CN117797761A - A kind of quaternary phosphonium carbon nanotube material for adsorbing and separating the nuclide Re/Tc and its preparation method and application - Google Patents

A kind of quaternary phosphonium carbon nanotube material for adsorbing and separating the nuclide Re/Tc and its preparation method and application Download PDF

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CN117797761A
CN117797761A CN202211166233.XA CN202211166233A CN117797761A CN 117797761 A CN117797761 A CN 117797761A CN 202211166233 A CN202211166233 A CN 202211166233A CN 117797761 A CN117797761 A CN 117797761A
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贾娜
周霞
胡孝强
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Shanghai Atom Kexing Pharmaceuticals Co ltd
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Abstract

The invention relates to a quaternary phosphonium carbon nanotube material for adsorbing and separating nuclide Re/Tc, and a preparation method and application thereof, wherein the material is prepared by adopting the following method: and dispersing the acidified carbon nano tube and the 4-vinyl phenyl triphenyl phosphonium chloride in an ethanol or acetone solution to obtain an acidified carbon nano tube solution, irradiating the acidified carbon nano tube solution with high-energy rays under an inert atmosphere to obtain a quaternary phosphonium acidified carbon nano tube solution, and filtering and drying the quaternary phosphonium acidified carbon nano tube solution to obtain the target product. The quaternary phosphonium carbon nanotube material is used for adsorbing and removing nuclide Re/Tc in radioactive wastewater. Compared with the prior art, the quaternary phosphonium carbon nano tube material of the inventionHas good ReO 4 ‑ The preparation method has good adsorption separation performance and good ion selectivity, adopts the irradiation grafting technology to prepare the quaternary phosphonium carbon nanotube material, does not introduce other impurity elements, is convenient for the separation, purification, analysis and characterization of subsequent products, and has simple preparation process and hopeful realization of industrialized application.

Description

Quaternary phosphonium carbon nanotube material for adsorbing and separating nuclide Re/Tc, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of radioactive wastewater treatment, and relates to a quaternary phosphonium carbon nanotube material for adsorbing and separating nuclide Re/Tc, and a preparation method and application thereof.
Background
Rhenium (Re) is one of the rarest elements in the crust, with a mass concentration of only 1. Mu.g/L. Re and Re alloy materials have important roles in the modern high and new technical fields of national defense, aerospace, nuclear energy, electronics, missile, petrochemical industry and the like due to the excellent performance. Technetium (Tc), the most important isotope of which is similar to Re in chemical nature 99 Tc is generated by 235U fission, has a longer half-life and a higher fission yield, and affects separation of uranium (U), plutonium (Pu) and other elements in the PUREX (PUREX) process. Tc is mainly based on 99 TcO 4 - Because Tc is free of stable isotopes, it is common in the laboratory to use 99 TcO 4 - ReO of similar properties 4 - Simulation 99 Adsorption of Tc. Thus, research into extraction of ReO from aqueous solutions 4 - Has important significance for Re/Tc recovery and environmental protection. The adsorption method is a method for recycling Re and Tc with great development prospect. There are many reports on Re/Tc adsorbents, but these generally exhibit slower adsorption kinetics, smaller adsorption capacity and poorer selectivity.
Disclosure of Invention
The invention aims to provide a quaternary phosphonium carbon nanotube material for adsorbing and separating nuclide Re/Tc, and a preparation method and application thereof, so as to overcome the defects of insufficient adsorption and separation performance or poor ion selectivity of Re/Tc adsorbents in the prior art.
The aim of the invention can be achieved by the following technical scheme:
one of the technical schemes of the invention provides a preparation method of a quaternary phosphonium carbon nanotube material for adsorbing and separating nuclide Re/Tc, which comprises the following steps:
and dispersing the acidified carbon nano tube and the 4-vinyl phenyl triphenyl phosphonium chloride in an ethanol or acetone solution to obtain an acidified carbon nano tube solution, irradiating the acidified carbon nano tube solution with high-energy rays under an inert atmosphere to obtain a quaternary phosphonium acidified carbon nano tube solution, and filtering and drying the quaternary phosphonium acidified carbon nano tube solution to obtain the target product.
Further, the acidified carbon nanotube is one or two of an acidified multi-wall carbon nanotube and an acidified single-wall carbon nanotube.
Further, the preparation process of the acidified carbon nanotube specifically comprises the following steps:
soaking the carbon nano tube in sulfuric acid or nitric acid for a period of time, and then filtering, washing and drying to obtain the acidified carbon nano tube.
Further, the concentration of sulfuric acid or nitric acid may be a concentration conventional in the art, with a concentration of 1 to 4mol/L.
Further, the soaking temperature is 50-95 ℃ and the soaking time is 1-24h.
Further, the mass ratio of the acidified carbon nano tube to the 4-vinyl phenyl triphenyl phosphonium chloride is 1: (6-300), wherein the concentration of the acidified carbon nano tube in the obtained acidified carbon nano tube solution is 1-10mg/ml.
Further, the radiation is gamma radiation or electron beam.
Further, the irradiation dose is 20-200 kGy, optionally 50-100 kGy.
Further, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.
Further, the filtering process is as follows:
and performing ultrasonic dispersion on the quaternary phosphonium acidified carbon nanotube solution, and then performing vacuum suction filtration on the stable dispersion quaternary phosphonium acidified carbon nanotube solution on the PVDF microporous filter membrane.
The second technical scheme of the invention provides a quaternary phosphonium carbon nanotube material for adsorbing and separating nuclide Re/Tc, and the quaternary phosphonium carbon nanotube material is prepared by adopting the preparation method.
The third technical scheme of the invention provides application of the quaternary phosphonium carbon nanotube material, and the quaternary phosphonium carbon nanotube material is used for adsorbing and removing nuclide Re/Tc in radioactive wastewater.
Compared with the base materials such as ion exchange resin, biological adsorbent, MOFs and COFs, the carbon nano tube has excellent chemical stability, thermal stability and mechanical property, and is more stable under extreme environments such as high acidity, high temperature and radioactivity.
The acidified carbon nanotube has a very stable tubular nanostructure, and the surface is rich in a large number of active groups such as hydroxyl groups, epoxy groups, carboxyl groups and the like. The super large specific surface area and the one-dimensional nano structure of the acidified carbon nano tube determine that the oxygen-containing groups enriched on the surface of the acidified carbon nano tube determine that the acidified carbon nano tube can be uniformly dispersed in a polar solvent, so that the acidified carbon nano tube has great potential and application prospect in the field of separation materials.
The invention provides a preparation method of a quaternary phosphonium carbon nanotube material for removing nuclide Re/Tc in radioactive wastewater, which solves the problem that the rejection rate of an ultrafiltration membrane to Re/Tc is reduced due to less complexing sites under the conditions of PH, ion concentration and the like.
The invention grafts 4-vinyl phenyl triphenyl phosphonium onto acidified carbon nano tube under inert atmosphere by radiation grafting method.
According to the invention, the carbon nano tube subjected to acidification treatment is used for irradiation grafting, so that the grafting reaction site of the carbon nano tube can be improved, the grafting rate is improved, and the unsaturated double bond of the 4-vinyl phenyl triphenyl phosphonium chloride can be used for irradiation grafting polymerization in the radiation irradiation process. The introduction of inert atmosphere is beneficial to the full reaction of free radicals induced by radiation irradiation, so that the irradiation dosage is reduced, and the cost is reduced.
The invention limits the technological conditions in the preparation process of the acidified carbon nano tube, such as the acid soaking temperature and the soaking time, and realizes the controllable acidification of the carbon nano tube by controlling the proportion, thereby realizing the aim of introducing hydrophilic functional groups such as carboxyl and the like into the surface of the carbon nano tube, and not excessively acidifying to etch the carbon nano tube to damage the original basic performance and structure, thereby reducing the cost and realizing the preparation of the acidified carbon nano tube of the target product.
Compared with the prior art, the invention has the following advantages:
(1) The invention introduces quaternary phosphonium salt and uses certain hydrophobicity thereofRealize the selective adsorption separation of the ReO with stronger hydrophobicity 4 - Repelling hydrophilic NO 3 - 、Cl - 、CO 3 2- And PO (PO) 4 3- ，SO 4 2- The quaternary phosphonium salt can be matched with metal ions to generate strong complexing reaction to generate macromolecular complex, thereby being capable of effectively adsorbing and separating ReO 4 - Solves the problem that the radioactive wastewater has fewer complexing sites under the condition of PH, ion concentration and the like to cause the reaction of ReO 4 - The adsorption separation rate is low; therefore, the quaternary phosphonium carbon nano tube material has good ReO 4 - The adsorption separation performance has good ion selectivity and cycle stability.
(2) The invention selects the carbon nano tube material with large specific surface area, acidizes the carbon nano tube, and improves the grafting rate of 4-vinyl phenyl triphenyl phosphonium chloride by means of the carboxyl functional group on the surface of the acidized carbon nano tube, thereby improving the ReO of the material 4 - Ion adsorption sites for adsorbing ReO by acidifying carboxyl, quaternary phosphonium salt and other multifunctional groups contained in the carbon nanotube material in radioactive aqueous solution 4 - Ions; acidizing the carbon nano tube also improves the hydrophilicity of the carbon nano tube.
(3) The invention adopts the irradiation grafting technology to prepare the quaternary phosphonium carbon nanotube material, does not introduce other impurity elements, and is convenient for the separation, purification, analysis and characterization of subsequent products.
(4) The raw material carbon nanotube for preparing the quaternary phosphonium carbon nanotube material has wide sources and simple preparation process, and is expected to realize industrial application.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the following examples, unless otherwise specified, the raw materials or processing techniques are indicated as being conventional commercially available raw material products or conventional processing techniques in the art.
In the following examples, the carbon nanotubes used were supplied from Shenzhen nanoport Inc., and the remaining raw materials were supplied from the national pharmaceutical systems chemical Co., ltd.
In the examples which follow, the pore size of the PVDF microporous filter used is 0.5. Mu.m.
Example 1:
soaking single-wall carbon nanotube with diameter of 1-3nm and length of 10-20 μm in sulfuric acid solution of 4mol/L at 50deg.C for 24 hr, filtering, washing and drying to obtain acidified carbon nanotube.
Mixing the acidified carbon nano tube and 4-vinyl phenyl triphenyl phosphonium chloride in an ethanol solution according to a mass ratio of 1:300, magnetically stirring to form a homogeneous and stable acidified carbon nano tube solution with the concentration of 1mg/ml of the acidified carbon nano tube, and finally grafting the 4-vinyl phenyl triphenyl phosphonium to the acidified carbon nano tube under the irradiation of gamma rays of 200kGy in a nitrogen atmosphere by a radiation grafting method to prepare the quaternary phosphonium acidified carbon nano tube solution.
Vacuum filtering the prepared quaternary phosphonium acidified carbon nanotube solution on a PVDF microporous filter membrane, washing for 5-10 times, drying to obtain a quaternary phosphonium carbon nanotube composite microporous filter membrane, and separating the quaternary phosphonium carbon nanotube from the PVDF microporous filter membrane to obtain the quaternary phosphonium carbon nanotube material.
To test the quaternary phosphonium carbon nanotube material pair ReO 4 - 10mg of the prepared quaternary phosphonium carbon nanotube material was charged with 100ml of 0.1mol/L NaReO 4 At the same time, 0.1mol/L NaNO is added in the solution 3 、NaCl，Na 2 CO 3 And Na (Na) 3 PO 4 ，Na 2 SO 4 The sodium salt interfering ions are adsorbed for a certain time by magnetic stirring to obtain the quaternary phosphonium carbon nano tube material to ReO 4 - Is contained in the adsorbent composition. The results are shown in Table 1.
Example 2:
immersing multi-wall carbon nano tube with the tube diameter of 10-20nm and the length of less than 2 mu m and single-wall carbon nano tube with the tube diameter of 1-3nm and the length of 5-10 mu m (the mass ratio of the multi-wall carbon nano tube to the single-wall carbon nano tube is 1:1) in sulfuric acid solution with the concentration of 2mol/L for 8h at 70 ℃, and filtering, washing and drying to obtain the acidified carbon nano tube. Mixing the acidified carbon nano tube and 4-vinyl phenyl triphenyl phosphonium chloride in an ethanol solution according to the mass ratio of 1:100, magnetically stirring to form a homogeneous and stable acidified carbon nano tube solution with the concentration of 5mg/ml of the acidified carbon nano tube, and finally grafting the 4-vinyl phenyl triphenyl phosphonium to the acidified carbon nano tube under the irradiation of gamma rays of 100kGy by a radiation grafting method to prepare the quaternary phosphonium acidified carbon nano tube solution.
Vacuum filtering the prepared quaternary phosphonium acidified carbon nanotube solution on a polyvinylidene fluoride microporous filter membrane, washing for 5-10 times, drying to obtain a quaternary phosphonium carbon nanotube composite microporous filter membrane, and separating the quaternary phosphonium carbon nanotubes from the PVDF microporous filter membrane to obtain the quaternary phosphonium carbon nanotube material.
To test the quaternary phosphonium carbon nanotube material pair ReO 4 - 10mg of the prepared quaternary phosphonium carbon nanotube material was charged with 100ml of 0.1mol/L NaReO 4 At the same time, 0.1mol/L NO is added in the solution 3 - 、Cl - ，CO 3 2- And PO (PO) 4 3- ，SO 4 2- The sodium salt interfering ions are adsorbed for a certain time by magnetic stirring to obtain the quaternary phosphonium carbon nano tube material to ReO 4 - Is contained in the adsorbent composition. The results are shown in Table 1.
Example 3:
the preparation method comprises the steps of soaking a multi-wall carbon nano tube with the tube diameter of 40-60nm and the length of 2-5 mu m and a single-wall carbon nano tube with the tube diameter of 1-3 nanometers and the length of 5-15 mu m (the mass ratio of the multi-wall carbon nano tube to the single-wall carbon nano tube is 9:1) in a sulfuric acid solution with the temperature of 95 ℃ for 1h, and filtering, washing and drying to obtain the acidified carbon nano tube. Mixing the acidified carbon nano tube and 4-vinyl phenyl triphenyl phosphonium chloride in an ethanol solution according to a mass ratio of 1:6, magnetically stirring to form a homogeneous and stable acidified carbon nano tube solution with the concentration of 10mg/ml of the acidified carbon nano tube, and finally grafting the 4-vinyl phenyl triphenyl phosphonium to the acidified carbon nano tube under the irradiation of gamma rays of 20kGy in a nitrogen atmosphere by a radiation grafting method to prepare the quaternary phosphonium acidified carbon nano tube solution.
Vacuum filtering the prepared quaternary phosphonium acidified carbon nanotube solution on a PVDF microporous filter membrane, washing for 5-10 times, drying to obtain a quaternary phosphonium carbon nanotube composite microporous filter membrane, and separating the quaternary phosphonium carbon nanotube from the PVDF microporous filter membrane to obtain the quaternary phosphonium carbon nanotube material.
To test the quaternary phosphonium carbon nanotube material pair ReO 4 - 10mg of the prepared quaternary phosphonium carbon nanotube material was charged with 100ml of 0.1mol/L NaReO 4 At the same time, 0.1mol/L NO is added in the solution 3 - 、Cl - ，CO 3 2- And PO (PO) 4 3- ，SO 4 2- The sodium salt interfering ions are adsorbed for a certain time by magnetic stirring to obtain the quaternary phosphonium carbon nano tube material to ReO 4 - Is contained in the adsorbent composition. The results are shown in Table 1.
Example 4:
soaking single-wall carbon nanotube with pipe diameter of 60-100nm and length of 5-15 μm in sulfuric acid solution of 3mol/L at 60 deg.c for 12 hr, filtering, washing and drying to obtain acidified carbon nanotube. Mixing the acidified carbon nano tube and 4-vinyl phenyl triphenyl phosphonium chloride in an ethanol solution according to a mass ratio of 1:50, magnetically stirring to form a homogeneous and stable acidified carbon nano tube solution with the concentration of 3mg/ml of the acidified carbon nano tube, and finally grafting the 4-vinyl phenyl triphenyl phosphonium to the acidified carbon nano tube under the irradiation of 50kGy gamma rays in a nitrogen atmosphere by a radiation grafting method to prepare the quaternary phosphonium acidified carbon nano tube solution.
Vacuum filtering the prepared quaternary phosphonium acidified carbon nanotube solution on a PVDF microporous filter membrane, washing for 5-10 times, drying to obtain a quaternary phosphonium carbon nanotube composite microporous filter membrane, and separating the quaternary phosphonium carbon nanotube from the PVDF microporous filter membrane to obtain the quaternary phosphonium carbon nanotube material.
To test the quaternary phosphonium carbon nanotube material pair ReO 4 - 10mg of the prepared quaternary phosphonium carbon nanotube material,100ml of NaReO at 0.1mol/L was introduced 4 At the same time, 0.1mol/L NO is added in the solution 3 - 、Cl - ，CO 3 2- And PO (PO) 4 3- ，SO 4 2- The sodium salt interfering ions are adsorbed for a certain time by magnetic stirring to obtain the quaternary phosphonium carbon nano tube material to ReO 4 - Is contained in the adsorbent composition. The results are shown in Table 1.
Example 5:
and soaking single-wall carbon nanotubes with the pipe diameter of 1-3nm and the pipe diameter of 5-15 mu m and multi-wall carbon nanotubes with the pipe diameter of 10-20nm and the length of less than 2 mu m (the mass ratio of the multi-wall carbon nanotubes to the single-wall carbon nanotubes is 1:9) in 2mol/L sulfuric acid solution at 70 ℃ for 12 hours, and filtering, washing and drying to obtain the acidified carbon nanotubes. Mixing the acidified carbon nano tube and 4-vinyl phenyl triphenyl phosphonium chloride in an ethanol solution according to a mass ratio of 1:20, magnetically stirring to form a homogeneous and stable acidified carbon nano tube solution with the concentration of 10mg/ml of the acidified carbon nano tube, and finally grafting the 4-vinyl phenyl triphenyl phosphonium to the acidified carbon nano tube under the irradiation of gamma rays of 100kGy in a nitrogen atmosphere by a radiation grafting method to prepare the quaternary phosphonium acidified carbon nano tube solution.
Vacuum filtering the prepared quaternary phosphonium acidified carbon nanotube solution on a PVDF microporous filter membrane, washing for 5-10 times, drying to obtain a quaternary phosphonium carbon nanotube composite microporous filter membrane, and separating the quaternary phosphonium carbon nanotube from the PVDF microporous filter membrane to obtain the quaternary phosphonium carbon nanotube material.
To test the quaternary phosphonium carbon nanotube material pair ReO 4 - 10mg of the prepared quaternary phosphonium carbon nanotube material was charged with 100ml of 0.1mol/L NaReO 4 At the same time, 0.1mol/L NO is added in the solution 3 - 、Cl - ，CO 3 2- And PO (PO) 4 3- ，SO 4 2- The sodium salt interfering ions are adsorbed for a certain time by magnetic stirring to obtain the quaternary phosphonium carbon nano tube material to ReO 4 - Is contained in the adsorbent composition. The results are shown in Table 1.
Example 6:
soaking single-wall carbon nanotube with diameter of 1-3nm and length of 10-20 μm in 4mol/L nitric acid solution at 50deg.C for 1 hr, filtering, washing and drying to obtain acidified carbon nanotube. Mixing the acidified carbon nano tube and 4-vinyl phenyl triphenyl phosphonium chloride in an ethanol solution according to a mass ratio of 1:6, magnetically stirring to form a homogeneous and stable acidified carbon nano tube solution with the concentration of 1mg/ml of the acidified carbon nano tube, and finally grafting the 4-vinyl phenyl triphenyl phosphonium to the acidified carbon nano tube under the irradiation of 200kGy of electron beam in an argon atmosphere by a radiation grafting method to prepare the quaternary phosphonium acidified carbon nano tube solution.
Vacuum filtering the prepared quaternary phosphonium acidified carbon nanotube solution on a PVDF microporous filter membrane, washing for 5-10 times, drying to obtain a quaternary phosphonium carbon nanotube composite microporous filter membrane, and separating the quaternary phosphonium carbon nanotube from the PVDF microporous filter membrane to obtain the quaternary phosphonium carbon nanotube material.
To test the quaternary phosphonium carbon nanotube material pair ReO 4 - 10mg of the prepared quaternary phosphonium carbon nanotube material was charged with 100ml of 0.1mol/L NaReO 4 At the same time, 0.1mol/L NO is added in the solution 3 - 、Cl - ，CO 3 2- And PO (PO) 4 3- ，SO 4 2- The sodium salt interfering ions are adsorbed for a certain time by magnetic stirring to obtain the quaternary phosphonium carbon nano tube material to ReO 4 - Is contained in the adsorbent composition. The results are shown in Table 1.
Comparative example 1:
in comparison with example 1, the same procedure was carried out for the most part, except that in this comparative example, 4-vinylphenyl triphenylphosphonium chloride was not added to the irradiation grafting process.
To test carbon nanotube material pair ReO 4 - 10mg of the prepared carbon nanotube material was charged with 100ml of 0.1mol/L NaReO 4 At the same time, 0.1mol/L NO is added in the solution 3 - 、 Cl - ，CO 3 2- And PO (PO) 4 3- ，SO 4 2- Iso sodium salt dryDisturbing ions, magnetically stirring and adsorbing for a certain time to obtain carbon nanotube material pair ReO 4 - Is contained in the adsorbent composition. The results are shown in Table 1. Comparative example 1, 4-vinylphenyl triphenylphosphonium chloride was not introduced, i.e., reO having selective absorption was not introduced 4 - Functional group of (2), thus for ReO 4 - The adsorption performance of the catalyst is obviously reduced, and the grafting of 4-vinyl phenyl triphenyl phosphonium chloride greatly improves the ReO of the carbon nano tube material 4 - Is used for the adsorption performance of the catalyst.
Comparative example 2:
all experimental procedures were the same as in example 1, except that the carbon nanotubes were not acidified. Mixing single-wall carbon nano tubes with the tube diameter of 1-3nm and the length of 10-20 mu m with 4-vinylphenyl triphenyl phosphonium chloride in ethanol solution according to the mass ratio of 1:300, magnetically stirring to form homogeneous and stable acidified carbon nano tube solution with the concentration of 1mg/ml, and finally grafting the 4-vinylphenyl triphenyl phosphonium to the acidified carbon nano tubes under the irradiation of 200kGy gamma rays in nitrogen atmosphere by a radiation grafting method to prepare the quaternary phosphonium carbon nano tube solution.
Vacuum filtering the prepared quaternary phosphonium acidified carbon nanotube solution on a PVDF microporous filter membrane, washing for 5-10 times, drying to obtain a quaternary phosphonium carbon nanotube composite microporous filter membrane, and separating the quaternary phosphonium carbon nanotube from the PVDF microporous filter membrane to obtain the quaternary phosphonium carbon nanotube material.
Adding 0.1mol/L NaReO into the prepared quaternary phosphonium carbon nanotube material 4 At the same time, 0.1mol/L NO is added in the solution 3 - 、Cl - ，CO 3 2- And PO (PO) 4 3- ，SO 4 2- The sodium salt interfering ions are adsorbed for a certain time by magnetic stirring to obtain the quaternary phosphonium carbon nano tube material to ReO 4 - Is used as a catalyst. Grafting ratio of carbon nanotubes and ReO 4 - The adsorption separation results are shown in the attached table 1. Comparative example 1 shows that the grafting ratio is significantly reduced with carbon nanotubes without acidification, thus for ReO 4 - Is of the adsorption of (a)Can obviously reduce the number of the carbon nanotubes, and greatly improves the ReO 4 - Is used for the adsorption performance of the catalyst.
TABLE 1 grafting ratio of carbon nanotubes and ReO for the same 4 - Maximum adsorption capacity of (2)
As is clear from Table 1, the retention rate of the maximum adsorption capacity of the quaternary phosphonium carbon nanotube material of examples 1 to 6, which was circulated 20 times, was not less than 94%, for ReO in the mixed solution 4 - The selective absorption ratio of (C) is not less than 97%. As can be seen, the quaternary phosphonium carbon nanotube material of the invention has good ReO 4- The adsorption separation performance has good ion selectivity and cycle stability.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.

Claims (10)

1.一种吸附分离核素Re/Tc的季鏻化碳纳米管材料的制备方法，其特征在于，该方法包括以下步骤：1. A method for preparing a quaternary phosphonium carbon nanotube material that adsorbs and separates the nuclide Re/Tc, characterized in that the method includes the following steps: 取酸化碳纳米管和氯化4-乙烯基苯基三苯基鏻分散于乙醇或丙酮溶液中，得到酸化碳纳米管溶液，然后在惰性气氛下使用高能射线辐照酸化碳纳米管溶液，得到季鏻化酸化碳纳米管溶液，然后将季鏻化酸化碳纳米管溶液过滤、干燥，即得目的产物。Disperse acidified carbon nanotubes and 4-vinylphenyltriphenylphosphonium chloride in an ethanol or acetone solution to obtain an acidified carbon nanotube solution, and then irradiate the acidified carbon nanotube solution with high-energy rays in an inert atmosphere to obtain Quaternary phosphonium acidified carbon nanotube solution is then filtered and dried to obtain the target product. 2.根据权利要求1所述的一种吸附分离核素Re/Tc的季鏻化碳纳米管材料的制备方法，其特征在于，所述的酸化碳纳米管为酸化多壁碳纳米管或酸化单壁碳纳米管中的一种或两种。2. The method for preparing a quaternary phosphonium carbon nanotube material for adsorbing and separating nuclides Re/Tc according to claim 1, characterized in that the acidified carbon nanotubes are one or both of acidified multi-walled carbon nanotubes and acidified single-walled carbon nanotubes. 3.根据权利要求1所述的一种吸附分离核素Re/Tc的季鏻化碳纳米管材料的制备方法，其特征在于，所述酸化碳纳米管的制备过程具体为：3. A method for preparing a quaternized carbon nanotube material that adsorbs and separates nuclide Re/Tc according to claim 1, characterized in that the preparation process of the acidified carbon nanotube is specifically: 取碳纳米管浸泡于硫酸或硝酸中，浸泡一段时间，然后经过滤、洗涤、干燥得到所述酸化碳纳米管。The carbon nanotubes are soaked in sulfuric acid or nitric acid for a period of time, and then filtered, washed, and dried to obtain the acidified carbon nanotubes. 4.根据权利要求3所述的一种吸附分离核素Re/Tc的季鏻化碳纳米管材料的制备方法，其特征在于，浸泡温度为50-95℃，浸泡时间为1-24h。4. The method for preparing a quaternary phosphonium carbon nanotube material for adsorbing and separating nuclides Re/Tc according to claim 3, characterized in that the immersion temperature is 50-95°C and the immersion time is 1-24h. 5.根据权利要求1所述的一种吸附分离核素Re/Tc的季鏻化碳纳米管材料的制备方法，其特征在于，所述酸化碳纳米管和氯化4-乙烯基苯基三苯基鏻的质量比为1：(6～300)，所得酸化碳纳米管溶液中酸化碳纳米管的浓度为1-10mg/ml。5. A method for preparing a quaternized carbon nanotube material that adsorbs and separates nuclide Re/Tc according to claim 1, characterized in that the acidified carbon nanotube and 4-vinylphenyl trichloride are The mass ratio of phenylphosphonium is 1: (6-300), and the concentration of acidified carbon nanotubes in the obtained acidified carbon nanotube solution is 1-10 mg/ml. 6.根据权利要求1所述的一种吸附分离核素Re/Tc的季鏻化碳纳米管材料的制备方法，其特征在于，所述射线为γ射线或电子束。6. A method for preparing a quaternary phosphonium carbon nanotube material for adsorbing and separating nuclides Re/Tc according to claim 1, characterized in that the rays are γ rays or electron beams. 7.根据权利要求1所述的一种吸附分离核素Re/Tc的季鏻化碳纳米管材料的制备方法，其特征在于，辐照剂量为20～200kGy。7. A method for preparing a quaternary phosphonium carbon nanotube material for adsorbing and separating nuclides Re/Tc according to claim 1, characterized in that the irradiation dose is 20 to 200 kGy. 8.根据权利要求1所述的一种吸附分离核素Re/Tc的季鏻化碳纳米管材料的制备方法，其特征在于，惰性气氛为氮气气氛或氩气气氛。8. A method for preparing a quaternary phosphonium carbon nanotube material for adsorbing and separating nuclides Re/Tc according to claim 1, characterized in that the inert atmosphere is a nitrogen atmosphere or an argon atmosphere. 9.一种吸附分离核素Re/Tc的季鏻化碳纳米管材料，其特征在于，该季鏻化碳纳米管材料采用如权利要求1-8任一所述的制备方法制备得到。9. A quaternary phosphonium carbon nanotube material for adsorbing and separating the nuclide Re/Tc, characterized in that the quaternary phosphonium carbon nanotube material is prepared by the preparation method as described in any one of claims 1-8. 10.如权利要求9所述的一种吸附分离核素Re/Tc的季鏻化碳纳米管材料的应用，其特征在于，该季鏻化碳纳米管材料用于吸附去除放射性废水中的核素Re/Tc。10. The application of a quaternary phosphonium carbon nanotube material for adsorbing and separating nuclide Re/Tc as claimed in claim 9, characterized in that the quaternary phosphonium carbon nanotube material is used to adsorb and remove nuclei in radioactive wastewater. Element Re/Tc.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090093664A1 (en) * 2007-10-09 2009-04-09 Chemnano Materials, Ltd. Carbon nanotubes using for recovery of radionuclides and separation of actinides and lanthanides
FR2945756A1 (en) * 2009-05-20 2010-11-26 Commissariat Energie Atomique NANOCOMPOSITE SOLID MATERIAL BASED ON HEXA AND OCTACYANOMETALLATES, PROCESS FOR PREPARING THE SAME AND METHOD FOR FIXING MINERAL POLLUTANTS USING THE SAME
CN106118198A (en) * 2016-07-06 2016-11-16 西南交通大学 The preparation method of carbon nano tube surface quaternized antibacterial in situ
CN112403439A (en) * 2020-10-11 2021-02-26 兰州大学 Uranium separation material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090093664A1 (en) * 2007-10-09 2009-04-09 Chemnano Materials, Ltd. Carbon nanotubes using for recovery of radionuclides and separation of actinides and lanthanides
FR2945756A1 (en) * 2009-05-20 2010-11-26 Commissariat Energie Atomique NANOCOMPOSITE SOLID MATERIAL BASED ON HEXA AND OCTACYANOMETALLATES, PROCESS FOR PREPARING THE SAME AND METHOD FOR FIXING MINERAL POLLUTANTS USING THE SAME
CN106118198A (en) * 2016-07-06 2016-11-16 西南交通大学 The preparation method of carbon nano tube surface quaternized antibacterial in situ
CN112403439A (en) * 2020-10-11 2021-02-26 兰州大学 Uranium separation material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SHOUCHAO ZHONG ET AL.: "Radiation Syntheses and Performance of Novel Hierarchically Macro-/Mesoporous Silica Adsorbents with Quaternary Phosphonium for the High Selective Removal of Perrhenate", 《ACS SUSTAINABLE CHEM. ENG.》, vol. 9, no. 21, 19 May 2021 (2021-05-19), pages 7379 - 7389 *

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