CN110923480B - Application of aminoimidazole type ionic liquid loaded resin in adsorption separation of rhenium or technetium - Google Patents
Application of aminoimidazole type ionic liquid loaded resin in adsorption separation of rhenium or technetium Download PDFInfo
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
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Abstract
The invention discloses an application of amino imidazole type ionic liquid loaded resin in adsorption separation of rhenium or technetium. The amino imidazole type ionic liquid loaded resin has a spherical particle structure, can be used in a wider acid-base range, has high adsorption capacity for both technetium and rhenium, and can meet the requirement of filling and using an adsorption column in industry. On the other hand, when the rhenium concentration is as low as 10ppb, the adsorption recovery rate of the aminoimidazole type ionic liquid supported resin related to the invention to rhenium still reaches more than 95%, and trace rhenium can be separated and enriched from the leaching solution containing rhenium uranium ore with high selectivity. The method is simple, does not produce secondary pollution and reduces the cost. The adsorbent has strong regeneration capacity, can be repeatedly used, has low production cost and is green and environment-friendly.
Description
Technical Field
The invention belongs to the field of hydrometallurgy and environmental chemical industry, and particularly relates to application of amino imidazole type ionic liquid loaded resin in adsorption separation of rhenium or technetium.
Background
99Technetium (C)99Tc) is one of the thermal cracking products of U-235 and Pu-239, producing approximately 40 kg per year in each nuclear facility99Tc, most of which are disposed of as nuclear waste. On the other hand, in the case of a liquid,99mtc is the most widely used technetium nuclide in clinical nuclear medicine diagnosis, accounting for 80%. Diagnosis of decay after formation99Tc may enter the environment with the patient's excretion, etc.99Tc, once released from the waste, is particularly fluid, since99Tc in aqueous solution as very stable pertechnetate TcO4 -In a form that is soluble in groundwater, difficult to eliminate under oxidizing conditions, and99the half-life of Tc is particularly as long as 2.13 × 105And (5) year. Therefore, the recovery and separation of technetium is receiving more and more attention. It is also impractical to conduct extensive high-concentration Tc studies in order to investigate the Tc recovery and separation capabilities of various processes, since large amounts of technetium are not paid for once they are inadvertently introduced into the environment. Therefore, to avoid the use of high concentrations of Tc, we often choose to use Tc in the same main group as TcRhenium (Re) was studied. Rhenium and technetium possess very similar electronic configuration, stereochemistry and thermodynamic properties, and thus have very high similarity in chemical properties.
In addition, the content of rhenium in the crust is less than 1.0ppb, belongs to rare metals and is expensive. Rhenium has excellent characteristics of high electron emission performance, high melting point, excellent strength, ductility and the like, and is widely applied to the fields of petroleum catalysis, aerospace, radio and the like. Rhenium does not have an independent natural ore and is often associated with other metal ores, such as copper ores, molybdenum ores and uranium ores. Separation and enrichment of rhenium is particularly difficult due to the very low content of rhenium in these metal ores.
At present, the methods for separating rhenium mainly comprise a chemical precipitation method, a solvent extraction method and an ion exchange method. Rhenium generally coexists with other metal ions (copper, molybdenum, zinc, etc.), and the chemical precipitation method has poor selectivity and difficulty in separation. The solution extraction method has complex process, uses a plurality of toxic and volatile solvents, and is not beneficial to environmental protection. Ion exchange is considered one of the best separation methods. The ionic liquid is completely composed of ions, and most of the ionic liquid refers to molten salt in a liquid state when the temperature is lower than 100 ℃. The ionic liquid has the characteristics of small vapor pressure, nonflammability, good chemical and thermal stability, good solubility and the like. The ion exchange resin can be obtained by chemically loading the ionic liquid on the solid. And the advantages of the solid and the physical and chemical properties of the ionic liquid are retained. The preparation of the adsorbent by loading the ionic liquid has been reported, but most of the adsorbents are nano materials or gel materials, have high cost, are difficult to fill in an adsorption column or have low treatment efficiency, and cannot be applied on a large scale.
Disclosure of Invention
In view of the above defects or improvement needs of the prior art, the present invention provides an application of an aminoimidazole type ionic liquid loaded resin in adsorption separation of rhenium or technetium, wherein the aminoimidazole type ionic liquid loaded resin is adopted to treat a solution containing rhenium or technetium, and rhenium or technetium in the solution is adsorbed and separated through ion exchange, so that technical problems of low separation efficiency, no large-scale application and the like of the separation and enrichment method for rhenium or technetium in the prior art are solved.
To achieve the above object, according to one aspect of the present invention, there is provided a use of an aminoimidazole-type ionic liquid-supported resin for adsorptive separation of rhenium or technetium, which is obtained by immobilizing an aminoimidazole-type ionic liquid on the surface of a resin substrate, treating a solution containing rhenium or technetium with the aminoimidazole-type ionic liquid-supported resin, and separating rhenium or technetium in the solution by ion exchange adsorption.
Preferably, the aminoimidazole type ionic liquid supported resin is obtained by: grafting a monomer containing an epoxy group onto the surface of a resin substrate, and then further introducing the aminoimidazole type ionic liquid onto the surface of the resin substrate through epoxy ring opening to obtain the aminoimidazole type ionic liquid loaded resin.
Preferably, the preparation method of the aminoimidazole type ionic liquid loaded resin specifically comprises the following steps:
(1) carrying out surface modification on the resin substrate, and introducing an unsaturated monomer containing an epoxy group to prepare an adsorption material precursor;
(2) leading the adsorbing material precursor obtained in the step (1) and the aminoimidazole type ionic liquid to perform epoxy ring-opening reaction, and introducing the aminoimidazole type ionic liquid component; and washing the adsorption material obtained after the reaction with a solvent, and drying to obtain the aminoimidazole type ionic liquid loaded resin material.
Preferably, the aminoimidazole-type ionic liquid has the following general structure:
wherein n is an integer of 1-8, and X is Cl, Br, NO3、BF4、NTf2Or PF6。
Preferably, the epoxy group-containing unsaturated monomer is one of glycidyl methacrylate and hydroxybutyl glycidyl acrylate monomers.
Preferably, when the epoxy group ring opening reaction is carried out, the concentration of the aminoimidazole type ionic liquid is 5-80 wt%; the solvent is water, ethanol or DMSO, and the reaction temperature is controlled at 40-85 ℃; the functional group density of the aminoimidazole type ionic liquid is 0.1mmol/g-5 mmol/g.
Preferably, the particle size of the aminoimidazole type ionic liquid loaded resin is 50-1000 μm.
Preferably, the solution containing rhenium or technetium has a pH of 1 to 11, wherein rhenium is in the solution as ReO4 -In anionic form, technetium being present in said solution as TcO4 -The anionic form exists.
Preferably, the solution containing rhenium is leaching solution containing rhenium associated uranium ore or ore treatment tail solution containing rhenium associated uranium ore; and adjusting the pH value of the ground immersion liquid or the tail liquid to be in the range of 2-3, and enabling the ground immersion liquid or the tail liquid to pass through an adsorption column filled with the aminoimidazole type ionic liquid loading resin to realize selective adsorption separation of trace rhenium in the ground immersion liquid or the tail liquid.
Preferably, after adsorption, the rhenium or technetium loaded on the resin is eluted and separated by using an eluent to regenerate the resin.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) the application of the amino imidazole type ionic liquid loaded resin in the adsorption separation of rhenium or technetium adopts the amino imidazole type ionic liquid loaded resin to process a solution containing rhenium or technetium, and the rhenium or technetium in the solution is adsorbed and separated through ion exchange, so that the high-concentration rhenium adsorption capacity (the highest adsorption capacity can be close to 800mg/g), the mechanical strength is high, the adsorption speed is high, the high-concentration rhenium adsorption capacity can be filled in an adsorption column, the desorption is easy, the high-concentration rhenium or technetium can be repeatedly used, and the high-concentration rhenium adsorption capacity can be used in a wider acid-base range.
(2) The ionic liquid adsorption resin provided by the invention simultaneously introduces secondary amine, imidazole groups and hydroxyl groups formed by epoxy ring opening, and the coexistence of the multifunctional groups can realize high-selectivity adsorption and separation on rhenium and technetium, wherein imidazole rings and-NH participate in ion exchange adsorption and separation.
(3) The aminoimidazole type ionic liquid loaded resin has high-efficiency separation and enrichment effects on trace rhenium.
(4) The research of carrying out adsorption separation on technetium and rhenium by immobilizing the aminoimidazole type ionic liquid on the surface of the resin microsphere is not reported. On the other hand, few studies have been reported on the separation and enrichment of low-concentration rhenium, especially rhenium from uranium solutions. The amino imidazole type ionic liquid loaded resin provided by the invention has a high-selectivity enrichment effect on trace associated rhenium in leaching solution and tail solution of rhenium-containing uranium ores.
(5) The preparation method of the amino imidazole type ionic liquid loaded resin is simple, easy to control conditions, low in energy consumption, safe and environment-friendly, and more suitable for industrial production.
(6) The amino imidazole type ionic liquid loaded resin obtained by the invention has the advantages of easily available raw materials, low cost and environmental protection, meets the requirements of filling and using adsorption columns in industry, and has great industrial application prospect.
Drawings
FIG. 1 is a graph of the adsorption effect of pH on Re.
Fig. 2 is a graph showing evaluation curves of dynamic adsorption characteristics of the aminoimidazole-type ionic liquid-supported resin for Re.
FIG. 3 shows the reusability of the aminoimidazole-type ionic liquid supported resin on Re.
Fig. 4 is a penetration curve of the aminoimidazole type ionic liquid loaded resin for separating and enriching low-concentration rhenium from simulated uranium ore solution.
Fig. 5 is a leaching curve of the aminoimidazole type ionic liquid loaded resin after separating and enriching low-concentration rhenium from simulated uranium ore solution.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides an application of aminoimidazole type ionic liquid loaded resin in adsorption separation of rhenium or technetium, wherein the aminoimidazole type ionic liquid loaded resin is obtained by immobilizing aminoimidazole type ionic liquid on the surface of a resin substrate, a solution containing rhenium or technetium is treated by the aminoimidazole type ionic liquid loaded resin, and the rhenium or technetium in the solution is separated by ion exchange adsorption.
The amino imidazole type ionic liquid loaded resin is obtained by modifying the surface of a base material; in some embodiments, the aminoimidazole-type ionic liquid-loaded resin is obtained by grafting an epoxy group onto the surface of a resin substrate, and then introducing an aminoimidazole-type ionic liquid on the surface of the resin substrate through epoxy ring opening. Specifically, amino imidazole type ionic liquid is introduced to the surface of a base material through the ring-opening reaction of amino on the amino imidazole type ionic liquid and epoxy to obtain the amino imidazole type ionic liquid loaded resin.
In some embodiments, the aminoimidazole-type ionic liquid supported resin has a general structural formula as shown in formula (one):
wherein n is an integer between 1 and 8, X is Cl, Br, NO3 -,BF4,NTf2Or PF6。
In some embodiments, the aminoimidazole-type ionic liquid has the following general structure:
wherein n is an integer between 1 and 8, X is Cl, Br, NO3 -,BF4,NTf2Or PF6。
The aminoimidazole-containing ionic liquid of the present invention includes, but is not limited to, 1-aminoethyl-3-methyl-imidazole chloride salt, 1-aminoethyl-3-methyl-imidazole bromide salt, 1-aminoethyl-3-methyl-imidazole nitrate salt, 1-aminoethyl-3-methyl-imidazole tetrafluoroborate salt, 1-aminoethyl-3-methyl-imidazole hexafluorophosphate salt, 1-aminoethyl-3-methyl-imidazole bistrifluoromethylsulfinate salt, 1-aminopropyl-3-methyl-imidazole chloride salt, 1-aminopropyl-3-methyl-imidazole bromide salt, 1-aminopropyl-3-methyl-imidazole nitrate salt, 1-aminopropyl-3-methyl-imidazole tetrafluoroborate salt, One or more of 1-aminopropyl-3-methyl-imidazolium hexafluorophosphate, 1-aminopropyl-3-methyl-imidazolium bistrifluoromethylsulfinate and 1-aminobutyl-3-methyl-imidazolium bromide.
The amino imidazole type ionic liquid loaded resin provided by the invention has the structural characteristics that secondary amine a, imidazole group b and hydroxyl group formed by epoxy ring opening of c are simultaneously introduced, and the coexistence of the multifunctional groups can realize high-selectivity adsorption and separation of rhenium and technetium; wherein the imidazole ring and-NH participate in ion exchange.
In some embodiments, the preparation method of the aminoimidazole-type ionic liquid supported resin specifically includes the following steps:
(1) carrying out surface modification on a resin base material, and introducing an unsaturated monomer containing an epoxy group to prepare an adsorption material precursor;
(2) carrying out epoxy ring opening reaction on the adsorbing material precursor obtained in the step (1) and imidazole ionic liquid containing amino, and introducing an aminoimidazole type ionic liquid component; and washing the adsorption material obtained after the reaction with a solvent, and drying in a vacuum drying oven to obtain the aminoimidazole type ionic liquid loaded resin material.
In some embodiments, in step (1), the resin substrate is selected from any one of natural polymers and derivatives thereof, synthetic polymers selected from polyethylene glycol, polyacrylate, polyvinylidene fluoride, silicon-based inorganic materials, and carbon-based inorganic materials.
In some embodiments, in step (1), the polymer substrate is selected from any one of cellulose and its derivatives, polyethylene glycol, polypropylene, or polyamide, which have a crystallinity of 30% or more.
In some preferred embodiments, a cellulose material having a crystallinity of 30% or more is selected as the resin base material.
In some embodiments, the surface modification is radiation grafting or chemical grafting. Irradiating the base material or treating the base material with a chemical initiator to generate chemical active ingredients such as free radicals capable of inducing a grafting reaction on the surface of the base material, and then performing a graft polymerization reaction on the chemical active ingredients and unsaturated monomers containing epoxy groups to prepare the adsorbing material precursor.
In some embodiments, the surface modification is radiation grafting, using60Co gamma-ray, electron beam or X-ray with the irradiation dose of 10-250 kGy; the graft ratio of the graft polymerization is 50% or more.
In some embodiments, the unsaturated monomer containing an epoxy group is glycidyl methacrylate and/or hydroxybutyl glycidyl acrylate.
In some embodiments, the epoxy group ring-opening reaction is performed in 5-40 wt% aqueous solution containing aminoimidazole type ionic liquid, ethanol or DMSO, and the reaction temperature is controlled at 40-85 ℃; the density of the functional group of the aminoimidazole-containing ionic liquid is 0.1mmol/g-5 mmol/g.
In some embodiments, the aminoimidazole type ionic liquid loaded resin is prepared into resin particles with the particle size of 50-1000 μm and used as an adsorption column filling material.
The solution containing rhenium or technetium of the present invention may be any solution containing rhenium or technetium. For example, the solution may be a self-prepared rhenium-containing solution, technetium-containing solution, uranium-rhenium blended solution, copper-rhenium blended solution, or a rhenium-or technetium-containing waste solution, such as an earth leaching solution of rhenium-containing uranium ore.
The amino imidazole type ionic liquid loaded resin can be used in a wider acid-base range, has very high adsorption capacity for rhenium or technetium, has the saturated adsorption capacity for rhenium of up to 300-800mg/g, and can be repeatedly utilized.
In some embodiments, the solution containing rhenium or technetium has a pH of 1 to 11, wherein rhenium is in the solution as ReO4 -In anionic form, technetium being present in said solution as TcO4 -The anionic form exists.
Experiments of the invention find that the aminoimidazole type ionic liquid supported resin has good enrichment effect on trace rhenium (0.1ppb-100 ppb).
When the immersion liquid containing rhenium uranium ore is treated by using the aminoimidazole type ionic liquid supported resin, trace rhenium in the immersion liquid can be selectively separated, and high selectivity is shown for rhenium.
In some embodiments, different ion forms of uranium rhenium are utilized, and in order to improve the separation selectivity of uranium rhenium, high-selectivity adsorption separation of trace rhenium in the immersion liquid can be realized by adjusting the pH value of the immersion liquid to 2-3.
The application method adopts the aminoimidazole type ionic liquid loaded resin to complete the adsorption of the solution containing rhenium or technetium, and then adopts corresponding leacheate to elute and separate the rhenium or technetium loaded on the resin, so as to regenerate the resin. In some embodiments, the leacheate is 1-4mol/L HNO31-4mol/L HCl or 5% -10% ammonia water solution.
The invention utilizes the aminoimidazole type ionic liquid supported resin to selectively separate trace rhenium in leaching solution or ore treatment tail solution containing rhenium associated uranium ore, and the specific method is that different ion forms of uranium and rhenium are utilized, the pH of the leaching solution or the tail solution is adjusted to be within the range of 2-3, and the high selective adsorption separation of the trace rhenium in the leaching solution or the tail solution can be realized through an adsorption column filled with the aminoimidazole type ionic liquid supported resin.
The invention discloses an application method for adsorbing and separating rhenium or technetium by using aminoimidazole type ionic liquid loaded resin. The application method comprises the following specific steps: adding aminoimidazole type ionic liquid loaded resin into a rhenium or technetium-containing solution, and performing ion exchange adsorption on rhenium or technetium in the solution by using the aminoimidazole type ionic liquid loaded resin; and after adsorption, eluting, separating and regenerating the rhenium or technetium loaded on the resin by using eluent. The amino imidazole type ionic liquid loaded resin has a spherical particle structure, can be used in a wider acid-base range, has high adsorption capacity for both technetium and rhenium, and can meet the requirement of filling and using an adsorption column in industry. On the other hand, when the rhenium concentration is as low as 10ppb, the adsorption recovery rate of the aminoimidazole type ionic liquid supported resin related to the invention to rhenium still reaches more than 95%, and trace rhenium can be separated and enriched from the leaching solution containing rhenium uranium ore with high selectivity. The method is simple, does not produce secondary pollution and reduces the cost. The adsorbent has strong regeneration capacity, can be repeatedly used, has low production cost and is green and environment-friendly.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The following are examples:
example 1
Preparing the aminoimidazole ionic liquid supported resin according to the following method:
1) 10g of crystalline cellulose microspheres with the particle size of about 150um are vacuumized and sealed, and an electron accelerator is used for electron beam radiation, so that active free radicals capable of being used for grafting reaction are generated. Irradiation conditions: the irradiation voltage is 2MeV, the irradiation dose is 30kGy, and the dose rate is 10 kGy/pass.
2) And (3) immediately adding the deoxygenated Glycidyl Methacrylate (GMA): tween 20: water 30: 3: carrying out graft polymerization reaction in an emulsion reaction system with the composition of 67 wt%. The graft polymerization reaction is carried out at 50 ℃, the reaction is terminated after about 2 hours (the grafting rate of the base material reaches about 250 percent), and the adsorbent precursor is obtained after being washed clean by water.
3) And adding the adsorbent precursor into 40 wt% of 1-aminopropyl-3-methyl-imidazole chloride aqueous solution to perform epoxy ring-opening reaction, performing oscillation reaction at 80 ℃ for 24 hours, taking out, washing with ethanol and water, and drying to obtain the aminoimidazole type ionic liquid supported resin, wherein the functional group density of the aminoimidazole type ionic liquid is 1.87 mmol/g-ad. The obtained resin had a white spherical shape and a particle diameter of about 400 μm.
Example 2
In accordance with the synthesis method of example 1, 1-aminopropyl-3-methyl-imidazole nitrate was used in place of 1-aminopropyl-3-methyl-imidazole chloride salt as a reaction monomer to obtain an aminoimidazole-type ionic liquid-supported resin, the functional group density of the aminoimidazole-type ionic liquid being 1.78 mmol/g-ad. The obtained resin had a white spherical shape and a particle diameter of about 400 μm.
Example 3
The static adsorption test procedure of the amino imidazole type ionic liquid supported resin is as follows:
weighing 0.05g of the prepared aminoimidazole type ionic liquid supported resin, putting into 50mL of aqueous solution containing Re at room temperature, adjusting the pH change range to 1-10 by dilute acid diluted alkali, and performing a static adsorption test. The adsorption test was carried out at room temperature under stirring for 24 hours, and then the resin adsorption amount (Qe) was calculated by collecting the clear solution and measuring the Re concentration in the solution by ICP.
The adsorption of Re by the aminoimidazole-type ionic liquid-supported resin of example 1 is influenced by pH as shown in fig. 1. It can be seen that the aminoimidazole ionic liquid supported resin maintains a high adsorption rate in the pH range of 2-10. And the saturated adsorption capacity of the aminoimidazole type ionic liquid supported resin prepared in example 1 is up to 584 mg/g.
Example 4
The dynamic adsorption test steps of the amino imidazole type ionic liquid supported resin are as follows:
the aminoimidazole type ionic liquid supported resin prepared in example 1 was packed in an adsorption column in a wet state, and dynamic adsorption evaluation conditions were as follows: the column volume was 1mL, the amount of resin was 1mL (0.5467g), the concentration of Re in aqueous solution was 25mg/L, the pH was 2, and the flow rate was 0.5mL/min (SV 30).
The dynamic adsorption evaluation test was performed under the above conditions, and the outlet liquid was sampled and analyzed at predetermined time intervals, whereby the adsorption behavior curve of the adsorbent was obtained as shown in fig. 2. The results show that the amino imidazole type ionic liquid supported resin has good adsorption to Re under the dynamic flow state, and starts to penetrate at 2000 BV. When the adsorption saturation is completely reached, 5mol/L HNO is used3The adsorption column is leached, and the elution rate of 90 percent can be realized only by using 40BV of leaching solution.
Example 5
The reusability verification steps of the aminoimidazole ionic liquid supported resin on Re are as follows:
in order to study the reusability of the aminoimidazole type ionic liquid supported resin, 4 adsorption-desorption-adsorption cycles were performed. In each adsorption experiment, 50mg of aminoimidazole type ionic liquid supported resin and 50mL of Re solution with a concentration of 2 at 400mg/L, pH were used for 24h of adsorption time. After the adsorption was completed, 50mL of 1mol/L HNO was added3And placing the mixture in a constant-temperature oscillator, taking out the mixture after 24 hours, and measuring the concentration of Re in the solution. Then washing Re with deionized water for three times to remove HNO adsorbed on the surface3Then, the next adsorption experiment was performed. The experimental result is shown in fig. 3, after four cycles of adsorption-desorption, the adsorption capacity of the aminoimidazole type ionic liquid supported resin to Re hardly changes, indicating that the reusability is good.
Example 6
Separating and enriching low-concentration Re by using aminoimidazole type ionic liquid supported resin:
in order to evaluate the recovery rate of the adsorbent for rhenium at a low concentration, the aminoimidazole-type ionic liquid-supported resin prepared in example 1 was packed in a wet state in an adsorption column, and dynamic adsorption evaluation conditions were as follows: the volume of the adsorption column was 1mL, the amount of the resin was 1mL (0.5467g), and the flow rate was 0.33mL/min (SV 20). The total amount of rhenium in the rhenium solution was kept fixed at 20 micrograms, pH 2, aqueous Re concentrations of 10ppb, 20ppb, and 100ppb, corresponding to rhenium solution volumes of 2000mL, 1000mL, and 200mL, respectively. As shown in Table 1, the aminoimidazole type ionic liquid supported resin has good enrichment capacity for rhenium as low as 10ppb, the recovery rate is as high as 96.58%, and the enrichment rate is as high as 417.5. These results show that the aminoimidazole type ionic liquid supported resin has ultrahigh separation and enrichment capacity for trace rhenium.
TABLE 1 recovery and enrichment factor as a function of sample volume and concentration
Example 7
Separating and enriching trace rhenium from simulated uranium ore leaching liquid by using aminoimidazole type ionic liquid supported resin:
uranium feedstocks having multimetallic properties are another source of rhenium, and reports indicate that the rhenium content of leachates from uranium ores is in the range of 0.1 to 0.8 ppm. Firstly, preparing a simulated uranium ore leaching solution, wherein the pH value of the solution is 2, the rhenium concentration is 0.1ppm, and the uranium concentration is 20 ppm. The simulated liquid is pumped into a 1mL adsorption column at the flow rate of SV45 h-1, and the uranium and rhenium concentrations at the outlet are detected at regular time.
Fig. 4 is a penetration curve of the aminoimidazole type ionic liquid loaded resin for separating and enriching low-concentration rhenium from simulated uranium ore solution. It is clear that the aminoimidazole type ionic liquid loaded resin has a very high Re/U selectivity, uranium breakthrough occurring initially and reaching a maximum, and rhenium breakthrough occurring at 2000BV and reaching saturation adsorption at 6500 BV. When the breakthrough curves were integrated, the saturation adsorption of rhenium was 756.9. mu.g/g.
After complete adsorption, 5mol/L HNO is used3The adsorption column was eluted as an eluent, and as a result, as shown in fig. 5, no uranium was detected in the eluted liquid, and the average concentration of rhenium in 30mL of the eluted liquid was 12.085ppm, which is 120 times the inlet concentration. The experimental result also proves the high selectivity separation and enrichment capacity of the aminoimidazole type ionic liquid loaded resin to rhenium.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The application of the aminoimidazole type ionic liquid loaded resin in adsorption separation of rhenium or technetium is characterized in that the aminoimidazole type ionic liquid loaded resin is obtained by fixing the aminoimidazole type ionic liquid on the surface of a resin substrate, a solution containing rhenium or technetium is treated by the aminoimidazole type ionic liquid loaded resin, and the rhenium or technetium in the solution is separated by ion exchange adsorption.
2. Use according to claim 1, wherein the aminoimidazole-type ionic liquid supported resin is obtained by: grafting a monomer containing an epoxy group onto the surface of a resin substrate, and then further introducing the aminoimidazole type ionic liquid onto the surface of the resin substrate through epoxy ring opening to obtain the aminoimidazole type ionic liquid loaded resin.
3. The use according to claim 2, wherein the preparation method of the aminoimidazole-type ionic liquid supported resin specifically comprises the following steps:
(1) carrying out surface modification on the resin substrate, and introducing an unsaturated monomer containing an epoxy group to prepare an adsorption material precursor;
(2) leading the adsorbing material precursor obtained in the step (1) and the aminoimidazole type ionic liquid to perform epoxy ring-opening reaction, and introducing the aminoimidazole type ionic liquid component; and washing the adsorption material obtained after the reaction with a solvent, and drying to obtain the aminoimidazole type ionic liquid loaded resin material.
4. Use according to claim 3, wherein the aminoimidazole-type ionic liquid has the following general structure:
wherein n is an integer of 1-8, and X is Cl, Br, NO3、BF4、NTf2Or PF6。
5. The use according to claim 3, wherein the unsaturated monomer containing an epoxy group is one of glycidyl methacrylate and hydroxybutyl glycidyl acrylate monomers.
6. The use according to claim 3, wherein the aminoimidazole-type ionic liquid is present in a concentration of 5 to 80 wt.% when the epoxy group ring opening reaction is carried out; the solvent is water, ethanol or DMSO, and the reaction temperature is controlled at 40-85 ℃; the functional group density of the aminoimidazole type ionic liquid is 0.1mmol/g-5 mmol/g.
7. The use according to claim 1, wherein the particle size of the aminoimidazole-type ionic liquid supported resin is between 50 and 1000 μm.
8. The use as claimed in claim 1, wherein the solution containing rhenium or technetium has a pH of 1 to 11, wherein rhenium is in said solution as ReO4 -In anionic form, technetium being present in said solution as TcO4 -The anionic form exists.
9. The use of claim 1, wherein the solution containing rhenium is a leaching solution containing rhenium associated uranium ore or an ore treatment tail solution containing rhenium associated uranium ore; and adjusting the pH value of the ground immersion liquid or the tail liquid to be in the range of 2-3, and enabling the ground immersion liquid or the tail liquid to pass through an adsorption column filled with the aminoimidazole type ionic liquid loading resin to realize selective adsorption separation of trace rhenium in the ground immersion liquid or the tail liquid.
10. The use according to claim 1, wherein, after adsorption, rhenium or technetium loaded on the resin is eluted and separated with an eluent to regenerate the resin.
Priority Applications (1)
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