Gel type imidazolyl anion exchange resin as well as preparation method and application thereof

Abstract

The invention relates to the technical field of water treatment, and provides gel type imidazolyl anion exchange resin as well as a preparation method and application thereof. According to the method, the gel type styrene-divinyl benzene copolymer is taken as a matrix, and the adsorption selectivity of the gel type imidazolyl anion exchange resin on rhenium / technetium is regulated and controlled by grafting imidazole with alkyl side chains with different lengths, so that the removal rate of rhenium / technetium is increased. The gel type imidazolyl anion exchange resin provided by the invention has relatively high adsorption capacity on ReO4 <-> and TcO4 <->, high selectivity, wide applicable pH value and temperature range, strong acid and alkali resistance and irradiation stability, and wide application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of water treatment, and in particular to a gel-type imidazole-based anion exchange resin and a preparation method and application thereof. Background Art

[0002] 99 Tc is a beta-emitting radioactive nuclide produced by the fission of uranium-235 and plutonium-239, with a half-life of 2.13×10 5 In 2017, the fission yield could reach 6.03%. 99 Tc is mainly present in the form of pertechnetate ( 99 T8h 4- ) exists in the nuclear fuel cycle and the natural environment. 99 T8h 4- It has the characteristics of high water solubility, rapid environmental mobility, radioactivity, low charge density, high stability and difficulty in complexation. These characteristics make 99 T8h 4- It can migrate quickly in the environment, which not only harms the natural environment and human health, but also affects the extraction of uranium, neptunium and plutonium. 99 T8h 4- It is essential for nuclear fuel reprocessing and environmental remediation. 99 The non-radioactive analogue of Tc is usually obtained in the laboratory using rhenium peroxide (ReO 4- ) instead of TcO 4- Conduct adsorption effect evaluation experiments.

[0003] At present, various radioactive TcO in water have been reported at home and abroad. 4- There are many methods to remove radioactive TcO, such as precipitation, extraction and ion exchange. The precipitation method is to add a precipitant to the water to make the radioactive TcO 4- The precipitation method is simple and effective, but the trace amount of radioactive wastewater 99 T8h 4- It is not conducive to the subsequent separation of the precipitated product. The extraction method uses the selective solubility of the solvent for radioactive elements to separate radioactive elements from water. This method is complex to operate, costly and has secondary pollution. The ion exchange method uses ion exchange resins or ion exchange membranes to remove radioactive ions from water through ion exchange. Ion exchange resins have the characteristics of strong stability, regeneration, high mechanical strength and high economy. They are the most effective in selectively removing radioactive ions at low concentrations. 99 T8h 4- effective method.

[0004] Currently, the adsorption 99 T8h 4- / ReO4- The commercial resins are strongly basic anion exchangers containing quaternary ammonium groups, which undergo irreversible Hofmann degradation to form tertiary amines and other non-basic groups, affecting 99 T8h 4- / ReO 4- In addition, the current anion exchange resin has a 99 T8h 4- / ReO 4- The selectivity is low and the removal effect is easily interfered by other ions in the wastewater. Summary of the invention

[0005] In view of this, the present invention provides a gel-type imidazole-based anion exchange resin and a preparation method and application thereof. The gel-type imidazole-based anion exchange resin provided by the present invention has high selectivity, high removal rate for perrhenate and pertechnetate, good stability, and strong acid and alkali resistance and radiation stability.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] A gel-type imidazole-based anion exchange resin having a structure shown in Formula I:

[0008]

[0009] In Formula I: X n- It is chloride ion, hydroxide ion, sulfate ion or nitrate ion; m is 0-5.

[0010] The present invention also provides a method for preparing the gel-type imidazole-based anion exchange resin described in the above scheme, comprising the following steps:

[0011] The gel-type chloromethylated styrene-divinylbenzene copolymer, N-alkyl imidazole and solvent are mixed for quaternization reaction to obtain a gel-type imidazole-based anion exchange resin whose anions are chloride ions; the carbon number of the alkyl group in the N-alkyl imidazole is 1-6.

[0012] Preferably, the mass ratio of the gel-type chloromethylated styrene-divinylbenzene copolymer to N-alkylimidazole is 10:(5.6-12).

[0013] Preferably, the temperature of the quaternization reaction is 60-80° C., and the reaction time is 48-72 hours.

[0014] Preferably, when the anion of the gel-type imidazole-based anion exchange resin is hydroxide ion, sulfate ion or nitrate ion, it also includes exchanging anions of the gel-type imidazole-based anion exchange resin whose anion is chloride ion; the reagent used for the anion exchange is sodium hydroxide solution, sodium sulfate solution or sodium nitrate solution.

[0015] The present invention also provides the use of the gel-type imidazole-based anion exchange resin described in the above scheme or the gel-type imidazole-based anion exchange resin prepared by the preparation method described in the above scheme in the adsorption of perrhenate and / or pertechnetate.

[0016] The present invention also provides a method for adsorbing perrhenate and / or pertechnetate in wastewater, comprising the following steps:

[0017] A gel-type imidazolyl anion exchange resin is added to wastewater containing perrhenate and / or pertechnetate for adsorption; the solid-liquid ratio of the gel-type imidazolyl anion exchange resin to the wastewater is 0.05-40 g / L; the gel-type imidazolyl anion exchange resin is the gel-type imidazolyl anion exchange resin described in the above scheme or the gel-type imidazolyl anion exchange resin prepared by the preparation method described in the above scheme.

[0018] Preferably, the adsorption temperature is 20-80°C.

[0019] Preferably, the adsorption time is 4 to 12 hours.

[0020] Preferably, the pH value of the wastewater containing perrhenate and / or pertechnetate is 1-14.

[0021] The present invention provides a gel-type imidazole-based anion exchange resin having a structure shown in Formula I (see above). The present invention uses a gel-type styrene-divinylbenzene copolymer as a matrix, and by grafting imidazoles with alkyl side chains of different lengths, the adsorption selectivity of the gel-type imidazole-based anion exchange resin for rhenium / technetium is regulated to improve the removal rate of rhenium / technetium. - OH - 、SO4 2 - 、NO 3- ) can preferentially react with perrhenate and pertechnetate in wastewater to produce ReO4 - and TcO4 - Removal; and, the gel-type imidazole anion exchange resin provided by the present invention is for ReO 4- and TcO 4- It has a high adsorption capacity and can achieve the adsorption of ReO in wastewater containing a large number of interfering factors. 4- and TcO in radioactive wastewater 4- The results of the embodiment show that at high concentrations of Cl - 、NO 3- , CO3- 、SO4 2- and NO 2- In the presence of 4- The removal rate of rhenium / technetium increases and can reach 96.36%; under the condition of pH value of 1 to 14, the gel-type imidazole-based anion exchange resin of the present invention has a high rhenium / technetium removal rate; after being soaked in acid and alkali solution or irradiated with β rays, the removal rate of perrhenate does not change; compared with macroporous resin, the gel-type imidazole-based anion exchange resin provided by the present invention has a smaller pore size and higher crushing strength, and has better selectivity and rhenium / technetium removal rate. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The resin has different pH values ​​for ReO4 in Example 2. - Adsorption effect diagram;

[0023] Figure 2 The resin in Example 2 is ReO4 - Adsorption capacity diagram of

[0024] Figure 3 In Example 2, SO4 2- or NO 3- In the presence of ReO 4- Adsorption effect diagram;

[0025] Figure 4 The resin to ReO at different temperatures in Example 2 4- Adsorption effect diagram;

[0026] Figure 5 The resin in Example 3 is used to simulate the ReO in Hanford wastewater. 4- Adsorption effect diagram. DETAILED DESCRIPTION

[0027] The present invention provides a gel-type imidazole-based anion exchange resin having a structure shown in Formula I:

[0028]

[0029] In Formula I: X n- It is chloride ion, hydroxide ion, sulfate ion or nitrate ion; m is 0-5.

[0030] In the present invention, m in Formula I can be 0, 1, 2, 3, 4 or 5, more preferably 3 or 5. In the present invention, the hydrophobicity of the resin can be increased by increasing the carbon chain length, thereby making the resin more hydrophobic to ReO 4- and TcO 4-The adsorption selectivity of the gel-type imidazole anion exchange resin for ReO4 - and TcO4 - The removal rate increased.

[0031] In the present invention, the particle size of the gel-type imidazole-based anion exchange resin is 0.4-1 mm, the pore size is less than 5 nm, and the average crushing strength is ≥320 g / particle.

[0032] The present invention also provides a method for preparing the gel-type imidazole-based anion exchange resin described in the above scheme, comprising the following steps:

[0033] The gel-type chloromethylated styrene-divinylbenzene copolymer, N-alkyl imidazole and solvent are mixed for quaternization reaction to obtain a gel-type imidazole-based anion exchange resin whose anions are chloride ions; the carbon number of the alkyl group in the N-alkyl imidazole is 1-6.

[0034] In the present invention, the mass ratio of the gel-type chloromethylated styrene-divinylbenzene copolymer and N-alkylimidazole is 10:(5.6-12); the carbon number of the alkyl group in the N-alkylimidazole is 1-6, specifically 1, 2, 3, 4, 5 or 6. In an embodiment of the present invention, the N-alkylimidazole is preferably N-methylimidazole, N-butylimidazole or N-hexylimidazole, more preferably N-butylimidazole or N-hexylimidazole; the solvent is preferably N,N-dimethylformamide; the temperature of the quaternization reaction is preferably 60-80°C, and the reaction time is preferably 48-72h; after the quaternization reaction is completed, the present invention preferably filters the obtained reaction liquid, mixes the obtained resin and ethanol for reflux, and then filters and dries in sequence to obtain the gel-type imidazole-based anion exchange resin whose anions are chloride ions; the reflux time is preferably 12h, and the reflux temperature is 65°C.

[0035] In the present invention, when the anions of the gel-type imidazole-based anion exchange resin are hydroxide ions, sulfate ions or nitrate ions, it also includes anion exchange of the gel-type imidazole-based anion exchange resin whose anions are chloride ions; the reagent used for the anion exchange is sodium hydroxide solution, sodium sulfate solution or sodium nitrate solution; the mass fraction of the sodium hydroxide solution, sodium sulfate solution and sodium nitrate solution is preferably 5%; the anion exchange is preferably carried out under shaking conditions.

[0036] The present invention also provides the use of the gel-type imidazole-based anion exchange resin described in the above scheme or the gel-type imidazole-based anion exchange resin prepared by the preparation method described in the above scheme in the adsorption of perrhenate and / or pertechnetate.

[0037] The present invention also provides a method for adsorbing perrhenate and / or pertechnetate in wastewater, comprising the following steps:

[0038] A gel-type imidazolyl anion exchange resin is added to wastewater containing perrhenate and / or pertechnetate for adsorption; the solid-liquid ratio of the gel-type imidazolyl anion exchange resin to the wastewater is 0.05-40 g / L; the gel-type imidazolyl anion exchange resin is the gel-type imidazolyl anion exchange resin described in the above scheme or the gel-type imidazolyl anion exchange resin prepared by the preparation method described in the above scheme.

[0039] In the present invention, the solid-liquid ratio of the gel-type imidazole anion exchange resin to the wastewater is preferably 2-20 g / L, more preferably 5-20 g / L; the pH value of the wastewater containing perrhenate and / or pertechnetate is preferably 1-14, more preferably 2-12; the adsorption temperature is preferably 20-80°C, more preferably 20-40°C, the adsorption time is preferably 4-12h, more preferably 6-10h; the adsorption is preferably carried out under stirring conditions; after the adsorption is completed, the resin in the system is preferably removed.

[0040] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0041] Example 1: Preparation of gel-type imidazole-based anion exchange resin

[0042] (1) Preparation of gel-type imidazole anion exchange resin with methyl side chains (MeMIMCl)

[0043] 10 g of chloromethylated styrene-divinylbenzene and 100 mL of N, N-dimethylformamide were added to a beaker and stirred for 2 h, then 4.56 g of N-methylimidazole was added and stirred at 80°C for 72 h. The resin was filtered, and the obtained product was refluxed with ethanol at 65°C for 12 h, filtered and dried in a vacuum oven to obtain a gel-type imidazole-based anion exchange resin with a methyl side chain.

[0044] (2) Preparation of gel-type imidazole anion exchange resin (BuMIMCl) with butyl side chains

[0045] 10 g of chloromethylated styrene-divinylbenzene and 100 mL of N, N-dimethylformamide were added to a beaker and stirred for 2 h, and then 6.80 g of N-butyl imidazole was added and stirred at 80°C for 72 h. The resin was filtered, and the obtained product was refluxed with ethanol at 65°C for 12 h, filtered, and dried in a vacuum oven to obtain a gel-type imidazole-based anion exchange resin with a butyl side chain.

[0046] (3) Preparation of gel-type imidazole anion exchange resin with hexyl side chains (HeMIMCl)

[0047] 10 g of chloromethylated styrene-divinylbenzene and 100 mL of N, N-dimethylformamide were added to a beaker and stirred for 2 h, and then 9.60 g of N-hexylimidazole was added and stirred at 80°C for 72 h. The resin was filtered, and the obtained product was refluxed with ethanol at 65°C for 12 h, filtered, and dried in a vacuum oven to obtain a gel-type imidazole-based anion exchange resin with a hexyl side chain.

[0048] Example 2: Gel-type imidazole anion exchange resin for ReO 4- Adsorption

[0049] (1) Adsorption under different pH conditions

[0050] Add 10 mg of MeMIMCl, BuMIMCl or HeMIMCl resin to 30 mL of 200 mg / L ReO4 - The solution was adjusted to a pH of 1 to 14 with NaOH and HCl, shaken at room temperature for 8 hours, and filtered to separate. The residual ReO in the filtrate was detected by colorimetry. 4- concentration, calculate the gel-type imidazolyl anion exchange resin for ReO 4- The test results are as follows: Figure 1 As shown, according to Figure 1 It can be seen that the three resins have a wide range of pH values ​​from 1 to 14 for ReO4 - All of them have good adsorption properties.

[0051] (2) Gel-type imidazolyl anion exchange resin for ReO 4- The adsorption capacity

[0052] ReO4 with initial concentrations of Re(VII) of 100, 200, 300, 400, 500, 600, 700, 800, 900, and 1000 mg / L were prepared respectively. - Solution, take 10 mL of the above solution, add 10 mg of gel-type imidazole anion exchange resin, shake at 25 ° C for 8 h, filter, and detect the ReO in the filtrate 4-The concentration of Re(VII) was calculated by using the gel-type imidazole anion exchange resin. Figure 2 As shown. Figure 2 It can be seen that the adsorption capacities of MeMIMCl, BuMIMCl and HeMIMCl resins for Re(VII) are 981.20, 822.60 and 789.34 mg / g, respectively, which are higher than those of most adsorbents.

[0053] (3) Gel-type imidazole anion exchange resin for ReO 4- The adsorption selectivity

[0054] 10 mg of gel-type imidazole anion exchange resin was added to 10 mL of 0.1 mM ReO4 - and different concentrations of NaNO3 (0.1mM, 1mM, 5mM, 10mM, 50mM, 100mM, 200mM, 500mM) or Na2SO4 (0.1mM, 1mM, 5mM, 10mM, 50mM, 100mM, 200mM, 500mM), shaken at room temperature for 8h, filtered, and the ReO in the filtrate was detected. 4- The removal rate of Re(VII) by gel-type imidazole anion exchange resin was calculated based on the concentration of 2.5 wt.-1 mol / L and 1.5 wt.-1 mol / L. At the same time, a control experiment was carried out using the commercially available ion exchange resin ZGANR170 under the same conditions.

[0055] Test results such as Figure 3 As shown, according to Figure 3 It can be seen that when the concentration of NaNO3 and Na2SO4 is low, MeMIMCl, BuMIMCl and HeMIMCl resins all have higher ReO 4- The removal rate of MeMIMCl on ReO 4- The removal rate of ReO decreased slightly, while the removal rate of BuMIMCl and HeMIMCl resins 4- The removal rate is still high. When BuMIMCl resin is used, when the NaNO3 concentration is ReO 4- When the concentration was 500 and 1000 times higher, ReO 4- The removal rate can still reach 97.58% and 95.10%; when NaNO3 is ReO 4- When the concentration is 5000 times that of ReO 4- The removal rate can still reach 87.33%; when the concentration of Na2SO4 is ReO 4- When the concentration is 5000 times that of ReO 4- The removal rate can still reach 97.24%; when ZGANR170 resin is used, as the concentration of NaNO3 and Na2SO4 increases, the removal rate of ReO4- The removal rate of NaNO3 and Na2SO4 decreased sharply. 4- When the concentration is 5000 times higher, ZGANR170 resin can no longer remove ReO 4- The above results show that the gel-type imidazole-based anion exchange resin provided by the present invention exhibits excellent selectivity, and as the carbon chain length increases, the selectivity of the resin is better.

[0056] (4) Effect of gel-type imidazolyl anion exchange resin on ReO at different temperatures 4- Adsorption performance

[0057] 10 mg of gel-type imidazole anion exchange resin was added to 30 mL of ReO4 with a Re(VII) concentration of 200 mg / L. - The solution was shaken at 25℃, 40℃, 60℃ and 80℃ for 8h, filtered and the ReO4 content in the filtrate was detected. - The removal rate of Re(VII) by gel-type imidazolyl anion exchange resin was calculated based on the concentration of .

[0058] Test results such as Figure 4 As shown, according to Figure 4 It can be seen that within the range of 25-80° C., the removal rate of the gel-type imidazole-based anion exchange resin for Re(VII) is above 90%, indicating that it has good temperature applicability.

[0059] (5) Stability test

[0060] In addition, MeMIMCl, BuMIMCl and HeMIMCl resins were soaked in 5 mol / L NaOH solution and 5 mol / L HCl for 24 h, respectively. Then, adsorption experiments were carried out according to the above method at a pH of 7, a solid-liquid ratio of 1 g / L, and a Re(VII) concentration of 0.1 mM / L. The results showed that the performance of the resins was basically unchanged.

[0061] After MeMIMCl, BuMIMCl and HeMIMCl resins were irradiated with 300KGyβ-rays, adsorption experiments were carried out according to the above method under the conditions of pH 7, solid-liquid ratio of 1g / L and Re(VII) concentration of 20mg / L. The results showed that the performance of the resins was basically unchanged, indicating that the gel-type imidazole-based anion exchange resin of the present invention has excellent stability.

[0062] Example 3: Effect of gel-type imidazolyl anion exchange resin on ReO in simulated wastewater 4- Adsorption performance

[0063] A certain amount of gel-type imidazole anion exchange resin was added to 10 mL of simulated Hanford waste liquid. The composition of the waste liquid is shown in Table 1. The filtrate was shaken at room temperature for 8 h, filtered, and the ReO content in the filtrate was detected. 4- The removal rate of Re(VII) by gel-type imidazolyl anion exchange resin was calculated based on the concentration of .

[0064] In addition, the same experiment was carried out using a macroporous imidazole anion exchange resin with a methyl side chain under the condition of a solid-liquid ratio of 5g / L as a comparison; the preparation method of the macroporous imidazole anion exchange resin is as follows: 5g of macroporous chloromethylated styrene divinylbenzene copolymer is added to a 100mL round-bottom flask, stirred with 40mL N,N-dimethylformamide for 2h, and then 1.85g of N-methylimidazole is added and stirred at 70°C for 24h. The resin is filtered, washed with ethanol, and dried in a vacuum oven to obtain a macroporous N-methylimidazole-based strongly basic anion exchange resin with an average pore size of ≥400nm, which is recorded as a macroporous methylimidazole resin.

[0065] The results are shown in Table 2 and Figure 5 shown.

[0066] Table 1 Composition of simulated Hanford wastewater

[0067] Type of substance <![CDATA[ReO4 - or TcO4 - ]]> <![CDATA[NO2 - ]]> <![CDATA[Cl - ]]> <![CDATA[NO3 - ]]> <![CDATA[CO3 2- ]]> <![CDATA[SO4 2- ]]> Molar concentration (mol / L) <![CDATA[1.94×10 -4 ]]> <![CDATA[1.69×10 -1 ]]> <![CDATA[6.39×10 -2 ]]> <![CDATA[6.07×10 -2 ]]> <![CDATA[4.30×10 -5 ]]> <![CDATA[6.64×10 -6 ]]> Molar ratio 1.0 873 330 314 0.222 0.0343

[0068] Table 2 Removal efficiency of Re(VII) by gel resin in simulated Hanford wastewater

[0069]

[0070] From Table 2 and Figure 5 It can be seen that the gel-type imidazole anion exchange resin provided by the present invention has a high removal rate for Re(VII) in the simulated Hanford wastewater, and the gel-type imidazole anion exchange resin with a longer carbon chain has a higher removal rate for Re(VII), wherein HeMIMCl can achieve a removal rate of 91.32% for Re(VII) at a solid-liquid ratio of 5 g / L, showing excellent selectivity. Moreover, according to the test results of the macroporous methylimidazole resin, under the same solid-liquid ratio, MeMIMCl has a higher removal rate for Re(VII), indicating that the removal rate of the gel-type imidazole anion exchange resin for Re(VII) is higher than that of the macroporous type.

[0071] Example 4: Effect of gel-type imidazole anion exchange resin on TcO in simulated wastewater 4- Adsorption performance

[0072] The simulated Hanford high-level waste liquid was prepared according to the ratio of each anion in Table 1. Then 25 mg of gel-type imidazole anion exchange resin was weighed and added to 5 mL of the waste liquid. The mixed solution was shaken at room temperature for 6 h and then filtered. The TcO content in the filtrate was measured by liquid scintillation. 4- The concentration of gel-type imidazolyl anion exchange resin in simulated wastewater was calculated. 4- The removal rate is shown in Table 3.

[0073] Table 3 Effect of gel resin on TcO4 in simulated Hanford wastewater - Removal rate

[0074] Resin Solid-liquid ratio g / L <![CDATA[TcO4 - Removal rate (%)]]> MeMIMCl 5 90.90 BuMIM 5 96.36 HeMIMCl 5 95.52

[0075] According to the data in Table 3, it can be seen that the gel-type imidazole-based anion exchange resin of the present invention has an effect on TcO in simulated wastewater. 4- Has a higher removal rate.

[0076] Example 5: Gel-type imidazole anion exchange resin for TcO4 in simulated high-level wastewater - Adsorption performance

[0077] The simulated SRS wastewater was prepared according to the ratio of each anion in Table 4. Then, 100 mg of gel-type imidazole anion exchange resin was weighed and added to 5 mL of the wastewater. The mixed solution was shaken at room temperature for 6 h and then filtered. The TcO content in the filtrate was measured using a liquid scintillation spectrometer. 4- The concentration of gel-type imidazolyl anion exchange resin in simulated wastewater was calculated. 4- The removal rate is shown in Table 5.

[0078] Table 4 Composition of simulated SRS wastewater

[0079]

[0080] Table 5 Effect of gel resin on TcO4 in simulated SRS wastewater - Removal rate

[0081] Resin Solid-liquid ratio g / L <![CDATA[TcO4 - Removal rate (%)]]> MeMIMCl 20 77.36 BuMIM 20 86.94 HeMIMCl 20 83.63

[0082] It can be seen from Table 5 that the gel-type imidazole-based anion exchange resin of the present invention has an effect on TcO in simulated wastewater. 4- The resin with a long carbon chain has a higher removal rate for TcO 4- The removal rate is higher.

[0083] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A gel-type imidazole-based anion exchange resin, characterized in that: It has the structure shown in formula I: In Formula I: X n- It is chloride ion, hydroxide ion, sulfate ion or nitrate ion; m is 0-5.

2. The method for preparing the gel-type imidazole-based anion exchange resin according to claim 1, characterized in that: The following steps are involved: The gel-type chloromethylated styrene-divinylbenzene copolymer, N-alkyl imidazole and solvent are mixed for quaternization reaction to obtain a gel-type imidazole-based anion exchange resin whose anions are chloride ions; the carbon number of the alkyl group in the N-alkyl imidazole is 1-6.

3. The preparation method according to claim 2, characterized in that: The mass ratio of the gel-type chloromethylated styrene-divinylbenzene copolymer to N-alkylimidazole is 10:(5.6-12).

4. The preparation method according to claim 2, characterized in that: The temperature of the quaternization reaction is 60-80° C., and the reaction time is 48-72 hours.

5. The preparation method according to claim 2, characterized in that: When the anions of the gel-type imidazole-based anion exchange resin are hydroxide ions, sulfate ions or nitrate ions, the method further includes subjecting the gel-type imidazole-based anion exchange resin whose anions are chloride ions to anion exchange; the reagent used in the anion exchange is sodium hydroxide solution, sodium sulfate solution or sodium nitrate solution.

6. Use of the gel-type imidazolyl anion exchange resin according to claim 1 or the gel-type imidazolyl anion exchange resin prepared by the preparation method according to any one of claims 2 to 5 in the adsorption of perrhenate and / or pertechnetate.

7. A method for adsorbing perrhenate and / or pertechnetate in wastewater, characterized in that: The following steps are involved: A gel-type imidazolyl anion exchange resin is added to wastewater containing perrhenate and / or pertechnetate for adsorption; the solid-liquid ratio of the gel-type imidazolyl anion exchange resin to the wastewater is 0.05-40 g / L; the gel-type imidazolyl anion exchange resin is the gel-type imidazolyl anion exchange resin according to claim 1 or the gel-type imidazolyl anion exchange resin prepared by the preparation method according to any one of claims 2 to 5.

8. The method according to claim 7, characterized in that The adsorption temperature is 20-80°C.

9. The method according to claim 7, characterized in that: The adsorption time is 4 to 12 hours.

10. The method according to claim 7, characterized in that The pH value of the wastewater containing perrhenate and / or pertechnetate is 1-14.

Images