CN109174049B - Preparation method and application of imprinted porous lithium/rubidium ion adsorption material - Google Patents

Preparation method and application of imprinted porous lithium/rubidium ion adsorption material Download PDF

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CN109174049B
CN109174049B CN201810886657.0A CN201810886657A CN109174049B CN 109174049 B CN109174049 B CN 109174049B CN 201810886657 A CN201810886657 A CN 201810886657A CN 109174049 B CN109174049 B CN 109174049B
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rubidium ion
porous lithium
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CN109174049A (en
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邱凤仙
王媛媛
蒲志龙
徐吉成
张涛
杨冬亚
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Jiangsu University
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    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
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Abstract

The invention belongs to the technical field of material preparation and separation, relates to preparation of a lithium/rubidium ion double-adsorption material, and particularly relates to a preparation method and application of a imprinted porous adsorption material. The method comprises the steps of firstly carrying out hydroxylation treatment on a carbon nano tube, and introducing an epoxy group through the reaction of silicon-connected trimethoxy in 3-glycidoxypropyltrimethoxysilane KH560 and hydroxyl on the carbon nano tube; and then carrying out ring-opening recombination with the phenolic hydroxyl of imprinting p-tert-butylcalix [4] arene IC4A to obtain the imprinting porous adsorption material. The complex effect on tert-butyl calix [4] arene is combined with an ion imprinting technology, and the efficient selective double adsorption of lithium/rubidium ions can be carried out. The invention also discloses application of the prepared material in adsorption of lithium ions and rubidium ions in salt lake brine. The method provided by the invention is simple to operate, the prepared imprinted porous adsorption material is stable in structure and large in specific surface, and the adsorption sites of the material can be increased by combining the ion imprinting technology, so that the adsorption performance of the material is improved.

Description

Preparation method and application of imprinted porous lithium/rubidium ion adsorption material
Technical Field
The invention belongs to the technical field of material preparation and separation, relates to preparation of a lithium/rubidium ion double-adsorption material, and particularly relates to a preparation method and application of a imprinted porous adsorption material.
Background
Since their discovery by lijima, a scientist of NEC corporation of japan in 1991, Carbon Nanotubes (CNTs) have been the focus of attention because of their unique properties. Until now, carbon nanotubes have been the subject of major attention of experts, scholars and researchers in various countries. With the progress of research, carbon nanotube functional materials are being gradually applied to various fields of industrial production. This rapid development is mainly due to the structure of the carbon nanotube itself, which imparts very excellent mechanical, electrical, and thermal properties and a large aspect ratio.
CNTs have a hollow porous multilayer structure, a large specific surface area, high chemical inertness and strong hydrophobicity, so that the CNTs are widely applied to treatment of organic pollutants, metal ions, complexes thereof and the like in a water environment. With the development of carbon nanotechnology, CNTs composite materials are receiving more and more attention; unlike a single nano material, the CNTs composite material is formed by compounding two or more nano-scale materials, and can integrate materials with multiple functions, so that the characteristics of multiple functions of the materials can be fully utilized, and the CNTs composite material has great potential. Previous studies have shown that modification of CNTs with organic polymers, metals, chelated metal oxides, and the like, can significantly improve the properties of CNTs.
Nevertheless, some problems of the CNTs composite material, such as dispersibility of CNTs in the matrix, interfacial adhesion, and orientation, have not been solved well. CNTs are highly susceptible to agglomeration due to their large specific surface area and surface energy, which can virtually limit their dispersibility in a matrix. How to effectively improve the dispersion of CNTs in a matrix so that the CNTs can effectively transfer load becomes an urgent problem to be solved for the application of the CNTs. Thus, surface modification of CNTs is particularly important.
The functionalization can change the physicochemical properties of CNTs, making them more suitable for chemical and biological applications. The research on the CNTs composite material is started from the compounding of the CNTs and a metal base material, namely, the surface of the CNTs is modified with metal, metal oxide, chelated metal oxide or polymer and the like, so that the characteristics of the CNTs can be improved, and the CNTs composite material can be successfully prepared. The composite materials can integrate materials with multiple functions, so that the CNTs composite material has multiple functions, the dispersibility of the CNTs is greatly improved, and the CNTs composite material can be better applied to removing pollutants in a water environment, and therefore, the CNTs composite material has great potential.
According to the invention, the carbon nano tube and the calixarene are chemically bonded through the silane coupling agent, and meanwhile, the imprinted porous adsorption material (IC4ABC) with high specificity and stability is prepared by combining the ion imprinting technology, and the performances of the material on Li (I), Rb (I) ion adsorption separation and other aspects are researched, so that the material can be effectively applied to industrial production.
Disclosure of Invention
The invention aims to overcome the defects of few reactive groups on the surface of a carbon nano tube, easiness in agglomeration and the like, and the carbon nano tube is provided with different functional groups by chemically grafting a silane coupling agent so as to relieve the agglomeration phenomenon, further participate in the next step of calixarene compounding, and realize the application of the carbon nano tube in the field of lithium/rubidium ion adsorption and separation. The invention discloses a preparation method of a imprinted porous adsorption material, and the prepared adsorption material is applied to extraction of lithium/rubidium resources in salt lake brine.
The invention discloses a preparation method of a imprinted porous adsorption material, which comprises the steps of firstly carrying out hydroxylation treatment on a carbon nano tube, and introducing an epoxy group through the reaction of silicon-connected trimethoxy in 3-glycidyloxypropyltrimethoxysilane (KH560) and hydroxyl on the carbon nano tube; and then the obtained product is subjected to ring-opening recombination with the phenolic hydroxyl of imprinted p-tert-butylcalix [4] arene (IC4A) to obtain an imprinted porous adsorbing material (IC4 ABC).
The preparation method of the imprinted porous lithium/rubidium ion adsorption material comprises the following steps:
A. measuring KH560 and dry toluene in a container, adding hydroxylated carbon nanotubes (MWCNTs) and triethylamine under magnetic stirring, stirring in dry nitrogen, and refluxing at 110-130 ℃ for 5-8 h, preferably at 120 ℃ for 6 h;
B. filtering, washing with toluene, acetone, deionized water and acetone in sequence, and vacuum drying at 70-90 deg.C for 6-10 hr, preferably 80 deg.C for 8 hr; obtaining KH560 grafted carbon nanotubes (KH 560/MWCNTs);
C. IC4A was placed in toluene at a solid to liquid ratio of 50mg:1mL, NaH was added with magnetic stirring, and the solution was stirred under N2Protection at 70-90 DEG CPerforming oil bath for 20-40 min, preferably 80 ℃, and 30 min;
D. standing to obtain supernatant, adding tetrabutylammonium bromide and KH560/MWCNTs, and drying N2Stirring and carrying out micro-reflux reaction at 80 ℃ for 20-30 h, preferably 24 h;
E. filtering while hot, washing, and drying in vacuum at 100-140 ℃ for 8-12 h, preferably 120 ℃ for 10h to obtain the imprinted porous adsorption material (IC4 ABC).
Wherein the ratio of each reactant is as follows:
the volume ratio of the toluene to the KH560 is 9 mL-11 mL:1mL, preferably 10mL:1 mL;
the solid-to-liquid ratio of MWCNTs to KH560 is 3 g-5 g:8mL, preferably 4g:8 mL;
the volume ratio of triethylamine to KH560 is 1mL:20 mL-80 mL, preferably 1mL:40 mL;
the mass ratio of NaH to IC4A is 11-13 mg:25mg, preferably 12mg:25 mg;
the mass ratio of GBC to IC4A is 3mg to 5mg, preferably 4mg to 5 mg.
The hydroxylated carbon nano tube (MWCNTs) adopts oxidation modification to carry out hydroxylation treatment on the carbon nano tube, and distilled water and 98% H are added2SO4And 70% HNO3The volume ratio is 3: 2: 1, pouring the mixed acid into a polytetrafluoroethylene reaction kettle, and standing to room temperature; adding carbon nano tubes, and carrying out hydrothermal reaction at 100-140 ℃ for 2-4 h, preferably 120 ℃ for 3 h; pouring into a large amount of deionized water for dilution and standing, then pouring out supernatant, and repeating for multiple times until the pH value of the solution is about 2; filtering with 0.45 μm cellulose acetate membrane, washing with ethanol for several times to neutrality, and vacuum drying at 40-60 deg.C, preferably 50 deg.C; obtaining the hydroxylated carbon nano-tubes (MWCNTs), wherein the solid-to-liquid ratio of the mixed acid to the carbon nano-tubes is 5 mg-7 mg:6mL, preferably 5mg:5 mL.
The IC4A is prepared by a dispersion polymerization method, and comprises the following steps: placing butyl titanate in a conical flask, and sequentially adding absolute ethyl alcohol, deionized water and glacial acetic acid; carrying out ultrasonic treatment for 2-4 h, preferably for 3 h; adding a proper amount of hydrochloric acid, adjusting the pH value to 2-3, and standing for later use. P-tert-butyl cup [4]]Aromatic hydrocarbon, LiCl. H2Dissolving O and RbCl in absolute ethyl alcohol, adding and standingSealing the bottle mouth of the butyl titanate solution to be used, then pricking small holes, and carrying out ultrasonic treatment at 20-40 ℃ for 4-8 h, preferably 30 ℃ for 6 h; obtaining a gum, washing with distilled water to remove unreacted residues, and washing with 1 mol. L-1Hydrochloric acid elution of Li+And Rb+Then, vacuum drying at 60-100 ℃, preferably 80 ℃; grinding to obtain Li-containing material+/Rb+Imprint of cavity vs. tert-butyl cup [4]]Aromatic hydrocarbons (IC 4A).
Wherein the ratio of each reactant is as follows:
the solid-to-liquid ratio of the butyl titanate to the ethanol is 4g:10 mL-12 mL, preferably 4g:11 mL;
the solid-to-liquid ratio of the butyl titanate to the deionized water is 4g:5 mL-7 mL, preferably 4g:6 mL;
the solid-to-liquid ratio of the butyl titanate to the glacial acetic acid is 4g:4 mL-6 mL, preferably 4g:5 mL;
the mass ratio of the butyl titanate to the tert-butylcalix [4] arene is 7 g-9 g:1g, preferably 8g:1 g;
para-tert-butyl cup [4]Aromatic hydrocarbons and LiCl. H2The mass ratio of O is 1g:1 g-3 g, preferably 1g:2 g;
the mass ratio of the tert-butylcalix [4] arene to the RbCl is 1g:2 g-4 g, preferably 1g:3 g;
the solid-to-liquid ratio of the tert-butylcalix [4] arene to the ethanol is 50mg:4 mL-6 mL, preferably 50mg:5 mL.
According to another object of the invention, the imprinted porous adsorption material prepared by the method can be applied to adsorption of lithium ions and rubidium ions in salt lake brine.
The invention carries out adsorption test by simulating salt lake brine.
(1) Preparing a mixed solution of lithium, rubidium, sodium, potassium, calcium, magnesium and cesium ions with certain concentrations.
(2) Adding the solution into a 10mL colorimetric tube, adding a certain amount of imprinted porous adsorption material serving as an adsorbent, oscillating, statically adsorbing at room temperature until the adsorption is balanced, centrifugally separating the adsorbed solution, taking supernatant, and determining the ion concentration of the residual solution.
The adsorption capacity Q of the imprinted porous adsorption material to lithium/rubidium ions at time t tThe following equation can be used for calculation.
Qt=(C0-Ct)V/W
In the formula: initial solubility of lithium/rubidium ions is C0(mg/L) and the concentration of adsorbed lithium/rubidium ions is Ct (mg/L); w is the mass (g) of the imprinted porous adsorbent; v is the volume (L) of the Li (I)/Rb (I) ion solution.
Sulfuric acid, nitric acid, hydrochloric acid, toluene, acetone, ethanol, lithium chloride (LiCl. H) used in the present invention2O), rubidium chloride (RbCl), 3-glycidyloxypropyltrimethoxysilane (KH560), national chemical group Chemicals Co., Ltd; NaH, tetrabutylammonium bromide, p-tert-butylcalix [4]]Aromatic hydrocarbons, Shanghai Aladdin Biotechnology Ltd.
Advantageous effects
The imprinting porous adsorption material synthesized by taking the carbon nano tube as the matrix has larger specific surface, and can increase the adsorption sites of the material to a great extent by combining the ion imprinting technology, thereby improving the adsorption performance of the material. The complex effect of tert-butyl calix [4] arene is combined with an ion imprinting technology, so that efficient selective double adsorption can be performed on lithium/rubidium ions; the imprinting porous adsorption material synthesized by using the carbon nano tube as the matrix by utilizing the method disclosed by the invention has the advantages of stable structure, simplicity in operation and good adsorption performance.
Drawings
FIG. 1 shows a schematic synthesis of a imprinted porous adsorbent material (IC4 ABC).
FIG. 2 scanning electron micrographs of MWCNTs (a) and IC4ABC (b).
FIG. 3 FT-IR spectra of MWCNTs (a), KH560/MWCNTs (b), IC4ABC (c).
FIG. 4 XRD spectra of MWCNTs and IC4 ABC.
FIG. 5 XPS spectra (a) of MWCNTs and IC4 ABC; an O1s map (b); c1s gaussian deconvolution spectrum (C, d); si2p map (e) of IC4 ABC.
FIG. 6 influence of pH on adsorption effect of imprinted porous adsorbent (IC4ABC) and non-imprinted porous adsorbent (C4 ABC).
Fig. 7 analysis of lithium/rubidium ion selectivity by imprinted porous adsorbent materials (IC4ABC) and non-imprinted porous adsorbent materials (C4 ABC).
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Example 1
(1) 4mL of KH560 and 44 mL of dry toluene were placed in a 100 mL three-necked round-bottom flask, 2.5 g of carboxylated carbon nanotubes and 0.2 mL of triethylamine were added under magnetic stirring, stirred under dry nitrogen and refluxed at 130 ℃ for 8 h; filtering, washing with toluene, acetone, deionized water and acetone in sequence, and vacuum drying at 90 deg.C for 10 hr; KH560 grafted carbon nanotubes (KH 560/MWCNTs) were obtained.
(2) 2.5 g of IC4A were placed in a 100 mL three necked round bottom flask, 50 mL of toluene was added, and 1.3 g of NaH, N was added with magnetic stirring2Oil bath at 90 deg.C for 40 min under protection; standing to obtain supernatant, adding tetrabutylammonium bromide and 2.5 g KH560/MWCNTs, and drying N2Stirring and carrying out micro reflux reaction at 80 ℃ for 30 h; filtering while the solution is hot, and washing until the filtrate is colorless and clear. The obtained solid is dried for 12 h in vacuum at 140 ℃ to obtain the imprinted porous adsorption material (IC4 ABC).
Experiment for simulating adsorption of salt lake brine
Adding the prepared lithium chloride/rubidium chloride mixed solution into a 10mL colorimetric tube, adding a certain amount of imprinted porous adsorption material (IC4ABC) as an adsorbent, oscillating, and statically adsorbing at room temperature to obtain a solution with maximum adsorption capacity of about 15.77 mg/g for lithium/rubidium ions-1And 13.91mg g-1。
Example 2
(1) 4mL of KH560 and 38 mL of dry toluene were placed in a 100 mL three-necked round-bottom flask, 1.6 g of carboxylated carbon nanotubes and 0.16 mL of triethylamine were added under magnetic stirring, stirred under dry nitrogen and refluxed at 120 ℃ for 6 hours; filtering, washing with toluene, acetone, deionized water and acetone in sequence, and vacuum drying at 90 deg.C for 8 hr; KH560 grafted carbon nanotubes (KH 560/MWCNTs) were obtained.
(2) 2.5 g of IC4A were placed in a 100 mL three necked round bottom flask and added50 mL of toluene are added and 1.2 g of NaH, N are added with magnetic stirring2Oil bath at 80 deg.C for 40 min under protection; standing to obtain supernatant, adding tetrabutylammonium bromide and 1.7 g KH560/MWCNTs, and drying N2Stirring and carrying out micro reflux reaction at 80 ℃ for 22 h; filtering while the solution is hot, and washing until the filtrate is colorless and clear. The obtained solid is dried for 10h in vacuum at 140 ℃ to obtain the imprinted porous adsorption material (IC4 ABC).
Experiment for simulating adsorption of salt lake brine
Adding the prepared lithium chloride/rubidium chloride mixed solution into a 10mL colorimetric tube, adding a certain amount of imprinted porous adsorption material (IC4ABC) as an adsorbent, oscillating, and statically adsorbing at room temperature to obtain a solution with maximum adsorption capacity of about 16.01 mg/g of lithium/rubidium ions-1And 12.97mg g-1。
Example 3
(1) 4mL of KH560 and 41 mL of dry toluene were placed in a 100 mL three-necked round-bottom flask, 2.2 g of carboxylated carbon nanotubes and 0.12 mL of triethylamine were added under magnetic stirring, stirred under dry nitrogen and refluxed at 130 ℃ for 5 hours; filtering, washing with toluene, acetone, deionized water and acetone in sequence, and vacuum drying at 80 deg.C for 10 hr; KH560 grafted carbon nanotubes (KH 560/MWCNTs) were obtained.
(2) 2.5 g of IC4A were placed in a 100 mL three necked round bottom flask, 50 mL of toluene was added, and 1.1 g of NaH, N was added with magnetic stirring2Oil bath at 90 deg.C for 20 min under protection; standing to obtain supernatant, adding tetrabutylammonium bromide and 2.1 g KH560/MWCNTs, and drying N2Stirring and carrying out micro-reflux reaction at 80 ℃ for 26 h; filtering while the solution is hot, and washing until the filtrate is colorless and clear. And (3) drying the obtained solid at 130 ℃ for 8h in vacuum to obtain the imprinted porous adsorption material (IC4 ABC).
Experiment for simulating adsorption of salt lake brine
Adding the prepared lithium chloride/rubidium chloride mixed solution into a 10mL colorimetric tube, adding a certain amount of imprinted porous adsorption material (IC4ABC) as an adsorbent, oscillating, and statically adsorbing at room temperature to obtain a solution with maximum adsorption capacity of about 15.49 mg/g for lithium/rubidium ions-1And 14.08mg g-1。
Example 4
(1) 4mL of KH560 and 40mL of dry toluene were placed in a 100 mL three-necked round-bottom flask, 2.0 g of carboxylated carbon nanotubes and 0.1 mL of triethylamine were added under magnetic stirring, stirred under dry nitrogen and refluxed at 120 ℃ for 6 hours; filtering, washing with toluene, acetone, deionized water and acetone in sequence, and vacuum drying at 80 deg.C for 8 hr; KH560 grafted carbon nanotubes (KH 560/MWCNTs) were obtained.
(2) 2.5 g of IC4A were placed in a 100 mL three necked round bottom flask, 50 mL of toluene was added, and 1.2 g of NaH, N was added with magnetic stirring2Oil bath at 80 deg.C for 30min under protection; standing to obtain supernatant, adding tetrabutylammonium bromide and 2.0 g KH560/MWCNTs, and drying N2Stirring and carrying out micro reflux reaction at 80 ℃ for 24 hours; filtering while the solution is hot, and washing until the filtrate is colorless and clear. And (3) drying the obtained solid for 10 hours in vacuum at 120 ℃ to obtain the imprinted porous adsorption material (IC4 ABC).
Experiment for simulating adsorption of salt lake brine
Adding the prepared lithium chloride/rubidium chloride mixed solution into a 10mL colorimetric tube, adding a certain amount of imprinted porous adsorption material (IC4ABC) as an adsorbent, oscillating, and statically adsorbing at room temperature to obtain a solution with maximum adsorption capacity of about 16.15 mg/g for lithium/rubidium ions-1And 14.36mg g-1。
Example 5
(1) 4mL of KH560 and 39 mL of dry toluene were placed in a 100 mL three-necked round-bottom flask, 2.4 g of carboxylated carbon nanotubes and 0.18 mL of triethylamine were added under magnetic stirring, stirred under dry nitrogen and refluxed at 120 ℃ for 7 h; filtering, washing with toluene, acetone, deionized water and acetone in sequence, and vacuum drying at 90 deg.C for 6 h; KH560 grafted carbon nanotubes (KH 560/MWCNTs) were obtained.
(2) 2.5 g of IC4A were placed in a 100 mL three necked round bottom flask, 50 mL of toluene was added, and 1.3 g of NaH, N was added with magnetic stirring2Oil bath at 80 deg.C for 20 min under protection; standing to obtain supernatant, adding tetrabutylammonium bromide and 2.3 g KH560/MWCNTs, and drying N2Stirring and carrying out micro reflux reaction at 80 ℃ for 28 h; filtering while the solution is hot, and washing until the filtrate is colorless and clear. And (3) drying the obtained solid for 12 h in vacuum at 120 ℃ to obtain the imprinted porous adsorption material (IC4 ABC).
Experiment for simulating adsorption of salt lake brine
Adding the prepared lithium chloride/rubidium chloride mixed solution into a 10mL colorimetric tube, adding a certain amount of imprinted porous adsorption material (IC4ABC) as an adsorbent, oscillating, and statically adsorbing at room temperature to obtain a solution with maximum adsorption capacity of 13.64 mg/g for lithium/rubidium ions-1And 13.17mg g-1。
Example 6
(1) 4mL of KH560 and 36 mL of dry toluene were placed in a 100 mL three-necked round-bottom flask, 1.5 g of carboxylated carbon nanotubes and 0.05 mL of triethylamine were added under magnetic stirring, stirred under dry nitrogen and refluxed at 110 ℃ for 5 hours; filtering, washing with toluene, acetone, deionized water and acetone in sequence, and vacuum drying at 70 deg.C for 6 h; KH560 grafted carbon nanotubes (KH 560/MWCNTs) were obtained.
(2) 2.5 g of IC4A were placed in a 100 mL three necked round bottom flask, 50 mL of toluene was added, and 1.1 g of NaH, N was added with magnetic stirring2Oil bath at 70 deg.C for 20 min under protection; standing to obtain supernatant, adding tetrabutylammonium bromide and 1.5 g KH560/MWCNTs, and drying N2Stirring and carrying out micro reflux reaction at 80 ℃ for 20 hours; filtering while the solution is hot, and washing until the filtrate is colorless and clear. And (3) drying the obtained solid for 8h in vacuum at 100 ℃ to obtain the imprinted porous adsorption material (IC4 ABC).
Experiment for simulating adsorption of salt lake brine
Adding the prepared lithium chloride/rubidium chloride mixed solution into a 10mL colorimetric tube, adding a certain amount of imprinted porous adsorption material (IC4ABC) as an adsorbent, oscillating, and statically adsorbing at room temperature to obtain a solution with maximum adsorption capacity of about 12.83 mg/g for lithium/rubidium ions-1And 12.06mg g-1。
Example 7
(1) 4mL of KH560 and 42 mL of dry toluene were placed in a 100 mL three-necked round-bottom flask, 2.1 g of carboxylated carbon nanotubes and 0.15 mL of triethylamine were added under magnetic stirring, stirred under dry nitrogen and refluxed at 110 ℃ for 8 h; filtering, washing with toluene, acetone, deionized water and acetone in sequence, and vacuum drying at 80 deg.C for 6 h; KH560 grafted carbon nanotubes (KH 560/MWCNTs) were obtained.
(2) 2.5 g of IC4A were placed in a 100 mL three necked round bottom flask, 50 mL of toluene was added, and 1.3 g of NaH, N was added with magnetic stirring2Oil bath at 70 deg.C for 40 min under protection; standing to obtain supernatant, adding tetrabutylammonium bromide and 2.2 g KH560/MWCNTs, and drying N2Stirring and carrying out micro reflux reaction at 80 ℃ for 24 hours; filtering while the solution is hot, and washing until the filtrate is colorless and clear. The obtained solid is dried for 12 h in vacuum at 110 ℃ to obtain the imprinted porous adsorption material (IC4 ABC).
Experiment for simulating adsorption of salt lake brine
Adding the prepared lithium chloride/rubidium chloride mixed solution into a 10mL colorimetric tube, adding a certain amount of imprinted porous adsorption material (IC4ABC) as an adsorbent, oscillating, and statically adsorbing at room temperature to obtain a solution with maximum adsorption capacity of about 14.87 mg/g for lithium/rubidium ions-1And 13.51mg g-1。
Example 8
(1) 4mL of KH560 and 37 mL of dry toluene were placed in a 100 mL three-necked round-bottom flask, 1.8 g of carboxylated carbon nanotubes and 0.07 mL of triethylamine were added under magnetic stirring, stirred under dry nitrogen and refluxed at 130 ℃ for 7 h; filtering, washing with toluene, acetone, deionized water and acetone in sequence, and vacuum drying at 70 deg.C for 10 hr; KH560 grafted carbon nanotubes (KH 560/MWCNTs) were obtained.
(2) 2.5 g of IC4A were placed in a 100 mL three necked round bottom flask, 50 mL of toluene was added, and 1.3 g of NaH, N was added with magnetic stirring2Oil bath at 70 deg.C for 40 min under protection; standing to obtain supernatant, adding tetrabutylammonium bromide and 1.9 g KH560/MWCNTs, and drying N2Stirring and carrying out micro reflux reaction at 80 ℃ for 20 hours; filtering while the solution is hot, and washing until the filtrate is colorless and clear. And (3) drying the obtained solid for 8h at 120 ℃ in vacuum to obtain the imprinted porous adsorption material (IC4 ABC).
Experiment for simulating adsorption of salt lake brine
Adding the prepared lithium chloride/rubidium chloride mixed solution into a 10mL colorimetric tube, adding a certain amount of imprinted porous adsorption material (IC4ABC) as an adsorbent, oscillating, and statically adsorbing at room temperature to obtain a solution with maximum adsorption capacity of 13.83 mg/g for lithium/rubidium ions-1And 13.11mg g-1。
The result shows that the imprinted porous adsorption material prepared by the invention has good structural stability, is simple to operate, is easy to separate and cannot pollute the environment. The imprinted porous adsorption material is used as an adsorbent, and the lithium chloride/rubidium chloride mixed solution is used as an adsorption object, so that the adsorbent has good adsorption capacity and selectivity. The adsorbent has a stable structure, high adsorption rate and good selectivity on lithium/rubidium ions in salt lake brine, and has a certain practical value.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.

Claims (14)

1. The preparation method of the imprinted porous lithium/rubidium ion adsorption material is characterized by comprising the following steps:
A. measuring KH560 and dry toluene in a container, adding the hydroxylated carbon nano-tube MWCNTs and triethylamine under magnetic stirring, stirring in dry nitrogen, and refluxing for 5-8 h at 110-130 ℃;
B. filtering, washing with toluene, acetone, deionized water and acetone in sequence, and vacuum-drying at 70-90 ℃ for 6-10 h to obtain KH560 grafted carbon nanotubes KH 560/MWCNTs;
C. IC4A was placed in toluene at a solid to liquid ratio of 50mg:1mL, NaH was added with magnetic stirring, and the solution was stirred under N2Under protection, oil bath is carried out for 20-40 min at 70-90 ℃, and the IC4A is Li-containing+/Rb+Imprint of cavity vs. tert-butyl cup [4]]Aromatic hydrocarbons;
D. standing to obtain supernatant, adding tetrabutylammonium bromide and KH560/MWCNTs, and drying N2Stirring and carrying out micro-reflux reaction at 80 ℃ for 20-30 h;
E. filtering while the mixture is hot, washing, and vacuum drying at 100-140 ℃ for 8-12 h to obtain the product.
2. The preparation method of the imprinted porous lithium/rubidium ion adsorption material according to claim 1, wherein the ratio of reactants participating in the reaction is as follows:
the volume ratio of the toluene to the KH560 is 9 mL-11 mL:1mL,
the solid-to-liquid ratio of MWCNTs to KH560 is 3 g-5 g:8mL,
the volume ratio of triethylamine to KH560 is 1mL:20 mL-80 mL,
the mass ratio of NaH to IC4A is 11-13 mg to 25mg,
the mass ratio of GBC to IC4A is 3-5 mg:5 mg.
3. The preparation method of the imprinted porous lithium/rubidium ion adsorption material according to claim 2, which is characterized by comprising the following steps: the volume ratio of toluene to KH560 participating in the reaction was 10mL:1 mL.
4. The preparation method of the imprinted porous lithium/rubidium ion adsorption material according to claim 2, which is characterized by comprising the following steps: the solid-to-liquid ratio of MWCNTs and KH560 participating in the reaction is 4g:8 mL.
5. The preparation method of the imprinted porous lithium/rubidium ion adsorption material according to claim 2, which is characterized by comprising the following steps: the volume ratio of the triethylamine to the KH560 which participate in the reaction is 1mL to 40 mL.
6. The preparation method of the imprinted porous lithium/rubidium ion adsorption material according to claim 2, which is characterized by comprising the following steps: the mass ratio of NaH and IC4A participating in the reaction was 12mg to 25 mg.
7. The preparation method of the imprinted porous lithium/rubidium ion adsorption material according to claim 2, which is characterized by comprising the following steps: the mass ratio of GBC and IC4A participating in the reaction was 4mg:5 mg.
8. The preparation method of the imprinted porous lithium/rubidium ion adsorption material according to claim 1, which is characterized by comprising the following steps: step A the mixture was stirred under dry nitrogen and refluxed at 120 ℃ for 6 h.
9. The preparation method of the imprinted porous lithium/rubidium ion adsorption material according to claim 1, which is characterized by comprising the following steps: and B, filtering, washing with toluene, acetone, deionized water and acetone in sequence, and vacuum-drying at 80 ℃ for 8 hours.
10. The preparation method of the imprinted porous lithium/rubidium ion adsorption material according to claim 1, which is characterized by comprising the following steps: step C is described in N2Oil bath at 80 deg.C for 30min under protection.
11. The preparation method of the imprinted porous lithium/rubidium ion adsorption material according to claim 1, which is characterized by comprising the following steps: step D said drying N2Stirring and refluxing at 80 deg.c for 24 hr.
12. The preparation method of the imprinted porous lithium/rubidium ion adsorption material according to claim 1, which is characterized by comprising the following steps: and E, filtering while the mixture is hot, washing, and vacuum-drying at 120 ℃ for 10 hours.
13. The imprinted porous lithium/rubidium ion adsorption material prepared by the method of any one of claims 1-12.
14. The application of the imprinted porous lithium/rubidium ion adsorption material of claim 13, which is characterized in that: the method is applied to the adsorption of lithium ions and rubidium ions in salt lake brine.
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