CN114904490A - Preparation method of degradable chitosan-based lithium ion imprinted membrane - Google Patents
Preparation method of degradable chitosan-based lithium ion imprinted membrane Download PDFInfo
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- CN114904490A CN114904490A CN202210615204.0A CN202210615204A CN114904490A CN 114904490 A CN114904490 A CN 114904490A CN 202210615204 A CN202210615204 A CN 202210615204A CN 114904490 A CN114904490 A CN 114904490A
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 70
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 69
- 239000012528 membrane Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 19
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 70
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 29
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 18
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 17
- 239000007822 coupling agent Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-BKFZFHPZSA-N lithium-12 Chemical compound [12Li] WHXSMMKQMYFTQS-BKFZFHPZSA-N 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 210000004379 membrane Anatomy 0.000 abstract description 37
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 5
- 210000002469 basement membrane Anatomy 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 21
- 229910052744 lithium Inorganic materials 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 14
- 239000003463 adsorbent Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 150000003983 crown ethers Chemical class 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
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- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 nuclear industry Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000005191 phase separation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
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- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
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- 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
- B01J20/28014—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 form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
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- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
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Abstract
The invention discloses a preparation method of a degradable chitosan-based lithium ion imprinted membrane, belonging to the technical field of functional material preparation. Firstly, preparing a hybrid basement membrane by utilizing the degradable characteristic of chitosan; then taking the film as a carrier, Li + The chitosan-based lithium ion imprinted membrane is prepared by taking template ions, 12-crown ether-4 as a functional monomer and tetraethoxysilane as a cross-linking agent through a simple hydrolytic polymerization process, and is renewable and easily degradable and used for selectively recovering lithium ions. The method aims to synthesize a novel low-cost and environment-friendly adsorbing material and promote the ecological environmentThe health development of the human body.
Description
Technical Field
The invention relates to a preparation method of a degradable chitosan-based lithium ion imprinted membrane, belonging to the technical field of functional material preparation.
Background
In the 21 st century of the new and advanced development of science and technology, lithium resources are important energy materials and strategic resources. As the least dense metal, lithium plays an important role in many industries, such as: lithium ion batteries, ceramic glass, medicine, nuclear industry, lubricants and the like. Accordingly, the market demand for lithium resources has increased dramatically in recent years. There are three major classifications of lithium resources today: 1. ore resources on land, mainly including spodumene, lepidolite, petalite and the like; 2. lithium resources existing in the form of lithium ions in oceans and salt lakes; 3. lithium resources present in waste batteries. Compared with the two resources, the lithium content in the current waste lithium battery reaches 5% -8% and is higher than that in the nature, so that the waste lithium battery has great potential in the aspect of lithium resource acquisition. The high-efficiency environment-friendly liquid-phase lithium extraction technology can effectively relieve the pressure of lithium resource market demand and has profound strategic significance on the national level.
To date, many techniques for liquid phase extraction of lithium have been developed, some of which have been applied to the actual lithium production industry. The 'adsorption lithium extraction technology' is a novel lithium extraction technology which has high cost performance and is environment-friendly. The early lithium adsorbent was a strong acid ion exchange resin, a high molecular organic compound. The working principle is that the absorption and desorption of lithium ions are realized by utilizing the ion exchange performance of the adsorbent. However, the early lithium adsorbent has poor selectivity, can adsorb other metal ions while adsorbing lithium ions, and has higher production cost than other materials, so the method has limited industrial application prospect.
Besides the adsorption materials such as ion exchange resin, the membrane adsorption has the advantages of simple operation, low energy consumption, strong expandability and the like, and is a research hotspot in the field of separation at present. Conventional membrane materials such as polyvinylidene fluoride (PVDF), Polysulfone (PSF), Polytetrafluoroethylene (PTFE), etc. are commonly used in the separation field. However, most of the membrane materials are synthesized from non-renewable resources, are widely used, are difficult to degrade by themselves after being discarded, and need to be treated in a centralized manner, but treatment methods such as landfill and combustion are likely to affect the environment.
Chitosan, as the second most natural polysaccharide of cellulose, has the advantages of biodegradability, nontoxicity, antibacterial property, chemical stability, etc. The chitosan is used as a raw material for synthesizing the base membrane, the imprinted polymer with selective adsorption performance on lithium ions is introduced on the surface of the membrane formed by the chitosan, and the synthesized membrane material with selective adsorption performance on lithium ions is an environment-friendly lithium recovery way.
The invention with application number 201510577040.7 provides a method for preparing imprinted polymer with high selective adsorption performance on lithium ions by taking orange peel cellulose as a matrix through graft modification, the method comprises the steps of firstly pretreating the cellulose to obtain alkalized alcoholized orange peel cellulose; then carrying out alkylation and grafting reaction to obtain modified orange peel cellulose with high-activity adsorption sites; and then adding the solution into a lithium ion aqueous solution, after adsorption equilibrium, adding a cross-linking agent for cross-linking, surrounding adsorption sites and lithium ions to form a semi-closed space, and finally eluting the lithium ions by using a regenerant to obtain the lithium ion imprinted polymer with high selective adsorption performance. However, the finally prepared lithium ion imprinted polymer is a powdery adsorbent, and an additional filtering operation is required in the adsorption and separation process, so that the adsorbent is very easily lost in the recovery process after adsorption is completed. The adsorption sites of the polymer are easily embedded in the adsorption process, and the subsequent imprinted polymer is not beneficial to recovery, so that the reuse efficiency is influenced.
The invention with application number 202110433243.4 provides a preparation method of a lithium ion imprinting nano composite membrane with high magnetism, high adsorption quantity and high selectivity, and the method solves the problems of low adsorption quantity and long adsorption balance time in the process of recovering lithium ions by an ion imprinting membrane. However, the polyvinylidene fluoride (PVDF) used as the base film material of the film is difficult to degrade automatically after being discarded without special treatment, and is easy to cause secondary environmental pollution.
Disclosure of Invention
In order to solve the environmental-related problems brought by the existing adsorption material, the invention aims to provide a preparation method of a degradable chitosan-based lithium ion imprinted membrane. The method not only realizes the selective enrichment of lithium ions in a lithium-containing solution system, but also solves the problems of environmental pollution and the like caused by difficult degradation after most of base film materials are discarded. The specific process is as follows: firstly, preparing a hybrid basement membrane by utilizing the biodegradable characteristic of chitosan; then using the hybrid membrane as a carrier and Li + As template ions, a chitosan-based lithium ion imprinted membrane with high stability and easy degradation is prepared by adopting a simple hydrolytic polymerization process.
The invention is realized by the following technical scheme: a preparation method of a degradable chitosan-based lithium ion imprinted membrane comprises the following steps:
(1) dissolving Chitosan (CTS) in a glacial acetic acid solution according to a solid-to-liquid ratio g/mL of (0.5-2): 50-100, heating and stirring at 40-50 ℃ by a magnetic stirrer until the chitosan is completely dissolved, and standing for 10-16 h to realize defoaming to obtain a chitosan solution;
(2) mixing a polyvinyl alcohol solution with the mass concentration of 4-6% with the chitosan solution in the step (1) according to the mass ratio of the polyvinyl alcohol solution to the chitosan solution of 1: 2-5 to obtain a mixed solution;
(3) adding a glutaraldehyde solution with the mass concentration of 20-25% into the mixed solution obtained in the step (2) as a cross-linking agent, and stirring for 4-6 hours at room temperature by using a magnetic stirrer to enable the mixed solution to react fully; then, casting the mixed solution into a film, drying the film in a constant-temperature air-blast drying oven at 45 ℃ until the film is completely transparent, putting the film into a sodium hydroxide solution for demoulding, repeatedly washing the film by using deionized water until the washing liquid is neutral, and naturally drying the film to obtain a film;
(4) taking 12-crown ether-4 and ethanol according to the volume ratio of 12-crown ether-4 to ethanol being (0.5-1): 20-30), and taking lithium chloride according to the solid-to-liquid ratio g/mL of lithium chloride to 12-crown ether-4 being (0.5-1): 0.5-1); dissolving lithium chloride and 12-crown ether-4 in ethanol, and stirring for 1-2 min to obtainMixing the materials I; then, preparing materials according to the volume ratio of the vinyltrimethoxysilane coupling agent to the ethyl orthosilicate of (0.2-0.5) to (0.2-0.8), adding the vinyltrimethoxysilane coupling agent and the ethyl orthosilicate into the mixed material I according to the volume ratio of the total amount of the vinyltrimethoxysilane coupling agent and the ethyl orthosilicate to the mixed material I of 1: 20, and continuously stirring for 5-10 min to obtain a mixed material II; according to the solid-liquid ratio g/mL (1-3): (40-60), adding the film obtained in the step (3) into the mixed material II, and continuously stirring for 5-10 min to obtain a mixed material III; finally, press H 2 O 2 Mixing the mixed solution with mixed material III at a volume ratio of 1: 2, and adding H into the mixed material III 2 O 2 Stirring the mixed solution at the temperature of 30-40 ℃ for 6-8 h to react so as to introduce adsorption sites on the surface of the film, endowing the film with the capability of selectively adsorbing lithium ions, and taking out the film;
(5) and (4) washing the film obtained in the step (4) with acid until lithium ions are completely eluted, washing the film with deionized water to be neutral, and drying the film to obtain the degradable lithium ion imprinted film.
Preferably, the mass concentration of the glacial acetic acid solution in the step (1) is 1-2%.
Preferably, the polyvinyl alcohol solution in the step (2) is obtained by dissolving a certain amount of polyvinyl alcohol (PVA) in deionized water at 50-60 ℃ by heating in a water bath.
Preferably, the concentration of the sodium hydroxide solution in the step (3) is 1 mol/L.
Preferably, said step (4) is H 2 O 2 The mixed solution is H 2 O 2 Mixing with deionized water at a mass ratio of 1: 10.
Preferably, the acid washing in the step (5) is performed by using HCl solution with the concentration of 0.5-1.0 mol/L.
The invention has the beneficial effects that:
(1) most of the currently synthesized adsorbents are mostly in powder form, and although the adsorbents have good adsorption capacity and selective adsorption capacity, the flowability and permeability of the adsorbents are poor, and the adsorbents are easy to run off and difficult to recover. The chitosan-based lithium ion imprinted composite membrane prepared by the invention combines a membrane separation technology and an ion imprinted technology, can be directly taken out without filtration operation in an adsorption and desorption process, and simplifies a recovery process.
(2) According to the invention, moist soil in a real environment is taken, the chitosan-based lithium ion imprinted composite membrane is subjected to landfill treatment, and the weight change of the chitosan-based lithium ion imprinted composite membrane is measured at different times to evaluate the environmental degradation characteristic of the chitosan-based lithium ion imprinted composite membrane. On the fifth day of the landfill treatment, the chitosan-based lithium ion imprinted composite membrane begins to have obvious weight loss; and after the fifteenth day, the weight loss rate of the chitosan-based lithium ion imprinted composite membrane reaches 60 percent. The chitosan is adopted to replace traditional plastic which cannot be degraded such as polyvinylidene fluoride and the like, and the environment protection after the service life of the film material is finished is facilitated.
(3) Crown ether is selected as a ligand, is combined with chitosan in a special way, and a phase separation technology is utilized to prepare the degradable chitosan-based lithium ion imprinted membrane capable of selectively adsorbing lithium ions.
Drawings
FIG. 1 is a thermogravimetric curve of the degradable chitosan-based lithium ion imprinted membrane prepared in example 1;
fig. 2 is an environmental degradation characteristic curve of the degradable chitosan-based lithium ion imprinted membrane prepared in example 1.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
(1) Dissolving Chitosan (CTS) in 2% glacial acetic acid solution at solid-to-liquid ratio g/mL of 2: 100, heating and stirring at 40 deg.C with a magnetic stirrer to dissolve completely, standing for 10h to achieve defoaming to obtain chitosan solution;
(2) mixing a polyvinyl alcohol solution with the mass concentration of 6% and the chitosan solution in the step (1) according to the mass ratio of the polyvinyl alcohol solution to the chitosan solution of 1: 3 to obtain a mixed solution; wherein the polyvinyl alcohol solution is prepared by dissolving a certain amount of polyvinyl alcohol (PVA) in deionized water at 60 ℃ by heating in a water bath;
(3) adding 1-2 drops of 25% glutaraldehyde solution serving as a cross-linking agent into the mixed solution obtained in the step (2), and stirring for 5 hours at room temperature by using a magnetic stirrer to enable the mixed solution to react fully; then the mixed solution is cast into a film, the film is dried to be completely transparent at the temperature of 45 ℃ by a constant temperature blast drying oven, the film is removed by being placed into a sodium hydroxide solution with the concentration of 1mol/L, deionized water is used for repeatedly washing until the washing liquid is neutral, and the film is obtained after natural drying;
(4) taking 12-crown ether-4 and ethanol according to the volume ratio of 12-crown ether-4 to ethanol of 0.5: 20, and taking lithium chloride according to the solid-to-liquid ratio g/mL of lithium chloride to 12-crown ether-4 of 0.5: 0.5; dissolving lithium chloride and 12-crown ether-4 in ethanol, and stirring for 2min to obtain a mixed material I; then, preparing materials according to the volume ratio of the vinyltrimethoxysilane coupling agent to the ethyl orthosilicate being 0.2: 0.5, adding the vinyltrimethoxysilane coupling agent and the ethyl orthosilicate into the mixed material I according to the volume ratio of the total amount of the vinyltrimethoxysilane coupling agent and the ethyl orthosilicate to the mixed material I being 1: 20, and continuously stirring for 5min to obtain a mixed material II; according to the solid-liquid ratio g/mL of 1: 40, putting the film obtained in the step (3) into the mixed material II, and continuously stirring for 5min to obtain a mixed material III; finally, press H 2 O 2 Mixing the mixed solution with mixed material III at a volume ratio of 1: 2, and adding H into the mixed material III 2 O 2 Mixing the solution, stirring and reacting for 6h at the temperature of 30 ℃ to introduce adsorption sites on the surface of the film, endowing the film with the capability of selectively adsorbing lithium ions, and taking out the film; wherein H 2 O 2 The mixed solution is H 2 O 2 Mixing with deionized water at a mass ratio of 1: 10;
(5) and (4) pickling the film obtained in the step (4) with HCl solution with the concentration of 0.5mol/L until lithium ions are completely eluted, washing with deionized water to be neutral, and drying to obtain the degradable lithium ion imprinted film.
As can be seen from FIG. 1, when the pyrolysis temperature reaches 89 ℃ under the oxygen atmosphere, the weight loss of the chitosan-based lithium ion imprinted membrane is 54.3%, which is attributable to the evaporation of water in the adsorption material; between 100 ℃ and 300 ℃, a mass loss of about 17.7% may occur, with C = C, C-O-C chemical bond breakage; the mass loss is about 28% between 300 ℃ and 500 ℃. After three stages, the chitosan-based lithium ion imprinted membrane is almost completely weightless.
In fig. 2, the chitosan-based lithium ion imprinted composite membrane was subjected to soil landfill treatment in a natural environment, and the weight change thereof was measured at different times to evaluate the environmental degradation characteristics thereof. Within three days before the landfill treatment, the weight of the film hardly changes obviously; on the fifth day of the landfill treatment, the chitosan-based lithium ion imprinted composite membrane begins to have obvious weight loss, which is about 10 percent; and after the fifteenth day, the weight loss rate of the chitosan-based lithium ion imprinted composite membrane reaches 60 percent. Fig. 2 demonstrates the natural degradation characteristic of the chitosan-based lithium ion imprinted membrane in the actual environment.
Example 2
(1) Dissolving Chitosan (CTS) in 1% glacial acetic acid solution at solid-to-liquid ratio g/mL of 1: 50, heating and stirring at 45 deg.C with a magnetic stirrer to dissolve completely, standing for 13h to achieve defoaming to obtain chitosan solution;
(2) mixing a polyvinyl alcohol solution with the mass concentration of 5% with the chitosan solution in the step (1) according to the mass ratio of the polyvinyl alcohol solution to the chitosan solution of 1: 2 to obtain a mixed solution; wherein the polyvinyl alcohol solution is prepared by dissolving a certain amount of polyvinyl alcohol (PVA) in deionized water at 55 ℃ by heating in a water bath;
(3) adding 1-2 drops of glutaraldehyde solution with the mass concentration of 22% as a cross-linking agent into the mixed solution obtained in the step (2), and stirring for 4 hours at room temperature by using a magnetic stirrer to enable the glutaraldehyde solution to react fully; then, casting the mixed solution into a film, drying the film in a constant-temperature air-blast drying oven at 45 ℃ until the film is completely transparent, putting the film into a sodium hydroxide solution with the concentration of 1mol/L for demoulding, repeatedly washing the film by using deionized water until the washing liquid is neutral, and naturally drying the film to obtain a film;
(4) taking 12-crown-4 and ethanol according to the volume ratio of 12-crown-4 to ethanol being 0.8: 25, and taking lithium chloride according to the solid-to-liquid ratio g/mL of lithium chloride to 12-crown-4 being 0.8: 1; dissolving lithium chloride and 12-crown ether-4 in ethanol, and stirring for 1min to obtain a mixed material I; then, preparing the material according to the volume ratio of the vinyltrimethoxysilane coupling agent to the ethyl orthosilicate of 0.3: 0.2The volume ratio of the total amount of the vinyltrimethoxysilane coupling agent and the ethyl orthosilicate to the mixed material I is 1: 20, the vinyltrimethoxysilane coupling agent and the ethyl orthosilicate are added into the mixed material I, and the mixture is continuously stirred for 8min to obtain a mixed material II; according to the solid-liquid ratio g/mL of 2: 50, putting the film obtained in the step (3) into the mixed material II, and continuously stirring for 8min to obtain a mixed material III; finally, press H 2 O 2 Mixing the mixed solution with mixed material III at a volume ratio of 1: 2, and adding H into the mixed material III 2 O 2 Mixing the solution, stirring and reacting for 7h at the temperature of 35 ℃ to introduce adsorption sites on the surface of the film, endowing the film with the capability of selectively adsorbing lithium ions, and taking out the film; wherein H 2 O 2 The mixed solution is H 2 O 2 Mixing with deionized water at a mass ratio of 1: 10;
(5) and (4) pickling the film obtained in the step (4) with HCl solution with the concentration of 0.8mol/L until lithium ions are completely eluted, washing with deionized water to be neutral, and drying to obtain the degradable lithium ion imprinted film.
Example 3
(1) Dissolving Chitosan (CTS) in 1.5% glacial acetic acid solution at a solid-to-liquid ratio g/mL of 1: 80, heating and stirring at 50 ℃ by using a magnetic stirrer until the chitosan is completely dissolved, and standing for 16h to realize defoaming to obtain a chitosan solution;
(2) mixing a polyvinyl alcohol solution with the mass concentration of 4% with the chitosan solution in the step (1) according to the mass ratio of the polyvinyl alcohol solution to the chitosan solution of 1: 5 to obtain a mixed solution; wherein the polyvinyl alcohol solution is prepared by dissolving a certain amount of polyvinyl alcohol (PVA) in deionized water at 50 ℃ by heating in a water bath;
(3) adding 1-2 drops of glutaraldehyde solution with the mass concentration of 20% as a cross-linking agent into the mixed solution obtained in the step (2), and stirring for 6 hours at room temperature by using a magnetic stirrer to enable the glutaraldehyde solution to react fully; then the mixed solution is cast into a film, the film is dried to be completely transparent at the temperature of 45 ℃ by a constant temperature blast drying oven, the film is removed by being placed into a sodium hydroxide solution with the concentration of 1mol/L, deionized water is used for repeatedly washing until the washing liquid is neutral, and the film is obtained after natural drying;
(4) taking 12-crown ether-4 and ethanol according to the volume ratio of 12-crown ether-4 to ethanol being 1: 30, and taking lithium chloride according to the solid-to-liquid ratio g/mL of lithium chloride to 12-crown ether-4 being 1: 0.8; dissolving lithium chloride and 12-crown ether-4 in ethanol, and stirring for 2min to obtain a mixed material I; then, preparing materials according to the volume ratio of the vinyltrimethoxysilane coupling agent to the tetraethoxysilane being 0.5: 0.8, adding the vinyltrimethoxysilane coupling agent and the tetraethoxysilane into the mixed material I according to the volume ratio of the total amount of the vinyltrimethoxysilane coupling agent and the tetraethoxysilane to the mixed material I being 1: 20, and continuously stirring for 10min to obtain a mixed material II; according to the solid-liquid ratio g/mL of 3: 60, putting the film obtained in the step (3) into the mixed material II, and continuously stirring for 10min to obtain a mixed material III; finally, press H 2 O 2 Mixing the mixed solution with mixed material III at a volume ratio of 1: 2, and adding H into the mixed material III 2 O 2 Mixing the solution, stirring and reacting for 8h at the temperature of 40 ℃ to introduce adsorption sites on the surface of the film, endowing the film with the capability of selectively adsorbing lithium ions, and taking out the film; wherein H 2 O 2 The mixed solution is H 2 O 2 Mixing with deionized water at a mass ratio of 1: 10;
(5) and (5) pickling the film obtained in the step (4) by using a HCl solution with the concentration of 1.0mol/L until lithium ions are completely eluted, washing the film to be neutral by using deionized water again, and drying the film to obtain the degradable lithium ion imprinted film.
Comparative example 1: like example 1, only step (2) was deleted, i.e. no polyvinyl alcohol solution was added.
Comparative example 2: as in example 1, no glutaraldehyde solution was added only in step (3).
Comparative example 3: as in example 1, lithium chloride was not added only in step (4).
Comparative example 4: as in example 1, no vinyltrimethoxysilane coupling agent was added in step (4) only.
0.02g of chitosan-based lithium ion imprinted membrane obtained in the above examples 1 to 3 and comparative examples 1 to 4 is respectively statically placed in 10mL of lithium chloride solution with the volume of 40mg/L for 2h at a constant temperature to reach adsorption balance; the concentrations of the lithium solution before and after adsorption are measured, and the equilibrium adsorption capacity of the chitosan-based lithium ion imprinted membrane is calculated, and the result is as follows:
| initial concentration | Equilibrium concentration | Equilibrium adsorption capacity | |
| Example 1 | 40.0mg/L | 6.20 mg/L | 15.08 mg/g |
| Example 2 | 40.0 mg/L | 5.80mg/L | 15.26 mg/g |
| Example 3 | 40.0 mg/L | 6.40mg/L | 15.00 mg/g |
| Comparative example 1 | 40.0mg/L | 24.68mg/L | 7.66mg/ |
| Comparison ofExample | |||
| 2 | 40.0mg/L | 19.33mg/L | 10.34mg/g |
| Comparative example 3 | 40.0 mg/L | 35.16mg/L | 2.42mg/g |
| Comparative example 4 | 40.0mg/L | 39.64mg/L | 0.18 mg/g |
Therefore, compared with the comparative example 1, the polyvinyl alcohol solution is added in the embodiment of the invention, and the addition of the polyvinyl alcohol component in the chitosan film obviously improves the swelling performance of the pure chitosan film and simultaneously improves the mechanical performance of the pure chitosan film.
Compared with the comparative example 2, the swelling performance of the chitosan/polyvinyl alcohol membrane is further improved after glutaraldehyde crosslinking by adding the glutaraldehyde solution, the wet membrane is not brittle and has good toughness, and the chitosan/polyvinyl alcohol membrane has good spreadability when being soaked in the solution.
Compared with the comparative example 3, in the comparative example 3, lithium chloride is not added, the adsorption capacity is reduced due to the fact that specific recognition imprinting sites cannot be formed on the surface of the film, and the film material which is not subjected to ion imprinting treatment hardly generates an adsorption effect. According to the invention, crown ether capable of interacting with template lithium ions is selected in the process of ion imprinting polymerization, the template lithium ions and the crown ether are chelated together through coordination and non-covalent bond action, then a polymer is formed through the process of hydrolytic polymerization, and finally the template lithium ions are removed through acid with a certain concentration to obtain imprinting cavities matched with the template lithium ions in space size and structure, so as to form specific recognition imprinting sites, wherein the imprinting sites can show strong specific recognition effect on target lithium ions.
Compared with the comparative example 4, the embodiment of the invention integrally utilizes the silane coupling agent to carry out hydrolytic polymerization reaction to introduce crown ether sites and the surface of the film, and endows the film with the capability of selectively absorbing lithium ions. In the comparative example, no vinyltrimethoxysilane coupling agent is added, the hydrolytic polymerization reaction can not occur in the reaction process of a solution system, crown ether sites can not be successfully introduced, and the adsorption capacity to lithium ions is almost zero.
Claims (6)
1. A preparation method of a degradable chitosan-based lithium ion imprinted membrane is characterized by comprising the following steps:
(1) dissolving chitosan into a glacial acetic acid solution according to a solid-to-liquid ratio g/mL of (0.5-2): 50-100, heating and stirring at 40-50 ℃ until the chitosan is completely dissolved, and standing for 10-16 h to achieve defoaming, thereby obtaining a chitosan solution;
(2) mixing a polyvinyl alcohol solution with the mass concentration of 4-6% with the chitosan solution in the step (1) according to the mass ratio of the polyvinyl alcohol solution to the chitosan solution of 1: 2-5 to obtain a mixed solution;
(3) adding a glutaraldehyde solution with the mass concentration of 20-25% as a cross-linking agent into the mixed solution obtained in the step (2), and stirring at room temperature for 4-6 hours to enable the mixed solution to react fully; then the mixed solution is cast into a film, dried at 45 ℃ to be completely transparent, put into sodium hydroxide solution for demoulding, repeatedly washed by deionized water until the washing liquid is neutral, and naturally dried to obtain a film;
(4) taking 12-crown ether-4 and ethanol according to the volume ratio of 12-crown ether-4 to ethanol being (0.5-1): 20-30), and taking lithium chloride according to the solid-to-liquid ratio g/mL of lithium chloride to 12-crown ether-4 being (0.5-1): 0.5-1); dissolving lithium chloride and 12-crown ether-4 in ethanol, and stirring for 1-2 min to obtain a mixed material I; then, preparing materials according to the volume ratio of the vinyl trimethoxy silane coupling agent to the tetraethoxysilane of (0.2-0.5) to (0.2-0.8), and mixing the materials according to the total amount of the vinyl trimethoxy silane coupling agent and the tetraethoxysilaneAdding a vinyltrimethoxysilane coupling agent and ethyl orthosilicate into the mixed material I at a volume ratio of 1: 20, and continuously stirring for 5-10 min to obtain a mixed material II; according to the solid-liquid ratio g/mL (1-3): (40-60), adding the film obtained in the step (3) into the mixed material II, and continuously stirring for 5-10 min to obtain a mixed material III; finally, press H 2 O 2 Mixing the mixed solution with mixed material III at a volume ratio of 1: 2, and adding H into the mixed material III 2 O 2 Mixing the solution, stirring and reacting for 6-8 h at the temperature of 30-40 ℃, and taking out the film;
(5) and (4) washing the film obtained in the step (4) with acid until lithium ions are completely eluted, washing the film with deionized water to be neutral, and drying the film to obtain the degradable lithium ion imprinted film.
2. The method for preparing a degradable chitosan-based lithium ion imprinted membrane according to claim 1, characterized in that: the mass concentration of the glacial acetic acid solution in the step (1) is 1-2%.
3. The method for preparing a degradable chitosan-based lithium ion imprinted membrane according to claim 1, characterized in that: and (3) the polyvinyl alcohol solution in the step (2) is obtained by heating a certain amount of polyvinyl alcohol in a water bath at 50-60 ℃ and dissolving in deionized water.
4. The method for preparing a degradable chitosan-based lithium ion imprinted membrane according to claim 1, characterized in that: the concentration of the sodium hydroxide solution in the step (3) is 1 mol/L.
5. The method for preparing a degradable chitosan-based lithium ion imprinted membrane according to claim 1, characterized in that: h in the step (4) 2 O 2 The mixed solution is H 2 O 2 Mixing with deionized water at a mass ratio of 1: 10.
6. The method for preparing a degradable chitosan-based lithium ion imprinted membrane according to claim 1, characterized in that: the acid washing in the step (5) is performed by using HCl solution with the concentration of 0.5-1.0 mol/L.
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