the adsorbent mass, the adsorption kinetics of palladium ions at each time point is shown in fig. 6, the adsorption degree of palladium ions with time is detected within 0-24 h, the abscissa is time (h), the ordinate is the adsorption capacity qe (mg/g), the result shown in fig. 6 shows that the adsorption reaction reaches rapid adsorption in the first 2h, the adsorption reaction gradually approaches to balance and maintains the maximum adsorption capacity in the subsequent time, and the adsorption process can complete the sufficient adsorption reaction within 24 h.
Example 3
30Mg PyCNT powder was added to 10ml of a reaction solution having an initial palladium ion concentration in the range of 50 to 700 mg/L in a 3M nitric acid medium, and the adsorption reaction was carried out at room temperature of 25℃for 9 hours on a water bath thermostatic shaker at a rotation speed of 140rpm, and the adsorption isotherm of PyCNT to palladium ions was evaluated, and the result is shown in FIG. 7. Wherein the abscissa represents the equilibrium concentration C e of palladium by the formulaThe unit is mmol/L obtained by calculation; the ordinate represents the adsorption amount Qe of palladium by the unit adsorbent, and/>, is calculated by the formulaThe unit is mmol/g. Wherein V is the volume of the reaction solution, and the unit is ml; m is PyCNT mass, unit is mg; p 0 is the concentration of palladium ions in the stock solution, and p e is the concentration of palladium ions in the solution in an equilibrium state, wherein the unit is mg/L; m is the molecular weight of palladium. As can be seen from FIG. 7, the adsorption amount increases with the increase of the equilibrium concentration of palladium, which indicates that PyCNT has excellent capability of adsorbing palladium ions and can efficiently adsorb palladium ions in the reaction system.
Example 5
Adding 30ml of the prepared simulated high-level radioactive waste liquid under 3M nitric acid medium into 90mg PyCNT black powder, carrying out adsorption reaction on the mixture for 9 hours at room temperature and 25 ℃ on a water bath constant temperature oscillator according to the rotating speed of 140rpm, filtering the supernatant after the reaction by using a pinhole filter and a filtering membrane of 0.22 mu M, measuring the concentration rho e of palladium ions in the supernatant by using Inductively Coupled Plasma (ICP), collecting the black solid of PyCNT with the palladium ions adsorbed on the bottom layer in a reaction bottle to the maximum extent by a suction filtration mode, transferring the powder into an oven, and drying the powder at the temperature of 60 ℃.
Preparation of 1M thiourea: 1M nitric acid=1:1 extract, weighing the completely dried black powder, adding the powder and 3g/L extract, reacting for 1 hour at a constant temperature of 50 ℃ and a rotation speed of 180rpm in a water bath oscillator, performing desorption experiments in the extract, monitoring the concentration of palladium ions in supernatant after the reaction, washing the black powder after the desorption reaction with deionized water and absolute ethyl alcohol, centrifuging, and drying solid powder at a temperature of 60 ℃ in a vacuum drying oven to obtain PyCNT after the desorption.
The above extraction experiment was repeated 5 times for the obtained desorbed PyCT times to investigate the reusability of the adsorbent PyCNT in the 3M high level waste liquid. By the formulaThe adsorption capacity in 5 cycles was calculated, the detection result is shown in FIG. 8, the abscissa represents the number of times of cycle adsorption, and the ordinate represents the adsorption capacity Q e in mmol/g after the desorbed sample PyCNT was used again for the adsorption reaction. Wherein V is the volume of the reaction solution, and the unit is ml; m is PyCNT mass, unit is mg; p 0 is the concentration of palladium ions in the stock solution, and p e is the concentration of palladium ions in the solution in an equilibrium state, wherein the unit is mg/L; m is the molecular weight of palladium. As shown in FIG. 8, after PyCNT cyclic desorption experiments, the adsorption capacity of palladium is reduced from 0.68 to 0.66mmol/g and is reduced by only 0.02mmol/g, so that PyCNT has excellent stability, can be recycled and is an adsorbent for efficiently adsorbing palladium ions in high-level waste liquid.
Claims (9)
1. The preparation method of the adsorbent for selectively extracting palladium nuclide from the high-level radioactive waste liquid is characterized by comprising the following steps of:
Mixing an aqueous solution of the double-walled carbon nanotube with 5-amino-3- (2-thienyl) pyrazole, performing hydrothermal reaction after the 5-amino-3- (2-thienyl) pyrazole is completely dissolved, finishing grafting of functional additive substance pyrazole, and separating, washing and drying after the reaction is finished to prepare an adsorbent for selectively extracting palladium nuclide from the high-level radioactive waste liquid;
When the aqueous solution of the double-walled carbon nanotube and 5-amino-3- (2-thienyl) pyrazole are subjected to hydrothermal reaction, the reaction temperature is 48-52 ℃.
2. The method for preparing the adsorbent for selectively extracting palladium nuclide from high-level radioactive waste liquid according to claim 1, wherein the mass ratio of the double-walled carbon nanotube to the 5-amino-3- (2-thienyl) pyrazole is (0.495-0.505): (0.995-1.005).
3. The method for preparing the adsorbent for selectively extracting palladium nuclide from high-level radioactive waste liquid according to claim 1, wherein the mass ratio of the double-walled carbon nanotube to deionized water in the aqueous solution of the double-walled carbon nanotube is (0.495-0.505): 300.
4. The method for preparing the adsorbent for selectively extracting palladium nuclides from the high-level radioactive waste liquid according to claim 1, wherein the washing and drying of the product separated after the completion of the hydrothermal reaction are sequentially repeated for a plurality of times by washing with water, ethanol and tetrahydrofuran, and freeze-drying is performed after the completion of the washing.
5. An adsorbent for selectively extracting palladium nuclides from high-level waste liquid, which is characterized in that the adsorbent for selectively extracting palladium nuclides from high-level waste liquid is prepared by the preparation method of any one of claims 1-4.
6. The use of an adsorbent for selectively extracting palladium species from a high level waste liquid as claimed in claim 5, wherein the adsorbent for selectively extracting palladium species from a high level waste liquid is used for adsorbing palladium species.
7. The method of claim 6, wherein when the adsorbent for selectively extracting palladium species from the high-level waste liquid adsorbs palladium species, a sufficient amount of the adsorbent for selectively extracting palladium species from the high-level waste liquid is added into the waste liquid containing palladium species, and stirring reaction is performed at room temperature.
8. The desorption method of the adsorbent for selectively extracting palladium nuclide from the high-level radioactive waste liquid as claimed in claim 5, which is characterized by comprising the following steps:
Drying an adsorbent for selectively extracting palladium nuclide from the high-level radioactive waste liquid for adsorbing palladium nuclide, performing hydrothermal reaction with the extract, and separating, washing and vacuum drying after the hydrothermal reaction is finished to obtain the adsorbent for selectively extracting palladium nuclide from the desorbed high-level radioactive waste liquid;
the extract is a mixed solution of thiourea and nitric acid.
9. The desorption method of the adsorbent for selectively extracting palladium nuclide from the high-level radioactive waste liquid according to claim 8, which is characterized in that:
the extract is prepared by mixing 1M thiourea and 1M nitric acid with equal volume; the dosage of the adsorbent for selectively extracting palladium nuclide in the dried high-level radioactive waste liquid for adsorbing palladium nuclide in the extract is 3g/L;
when the adsorbent for selectively extracting palladium nuclide from the high-level waste liquid for adsorbing palladium nuclide is dried, the drying temperature is 58-62 ℃;
When the hydrothermal reaction is carried out, the reaction temperature is 48-52 ℃;
During washing, deionized water and absolute ethyl alcohol are used for washing for a plurality of times;
And in vacuum drying, the drying temperature is 58-62 ℃.
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| CN87103759A (en) * | 1987-05-22 | 1988-12-07 | 南开大学 | Synthesis and application of cross-linked 2-ethylpyridyl polystyrene resin |
| CN105617979A (en) * | 2016-03-09 | 2016-06-01 | 清华大学 | Modified mesoporous silica adsorbent and preparation method and application thereof |
| CN106057263A (en) * | 2016-05-27 | 2016-10-26 | 东莞市联洲知识产权运营管理有限公司 | Technical method for absorbing palladium from high-level radioactive waste liquid |
| JP2018141189A (en) * | 2017-02-27 | 2018-09-13 | 国立研究開発法人日本原子力研究開発機構 | Method for separating metal from each other |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103759A (en) * | 1987-05-22 | 1988-12-07 | 南开大学 | Synthesis and application of cross-linked 2-ethylpyridyl polystyrene resin |
| CN105617979A (en) * | 2016-03-09 | 2016-06-01 | 清华大学 | Modified mesoporous silica adsorbent and preparation method and application thereof |
| CN106057263A (en) * | 2016-05-27 | 2016-10-26 | 东莞市联洲知识产权运营管理有限公司 | Technical method for absorbing palladium from high-level radioactive waste liquid |
| JP2018141189A (en) * | 2017-02-27 | 2018-09-13 | 国立研究開発法人日本原子力研究開発機構 | Method for separating metal from each other |
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