CN114733494B - Cesium ion adsorbent and preparation method and application thereof - Google Patents
Cesium ion adsorbent and preparation method and application thereof Download PDFInfo
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- CN114733494B CN114733494B CN202210357781.4A CN202210357781A CN114733494B CN 114733494 B CN114733494 B CN 114733494B CN 202210357781 A CN202210357781 A CN 202210357781A CN 114733494 B CN114733494 B CN 114733494B
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Abstract
The invention provides a cesium ion adsorbent, a preparation method and application thereof. The cesium ion adsorbent comprises a raw material including a phenolic hydroxyl group-containing monomer. The preparation method of the cesium ion adsorbent provided by the invention comprises the following steps: performing Friedel-crafts alkylation reaction on the monomer containing phenolic hydroxyl to obtain the cesium ion adsorbent. The cesium ion adsorbent provided by the invention forms a super-crosslinked polymer by selecting the monomer containing phenolic hydroxyl, has high selectivity and high adsorption quantity on cesium ions, has excellent cycle performance, can realize rapid desorption, has a simple preparation process, reduces the production cost, is environment-friendly, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of adsorption separation materials, and particularly relates to a cesium ion adsorbent, and a preparation method and application thereof.
Background
Cesium is an important strategic resource, and is widely applied to high-tech fields such as energy sources, medicines, aerospace, catalysis, photoelectric communication, oil gas drilling and the like at present due to the special physicochemical properties of cesium.
The brine of salt lakes in Qinghai, tibet, sichuan and other areas in China is reserved with abundant metal resources including cesium. Despite the relatively high total cesium storage in salt lake brines, it is most present in ionic form (Cs + ) Low concentration (less than 40mg L -1 ) And contains a plurality of associated ions, in particular physical and chemical properties and Cs + Very close potassium ions are extremely difficult to separate and extract, and no industrialized salt lake brine cesium separation and extraction process technology is successful at present.
In the prior art, cesium ions are adsorbed and separated by an extraction method and an adsorption method. The extractant used in the extraction method, such as crown ethers and substituted phenols, contains oxygen-containing functional groups with strong affinity for cesium, such as ether oxygen group and phenolic hydroxyl group, and Cs is combined by multi-coordination + Extremely high selectivity separations are achieved. For example, CN106435180a discloses an extraction method of rubidium ions and cesium ions, which comprises subjecting a mixed solution containing rubidium ions and cesium ions to extraction treatment with a composite extractant comprising a phenol extractant and at least one component of an acidic extractant and a neutral organic substance; the extraction method improves the Rb + And Cs + Is effective in extraction. However, the extractant is not easy to synthesize, is expensive, is easy to run off, needs to use organic solvents, is not environment-friendly, needs strong acid or alkali and the like in the extraction process, and is not suitable for the extremely low concentration Cs in the salt lake + Is separated and extracted.
The adsorption method is the most suitable separation method for low concentration system, and mainly comprises two kinds of inorganic adsorbent and organic adsorbent. For example, CN104692406a discloses a preparation method of an adsorbent for selectively separating cesium ions from salt lake brine, comprising: mixing a surfactant, soluble cesium salt, water glass and sodium aluminate according to a certain proportion by taking cesium ions as a template agent to prepare an artificial zeolite ion sieve with a cesium ion customized pore structure, wherein Cs in salt lake brine is treated by the artificial zeolite ion sieve + The selective adsorption performance is excellent. CN105363414a discloses a cesium ion adsorbent, the preparation raw materials of which comprise aminated ferroferric oxide, carboxylated crown ether derivative and condensing agent. The cesium ion adsorbent has the following functionsStronger cesium ion adsorption selectivity and magnetism, and stable adsorption performance is maintained in the cyclic use of multiple adsorption-desorption. However, the preparation method of the adsorbent is complex and has high cost.
The common defect in the prior art is that part of the inorganic adsorbent is unstable, easy to gel and difficult to desorb, and the research is concentrated on the spent fuel system in the strong radiation environment. The organic adsorbent is not radiation-resistant, the selectivity is to be improved, the preparation method is complex, and the cost is high.
Therefore, developing an adsorbent with high selectivity to cesium ions, high adsorption rate, high desorption rate, good cycle performance and simple preparation method is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a cesium ion adsorbent, and a preparation method and application thereof. The cesium ion adsorbent forms a super-crosslinked polymer through self-crosslinking of a phenolic hydroxyl group-containing monomer, and has high selectivity, high adsorption capacity and excellent desorption and circulation performances for cesium ions.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a cesium ion adsorbent whose starting material includes a phenolic hydroxyl group-containing monomer; the phenolic hydroxyl group-containing monomer has a structure shown in a formula I;
wherein R is any one of-OH or halogen group.
In the invention, the dotted line in the formula I represents that the hydroxyl is connected at any position on the benzene ring.
In the present invention, the "halogen" means F, cl, br, I.
In the invention, the phenolic hydroxyl group-containing monomer is selected as a raw material, so that the adsorbent is rich in phenolic hydroxyl groups and can coordinate with cesium ions, thereby being capable of adsorbing and separating cesium ions; and the adoption of the specific monomer containing phenolic hydroxyl can realize high selectivity and high adsorption quantity for cesium ions and has excellent desorption performance and cycle performance.
As a preferred embodiment of the present invention, the phenolic hydroxyl group-containing monomer comprises any one or a combination of at least two of parahydroxybenzyl alcohol, orthohydroxybenzyl alcohol and m-hydroxybenzyl alcohol.
Preferably, the phenolic hydroxyl group-containing monomer comprises o-hydroxybenzyl alcohol.
In the invention, when the monomer containing phenolic hydroxyl groups is o-hydroxybenzyl alcohol, the selectivity to cesium ions is higher.
Preferably, the cesium ion adsorbent has a pore size of 2 to 4nm, and may be, for example, 2.1nm, 2.2nm, 2.3nm, 2.4nm, 2.5nm, 2.6nm, 2.7nm, 2.8nm, 3nm, 3.1nm, 3.2nm, 3.4nm, 3.6nm, 3.8nm, 3.9nm, or the like.
In the invention, the pore diameter of the cesium ion adsorbent is characterized by adopting a physical adsorption instrument.
In a second aspect, the present invention provides a method for preparing the cesium ion adsorbent according to the first aspect, the method comprising:
performing Friedel-crafts alkylation reaction on the monomer containing phenolic hydroxyl to obtain the cesium ion adsorbent.
Preferably, the reaction is carried out in the presence of a catalyst.
Preferably, the molar ratio of the catalyst to the phenolic hydroxyl group-containing monomer is (1-2): 1, and may be, for example, 1:1, 1:1.5, 1:1.8, 1:2, etc.
In the invention, the selectivity and the adsorption amount of the cesium ion adsorbent to cesium ions are high in a specific molar ratio of the catalyst to the monomer, and when the catalyst dosage is too low, the material polymerization is difficult and the yield is low; when the dosage is too high, the crosslinking degree of the material is too high, the hydrophobicity is enhanced, the diffusion of adsorbate is not facilitated, and the adsorbability is greatly reduced.
Preferably, the catalyst comprises a lewis acid catalyst.
Preferably, the lewis acid catalyst comprises any one or a combination of at least two of anhydrous ferric chloride, anhydrous aluminum chloride, anhydrous tin chloride, or anhydrous zinc chloride.
In the invention, under the catalysis of Lewis acid, the monomer containing phenolic hydroxyl groups can be subjected to Friedel-crafts alkylation reaction to self-crosslink and synthesize the super-crosslinked polymer by a one-step method, so that the defects of extractants and adsorbents in the prior art are overcome, the high selectivity of the multi-coordination extractant, the high adsorption capacity of the adsorbents, the rapid adsorption rate and the excellent desorption and circulation performances are realized, the pre-crosslinking step with complicated operation and the use of external crosslinking agents are avoided, the synthesis process is simplified, and the cost is reduced.
Preferably, the reaction is carried out in a solvent.
Preferably, the solvent comprises dichloroethane.
In the present invention, the volume of the solvent is 15 to 25mL, based on 1g of the mass of the phenolic hydroxyl group-containing monomer, and may be 16mL, 18mL, 20mL, 22mL, 24mL, or the like, for example.
Preferably, the reaction is carried out in the presence of a protective atmosphere.
Preferably, the protective atmosphere comprises nitrogen and/or argon.
Preferably, the reaction comprises a first stage reaction and a second stage reaction.
Preferably, the temperature of the first stage reaction is 40 to 50℃and may be, for example, 42℃44℃45℃46℃48 ℃.
Preferably, the time of the first stage reaction is 4 to 6 hours, for example, 4.5 hours, 5 hours, 5.5 hours, etc.
Preferably, the temperature of the second stage reaction is 75 to 85 ℃, for example, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, and the like.
Preferably, the second stage reaction time is 15 to 25 hours, for example, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, etc.
In the invention, the reaction further comprises the steps of suction filtration, washing and drying.
Preferably, the washing includes a step of washing with hydrochloric acid, ultrapure water and methanol in this order.
The concentration of the hydrochloric acid is preferably 0.04 to 0.06mol/L, and may be, for example, 0.045mol/L, 0.05mol/L, 0.055mol/L, or the like.
Preferably, the washing with hydrochloric acid is performed for 1 to 3 hours, for example, 1.5 hours, 2 hours, 2.5 hours, or the like.
Preferably, the washing with ultrapure water is performed until the filtrate is neutral.
Preferably, the washing with methanol is performed until the filtrate becomes clear.
Preferably, the washing with methanol further comprises a step of performing a soxhlet extraction.
Preferably, the solvent of the soxhlet extraction comprises methanol.
Preferably, the Soxhlet extraction time is 20 to 28 hours, for example, 22 hours, 24 hours, 26 hours, 27 hours, etc.
In the present invention, the purpose of the Soxhlet extraction is to remove residual solvent and catalyst.
Preferably, the drying temperature is 55 to 65 ℃, for example, 56 ℃, 58 ℃, 60 ℃, 62 ℃, 64 ℃ and the like.
Preferably, the drying time is 20 to 28 hours, for example, 22 hours, 24 hours, 26 hours, 27 hours, etc.
Preferably, the drying is performed in a vacuum drying oven.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
and in the presence of protective atmosphere, mixing the phenolic hydroxyl group-containing monomer with a catalyst and a solvent, reacting for 4-6 hours at 40-50 ℃, and reacting for 15-25 hours at 75-85 ℃ to obtain the cesium ion adsorbent.
In a third aspect, the present invention provides a use of the cesium ion adsorbent according to the first aspect for selective adsorption separation of cesium ions.
In a fourth aspect, the present invention provides a method for adsorptive separation of cesium ions, comprising the steps of:
the cesium ion adsorbent according to the first aspect is mixed with a cesium chloride solution to perform adsorption separation.
Preferably, the mixed metal salt solution further comprises any one or a combination of at least two of potassium chloride, rubidium chloride or magnesium chloride.
Preferably, the mixing is performed under alkaline conditions.
The concentration of hydroxide ions in the mixed solution is preferably 0 to 0.1mol/L, and may be, for example, 0.01mol/L, 0.02mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, 0.1mol/L, etc., and more preferably 0.01 to 0.05mol/L.
In the invention, the alkaline condition is realized by adding sodium hydroxide when the concentration of the NaOH is 0mol L -1 When, i.e., under neutral conditions, all the adsorbents hardly adsorb Cs + This is because the pKa value of the phenolic hydroxyl group is 9.99, and it is difficult to deprotonate under neutral conditions, and the pH of the solution needs to be raised by adding a base to promote the deprotonation of the phenolic hydroxyl group. Wherein, the optimal NaOH concentration is 0.025mol L -1 。
Preferably, the mixing time is 20 to 26 hours, for example, 22 hours, 24 hours, 25 hours, etc.
Preferably, the mass ratio of cesium chloride to cesium ion adsorbent is (0.002-0.34): 1, for example, may be 0.004:1, 0.008:1, 0.01:1, 0.015:1, 0.02:1, 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, etc.
In the present invention, the mixing is carried out in a constant temperature rotary shaker.
Preferably, the temperature of the constant temperature rotary table is 24 to 26 ℃, for example, 24 ℃, 25 ℃, 26 ℃ and the like.
Preferably, the rotation speed of the constant temperature rotary table is 150 to 250rpm, for example, 160rpm, 180rpm, 200rpm, 220rpm, 240rpm, etc.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the beneficial effects that:
the cesium ion adsorbent provided by the invention forms a super-crosslinked polymer through self-crosslinking of a specific phenolic hydroxyl group-containing monomer, and has high selectivity, high adsorption capacity and excellent desorption and circulation performances on cesium ions; the separation factor of the adsorbent for cesium ions and potassium ions is more than or equal to 6.8, the adsorption capacity for cesium ions is more than or equal to 229.5mg/g, the desorption rate is more than or equal to 90.2%, and the circulation retention rate is more than or equal to 87.3%.
Drawings
FIG. 1 is an infrared spectrum of cesium ion adsorbents provided in examples 1 to 3 of the present invention;
FIG. 2 is a scanning electron microscope image of cesium ion adsorbents provided in examples 1 to 3 of the present invention;
wherein a is a scanning electron microscope image of the cesium ion adsorbent provided in example 1, B is a scanning electron microscope image of the cesium ion adsorbent provided in example 2, and C is a scanning electron microscope image of the cesium ion adsorbent provided in example 3.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a cesium ion adsorbent, wherein the raw material of the cesium ion adsorbent is p-hydroxybenzyl alcohol, and the pore diameter of the cesium ion adsorbent is 2.38nm.
The embodiment provides a preparation method of the cesium ion adsorbent, which comprises the following specific steps:
p-hydroxybenzyl alcohol (2.48 g,0.02 mol) was dissolved in 50mL of dichloroethane under nitrogen atmosphere, anhydrous ferric trichloride (3.25 g,0.02 mol) was added and reacted at 45℃for 5h, then the reaction temperature was raised to 80℃for 19h; after the reaction is finished, cooling to room temperature, and carrying out suction filtration to obtain insoluble black solid; the solid was successively subjected to 0.05mol L -1 Washing with ultrapure water for 2h until the filtrate is neutral, washing with methanol until the filtrate becomes clear, and then further purifying the separated solid product with methyl acetateSoxhlet extraction with alcohol for 24h, removal of residual solvent and catalyst, and finally vacuum drying at 60 ℃ for 24h, grinding into fine powder, obtaining the cesium ion adsorbent (HCP-pP).
Example 2
The embodiment provides a cesium ion adsorbent, wherein the raw material of the cesium ion adsorbent is o-hydroxybenzyl alcohol, and the pore diameter of the cesium ion adsorbent is 3.19nm.
The embodiment provides a preparation method of the cesium ion adsorbent, which comprises the following specific steps:
o-hydroxybenzyl alcohol (2.48 g,0.02 mol) was dissolved in 50mL of dichloroethane under nitrogen atmosphere, anhydrous ferric trichloride (3.25 g,0.02 mol) was added and reacted at 45℃for 5 hours, and then the reaction temperature was raised to 80℃for 19 hours; after the reaction is finished, cooling to room temperature, and carrying out suction filtration to obtain insoluble black solid; the solid was successively subjected to 0.05mol L -1 Washing with ultrapure water for 2 hours, washing with ultrapure water until the filtrate is neutral, washing with methanol until the filtrate becomes clear, then further Soxhlet extracting the separated solid product with methanol for 24 hours, removing residual solvent and catalyst, finally drying in vacuum at 60 ℃ for 24 hours, and grinding into fine powder to obtain the cesium ion adsorbent (HCP-cP).
Example 3
The embodiment provides a cesium ion adsorbent, wherein the raw material of the cesium ion adsorbent is m-hydroxybenzyl alcohol, and the pore diameter of the cesium ion adsorbent is 3.91nm.
The embodiment provides a preparation method of the cesium ion adsorbent, which comprises the following specific steps:
m-hydroxybenzyl alcohol (2.48 g,0.02 mol) was dissolved in 50mL of dichloroethane under nitrogen atmosphere, anhydrous ferric trichloride (3.25 g,0.02 mol) was added and reacted at 45℃for 5h, then the reaction temperature was raised to 80℃for 19h; after the reaction is finished, cooling to room temperature, and carrying out suction filtration to obtain insoluble black solid; the solid was successively subjected to 0.05mol L -1 Washing with ultrapure water for 2h until the filtrate is neutral, washing with methanol until the filtrate becomes clear, and separatingFurther soxhlet extraction with methanol for 24 hours, removal of residual solvent and catalyst, final vacuum drying at 60 ℃ for 24 hours, grinding to fine powder, obtaining the cesium ion adsorbent (HCP-rP).
The structure of the cesium ion adsorbents provided in examples 1 to 3 was characterized by an infrared spectrometer (Bruker, tensor 27, germany) and the results are shown in FIG. 1 at 1625cm -1 To 1591cm -1 The characteristic peak observed nearby corresponds to the c=c stretching vibration peak of the benzene ring skeleton; 3446cm -1 The characteristic peak at the position corresponds to the stretching vibration peak of-OH; the structure of the phenol monomer is completely preserved after polymerization; 3 adsorbents at 2920cm -1 To 2912cm -1 A new characteristic peak appears in the range, and the peak belongs to the stretching vibration peak of methylene, which proves that the crosslinking reaction is successful.
The morphology of the cesium ion adsorbents provided in examples 1-3 was characterized using a scanning electron microscope (zeiss, sigma 300) and the results are shown in fig. 2, wherein HCP-pP and HCP-cP are based on irregular spherical particles with rough surfaces, and HCP-rP is an irregular bulk solid. The particle size of HCP-pP is obviously smaller, belonging to nano-scale particles, while the particle size of HCP-cP is larger, and the diameter is in the micron scale.
The pore sizes of cesium ion adsorbents provided in examples 1 to 3 were characterized using a physical adsorption instrument.
Example 4
This example provides a cesium ion adsorbent which differs from example 2 only in that the amount of anhydrous ferric trichloride in the preparation method is 0.04mol, and the other steps and parameters are the same as in example 2.
Example 5
This example provides a cesium ion adsorbent which differs from example 2 only in that the amount of anhydrous ferric trichloride in the preparation method is 0.08mol, and the other steps and parameters are the same as in example 2.
Example 6
This example provides a cesium ion adsorbent which differs from example 2 only in that the o-hydroxybenzyl alcohol is replaced with an equimolar amount of p-hydroxybenzyl bromide.
This example provides a method for preparing cesium ion adsorbent, the specific procedure being the same as example 2.
Example 7
This example provides a cesium ion adsorbent which differs from example 2 only in that the o-hydroxybenzyl alcohol is replaced with an equimolar amount of o-hydroxybenzyl bromide.
This example provides a method for preparing cesium ion adsorbent, the specific procedure being the same as example 2.
Example 8
This example provides a cesium ion adsorbent which differs from example 2 only in that the o-hydroxybenzyl alcohol is replaced with an equimolar amount of m-hydroxybenzyl bromide.
This example provides a method for preparing cesium ion adsorbent, the specific procedure being the same as example 2.
Example 9
This example provides a cesium ion adsorbent which differs from example 2 only in that the o-hydroxybenzyl alcohol is replaced with an equimolar amount of p-hydroxybenzyl chloride.
This example provides a method for preparing cesium ion adsorbent, the specific procedure being the same as example 2.
Example 10
This example provides a cesium ion adsorbent which differs from example 2 only in that the o-hydroxybenzyl alcohol is replaced with an equimolar amount of o-hydroxybenzyl chloride.
This example provides a method for preparing cesium ion adsorbent, the specific procedure being the same as example 2.
Example 11
This example provides a cesium ion adsorbent which differs from example 2 only in that the o-hydroxybenzyl alcohol is replaced with an equimolar amount of m-hydroxybenzyl chloride.
This example provides a method for preparing cesium ion adsorbent, the specific procedure being the same as example 2.
Experimental example
Respectively prepare 0mol L -1 、0.005mol L -1 、0.02mol L -1 、0.05mol L -1 、0.1mol L -1 、0.2mol L -1 NaOH solution of (C) and 10.0mmol L -1 0.01g of cesium ion adsorbent provided in examples 1-3 was weighed into a 10mL centrifuge tube, 2mL of NaOH solution and 2mL of CsCl solution were added, the mixture was placed in a constant temperature rotary shaking table (25 ℃ C., 200 rpm) and was subjected to constant temperature shaking for 24 hours to reach adsorption equilibrium, the supernatant was collected by a syringe after high-speed centrifugation, and was diluted 20 times after filtration by a 0.22 μm aqueous filter, the concentration of cesium ions in the solution was measured by an inductively coupled plasma emission spectrometer (ICP-AES), and the adsorption amount of cesium ions was calculatedWherein C is 0 (mg L -1 ) Is the concentration of the initial metal ion, ce (mg L -1 ) Is the concentration of metal ions in the solution at adsorption equilibrium, V (L) is the volume of the solution, and m (g) is the mass of the added adsorbent; the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the adsorbent pair Cs as the NaOH concentration increases + The adsorption amount of (C) shows a tendency of rapid increase and then decrease, and the concentration of NaOH in the final solution is optimally 0.025mol L -1 Thus, the final concentration of sodium hydroxide in the performance test is 0.025mol L -1 。
Performance testing
(1) Selectivity is as follows: 0.01g of cesium ion adsorbent provided in examples 1-11 was weighed into a 10mL centrifuge tube, and 2mL, 0.05mol L was added -1 Placing into a constant temperature rotary table (25deg.C, 200 rpm) and shaking for 24 hr to reach adsorption equilibrium, centrifuging at high speed, collecting supernatant by syringe, filtering with 0.22 μm water filter head, diluting for 20 times, and measuring the solution by ICP-AESCalculating separation factors according to cesium ion concentration in the liquid;
balance distribution coefficientSeparation factor->
Wherein C is 0 (mg L -1 ) Is the concentration of the initial metal ion, C e (mg L -1 ) Is the concentration of metal ions in the solution at adsorption equilibrium, V (L) is the volume of the solution, and m (g) is the mass of the added adsorbent;for the equilibrium partition coefficient of cesium ions,a balance distribution coefficient for interfering ions;
in the invention, when the interfering ions are potassium ions, mixed solutions with the molar ratio of potassium ions to cesium ions of 14:1, 69:1, 357:1, 684:1 and 1358:1 are prepared, and the average value of separation factors under 5 concentrations is calculated;
when the interfering ions are rubidium ions, the molar ratio of rubidium to cesium ions is 15:1;
the interfering ion is magnesium ion, and the molar ratio of magnesium ion to cesium ion is 467:1.
(2) Adsorption amount: respectively prepare 10mg L -1 、50mg L -1 、100mg L -1 、550mg L -1 、630mg L -1 、720mg L -1 、870mg L -1 、1270mg L -1 、1700mg L -1 CsCl solution of (a); weighing 0.01g of cesium ion adsorbent provided in examples 1-11 into a 10mL centrifuge tube, adding 2mL of NaOH solution and 2mL of CsCl solution, placing in a constant-temperature rotary shaking table (25 ℃ C., 200 rpm) for constant-temperature shaking for 24 hours to reach adsorption balance, centrifuging at a high speed, taking supernatant by a syringe, filtering by a water filter of 0.22 mu m, diluting by 20 times, and measuring the concentration of cesium ions in the solution by using ICP-AES;
the expression equation for calculating the maximum adsorption capacity by using Langmuir adsorption isothermal model is as follows:
wherein C is e (mg L -1 ) Is the concentration of the adsorbate in the solution at adsorption equilibrium, q e (mg g -1 ) Is the adsorption capacity at adsorption equilibrium, q m (mg g -1 ) Is the maximum adsorption capacity of the adsorbent, K L (L mg -1 ) Is a Langmuir model constant.
(3) Desorption and cycle performance: 0.01g of the cesium ion adsorbent provided in examples 1 to 11 was weighed into a 10mL centrifuge tube, and 2mL of NaOH solution and 2mL of 10mmol L were added -1 Placing in a constant temperature rotary shaking table (25 ℃ C., 200 rpm) for constant temperature shaking for 24 hours to reach adsorption equilibrium, sucking out supernatant by a syringe after high-speed centrifugation, diluting by 20 times after filtering by a water filter head with the thickness of 0.22 mu m, measuring the concentration of cesium ions in the solution by ICP-AES, and calculating the adsorption quantity; 4mL of 0.05mol L was added to the remaining adsorbent -1 Desorbing HCl of (2) for 1 hour under the same condition as adsorption, sucking out supernatant by a syringe after high-speed centrifugation, diluting 20 times after filtering by a water filter head with the thickness of 0.22 mu m, measuring the concentration of cesium ions in the solution by using ICP-AES, and calculating the desorption rate; then repeatedly washing the adsorbent to be neutral, continuing the next adsorption-desorption experiment, and continuously circulating for 5 times; calculating the average desorption rate of 5 cycles;
desorption rate = mass of adsorbent desorbed per mass of adsorbent/mass of adsorbent adsorbed per mass of adsorbent x 100%;
cycle retention = adsorption capacity of first cycle adsorbent/adsorption capacity of fifth cycle adsorbent x 100%.
The specific test results are shown in table 2:
TABLE 2
As can be seen from the table, the cesium ion adsorbent provided by the invention has high selectivity and high adsorption capacity on cesium ions, and has the advantages of high desorption rate, high efficiency and good cycle performance by selecting specific phenolic hydroxyl group-containing monomers to form the super-crosslinked porous adsorbent. From examples 1 to 4, the separation factor of cesium ion adsorbent for cesium potassium ions is 13.6 to 44.7, the separation factor for cesium rubidium ions is 6.3 to 13.8, the separation factor for cesium magnesium is 2.9 to 10.1, and the cesium ion adsorbent has high selectivity for cesium ions; the maximum adsorption capacity of cesium ions is 229.5-302.1 mg/g, the desorption rate is 90.4-93.8%, and the circulation retention rate is 87.36-91.3%.
As is clear from comparison of example 2 with examples 1 and 3, when o-hydroxybenzyl alcohol is selected, the adsorption and separation effect of the adsorbent on cesium ions is better; as is clear from comparison of example 2 with example 5, the selectivity for cesium ions is deteriorated and the adsorption amount is lowered in the range where the mass ratio of the catalyst to the monomer is no longer specified; as is clear from a comparison of example 2 with examples 6 to 11, the selectivity of the adsorbent to cesium ions is deteriorated when the monomer is not specific to the present invention.
In summary, the cesium ion adsorbent provided by the invention is prepared by selecting a specific phenolic hydroxyl group-containing monomer and self-crosslinking the monomer to form the porous organic adsorbent, so that the cesium ion adsorbent not only realizes high selectivity on cesium ions, but also realizes high adsorption capacity on cesium ions, and has excellent desorption cycle performance, so that the external crosslinking agent is avoided, and the preparation method is simple, saves cost and is environment-friendly.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (14)
1. The cesium ion adsorbent is characterized in that the cesium ion adsorbent is prepared from a monomer containing phenolic hydroxyl groups;
the monomer containing phenolic hydroxyl is any one or a combination of at least two of p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol and m-hydroxybenzyl alcohol;
the cesium ion adsorbent forms a super-crosslinked polymer through self-crosslinking of a phenolic hydroxyl group-containing monomer;
the cesium ion adsorbent is prepared by a method comprising:
carrying out Friedel-crafts alkylation reaction on a monomer containing phenolic hydroxyl in the presence of a catalyst to obtain the cesium ion adsorbent; the molar ratio of the catalyst to the phenolic hydroxyl group-containing monomer is (1-2): 1.
2. The cesium ion adsorbent of claim 1, wherein the phenolic hydroxyl group-containing monomer is o-hydroxybenzyl alcohol.
3. The cesium ion adsorbent of claim 1, wherein the pore size of the cesium ion adsorbent is 2-4 nm.
4. A method for preparing the cesium ion adsorbent according to any one of claims 1 to 3, characterized in that the method comprises:
carrying out Friedel-crafts alkylation reaction on a monomer containing phenolic hydroxyl in the presence of a catalyst to obtain the cesium ion adsorbent; the molar ratio of the catalyst to the phenolic hydroxyl group-containing monomer is (1-2): 1.
5. The method of preparation of claim 4, wherein the catalyst comprises a lewis acid catalyst;
the Lewis acid catalyst comprises any one or a combination of at least two of anhydrous ferric chloride, anhydrous aluminum chloride, anhydrous tin chloride or anhydrous zinc chloride.
6. The process according to claim 4, wherein the reaction is carried out in a solvent;
the solvent comprises dichloroethane.
7. The process of claim 4, wherein the reaction is carried out in the presence of a protective atmosphere.
8. The method of claim 4, wherein the reaction comprises a first stage reaction and a second stage reaction;
the temperature of the first-stage reaction is 40-50 ℃;
the reaction time of the first stage is 4-6 hours;
the temperature of the second-stage reaction is 75-85 ℃;
the reaction time of the second stage is 15-25 h.
9. The preparation method according to claim 4, characterized in that the preparation method comprises the steps of:
mixing a monomer containing phenolic hydroxyl groups with a catalyst and a solvent in the presence of a protective atmosphere, reacting for 4-6 hours at 40-50 ℃, and reacting for 15-25 hours at 75-85 ℃ to obtain the cesium ion adsorbent; the molar ratio of the catalyst to the phenolic hydroxyl group-containing monomer is (1-2): 1.
10. Use of the cesium ion adsorbent according to any one of claims 1 to 3 for selective adsorption separation of cesium ions.
11. An adsorption separation method of cesium ions, characterized in that the adsorption separation method comprises the steps of:
the cesium ion adsorbent according to any one of claims 1 to 3, wherein the cesium ion adsorbent is mixed with a cesium chloride solution under alkaline conditions to perform adsorption separation.
12. The adsorptive separation process of claim 11, wherein said mixed solution further comprises any one or a combination of at least two of potassium chloride, rubidium chloride, or magnesium chloride;
the concentration of hydroxyl ions in the mixed solution is 0.01-0.1 mol/L.
13. The adsorption separation method according to claim 12, wherein the concentration of hydroxide ions in the mixed solution is 0.01 to 0.05 mol/L;
the mixing time is 20-26 hours.
14. The adsorption separation method according to claim 11, wherein the mass ratio of cesium chloride to cesium ion adsorbent is (0.002-0.34): 1.
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| CN101670271A (en) * | 2009-10-14 | 2010-03-17 | 福州大学 | Condensation-type adsorbent resin microballon containing phenolic hydroxyl and preparation method thereof |
| CN111604037A (en) * | 2020-05-12 | 2020-09-01 | 中国人民解放军陆军军医大学 | Polyphenol microsphere for treating heavy metal ions and radioactive nuclide in industrial wastewater and preparation method and application thereof |
| CN113769719A (en) * | 2021-09-28 | 2021-12-10 | 中南林业科技大学 | Lignin-based super-crosslinked porous resin ball and preparation method and application thereof |
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| DE19954153A1 (en) * | 1999-11-10 | 2001-05-17 | Michael Preidl | Process for the preservation of hemp seeds |
| IL144058A (en) * | 2001-06-28 | 2006-10-05 | Yaakov Lahav | Composition for coating fruits, vegetables and fowl eggs, especially useful for organic produce |
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