CN114733494A - Cesium ion adsorbent and preparation method and application thereof - Google Patents
Cesium ion adsorbent and preparation method and application thereof Download PDFInfo
- Publication number
- CN114733494A CN114733494A CN202210357781.4A CN202210357781A CN114733494A CN 114733494 A CN114733494 A CN 114733494A CN 202210357781 A CN202210357781 A CN 202210357781A CN 114733494 A CN114733494 A CN 114733494A
- Authority
- CN
- China
- Prior art keywords
- ion adsorbent
- cesium
- cesium ion
- phenolic hydroxyl
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D17/00—Rubidium, caesium or francium compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention provides a cesium ion adsorbent and a preparation method and application thereof. The raw material of the cesium ion adsorbent comprises a phenolic hydroxyl group-containing monomer. The preparation method of the cesium ion adsorbent provided by the invention comprises the following steps: and carrying out Friedel-crafts alkylation reaction on the monomer containing the 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 capacity on cesium ions, has excellent cycle performance, can realize rapid desorption, is simple in 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 due to its special physicochemical properties, is currently widely used in high-tech fields such as energy, medicine, aerospace, catalysis, photoelectric communication, and oil and gas drilling.
China reserves abundant metal resources including cesium in salt lake brine in Qinghai, Tibet, Sichuan and other areas. Although the total amount of cesium stored in the salt lake brine is high, it is mostly present in the form of ions (Cs)+) Low concentration (less than 40mg L)-1) And contains a plurality of associated ions, particularly physical and chemical properties and Cs+Very close potassium ions, extremely high separation and extraction difficulty, and no industrial salt lake brine cesium separation and extraction process technology exists at present.
In the prior art, extraction method and adsorption method are mostly adopted to adsorb and separate cesium ions. The extractant such as crown ether and substituted phenol used in the extraction method contains oxygen-containing functional groups with strong affinity to cesium, such as ether oxygen group and phenolic hydroxyl group, and combines with Cs by multi-coordination+Extremely high selectivity separation is achieved. For example, CN106435180A discloses an extraction method of rubidium ions and cesium ions, which comprises performing extraction treatment on a mixed solution containing rubidium ions and cesium ions by using a composite extractant, wherein the composite extractant comprises an acidic extractant, at least one component of a neutral organic substance, and a phenol-based extractant; the extraction method improves the Rb pair+And Cs+The effect of extraction. However, the extractant is not easy to synthesize, expensive, easy to run off, needs to use organic solvent, is not environment-friendly, needs strong acid or strong base and the like in the extraction process, and is not suitable for salt lake with extremely low concentration Cs+The separation and extraction of (3).
The adsorption method is the most suitable separation method for low-concentration systems, and mainly comprises two types of inorganic adsorbents and organic adsorbents. For example, CN104692406A discloses a preparation method of an adsorbent for selectively separating cesium ions from salt lake brine, which comprises: cesium ions are used as a template agent, and a surfactant, soluble cesium salt, sodium silicate and sodium aluminate are mixed according to a certain proportion to prepare the artificial zeolite ion sieve with the cesium ion customized pore channel structure for Cs in salt lake brine+The selective adsorption performance is excellent. CN105363414A discloses a cesium ion adsorbent, and the preparation raw materials of the adsorbent comprise aminated ferroferric oxide, carboxylated crown ether derivatives and a condensing agent. The cesium ion adsorbent has high cesium ion adsorption selectivity and magnetism, and can maintain stable adsorption performance in multiple adsorption-desorption cycle use. However, the preparation method of the adsorbent is complex and high in cost.
The common defects in the prior art are that part of materials of an inorganic adsorbent are unstable, easy to be dissolved and gelled and generally difficult to be desorbed, and the research is mostly focused on a spent fuel system in a strong radiation environment. The organic adsorbent is not resistant to radiation, the selectivity needs to be improved, the preparation method is complex, and the cost is high.
Therefore, the development of an adsorbent having high selectivity to cesium ions, high adsorption capacity, high desorption rate, good cycle performance and simple preparation method is an urgent problem to be solved in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a cesium ion adsorbent and a preparation method and application thereof. The cesium ion adsorbent is a super-crosslinked polymer formed by self-crosslinking of a phenolic hydroxyl group-containing monomer, and has high selectivity and high adsorption capacity on cesium ions and excellent desorption and cycle performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a cesium ion adsorbent whose raw material includes a phenolic hydroxyl group-containing monomer; the monomer containing the phenolic hydroxyl 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 a hydroxyl is connected to any position on a benzene ring.
In the invention, the halogen refers to F, Cl, Br and I.
According to the invention, a monomer containing phenolic hydroxyl is selected as a raw material, so that the adsorbent is rich in phenolic hydroxyl and can coordinate with cesium ions, and the cesium ions can be adsorbed and separated; and the specific phenolic hydroxyl group-containing monomer can realize high selectivity and high adsorption capacity to cesium ions, and has excellent desorption performance and cycle performance.
As a preferred technical scheme of the invention, the monomer containing the phenolic hydroxyl comprises any one or a combination of at least two of p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol or m-hydroxybenzyl alcohol.
Preferably, the phenolic hydroxyl group-containing monomer includes o-hydroxybenzyl alcohol.
In the invention, when the phenolic hydroxyl group-containing monomer is o-hydroxybenzyl alcohol, the selectivity to cesium ions is higher.
Preferably, the pore diameter of the cesium ion adsorbent is 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 aperture of the cesium ion adsorbent is characterized by adopting a physical adsorption instrument.
In a second aspect, the present invention provides a method for producing a cesium ion adsorbent according to the first aspect, comprising:
and carrying out Friedel-crafts alkylation reaction on the monomer containing the 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, and the like.
In the invention, the catalyst and the monomer are in a specific molar ratio, the cesium ion adsorbent has high selectivity and adsorption capacity to cesium ions, 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 adsorption performance is greatly reduced.
Preferably, the catalyst comprises a lewis acid catalyst.
Preferably, the lewis acid catalyst comprises any one of anhydrous ferric chloride, anhydrous aluminum chloride, anhydrous stannic chloride or anhydrous zinc chloride or a combination of at least two thereof.
In the invention, under the catalysis of Lewis acid, the monomer containing phenolic hydroxyl can be subjected to Friedel-crafts alkylation reaction to synthesize the hypercrosslinked polymer by one-step self-crosslinking, so that the defects of an extracting agent and an adsorbing agent in the prior art are overcome, the high selectivity of a multi-coordination extracting agent, the high adsorption capacity and the rapid adsorption rate of the adsorbing agent and the excellent desorption and cycle performance are realized, the pre-crosslinking step with complicated operation and the use of an external crosslinking agent 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, for example, 16mL, 18mL, 20mL, 22mL, 24mL, or the like, based on 1g of the mass of the phenolic hydroxyl group-containing monomer.
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 ℃, for example, 42 ℃, 44 ℃, 45 ℃, 46 ℃, 48 ℃ and the like.
Preferably, the time of the first stage reaction is 4-6 h, for example, 4.5h, 5h, 5.5h, 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 time of the second stage reaction is 15-25 h, for example, 16h, 18h, 20h, 22h, 24h and the like.
In the invention, the reaction also comprises the steps of suction filtration, washing and drying.
Preferably, the washing comprises the step of washing with hydrochloric acid, ultrapure water and methanol in this order.
Preferably, the concentration of the hydrochloric acid is 0.04-0.06 mol/L, for example, 0.045mol/L, 0.05mol/L, 0.055mol/L and the like.
Preferably, the washing time with hydrochloric acid is 1 to 3 hours, for example, 1.5 hours, 2 hours, 2.5 hours, and the like.
Preferably, the washing with ultrapure water is carried out until the filtrate is neutral.
Preferably, the washing with methanol is carried out until the filtrate becomes clear.
Preferably, the washing with methanol further comprises a step of performing soxhlet extraction.
Preferably, the solvent of the soxhlet extraction comprises methanol.
Preferably, the soxhlet extraction time is 20-28 h, for example, 22h, 24h, 26h, 27h and the like.
In the present invention, the objective of the soxhlet extraction is to remove residual solvent and catalyst.
Preferably, the drying temperature is 55-65 ℃, for example 56 ℃, 58 ℃, 60 ℃, 62 ℃, 64 ℃ and the like.
Preferably, the drying time is 20-28 h, for example, 22h, 24h, 26h, 27h and the like.
Preferably, the drying is carried out in a vacuum drying oven.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
in the presence of a protective atmosphere, mixing a monomer containing phenolic hydroxyl with a catalyst and a solvent, reacting for 4-6 h at 40-50 ℃, and then reacting for 15-25 h 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 adsorptive separation of cesium ions.
In a fourth aspect, the present invention provides an adsorptive separation method for cesium ions, comprising the steps of:
the cesium ion adsorbent according to the first aspect is mixed with a cesium chloride solution to perform adsorptive separation.
Preferably, the mixed metal salt solution further comprises any one of potassium chloride, rubidium chloride or magnesium chloride or a combination of at least two of them.
Preferably, the mixing is performed under alkaline conditions.
Preferably, the concentration of the hydroxide ions in the mixed solution is 0 to 0.1mol/L, 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 0.05 mol/L.
In the invention, the alkaline condition is realized by adding sodium hydroxide, and when the concentration of NaOH is 0mol L-1When the adsorbent is almost free from adsorption of Cs, i.e., under neutral conditions+This is because the phenolic hydroxyl group has a pKa of 9.99 and is difficult to deprotonate under neutral conditions, requiring the addition of a base to raise the pH of the solution to drive the deprotonation of the phenolic hydroxyl group. Wherein the optimum NaOH concentration is 0.025mol L-1。
Preferably, the mixing time is 20-26 h, for example, 22h, 24h, 25h and the like.
Preferably, the mass ratio of the cesium chloride to the cesium ion adsorbent is (0.002-0.34): 1, and may be, for example, 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, or the like.
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 24-26 ℃, for example, 24 ℃, 25 ℃, 26 ℃ and the like.
Preferably, the rotation speed of the constant temperature rotary table is 150-250 rpm, such as 160rpm, 180rpm, 200rpm, 220rpm, 240rpm, etc.
The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.
Compared with the prior art, the invention has the following beneficial effects:
according to the cesium ion adsorbent provided by the invention, a hypercrosslinked polymer is formed by self-crosslinking of a specific phenolic hydroxyl group-containing monomer, and the cesium ion adsorbent has high selectivity, high adsorption capacity and excellent desorption and cycle performance on cesium ions; the separation factor of the adsorbent to cesium ions and potassium ions is more than or equal to 6.8, the adsorption capacity to the cesium ions is more than or equal to 229.5mg/g, the desorption rate is more than or equal to 90.2%, and the cycle retention rate is more than or equal to 87.3%.
Drawings
FIG. 1 is an infrared spectrum of a cesium ion adsorbent provided in embodiments 1 to 3 of the present invention;
FIG. 2 is a scanning electron microscope image of cesium ion adsorbents provided in embodiments 1 to 3 of the present invention;
wherein, a is a scanning electron micrograph of the cesium ion adsorbent provided in example 1, B is a scanning electron micrograph of the cesium ion adsorbent provided in example 2, and C is a scanning electron micrograph of the cesium ion adsorbent provided in example 3.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides a cesium ion adsorbent, which is prepared from p-hydroxybenzyl alcohol as a raw material and has a pore size of 2.38 nm.
The embodiment provides a preparation method of a cesium ion adsorbent, which specifically comprises the following steps:
dissolving p-hydroxybenzyl alcohol (2.48g, 0.02mol) in 50mL dichloroethane under nitrogen atmosphere, adding anhydrous ferric trichloride (3.25g, 0.02mol) to react at 45 ℃ for 5h, and then raising the reaction temperature to 80 ℃ for reacting for 19 h; after the reaction is finished, cooling to room temperature, and performing suction filtration to obtain an insoluble black solid; the solid is sequentially adopted to be 0.05mol L-1Washing with hydrochloric acid solution for 2h, washing with ultrapure water until the filtrate is neutral, washing with methanol until the filtrate becomes clear, further performing Soxhlet extraction on the separated solid product with methanol for 24h, removing residual solvent and catalyst, finally performing vacuum drying at 60 ℃ for 24h, and grinding into fine powder to obtain the cesium ion adsorbent (HCP-pP).
Example 2
This example provides a cesium ion adsorbent, which is prepared from o-hydroxybenzyl alcohol as a raw material and has a pore diameter of 3.19 nm.
The embodiment provides a preparation method of a cesium ion adsorbent, which specifically comprises the following steps:
dissolving o-hydroxybenzyl alcohol (2.48g, 0.02mol) in 50mL dichloroethane under nitrogen atmosphere, adding anhydrous ferric trichloride (3.25g, 0.02mol) to react for 5h at 45 ℃, and then raising the reaction temperature to 80 ℃ to react for 19 h; after the reaction is finished, cooling to room temperature, and performing suction filtration to obtain an insoluble black solid; the solid is sequentially adopted to be 0.05mol L-1Washing with hydrochloric acid solution for 2h, washing with ultrapure water until the filtrate is neutral, washing with methanol until the filtrate becomes clear, further performing Soxhlet extraction on the separated solid product with methanol for 24h, removing residual solvent and catalyst, finally performing vacuum drying at 60 ℃ for 24h, and grinding into fine powder to obtain the cesium ion adsorbent (HCP-cP).
Example 3
This example provides a cesium ion adsorbent, the raw material of which is m-hydroxybenzyl alcohol, and the pore diameter of which is 3.91 nm.
The embodiment provides a preparation method of a cesium ion adsorbent, which specifically comprises the following steps:
under the nitrogen atmosphere, dissolving m-hydroxybenzyl alcohol (2.48g, 0.02mol) in 50mL dichloroethane, adding anhydrous ferric trichloride (3.25g, 0.02mol) to react for 5h at 45 ℃, and then raising the reaction temperature to 80 ℃ to react for 19 h; after the reaction is finished, cooling to room temperature, and performing suction filtration to obtain an insoluble black solid; the solid is sequentially adopted by 0.05mol L-1Washing with hydrochloric acid solution for 2h, washing with ultrapure water until the filtrate is neutral, washing with methanol until the filtrate becomes clear, further performing Soxhlet extraction on the separated solid product with methanol for 24h, removing residual solvent and catalyst, finally performing vacuum drying at 60 ℃ for 24h, and grinding into fine powder to obtain the cesium ion adsorbent (HCP-rP).
The structures of the cesium ion adsorbents provided in examples 1 to 3 were characterized by an infrared spectrometer (Bruker, Tensor 27, Germany), and the results are shown in FIG. 1 at 1625cm-1To 1591cm-1The characteristic peak observed nearby corresponds to a C ═ C stretching vibration peak of the benzene ring skeleton; 3446cm-1The characteristic peak corresponds to the stretching vibration peak of-OH; the structure of the phenol monomer is completely reserved after polymerization; 3 adsorbents at 2920cm-1To 2912cm-1A new characteristic peak appears in the range, belongs to the stretching vibration peak of methylene, and proves that the crosslinking reaction is successfully generated.
The morphology of the cesium ion adsorbents provided in examples 1-3 was characterized by scanning electron microscopy (zeiss, Sigma 300, uk) and the results are shown in fig. 2, where HCP-pP and HCP-cP are predominantly irregular spherical particles and have a rough surface, whereas HCP-rP is an irregular bulk solid. The particle size of HCP-pP is significantly smaller and is of the nanoscale, while the particles of HCP-cP are larger and have a diameter in the micrometer range.
And (3) characterizing the pore diameter of the cesium ion adsorbent provided in the embodiment 1-3 by 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 production process is 0.04mol, and other steps and parameters are the same as those of 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 production process is 0.08mol, and other steps and parameters are the same as those of example 2.
Example 6
This example provides a cesium ion adsorbent that 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, which comprises the same steps as in example 2.
Example 7
This example provides a cesium ion adsorbent that differs from example 2 only in that the ortho-hydroxybenzyl alcohol is replaced with an equimolar amount of ortho-hydroxybenzyl bromide.
This example provides a method for preparing cesium ion adsorbent, which comprises the same steps as in example 2.
Example 8
This example provides a cesium ion adsorbent that differs from example 2 only in that the ortho-hydroxybenzyl alcohol is replaced with an equimolar amount of meta-hydroxybenzyl bromide.
This example provides a method for preparing cesium ion adsorbent, which includes the same steps as example 2.
Example 9
This example provides a cesium ion adsorbent that differs from example 2 only in that the ortho-hydroxybenzyl alcohol is replaced with an equimolar amount of para-hydroxybenzyl chloride.
This example provides a method for preparing cesium ion adsorbent, which comprises the same steps as in example 2.
Example 10
This example provides a cesium ion adsorbent that differs from example 2 only in that the ortho-hydroxybenzyl alcohol is replaced with an equimolar amount of ortho-hydroxybenzyl chloride.
This example provides a method for preparing cesium ion adsorbent, which comprises the same steps as in example 2.
Example 11
This example provides a cesium ion adsorbent that differs from example 2 only in that the ortho-hydroxybenzyl alcohol is replaced with an equimolar amount of meta-hydroxybenzyl chloride.
This example provides a method for preparing cesium ion adsorbent, which comprises the same steps as in example 2.
Examples of the experiments
Respectively preparing 0mol L-1、0.005mol L-1、0.02mol L-1、0.05mol L-1、0.1mol L-1、0.2mol L-1NaOH solution and 10.0mmol L-1Weighing 0.01g of the cesium ion adsorbent provided in examples 1 to 3 into a 10mL centrifuge tube, adding 2mL of NaOH solution and 2mL of CsCl solution, placing the CsCl solution into a constant-temperature rotary table (25 ℃, 200rpm), vibrating the CsCl solution at a constant temperature for 24 hours to achieve adsorption balance, centrifuging the CsCl solution at a high speed, taking supernate by using an injector, filtering the supernate by using a 0.22-micron water system filter head, diluting the supernate by 20 times, measuring the concentration of cesium ions in the solution by using an inductively coupled plasma emission spectrometer (ICP-AES), and calculating the adsorption capacity and the adsorption capacity of the cesium ions
Wherein, C0(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 equilibrium of adsorption, V (L) is the volume of the solution, and m (g) is the mass of added adsorbent; the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the adsorbent is directed to Cs as the concentration of NaOH increases+The adsorption amount of (A) showsThe trend of decreasing after rapid increase, the NaOH concentration in the final solution is optimally 0.025mol L-1Thus, the final concentration of sodium hydroxide in the performance test is 0.025mol L, infra-1。
Performance test
(1) And (3) selectivity: 0.01g of the cesium ion adsorbent provided in examples 1 to 11 was weighed into a 10mL centrifuge tube, and 2mL and 0.05mol L of the adsorbent were added-1Placing the NaOH solution and 2mL of cesium chloride solution containing interfering ions in a constant-temperature rotary shaking table (25 ℃, 200rpm) to vibrate at a constant temperature for 24 hours to enable the solution to reach adsorption balance, centrifuging at a high speed, taking supernate by using an injector, filtering by using a water system filter head with the diameter of 0.22 mu m, diluting by 20 times, measuring the cesium ion concentration in the solution by using ICP-AES, and calculating a separation factor;
equilibrium partition coefficient
Separation factor
Wherein, C0(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, m (g) is the mass of added adsorbent;
is the equilibrium partition coefficient of the cesium ions,
a balanced partition coefficient for interfering ions;
in the invention, when the interference ions are potassium ions, mixed solutions with molar ratios of potassium ions and 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 interference ions are rubidium ions, the molar ratio of rubidium ions to cesium ions is 15: 1;
the interfering ions are magnesium ions, and the molar ratio of magnesium ions to cesium ions is 467: 1.
(2) Adsorption capacity: 10mg L of each of the solutions was prepared-1、50mg L-1、100mg L-1、550mg L-1、630mg L-1、720mg L-1、870mg L-1、1270mg L-1、1700mg L-1The CsCl solution of (1); weighing 0.01g of the cesium ion adsorbent provided in examples 1 to 11 in a 10mL centrifuge tube, adding 2mL of NaOH solution and 2mL of CsCl solution, placing the centrifuge tube in a constant-temperature rotary shaking table (25 ℃, 200rpm), shaking the centrifuge tube at a constant temperature for 24 hours to achieve adsorption balance, centrifuging the centrifuge tube at a high speed, taking supernatant by using an injector, filtering the supernatant by using a 0.22-micron water system filter head, diluting the supernatant by 20 times, and measuring the cesium ion concentration in the solution by using ICP-AES;
the expression equation for calculating the maximum adsorption amount by adopting a Langmuir adsorption isothermal model is as follows:
wherein, Ce(mg L-1) Is the concentration of adsorbate in the solution at equilibrium of adsorption, qe(mg g-1) Is the adsorption capacity at adsorption equilibrium, qm(mg g-1) Is the maximum adsorption capacity, K, of the adsorbentL(L mg-1) Is a Langmuir model constant.
(3) Desorption and cycling 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-1Placing the CsCl solution in a constant-temperature rotary shaking table (25 ℃, 200rpm), vibrating for 24 hours at constant temperature, enabling the CsCl solution to reach adsorption balance, centrifuging at high speed, sucking out supernate by using an injector, filtering by using a water system filter head with the diameter of 0.22 mu m, diluting by 20 times, measuring the cesium ion concentration in the solution by using ICP-AES, and calculating the adsorption capacity; 4mL of 0.05mol L was added to the remaining adsorbent-1Desorbing HCl for 1 hour under the same condition with the adsorption, centrifuging at high speed, sucking out supernatant with an injector, filtering with a 0.22 μm water system filter head, diluting by 20 times, measuring cesium ion concentration in the solution with ICP-AES, and calculating desorption rate; then repeatedly washing the adsorbent to neutrality, continuing the next adsorption-desorption experiment, and continuously circulating for 5 times(ii) a Calculating the average desorption rate of 5 cycles;
the desorption rate is the mass of adsorbate desorbed per unit mass of adsorbent/mass of adsorbate adsorbed by the adsorbent × 100%;
the cycle retention ratio is the adsorption capacity of the adsorbent in the first cycle/the adsorption capacity of the adsorbent in the fifth cycle × 100%.
The specific test results are shown in table 2:
TABLE 2
From the above table, the cesium ion adsorbent provided by the invention is a super-crosslinked porous adsorbent formed by selecting a specific phenolic hydroxyl group-containing monomer, and has the advantages of high selectivity and high adsorption capacity for cesium ions, high desorption rate, high efficiency and good cycle performance. From examples 1 to 4, it is found that the cesium ion adsorbent has a separation factor for cesium potassium ions of 13.6 to 44.7, a separation factor for cesium rubidium ions of 6.3 to 13.8, a separation factor for cesium magnesium of 2.9 to 10.1, and a high selectivity for cesium ions; the maximum adsorption capacity of the adsorbent to cesium ions is 229.5-302.1 mg/g, the desorption rate is 90.4-93.8%, and the cycle retention rate is 87.36-91.3%.
As can be seen from the comparison between example 2 and examples 1 and 3, when the o-hydroxybenzyl alcohol is selected, the adsorbent has better adsorption and separation effects on cesium ions; as is clear from comparison between example 2 and example 5, the selectivity for cesium ions is deteriorated and the amount of adsorption is reduced when the mass ratio of the catalyst to the monomer is no longer within a specific range; as is clear from comparison between example 2 and examples 6 to 11, the selectivity of the adsorbent for cesium ions is poor when the monomer is not a specific monomer of the present invention.
In conclusion, the cesium ion adsorbent provided by the invention is a porous organic adsorbent formed by self-crosslinking through selecting a specific phenolic hydroxyl group-containing monomer, so that high selectivity and high adsorption capacity on cesium ions are realized, the cesium ion adsorbent has excellent desorption cycle performance, a crosslinking agent is not added, the preparation method is simple, the cost is saved, and the cesium ion adsorbent is environment-friendly.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A cesium ion adsorbent, characterized in that a raw material of the cesium ion adsorbent comprises a phenolic hydroxyl group-containing monomer;
the monomer containing the phenolic hydroxyl has a structure shown in a formula I;
wherein R is any one of-OH or halogen group.
2. The cesium ion adsorbent of claim 1, wherein the phenolic hydroxyl group-containing monomer comprises any one of or a combination of at least two of p-hydroxybenzyl alcohol, o-hydroxybenzyl alcohol or m-hydroxybenzyl alcohol;
preferably, the phenolic hydroxyl group-containing monomer includes o-hydroxybenzyl alcohol.
3. The cesium ion adsorbent according to claim 1 or 2, wherein the pore size of the cesium ion adsorbent is 2 to 4 nm.
4. A method for preparing a cesium ion adsorbent according to any one of claims 1 to 3, comprising:
and carrying out Friedel-crafts alkylation reaction on the monomer containing the phenolic hydroxyl to obtain the cesium ion adsorbent.
5. The production method according to claim 4, wherein the reaction is carried out in the presence of a catalyst;
preferably, the molar ratio of the catalyst to the monomer containing the phenolic hydroxyl is (1-2): 1;
preferably, the catalyst comprises a lewis acid catalyst;
preferably, the lewis acid catalyst comprises any one of anhydrous ferric chloride, anhydrous aluminum chloride, anhydrous stannic chloride or anhydrous zinc chloride or a combination of at least two thereof;
preferably, the reaction is carried out in a solvent;
preferably, the solvent comprises dichloroethane.
6. The method according to claim 4 or 5, wherein the reaction is carried out in the presence of a protective atmosphere;
preferably, the reaction comprises a first stage reaction and a second stage reaction;
preferably, the temperature of the first stage reaction is 40-50 ℃;
preferably, the time of the first-stage reaction is 4-6 h;
preferably, the temperature of the second-stage reaction is 75-85 ℃;
preferably, the time of the second-stage reaction is 15-25 h.
7. The method according to any one of claims 4 to 6, characterized by comprising the steps of:
in the presence of a protective atmosphere, mixing a monomer containing phenolic hydroxyl with a catalyst and a solvent, reacting for 4-6 h at 40-50 ℃, and then reacting for 15-25 h at 75-85 ℃ to obtain the cesium ion adsorbent.
8. Use of a cesium ion adsorbent according to any one of claims 1 to 3 for selective adsorptive separation of cesium ions.
9. An adsorption separation method of cesium ions, characterized in that the adsorption separation method comprises the steps of:
mixing the cesium ion adsorbent as claimed in any one of claims 1 to 3 with a cesium chloride solution to perform adsorptive separation.
10. The adsorptive separation process according to claim 9, wherein said 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 carried out under alkaline conditions;
preferably, the concentration of hydroxide ions in the mixed solution is 0-0.1 mol/L, and further preferably 0.01-0.05 mol/L;
preferably, the mixing time is 20-26 h;
preferably, the mass ratio of the cesium chloride to the cesium ion adsorbent is (0.002-0.34): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210357781.4A CN114733494B (en) | 2022-04-06 | 2022-04-06 | Cesium ion adsorbent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210357781.4A CN114733494B (en) | 2022-04-06 | 2022-04-06 | Cesium ion adsorbent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114733494A true CN114733494A (en) | 2022-07-12 |
| CN114733494B CN114733494B (en) | 2023-09-29 |
Family
ID=82280282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210357781.4A Active CN114733494B (en) | 2022-04-06 | 2022-04-06 | Cesium ion adsorbent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114733494B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521459A (en) * | 2022-11-02 | 2022-12-27 | 东华理工大学 | Nitrogen heterocyclic ring adsorption material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1113435A (en) * | 1964-05-06 | 1968-05-15 | Gen Foods Ltd | Improvements in or relating to a method of improving the shelf-life of dried plant tissues |
| EP1099383A2 (en) * | 1999-11-10 | 2001-05-16 | Prima materia GmbH | Process for preserving hemp seeds |
| IL144058A0 (en) * | 2001-06-28 | 2002-04-21 | Biocoat Ltd | Composition for coating fruits, vegetables and fowl eggs, especially useful for organic produce |
| WO2009074982A2 (en) * | 2007-12-10 | 2009-06-18 | Vitiva D.O.O | Antioxidant stabilisation of nuts and seeds and of products containing the same |
| 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 |
-
2022
- 2022-04-06 CN CN202210357781.4A patent/CN114733494B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1113435A (en) * | 1964-05-06 | 1968-05-15 | Gen Foods Ltd | Improvements in or relating to a method of improving the shelf-life of dried plant tissues |
| EP1099383A2 (en) * | 1999-11-10 | 2001-05-16 | Prima materia GmbH | Process for preserving hemp seeds |
| IL144058A0 (en) * | 2001-06-28 | 2002-04-21 | Biocoat Ltd | Composition for coating fruits, vegetables and fowl eggs, especially useful for organic produce |
| EP1399026A2 (en) * | 2001-06-28 | 2004-03-24 | Biocoat Ltd. | Composition for coating fruits, vegetables and fowl eggs, especially useful for organic produce |
| WO2009074982A2 (en) * | 2007-12-10 | 2009-06-18 | Vitiva D.O.O | Antioxidant stabilisation of nuts and seeds and of products containing the same |
| US20100266737A1 (en) * | 2007-12-10 | 2010-10-21 | Majda Hadolin Kolar | Antioxidant stabilisation of nuts and seeds and of products containing the same |
| 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 |
Non-Patent Citations (4)
| Title |
|---|
| WENLIANG SONG等: "Guided Assembly of Well-Defined Hierarchical Nanoporous Polymers by Lewis Acid-Base Interactions", 《ACS NANO》 * |
| WENLIANG SONG等: "Guided Assembly of Well-Defined Hierarchical Nanoporous Polymers by Lewis Acid-Base Interactions", 《ACS NANO》, vol. 13, 27 September 2019 (2019-09-27), pages 11753 * |
| ZIHAO XU等: "Fabrication of hypercrosslinked hydroxyl-rich solid phase extractants for cesium separation from the salt lake brine", 《CHEMICAL ENGINEERING JOURNAL》 * |
| ZIHAO XU等: "Fabrication of hypercrosslinked hydroxyl-rich solid phase extractants for cesium separation from the salt lake brine", 《CHEMICAL ENGINEERING JOURNAL》, 21 June 2020 (2020-06-21), pages 1 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521459A (en) * | 2022-11-02 | 2022-12-27 | 东华理工大学 | Nitrogen heterocyclic ring adsorption material and preparation method and application thereof |
| CN115521459B (en) * | 2022-11-02 | 2024-01-26 | 东华理工大学 | Nitrogen heterocycle adsorption material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114733494B (en) | 2023-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9937459B2 (en) | Materials for gas capture, methods of making materials for gas capture, and methods of capturing gas | |
| Cao et al. | A highly permeable mixed matrix membrane containing CAU-1-NH 2 for H 2 and CO 2 separation | |
| CN108201878B (en) | Preparation method of carbon-point-modified metal organic framework adsorption material and application of carbon-point-modified metal organic framework adsorption material in treatment of water pollutants | |
| US20050079374A1 (en) | Micro-porous noble metal material and method for preparation thereof | |
| Huang et al. | 2-Methylol-12-crown-4 ether immobilized PolyHIPEs toward recovery of lithium (i) | |
| CN108543516B (en) | Lithium ion selective adsorbent, preparation method and process for extracting lithium from brine | |
| CN113817116B (en) | Preparation of covalent organic framework material and application of covalent organic framework material in rare earth separation | |
| CN106987018B (en) | Phenolic resin-graphene aerogel and preparation and application thereof | |
| Wang et al. | Mesoporous hollow silicon spheres modified with manganese ion sieve: Preparation and its application for adsorption of lithium and rubidium ions | |
| CN109876774B (en) | Adsorption material for treating dye sewage and preparation method thereof | |
| KR101189593B1 (en) | Oxygen adsorbent having high sorption rate for oxygen and preparation method thereof | |
| CN114733494B (en) | Cesium ion adsorbent and preparation method and application thereof | |
| CN110639474B (en) | Adsorbent for separating propylene and propane and preparation method thereof | |
| CN109499527B (en) | Ca2+And Ag+Modified adsorption material and preparation method and application thereof | |
| CN105903458A (en) | Preparation method and application of calcium-based adsorbent | |
| CN113842889A (en) | Microwave synthesis metal organic framework material DUT-5(Al) and synthesis method and application thereof | |
| JP6483477B2 (en) | Method for producing calcium salt and method for producing porous carbon | |
| CN115501732B (en) | Porous liquid with small molecular gas adsorption function, preparation method thereof, method for removing small molecular gas by using porous liquid and application of porous liquid | |
| JP6663146B2 (en) | Mesoporous zirconium hydroxide having carbon dioxide adsorption, method for producing the same, and carbon dioxide adsorbent comprising mesoporous zirconium hydroxide | |
| CN113967461B (en) | Porous carbon material rich in amino groups and preparation method and application thereof | |
| WO2022088675A1 (en) | Carbon dioxide adsorbent, and preparation method and use method therefor | |
| CN112452303A (en) | Galla chinensis tannin/dendritic fiber-shaped mesoporous silica nanoparticle composite material and application thereof in gallium recovery | |
| CN114214831A (en) | Preparation method and application of electrostatic spinning fiber based on team boron affinity shikimic acid surface molecular imprinting | |
| JP2018154563A (en) | Porous polymer complex, gas adsorbent and gas separation device and gas storage device using the same | |
| CN112915966A (en) | Preparation method and application of polyaniline-based activated carbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |