Photo-thermal enhanced uranium adsorption material and preparation method thereof
By introducing amylopectin groups and polypyrrole derivatives onto natural fiber fabrics and combining them with photothermal conversion functions, the problems of low uranium adsorption efficiency and high cost of traditional AO-based adsorption materials in seawater have been solved, achieving efficient uranium adsorption and cost reduction.
Patent Information
- Application Number
- CN202510964743.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-14
- Publication Date
- 2025-12-05
AI Technical Summary
In existing technologies, the uranium adsorption kinetics of traditional AO-based adsorbent materials in seawater are limited by thermodynamic equilibrium, resulting in low adsorption capacity and high production costs, making it difficult to achieve engineering applications.
By using irradiation grafting, a methylamine oxime group and in-situ grown polypyrrole derivatives are introduced onto natural fiber fabrics. Combined with photothermal conversion function, a high-temperature microenvironment is constructed to accelerate the mass transfer and diffusion of UO22+ and improve adsorption efficiency.
By increasing the adsorption interface temperature through the photothermal effect, the adsorption equilibrium time can be shortened, the uranium adsorption efficiency can be enhanced, and the preparation cost can be reduced, laying the foundation for engineering applications.
Smart Images
Figure CN121060481A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to a photo-thermal enhanced uranium adsorption material and a preparation method thereof. BACKGROUND
[0002] Nuclear energy, as a core pillar of low-carbon energy system, its development is highly dependent on the stable supply of uranium resources. The ocean contains about 4.5 billion tons of uranium resources, which is more than 1000 times of the land reserves. However, uranium extraction from seawater faces technical challenges such as extremely low concentration of uranium in seawater (only 3.3 ppb), and serious coexisting ion interference (such as Na + The concentration is as high as 1.1 x 10 4 ppm). Although the traditional AO-based adsorption material (such as amidoxime polymer fiber) has high selectivity (distribution coefficient K d >10 5 mL / g) for UO22+, its adsorption kinetics is limited by thermodynamic equilibrium, and the adsorption capacity in natural seawater is usually less than 6 mg / g. More importantly, the complex three-dimensional pore-forming process leads to the production cost of the adsorption material as high as $120-150 / kg, which seriously restricts its engineering application.
[0003] Therefore, how to effectively improve the uranium extraction performance and efficiency of the AO-based adsorption material, while reducing the preparation cost of the adsorption material, is an important challenge for the engineering application of uranium extraction technology from seawater. SUMMARY
[0004] The purpose of the present application is to provide a uranium adsorption material with good uranium extraction performance and efficiency, and another purpose of the present application is to provide a preparation method of a uranium adsorption material with low preparation cost.
[0005] The uranium adsorption material according to the present application uses natural fiber fabric as a carrier, and has grafted amidoxime groups and in-situ grown polypyrrole derivatives on the carrier.
[0006] In the fabric, the loading amount of the amidoxime groups (relative to the mass of the fabric) is 8.2% to 8.5%, and the loading amount of the polypyrrole derivatives is 7.5 to 8.4%.
[0007] The preparation method of the above-mentioned uranium adsorption material comprises the following steps:
[0008] (1) Irradiation grafting: placing the natural fiber fabric in a monomer solution containing cyano groups, and performing irradiation grafting treatment by using a cobalt source or an electron beam to obtain a fabric grafted with cyano groups;
[0009] (2) Amidoximation: treating the fabric grafted with cyano groups by amidoximation to obtain an AO fabric;
[0010] (3) Chemical dyeing: the AO-treated fabric is immersed in an acidic finishing solution containing an aldehyde group-containing pyrrole derivative to perform a chemical dyeing reaction, thereby preparing a light-heat enhanced uranium adsorption material using the fabric as a carrier.
[0011] In step (1), the natural fiber fabric is one or more of cotton fabric, wool fabric, silk fabric or hemp fabric.
[0012] The natural fiber fabric material has an ordered and regular weaving structure, which can endow the material with rich porosity, large specific surface area and good mechanical stability, which helps to realize efficient material exchange in seawater environment; meanwhile, the abundant functional groups in the fabric can provide good hydrophilicity and reactivity.
[0013] In step (1), the cyano-containing monomer solution is obtained by dissolving cyano-containing vinyl monomers in water or an organic solvent; the vinyl monomer is one or more of acrylonitrile, 3-butene nitrile, acetic acid-1-cyanovinyl ester or 2-tricyanoethenyl anthracene; the organic solvent is one or more of ethanol, methanol, propanol, acetone, formamide, acetamide, dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, dioxane or methyl pyrrolidone. In the cyano-containing monomer solution, the mass concentration of the monomer is 10-40%.
[0014] In step (1), the irradiation source is an electron accelerator or cobalt-60 (cobalt-60 gamma rays), and the irradiation mode is co-irradiation; when the irradiation source is an electron accelerator, the irradiation dose rate is 1-5 kGy / s; when the irradiation source is cobalt-60, the irradiation dose rate is 1-5 kGy / h; the irradiation absorbed dose is 10-100 kGy, the irradiation temperature is room temperature, and the irradiation atmosphere is air, nitrogen or vacuum atmosphere.
[0015] In step (2), the amine oxime treatment process is as follows: the fabric grafted with cyano is placed in an ethanol / water solution of hydroxylamine hydrochloride, the pH of the solution is adjusted to 6-8 by adding alkali, then it is placed in a water bath for reaction, and the product after reaction is washed and dried to obtain the AO-treated fabric; in the solution of hydroxylamine hydrochloride, the mass concentration of hydroxylamine hydrochloride is 10-20%; the mass ratio of fabric to hydroxylamine hydrochloride solution is 5-10:100; the reaction temperature is 60-70℃, and the reaction time is 4-24h.
[0016] In step (3), the acid finishing liquid is obtained by dissolving an aldehyde group-containing pyrrole derivative into a solvent and adding acid to adjust the pH to 1.0-3.0; the aldehyde group-containing pyrrole derivative is one or more of pyrrole-2-carboxaldehyde, 1-methyl-2-pyrrole carboxaldehyde or 3,5-dimethyl-2-pyrrole carboxaldehyde; and the solvent is one or more of water, ethanol, methanol, propanol, acetone, formamide, acetamide, dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, dioxane or methyl pyrrolidone. In the acid finishing liquid, the mass concentration of the aldehyde group-containing pyrrole derivative is 0.5-1%.
[0017] In step (3), the mass ratio of the AO-treated fabric to the acid finishing liquid is 1-5:100; the temperature of the chemical dyeing reaction is 50-60 DEG C, and the reaction time is 8-24 h.
[0018] The present application first introduces a cyano group into a natural fiber fabric containing a large number of hydroxyl groups by irradiation grafting, then obtains amine oxime groups (AO groups, adsorption sites) through amine oxime treatment, and finally grows polypyrrole carboxaldehyde (light-heat agent) in situ on the fabric through chemical dyeing, so that the adsorption material has light-heat conversion function. The present application combines adsorption and light-heat effect to construct a high-temperature microenvironment in which the two are synergistic, which is beneficial to accelerate the mass transfer and diffusion of UO22+ in the adsorption material, thereby overcoming the thermodynamic limitation in the conventional uranium adsorption process and effectively improving the uranium adsorption efficiency.
[0019] Advantages: Compared with the prior art, the present application has the following obvious advantages: the present application selects a cheap and readily available commercially available natural fiber fabric as a substrate, performs irradiation grafting, amine oxime treatment and chemical dyeing, covalently grafts a polymer of a pyrrole derivative with light-heat conversion function onto the AO-treated fabric, realizes spatial co-localization of AO groups (adsorption sites) and polypyrrole carboxaldehyde (light-heat agent) on the surface of the fabric, and obtains an AO-treated light-heat fabric material; since the light-heat functional component on the material can absorb sunlight and convert it into heat, the temperature of the AO site microenvironment is effectively increased, the combination driving force of AO and uranyl ion is enhanced, the thermodynamic limitation in the conventional uranium adsorption process is overcome, and the uranium adsorption efficiency is effectively improved; compared with a fabric that has not been chemically dyed (AO-treated fabric), the present application increases the adsorption interface temperature by 10-15 DEG C through light-heat effect, shortens the UO22+ adsorption equilibrium time by 2 times, and increases the adsorption capacity by at least 20%; at the same time, the method of the present application is simple in process and can reduce the preparation cost of the adsorption material to $12-24 / kg, laying a foundation for engineering application. BRIEF DESCRIPTION OF DRAWINGS
[0020] Figure 1 The preparation flowchart of the adsorption material of the present application is shown in the figure;
[0021] Figure 2The schematic diagram of the light irradiation experiment for the adsorption material of the present application;
[0022] Figure 3 The infrared data change diagram of the adsorption material of Example 1;
[0023] Figure 4 The adsorption curve diagram of the adsorption material of Example 1 in a 20 ppm uranyl solution;
[0024] Figure 5 The temperature rising curve diagram of the product of each stage of Example 1;
[0025] Figure 6 The adsorption curve diagram of the adsorption material of Example 1 in real seawater. DETAILED DESCRIPTION
[0026] Example 1
[0027] The preparation method of the light-heat enhanced uranium adsorption material of the present application comprises the following steps:
[0028] (1) Irradiation grafting: cotton fabric (containing a large number of hydroxyl groups) is placed in an acrylonitrile dimethylformamide solution, the mass concentration of acrylonitrile in the dimethylformamide solution is 10%; a cobalt source is used for irradiation treatment, the irradiation dose is 10 kGy, the dose rate is 2 kGy / h, the irradiation temperature is room temperature, the irradiation atmosphere is air, after 5 h of reaction, the cotton fabric grafted with cyan groups is obtained, and the grafting rate of cyan groups is calculated to be 52.37% according to the change in the mass of the fabric before and after irradiation;
[0029] (2) Amine oximation: the cotton fabric grafted with cyan groups is placed in a solution prepared from pure water and hydroxylamine hydrochloride (in the solution, the mass concentration of hydroxylamine hydrochloride is 10%), the mass ratio of the cotton fabric grafted with cyan groups to the solution is 5:100, after sufficient soaking, NaOH is added to adjust the pH of the solution to 6.0, and then the solution is placed in a 60℃ water bath for reaction for 24 h, after reaction, the solution is cooled to room temperature, and the cotton fabric after reaction is sequentially washed with ethanol and pure water, and dried after washing, to obtain an AO-processed fabric, and the loading amount of amine oxime groups in the obtained fabric is measured by weighing to be 8.3%;
[0030] (3) Chemical dyeing: pyrrole-2-formaldehyde is dissolved in ethanol, sulfuric acid is added to adjust the pH to 1.0, and an acid finishing solution is prepared, in the acid finishing solution, the mass concentration of pyrrole-2-formaldehyde is 0.5%; the AO-processed fabric is immersed in the acid finishing solution, the mass ratio of the AO-processed fabric to the acid finishing solution is 1:100; and the chemical dyeing is performed at 60℃ for 8 h, to obtain a light-heat enhanced uranium adsorption material, and the loading amount of polypyrrole derivatives in the obtained fabric is measured by weighing to be 7.5%.
[0031] The adsorption material prepared in Example 1 is subjected to Figure 2The light irradiation experiment shown: The adsorbent material was placed in a uranyl solution with a concentration of 20 ppm. Under one day of sunlight irradiation, the adsorbent material adsorbed in the 20 ppm uranyl solution for 60 hours. The adsorbent material was then digested, and the adsorption capacity was tested using ICP-MS, which showed to be 542.36 mg / g. The adsorbent material was also placed in real seawater. Under one day of sunlight irradiation, the adsorbent material adsorbed in real seawater for 100 days. The adsorbent material was then digested, and the adsorption capacity was tested using ICP-MS, which showed to be 11.28 mg / g.
[0032] Figure 3 The following are the Fourier Transform Infrared (FTIR) spectra of the products from each step in Example 1. Qualitative analysis of the chemical structure of the original fabric, the fabric after oxime treatment, and the chemically dyed fabric was performed using FTIR spectroscopy at 2245 cm⁻¹. - 1 location (C≡N), 1650cm -1 (C=N), 1388cm -1 (CN) and 935cm -1 The characteristic peak of (NO) can confirm the successful synthesis of the product in each step.
[0033] pass Figure 4 It can be seen that the adsorption capacity of the material is close to saturation after 60 hours of adsorption, and its saturation adsorption capacity is 542.36 mg / g; through Figure 5 It can be seen that under simulated sunlight irradiation at a depth of 5 mm underwater, the chemically dyed fabric exhibits excellent photothermal conversion performance, while the original fabric and the amine-oxime-treated fabric not only show lower surface temperatures but also significantly lower solar heating efficiency; through Figure 6 It can be seen that, after 100 days of continuous adsorption experiments under simulated sunlight in actual seawater at room temperature, the fabric finally chelated uranium from seawater at a level of 11.28 mg / g.
[0034] Comparative Example 1
[0035] A method for preparing a uranium adsorbent material includes the following steps:
[0036] (1) Irradiation grafting: Cotton fabric (containing a large number of hydroxyl groups) was placed in a dimethylformamide solution of acrylonitrile, the mass concentration of acrylonitrile in the dimethylformamide solution of acrylonitrile was 10%; irradiation treatment was carried out using a cobalt source, the irradiation dose was 10 kGy, the dose rate was 2 kGy / h, the irradiation temperature was room temperature, the irradiation atmosphere was air, and after 5 h of reaction, cotton fabric grafted with cyano groups was obtained. The grafting rate of cyano groups was calculated to be 52.37% based on the change in fabric mass before and after irradiation.
[0037] (2) Amine oxime: the cotton fabric grafted with cyan group is placed in a solution prepared from pure water and hydroxylamine hydrochloride (the mass concentration of hydroxylamine hydrochloride in the solution is 10%), the mass ratio of the cotton fabric grafted with cyan group to the solution is 5:100, after soaking sufficiently, NaOH is added to adjust the pH of the solution to 6.0, and then the solution is placed in a water bath at 60°C for reaction for 24 hours, after reaction, the solution is cooled to room temperature, and the cotton fabric after reaction is washed with ethanol and pure water in sequence, and dried after washing, to obtain an AO treated fabric, and the loading amount of amine oxime group in the obtained fabric is 8.3% measured by weighing method.
[0038] The adsorbing material prepared in the preparation example 1 is subjected to Figure 2 The light irradiation experiment is shown in the following: the adsorbing material is placed in a uranyl solution with a concentration of 20 ppm, and the adsorbing material is adsorbed in the uranyl solution with a concentration of 20 ppm for 120 hours under the irradiation of one sun, the adsorbing material is digested, and the adsorption amount is 401.34 mg / g tested by ICP-MS; the adsorbing material is placed in real seawater, and the adsorbing material is adsorbed in the real seawater for 180 days under the irradiation of one sun, the adsorbing material is digested, and the adsorption amount is 7.55 mg / g tested by ICP-MS.
[0039] Comparative example 2
[0040] A preparation method of a photo-thermal enhanced uranium adsorbing material, comprising the following steps:
[0041] (1) Irradiation grafting: the cotton fabric (containing a large number of hydroxyl groups) is placed in an acrylonitrile dimethylformamide solution, the mass concentration of acrylonitrile in the dimethylformamide solution is 10%; a cobalt source is used for irradiation treatment, the irradiation dose is 10 kGy, the dose rate is 2 kGy / h, the irradiation temperature is room temperature, the irradiation atmosphere is air, and after reaction for 5 hours, the cotton fabric grafted with cyan group is obtained, and the grafting rate of cyan group is 52.37% calculated according to the change of fabric mass before and after irradiation;
[0042] (2) Amine oxime: the cotton fabric grafted with cyan group is placed in a solution prepared from pure water and hydroxylamine hydrochloride (the mass concentration of hydroxylamine hydrochloride in the solution is 10%), the mass ratio of the cotton fabric grafted with cyan group to the solution is 5:100, after soaking sufficiently, NaOH is added to adjust the pH of the solution to 6.0, and then the solution is placed in a water bath at 60°C for reaction for 24 hours, after reaction, the solution is cooled to room temperature, and the cotton fabric after reaction is washed with ethanol and pure water in sequence, and dried after washing, to obtain an AO treated fabric, and the loading amount of amine oxime group in the obtained fabric is 8.3% measured by weighing method;
[0043] (3) Chemical dyeing: pyrrole was dissolved in ethanol, and sulfuric acid was added to adjust the pH to 1.0 to prepare an acidic finishing liquor. In the acidic finishing liquor, the mass concentration of pyrrole was 0.5%; the AO-processed fabric was immersed in the acidic finishing liquor, and the mass ratio of the AO-processed fabric to the acidic finishing liquor was 1:100; and the chemical dyeing was carried out at 60°C for 8h to obtain a light-heat enhanced uranium adsorption material. The load of polypyrrole derivative in the obtained fabric was 0.5% by the weighing method.
[0044] The adsorption material prepared in Comparative Example 2 was subjected to Figure 2 The light irradiation experiment is shown in the following. The adsorption material was placed in a uranyl solution with a concentration of 20ppm, and the adsorption material was adsorbed in the 20ppm uranyl solution for 100 hours under the irradiation of 1 sun. The adsorption material was digested, and the adsorption amount was tested by ICP-MS, which was 442.36mg / g. The adsorption material was placed in real seawater, and the adsorption material was adsorbed in the real seawater for 150 days under the irradiation of 1 sun. The adsorption material was digested, and the adsorption amount was tested by ICP-MS, which was 8.28mg / g.
[0045] In Example 1, pyrrole-2-formaldehyde can react with the hydroxyl groups on the fabric under acidic conditions to be fixed on the surface of the cotton fabric, and further polymerize with the rest of the pyrrole-2-formaldehyde on the surface of the cotton fabric to form a polypyrrole-2-formaldehyde grafted chain. The chemical and mechanical stability of the obtained fabric is good, and the light-heat performance is excellent. In Comparative Example 1, pyrrole does not have an aldehyde group and cannot react with the hydroxyl groups on the fabric to conjugate. The polypyrrole generated by in-situ oxidation polymerization of the adsorbed pyrrole on the fabric is only a small amount of residue on the cotton fabric, so the adsorption amount is greatly reduced, and the residual polypyrrole gradually flows out, and the stability is poor.
[0046] Comparative Example 3
[0047] A preparation method of a uranium adsorption material, comprising the following steps:
[0048] (1) Irradiation grafting: the cotton fabric (containing a large amount of hydroxyl groups) was placed in an acrylonitrile dimethylformamide solution, and the mass concentration of acrylonitrile in the acrylonitrile dimethylformamide solution was 10%; a cobalt source was used for irradiation treatment, the irradiation dose was 10kGy, the dose rate was 2kGy / h, the irradiation temperature was room temperature, the irradiation atmosphere was air, and after 5h of reaction, the cotton fabric grafted with cyano groups was obtained. According to the change in the mass of the fabric before and after irradiation, the grafting rate of cyano groups was calculated to be 52.37%;
[0049] (2) Amine oxime: the cotton fabric grafted with cyan group was placed in a solution prepared from pure water and hydroxylamine hydrochloride (in the solution, the mass concentration of hydroxylamine hydrochloride was 10%), the mass ratio of the cotton fabric grafted with cyan group to the solution was 5:100, after soaking, NaOH was added to adjust the pH of the solution to 6.0, and then the solution was placed in a water bath at 40°C for 24 h, after the reaction, the solution was cooled to room temperature, and then the cotton fabric after the reaction was washed with ethanol and pure water in sequence, and dried after washing, to obtain an AO treated fabric, and the loading amount of amine oxime group in the obtained fabric was 4.1% by weighing method;
[0050] (3) Chemical dyeing: pyrrole-2-carboxaldehyde was dissolved in ethanol, and sulfuric acid was added to adjust the pH to 1.0 to prepare an acidic finishing solution, and in the acidic finishing solution, the mass concentration of pyrrole-2-carboxaldehyde was 0.5%; the AO treated fabric was immersed in the acidic finishing solution, and the mass ratio of the AO treated fabric to the acidic finishing solution was 1:100; and the chemical dyeing was carried out at 60°C for 8 h to obtain a light-heat enhanced uranium adsorption material, and the loading amount of polypyrrole derivative in the obtained fabric was 7.5% by weighing method.
[0051] The adsorption material prepared in Comparative Example 3 was subjected to Figure 2 The light irradiation experiment is shown in the following table: the adsorption material was placed in a uranyl solution with a concentration of 20 ppm, and under the irradiation of 1 sun, the adsorption material was adsorbed in the uranyl solution with a concentration of 20 ppm for 60 hours, the adsorption material was digested, and ICP-MS was used for testing, and the adsorption amount was 184.66 mg / g; the adsorption material was placed in real seawater, and under the irradiation of 1 sun, the adsorption material was adsorbed in the real seawater for 100 days, the adsorption material was digested, and ICP-MS was used for testing, and the adsorption amount was 4.98 mg / g.
[0052] Comparative Example 4
[0053] A preparation method of a uranium adsorption material, comprising the following steps:
[0054] (1) Irradiation grafting: the cotton fabric (containing a large number of hydroxyl groups) was placed in an acrylonitrile dimethylformamide solution, and the mass concentration of acrylonitrile in the acrylonitrile dimethylformamide solution was 10%; a cobalt source was used for irradiation treatment, the irradiation dose was 10 kGy, the dose rate was 20 kGy / h, the irradiation temperature was room temperature, the irradiation atmosphere was air, and after 0.5 h of reaction, a cotton fabric grafted with cyan group was obtained, and the grafting rate of cyan group was 12.68% according to the change of fabric mass before and after irradiation;
[0055] (2) Amine oxime: the cotton fabric grafted with cyan group is placed in a solution prepared from pure water and hydroxylamine hydrochloride (in the solution, the mass concentration of hydroxylamine hydrochloride is 10%), the mass ratio of the cotton fabric grafted with cyan group to the solution is 5:100, after soaking sufficiently, NaOH is added to adjust the pH of the solution to 6.0, and then the solution is placed in a water bath at 60 DEG C for 24 h, after the reaction, the solution is cooled to room temperature, and then the cotton fabric after the reaction is washed with ethanol and pure water in sequence, and dried after washing, to obtain an AO fabric, and the loading amount of amine oxime group in the obtained fabric is 2.7% by weighing method;
[0056] (3) Chemical dyeing: pyrrole-2-formaldehyde is dissolved in ethanol, and sulfuric acid is added to adjust the pH to 1.0, to prepare an acidic finishing solution, and in the acidic finishing solution, the mass concentration of pyrrole-2-formaldehyde is 0.5%; the AO fabric is immersed in the acidic finishing solution, and the mass ratio of the AO fabric to the acidic finishing solution is 1:100; and the chemical dyeing is carried out at 60 DEG C for 8 h, to obtain a light-heat enhanced uranium adsorption material, and the loading amount of polypyrrole derivative in the obtained fabric is 7.5% by weighing method.
[0057] The adsorption material prepared in Comparative Example 4 is subjected to Figure 2 The light irradiation experiment shown in the figure: the adsorption material is placed in a uranyl solution with a concentration of 20 ppm, and under the irradiation of 1 sun, the adsorption material is adsorbed in the uranyl solution with a concentration of 20 ppm for 60 hours, the adsorption material is digested, and ICP-MS is used for testing, and the adsorption amount is 182.78 mg / g; the adsorption material is placed in real seawater, and under the irradiation of 1 sun, the adsorption material is adsorbed in the real seawater for 100 days, the adsorption material is digested, and ICP-MS is used for testing, and the adsorption amount is 3.29 mg / g.
[0058] Example 2
[0059] The preparation method of the light-heat enhanced uranium adsorption material of the present application comprises the following steps:
[0060] (1) Irradiation grafting: the cotton fabric (containing a large number of hydroxyl groups) is placed in an acrylonitrile dimethylformamide solution, and the mass concentration of acrylonitrile in the acrylonitrile dimethylformamide solution is 10%; electron beam is used for irradiation treatment, the irradiation dose is 100 kGy, the dose rate is 2 kGy / s, the irradiation temperature is room temperature, the irradiation atmosphere is air, and after 50 s of reaction, the cotton fabric grafted with cyan group is obtained, and the grafting rate of cyan group is 55.63% according to the change of fabric mass before and after irradiation;
[0061] (2) Amine oxime: the cotton fabric grafted with cyan group is placed in a solution prepared from pure water and hydroxylamine hydrochloride (in the solution, the mass concentration of hydroxylamine hydrochloride is 10%), the mass ratio of the cotton fabric grafted with cyan group to the solution is 5:100, after soaking, NaOH is added to adjust the pH of the solution to 6.0, and then the solution is placed in a water bath at 60 DEG C for 24 h, after the reaction, the solution is cooled to room temperature, and then the cotton fabric after the reaction is washed with ethanol and pure water in sequence, and dried after washing, to obtain an AO fabric, and the loading amount of amine oxime groups in the obtained fabric is 8.4% by weighing method;
[0062] (3) Chemical dyeing: pyrrole-2-formaldehyde is dissolved in ethanol, and sulfuric acid is added to adjust the pH to 1.0 to prepare an acidic finishing solution, and in the acidic finishing solution, the mass concentration of pyrrole-2-formaldehyde is 0.5%; the AO fabric is immersed in the acidic finishing solution, and the mass ratio of the AO fabric to the acidic finishing solution is 1:100; and the chemical dyeing is carried out at 60 DEG C for 8 h to obtain a light-heat enhanced uranium adsorption material, and the loading amount of polypyrrole derivatives in the obtained fabric is 7.5% by weighing method.
[0063] The adsorption material prepared in Example 2 is subjected to Figure 2 The light irradiation experiment is shown in the following: the adsorption material is placed in a uranyl solution with a concentration of 20 ppm, and under the irradiation of 1 sun, the adsorption material is adsorbed in the uranyl solution with a concentration of 20 ppm for 60 hours, the adsorption material is digested, and the adsorption amount is 545.64 mg / g by ICP-MS testing; the adsorption material is placed in real seawater, and under the irradiation of 1 sun, the adsorption material is adsorbed in the real seawater for 100 days, the adsorption material is digested, and the adsorption amount is 11.37 mg / g by ICP-MS testing.
[0064] Example 3
[0065] The preparation method of the light-heat enhanced uranium adsorption material of the present application comprises the following steps:
[0066] (1) Irradiation grafting: the cotton fabric (containing a large number of hydroxyl groups) is placed in an acrylonitrile dimethylformamide solution, and the mass concentration of acrylonitrile in the acrylonitrile dimethylformamide solution is 10%; electron beam irradiation treatment is performed, the irradiation dose is 100 kGy, the dose rate is 2 kGy / s, the irradiation temperature is room temperature, the irradiation atmosphere is air, and after 50 s of reaction, the cotton fabric grafted with cyan group is obtained, and the grafting rate of cyan group is 55.63% according to the change in fabric mass before and after irradiation;
[0067] (2) Amine oxime: the cotton fabric grafted with cyano is placed in a solution prepared from ethanol and hydroxylamine hydrochloride (in the solution, the mass concentration of hydroxylamine hydrochloride is 10%), the mass ratio of the cotton fabric grafted with cyano to the solution is 10:100, after soaking sufficiently, ammonia water is added to adjust the pH of the solution to 7.0, and then the solution is placed in a water bath at 60 DEG C for reaction for 24 h, after reaction, the solution is cooled to room temperature, and the cotton fabric after reaction is washed with ethanol and pure water in sequence, and dried after washing, to obtain an AO fabric, and the loading amount of amine oxime groups in the obtained fabric is 8.8% by weighing method;
[0068] (3) Chemical dyeing: pyrrole-2-formaldehyde is dissolved in ethanol, and sulfuric acid is added to adjust the pH to 1.0, to prepare an acidic finishing solution, and in the acidic finishing solution, the mass concentration of pyrrole-2-formaldehyde is 0.5%; the AO fabric is immersed in the acidic finishing solution, and the mass ratio of the AO fabric to the acidic finishing solution is 1:100; and the chemical dyeing is carried out at 60 DEG C for 8 h, to obtain a light-heat enhanced uranium adsorption material, and the loading amount of polypyrrole derivatives in the obtained fabric is 7.5% by weighing method.
[0069] The adsorption material prepared in Example 3 is subjected to Figure 2 The light irradiation experiment shown in the figure: the adsorption material is placed in a uranyl solution with a concentration of 20 ppm, and under the irradiation of 1 sun, the adsorption material is adsorbed in the 20 ppm uranyl solution for 60 hours, the adsorption material is digested, and ICP-MS is used for testing, and the adsorption amount is 556.32 mg / g; the adsorption material is placed in real seawater, and under the irradiation of 1 sun, the adsorption material is adsorbed in the real seawater for 100 days, the adsorption material is digested, and ICP-MS is used for testing, and the adsorption amount is 11.78 mg / g.
[0070] Example 4
[0071] The preparation method of the light-heat enhanced uranium adsorption material of the application comprises the following steps:
[0072] (1) Irradiation grafting: the cotton fabric (containing a large number of hydroxyl groups) is placed in an acrylonitrile dimethylformamide solution, and the mass concentration of acrylonitrile in the acrylonitrile dimethylformamide solution is 10%; electron beam is used for irradiation treatment, the irradiation dose is 100 kGy, the dose rate is 2 kGy / s, the irradiation temperature is room temperature, the irradiation atmosphere is air, and after reaction for 50 s, the cotton fabric grafted with cyano is obtained, and the grafting rate of cyano is 55.63% according to the change of the mass of the fabric before and after irradiation;
[0073] (2) Amine oxime: the cotton fabric grafted with cyan group is placed in a solution prepared from ethanol and hydroxylamine hydrochloride (in the solution, the mass concentration of hydroxylamine hydrochloride is 10%), the mass ratio of the cotton fabric grafted with cyan group to the solution is 5:100, after soaking sufficiently, NaOH is added to adjust the pH of the solution to 6.0, and then the solution is placed in a water bath at 70 DEG C for reaction for 4 hours, after reaction, the solution is cooled to room temperature, and then the cotton fabric after reaction is washed with ethanol and pure water in sequence, and after washing, the cotton fabric is dried to obtain an AO fabric, and the loading amount of amine oxime group in the obtained fabric is 8.2% by weighing method;
[0074] (3) Chemical dyeing: pyrrole-2-formaldehyde is dissolved in ethanol, and sulfuric acid is added to adjust the pH to 1.0 to prepare an acidic finishing solution, and in the acidic finishing solution, the mass concentration of pyrrole-2-formaldehyde is 0.5%; the AO fabric is immersed in the acidic finishing solution, and the mass ratio of the AO fabric to the acidic finishing solution is 1:100; and the chemical dyeing is carried out at 60 DEG C for 8 hours to obtain a light-heat enhanced uranium adsorption material, and the loading amount of polypyrrole derivative in the obtained fabric is 7.5% by weighing method.
[0075] The adsorption material prepared in Example 4 is subjected to Figure 2 The light irradiation experiment is shown in the following table: the adsorption material is placed in a uranyl solution with a concentration of 20 ppm, and under the irradiation of 1 sun, the adsorption material is adsorbed in the uranyl solution with a concentration of 20 ppm for 60 hours, the adsorption material is digested, and ICP-MS is used for testing, and the adsorption amount is 544.23 mg / g; the adsorption material is placed in real seawater, and under the irradiation of 1 sun, the adsorption material is adsorbed in the real seawater for 100 days, the adsorption material is digested, and ICP-MS is used for testing, and the adsorption amount is 10.68 mg / g.
[0076] Example 5
[0077] The preparation method of the light-heat enhanced uranium adsorption material of the present application comprises the following steps:
[0078] (1) Irradiation grafting: the cotton fabric (containing a large number of hydroxyl groups) is placed in an acrylonitrile dimethylformamide solution, and the mass concentration of acrylonitrile in the acrylonitrile dimethylformamide solution is 10%; electron beam is used for irradiation treatment, the irradiation dose is 100 kGy, the dose rate is 2 kGy / s, the irradiation temperature is room temperature, the irradiation atmosphere is air, and after reaction for 50 s, the cotton fabric grafted with cyan group is obtained, and the grafting rate of cyan group is 55.63% according to the change of fabric mass before and after irradiation;
[0079] (2) Amine oxime: the cotton fabric grafted with cyan group is placed in a solution prepared from ethanol and hydroxylamine hydrochloride (in the solution, the mass concentration of hydroxylamine hydrochloride is 10%), the mass ratio of the cotton fabric grafted with cyan group to the solution is 5:100, after soaking sufficiently, NaOH is added to adjust the pH of the solution to 6.0, and then the solution is placed in a water bath at 60 DEG C for 24 h, after the reaction, the solution is cooled to room temperature, and then the cotton fabric after the reaction is washed with ethanol and pure water in sequence, and dried after washing, to obtain an AO fabric, and the loading amount of amine oxime group in the obtained fabric is 8.4% by weighing method;
[0080] (3) Chemical dyeing: pyrrole-2-formaldehyde is dissolved in ethanol, and sulfuric acid is added to adjust the pH to 2.0 to prepare an acidic finishing solution, and in the acidic finishing solution, the mass concentration of pyrrole-2-formaldehyde is 0.5%; the AO fabric is immersed in the acidic finishing solution, and the mass ratio of the AO fabric to the acidic finishing solution is 1:100; and the chemical dyeing is carried out at 60 DEG C for 8 h to obtain a light-heat enhanced uranium adsorption material, and the loading amount of polypyrrole derivative in the obtained fabric is 8.4% by weighing method.
[0081] The adsorption material prepared in Example 5 is subjected to a light irradiation experiment as shown in the following table: Figure 2 The adsorption material is placed in a uranyl solution with a concentration of 20 ppm, and under the irradiation of 1 sun, the adsorption material is adsorbed in the 20 ppm uranyl solution for 60 hours, the adsorption material is digested, and ICP-MS is used for testing, and the adsorption amount is 552.55 mg / g; the adsorption material is placed in real seawater, and under the irradiation of 1 sun, the adsorption material is adsorbed in the real seawater for 100 days, the adsorption material is digested, and ICP-MS is used for testing, and the adsorption amount is 11.84 mg / g.
[0082] Example 6
[0083] The preparation method of the light-heat enhanced uranium adsorption material of the present application comprises the following steps:
[0084] (1) Irradiation grafting: the cotton fabric (containing a large number of hydroxyl groups) is placed in an acrylonitrile dimethylformamide solution, and the mass concentration of acrylonitrile in the acrylonitrile dimethylformamide solution is 10%; electron beam is used for irradiation treatment, the irradiation dose is 100 kGy, the dose rate is 2 kGy / s, the irradiation temperature is room temperature, the irradiation atmosphere is air, and after 50 s of reaction, the cotton fabric grafted with cyan group is obtained, and the grafting rate of cyan group is 55.63% according to the change of fabric mass before and after irradiation;
[0085] (2) amine oxime: the cotton fabric grafted with cyan group was placed in a solution prepared from ethanol and hydroxylamine hydrochloride (in the solution, the mass concentration of hydroxylamine hydrochloride was 10%), the mass ratio of the cotton fabric grafted with cyan group to the solution was 5:100, after soaking, NaOH was added to adjust the pH of the solution to 6.0, and then the solution was placed in a water bath at 60°C for 24 h, after the reaction, the solution was cooled to room temperature, and then the cotton fabric after the reaction was washed with ethanol and pure water in sequence, and dried after washing, to obtain an AO fabric, and the loading amount of the amine oxime group in the obtained fabric was 8.4% by weighing method;
[0086] (3) chemical dyeing: pyrrole-2-formaldehyde was dissolved in ethanol, and sulfuric acid was added to adjust the pH to 1.0 to prepare an acidic finishing solution, and in the acidic finishing solution, the mass concentration of pyrrole-2-formaldehyde was 0.5%; the AO fabric was immersed in the acidic finishing solution, and the mass ratio of the AO fabric to the acidic finishing solution was 5:100; and the chemical dyeing was carried out at 50°C for 24 h to obtain a light-heat enhanced uranium adsorption material, and the loading amount of the polypyrrole derivative in the obtained fabric was 8.2% by weighing method.
[0087] The adsorption material prepared in Example 6 was subjected to a light irradiation experiment as shown in the following table: Figure 2 The adsorption material was placed in a uranyl solution with a concentration of 20 ppm, and under the irradiation of 1 sun, the adsorption material was adsorbed in the 20 ppm uranyl solution for 60 hours, the adsorption material was digested, and ICP-MS was used for testing, and the adsorption amount was 548.67 mg / g; the adsorption material was placed in real seawater, and under the irradiation of 1 sun, the adsorption material was adsorbed in the real seawater for 100 days, the adsorption material was digested, and ICP-MS was used for testing, and the adsorption amount was 11.69 mg / g.
[0088] The prior art amine oxime polymer fiber (AO-based adsorption material) was subjected to a light irradiation experiment as shown in the following table: Figure 2 The adsorption material was placed in a uranyl solution with a concentration of 20 ppm, and under the irradiation of 1 sun, the adsorption material was adsorbed in the 20 ppm uranyl solution for 60 hours, the adsorption material was digested, and ICP-MS was used for testing, and the adsorption amount was 548.67 mg / g; the adsorption material was placed in real seawater, and under the irradiation of 1 sun, the adsorption material was adsorbed in the real seawater for 100 days, the adsorption material was digested, and ICP-MS was used for testing, and the adsorption amount was 11.69 mg / g.
Claims
1. A photo-thermal enhanced uranium adsorbent material, characterized by: The uranium adsorption material takes natural fiber fabric as carrier, and has amine oxime groups grafted on the carrier and polypyrrole derivatives grown in situ.
2. The uranium adsorbent material of claim 1, wherein: In the fabric, the loading amount of the amine oxime groups is 8.2-8.8 wt.%, and the loading amount of the polypyrrole derivatives is 7.5-8.4 wt.%.
3. The method of claim 1, wherein the uranium adsorbent material is prepared by the steps of: The method comprises the following steps: (1) irradiation grafting: placing the natural fiber fabric in a solution of a cyan-containing monomer, and performing irradiation grafting treatment by using a cobalt source or an electron beam to obtain the fabric grafted with cyan groups; (2) amine oximation: treating the fabric grafted with cyan groups by amine oximation to obtain the AO-treated fabric; (3) chemical dyeing: immersing the AO-treated fabric in an acid finishing solution of an aldehyde group-containing pyrrole derivative to perform chemical dyeing reaction, thereby preparing the fabric-supported uranium adsorption material with enhanced photo-thermal effect.
4. The method of claim 3, wherein: In step (1), the natural fiber fabric is one or more of cotton fabric, wool fabric, silk fabric or hemp fabric.
5. The method of claim 3, wherein: In step (1), the solution of the cyan-containing compound is obtained by dissolving a cyan-containing vinyl monomer in water or an organic solvent; the vinyl monomer is one or more of acrylonitrile, 3-butene nitrile, acetic acid-1-cyanovinyl ester or 2-tricyanoethenyl anthracene; and the organic solvent is one or more of ethanol, methanol, propanol, acetone, formamide, acetamide, dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, dioxane or methyl pyrrolidone.
6. The method of claim 5, wherein: In the solution of the cyan-containing monomer, the mass concentration of the monomer is 10-40%.
7. The method of claim 3, wherein: In step (1), the irradiation source is an electron accelerator or cobalt-60, and the irradiation mode is co-irradiation; when the irradiation source is an electron accelerator, the irradiation dose rate is 1-5 kGy / s; when the irradiation source is cobalt-60, the irradiation dose rate is 1-5 kGy / h; the absorbed dose of irradiation is 10-100 kGy, the irradiation temperature is room temperature, and the irradiation atmosphere is air, nitrogen or vacuum atmosphere.
8. The method of claim 3, wherein: In step (2), the amine oximation treatment process is as follows: placing the fabric grafted with cyan groups in a solution of hydroxylamine hydrochloride, adjusting the pH of the solution to 6-8 by adding alkali, then placing in a water bath for reaction, and then washing and drying the product after reaction to obtain the AO-treated fabric; in the solution of hydroxylamine hydrochloride, the mass concentration of hydroxylamine hydrochloride is 10-20%; the mass ratio of the fabric to the solution of hydroxylamine hydrochloride is 5-10:100; the reaction temperature is 60-70°C, and the reaction time is 4-24 h.
9. The method of claim 3, wherein: In step (3), the acid finishing solution is obtained by dissolving an aldehyde group-containing pyrrole derivative in a solvent and adjusting the pH to 1.0-3.0 by adding acid; the aldehyde group-containing pyrrole derivative is one or more of pyrrole-2-formaldehyde, 1-methyl-2-pyrrole formaldehyde or 3,5-dimethyl-2-pyrrole formaldehyde; the solvent is one or more of water, ethanol, methanol, propanol, acetone, formamide, acetamide, dimethylformamide, dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, dioxane or methyl pyrrolidone; and in the acid finishing solution, the mass concentration of the aldehyde group-containing pyrrole derivative is 0.5-1%.
10. The method of claim 3, wherein: In step (3), the mass ratio of the AO-treated fabric to the acidic finishing solution is 1-5:100; the temperature of the chemical dyeing reaction is 50-60°C, and the reaction time is 8-24 h.