CN108970592B - Preparation method and application of sulfonic acid type silver porous adsorbent for ion adsorption - Google Patents
Preparation method and application of sulfonic acid type silver porous adsorbent for ion adsorption Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The invention discloses a preparation method and application of a sulfonic acid type silver porous adsorbent for ion adsorption. Dispersing a nanotube and a surfactant Tween 80 into deionized water, adding an acrylamide monomer, a sodium styrene sulfonate monomer, nitrogen-nitrogen methylene bisacrylamide and ammonium persulfate after ultrasonic treatment, adding liquid paraffin after stirring, and stirring to obtain a stable O/W Pickering high internal phase emulsion; removing residual surfactant and oil phase after polymerization of the high internal phase emulsion; drying and drying to obtain a blocky sulfonic acid type porous adsorbent; placing 5-15 mg sulfonic acid type porous adsorbent in a centrifuge tube, adding AgNO3The solution is sealed after nitrogen is blown to the pipe mouth, and is taken out and put into boiling NaBH immediately after being vibrated4And treating the solution, washing the solution by using deionized water, and drying the solution to obtain the sulfonic acid type silver porous adsorbent. The adsorbent provided by the invention has strong adsorption capacity, is particularly suitable for extracting lithium in salt lakes, and has high extraction rate.
Description
Technical Field
The invention relates to the technical field of preparation of specific separation functional materials, in particular to a preparation method and application of a sulfonic acid type silver porous adsorbent for ion adsorption.
Background
Lithium is widely applied to various fields of national economy due to excellent performance, the application field is continuously expanded, and the demand is highIncreasing year by year. Lithium mineral and salt lake are two main sources of lithium, the lithium is extracted from lithium ore in the early stage, and people aim at extracting lithium from salt lake with the decrease of content and quality of lithium ore, so that improvement of a production method for extracting lithium ions from salt lake is necessary. At present, Chinese salt lake resources are very rich, the lithium content is up to 35 percent, and the lithium is mainly distributed in salt lake deposits in Qinghai and Tibet regions. The extraction of lithium ions in salt lakes has the advantages of low price and environmental friendliness, but the current extraction method still has a lot of difficulties, especially due to interfering ions K+，Na+，Mg2+Is present.
Up to now, there have been a number of methods such as calcination, precipitation, and solvent extraction for extracting lithium. However, the calcining method is easy to corrode equipment, is easy to cause environmental pollution, and has the lithium extraction efficiency of about 3.54 percent; the precipitant used in the precipitation method is expensive, so that the industrial application prospect is poor, the transfer efficiency is low and is only 5.73 percent; the solvent extraction method is easy to generate a large amount of organic waste liquid, and also causes serious environmental pollution, and the mass transfer performance is about 6.21 percent. The adsorption separation method has the advantages of low cost, high efficiency, easy processing and recycling, and the like, so the adsorption separation method has wide prospect in this respect.
High Internal Phase Emulsions (HIPEs) refer to high viscosity emulsions having a small external phase volume and an internal phase volume fraction of more than 74% and HIPEs prepared from colloidal particles as stabilizers or colloidal particles and surfactants as co-stabilizers rather than conventional surfactants are known as PicKering HIPEs. The high internal phase material prepared by the high internal phase emulsion template method has a unique pore structure and a high specific surface area, so that the high internal phase material is selected as an adsorbent for extracting lithium ions.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method and application of a sulfonic acid type silver porous adsorbent for ion adsorption, wherein the sulfonic acid type silver porous adsorbent has strong adsorption capacity, is particularly suitable for extracting lithium in salt lakes, and has high extraction rate.
A process for preparing the sulfonic acid-type porous Ag adsorbent used for ion adsorptionThe sulfonic acid type silver porous adsorbent is a blocky porous polymer obtained by polymerizing through a high internal phase emulsion template method, wherein the mass fractions of N, C, H and S are respectively 3.72-4.86%, 26.7-46.9%, 3.48-5.32% and 2.82-4.89%; the preparation method of the sulfonic acid type silver porous adsorbent comprises the following steps: step 1, dispersing a nanotube and Tween 80 into 4 ml of deionized water, carrying out ultrasonic treatment for 30 min, adding an acrylamide monomer, a sodium p-styrenesulfonate monomer, nitrogen-nitrogen methylene bisacrylamide and ammonium persulfate, and stirring for 0.5-1.5 h to obtain a mixture; step 2, adding 10-22 mL of oil-phase liquid paraffin into the mixture, and stirring for 2.0-4.0 h to obtain a stable O/W Pickering high internal phase emulsion; step 3, transferring the O/W Pickering high internal phase emulsion into an ampere bottle, and polymerizing for 20-30 h in a water bath kettle at the temperature of 40-60 ℃; in an oil bath kettle at 70-90 ℃, soxhlet extraction is carried out on acetone for 4-6 days, and residual surfactant and oil phase are removed; then drying the mixture for 20 to 26 hours in a vacuum oven at the temperature of between 40 and 60 ℃ to obtain the blocky sulfonic acid type porous adsorbent; step 4, placing 5-15 mg of sulfonic acid type porous adsorbent into a centrifuge tube, and adding AgNO3The solution is sealed after being blown by nitrogen, is vibrated for 20 to 26 hours at the temperature of 25 ℃, is taken out and is immediately put into boiling NaBH4Treating the solution at 60-90 ℃ for 10-30 min, washing with deionized water, and drying at 60-80 ℃ to obtain the sulfonic acid type silver porous adsorbent; the AgNO3The solution is 0.7-2 mg AgNO3A solution of said NaBH dissolved in 10 mL of water4The solution of (A) is 15-35 mg NaBH4Dissolved in 20 mL of water.
According to a BET test, the half-pore diameter of the sulfonic acid type silver ion porous adsorbent is about 13.77 nm, and the sulfonic acid type silver ion porous adsorbent comprises two structures, namely a macroporous structure and an intercommunicating pore throat structure, wherein the macroporous structure is distributed most at 15-20 um, and the intercommunicating pore throat structure is distributed at 2-3 um mostly.
The improved materials include N, C, H and S in the mass portions of 4.25%, 36.1%, 4.22% and 3.74%.
The improvement is that in the step 1, the stirring time is 1.0 h, and the mass volume ratio of the nanotube, tween 80, acrylamide, sodium p-styrene sulfonate, nitrogen-nitrogen methylene bisacrylamide, ammonium persulfate and deionized water is 15-25 mg: 5-15 mg: 150-200 mg: 600-650 mg: 70-85 mg: 2-10 mg: 1L of the compound.
As a modification, the stirring time in step 2 was 3.0 h.
The improvement is that in the step 3, the temperature of the polymerization reaction is 50 ℃, the time of the polymerization reaction is 24h, the temperature of the Soxhlet extraction is 80 ℃, the extraction is 5 days, the drying temperature is 50 ℃, and the drying is 24 h.
The improvement is that in the step 4, the shaking time is 24h, and NaBH is added4The reaction temperature of the solution is 70 ℃, the reaction time is 15min, and the drying temperature is 70 ℃.
As a refinement, the nanotubes are single halloysite nanotubes.
The sulfonic acid type silver porous adsorbent prepared by the preparation method is applied to the extraction of lithium ions in salt lake brine.
As an improvement, the application comprises the following steps: preparing 10 mL of lithium ion solutions with different concentrations, adding 10 mg of sulfonic acid type silver porous adsorbent, oscillating, statically adsorbing at normal temperature, centrifugally separating the solutions adsorbed for different times, taking supernate to measure the residual ion concentration until the adsorption is finished.
Has the advantages that:
the sulfonic acid type silver porous adsorbent synthesized by the emulsion template method has a high specific surface area which reaches 16.545 m2 g-1The modified sulfonated polyether has the advantages of being capable of carrying more sulfonic acid group functional molecules, effectively improving adsorption capacity, modifying the surface of the modified sulfonated polyether and enabling the modified sulfonated polyether to have antibacterial performance. In the preparation method of the sulfonic acid type silver porous adsorbent, boiling NaBH is selected4The solution can effectively improve the oxidation-reduction reaction, greatly improve the loading efficiency of silver particles, and achieve the effects of saving energy and reducing energy consumption. The sulfonic acid type silver porous adsorbent prepared by the invention is used for separating lithium ions in brine, and has larger adsorption capacity of 13.682 mg g-1The selectivity reaches 45.6 percent; the antibacterial property is strong, an antibacterial zone is formed, lithium ions can be effectively adsorbed and separated on a salt lake, and the practical value is high.
Drawings
FIG. 1 is a scanning electron microscope photograph of a sulfonic acid type porous adsorbent and a sulfonic acid type silver porous adsorbent prepared in example 1, in which (a 1) is a 5 μm sulfonic acid type porous adsorbent and (a 2) is a1 μm sulfonic acid type porous adsorbent, (b 1) is a 5 μm sulfonic acid type silver porous adsorbent and (b 2) is a1 μm sulfonic acid type silver porous adsorbent;
fig. 2 is an EDS energy spectrum of the sulfonic acid type porous adsorbent and the sulfonic acid type silver porous adsorbent prepared in example 1, in which (a) is the sulfonic acid type porous adsorbent and (b) is the sulfonic acid type silver porous adsorbent;
FIG. 3 is a Fourier infrared spectrum of the sulfonic acid type porous adsorbent and the sulfonic acid type silver porous adsorbent prepared in example 1;
fig. 4 is XPS spectra of the sulfonic acid-type porous adsorbent and the sulfonic acid-type silver porous adsorbent prepared in example 1;
FIG. 5 is a thermogravimetric analysis chart of the sulfonic acid type porous adsorbent and the sulfonic acid type silver porous adsorbent prepared in example 1;
FIG. 6 is a graph showing different pH analyses of the sulfonic acid type silver porous adsorbent obtained in example 1;
FIG. 7 is a graph of a curve fit of the adsorption kinetics of the sulfonic acid type silver porous adsorbent obtained in example 1;
FIG. 8 is a graph of adsorption equilibrium isotherm fit of the sulfonic acid type silver porous adsorbent obtained in example 1;
fig. 9 is a graph showing the selective adsorption effect of the sulfonic acid type silver porous adsorbent obtained in example 1.
Detailed Description
The process of the present invention is described and illustrated in detail below with reference to specific examples. The content is to explain the invention and not to limit the scope of protection of the invention.
The reagents used in the invention: halloysite nanotubes, zhengzhou gold sunshine porcelain ltd, henna; tween-80, Acrylamide (AM), sodium p-styrenesulfonate (SS), N-methylenebisacrylamide (BAM), and silver nitrate (AgNO)3) Shanghai Aladdin Biotechnology, Inc.; ammonium Persulfate (APS), liquid paraffin, acetone, lithium chloride (LiCl. H)2O), sodium borohydride (NaBH)4) And ethanol, national drug group chemical reagents ltd, wherein the nanotubes are of various types, and one or more of silicon nanotubes, single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, graphitized multi-walled carbon nanotubes and halloysite nanotubes can achieve experimental effects.
The identification performance evaluation in the embodiment of the invention is carried out according to the following method: the method is completed by utilizing a static adsorption experiment and a selective adsorption experiment. 10 mL of lithium chloride (LiCl. H) with different concentrations of 50-400 mg/L2O) solution is added into a centrifuge tube, pH is adjusted to 7-11, 10 mg sulfonic acid type silver porous adsorbent (HIPEs-SS-Ag) is added, the mixture is placed in a constant temperature water bath at 15 ℃, 25 ℃ and 35 ℃ for standing for 10-720 min, and lithium chloride (LiCl. H) is adsorbed2O) the concentration of the solution is measured by an inductively coupled plasma spectrometer (ICP), and the adsorption capacity is calculated according to the result; selection of K+，Na+，Mg2+Three ions with similar structures are used as selective adsorbates and participate in the research of the recognition performance of the adsorbent.
Example 1
Preparation of sulfonic acid type porous adsorbent
Firstly, 0.08 g of halloysite nanotube and 0.04 g of surfactant Tween 80 are dispersed into 4.0 mL of deionized water, and ultrasonic treatment is carried out for 30 min under the ultrasonic condition; subsequently, 0.7 g of acrylamide monomer, 2.5 g of sodium p-styrenesulfonate monomer, 0.309 g of crosslinking agent N-methylenebisacrylamide and 0.02 g of initiator ammonium persulfate were added to the above-mentioned halloysite nanotube dispersion solution, and the mixture was stirred for 1.0 h. Then 16 mL of oil phase liquid paraffin is added into the mixed solution drop by drop under the condition of rapid stirring, and after stirring for 3.0 h, stable O/W PicKering high internal phase emulsion is obtained. The emulsion obtained was transferred to a 25 mL ampoule and polymerized at 50 ℃ for 24 h. And (3) in an oil bath kettle at the temperature of 80 ℃, performing Soxhlet extraction on the product for 5 d by acetone, removing residual surfactant and oil phase, and drying for 24h at the temperature of 50 ℃ to obtain the blocky sulfonic acid type porous adsorbent.
Preparation of sulfonic acid type silver porous adsorbent
10 mg of sulfonic acid type porous adsorbent is put into a centrifuge tube, and AgNO is added3(1.36 mg, 10 mL) solution, sealing after nitrogen gas blowing, shaking for 24h, taking out and immediately adding boiling NaBH4(24.2 mg, 20 mL) and treated at 70 ℃ for 15 min. Washing with deionized water, and drying at 70 ℃ to obtain the sulfonic acid type silver porous adsorbent.
Through the detection of an instrument, the mass fractions of N, C, H and S in the sulfonic acid type silver porous adsorbent are respectively 4.25%, 36.1%, 4.22% and 3.74%.
From the scanning electron micrograph (fig. 1), it is demonstrated that the modification of the silver particles on the inner surface of the porous polymer material is achieved. Furthermore, the introduction of silver particles during the modification was illustrated by means of characterization of fourier infrared spectroscopy (fig. 3), XPS analysis spectrum (fig. 4).
Example 2
Preparation of sulfonic acid type porous adsorbent
Firstly, 0.076 g of halloysite nanotube and 0.036 g of surfactant Tween 80 are dispersed into 4.0 mL of deionized water, and ultrasonic treatment is carried out for 30 min under the ultrasonic condition; subsequently, 0.68 g of acrylamide monomer, 2.48 g of sodium p-styrenesulfonate monomer, 0.3 g of crosslinking agent N-methylenebisacrylamide and 0.016 g of initiator ammonium persulfate were added to the above-mentioned halloysite nanotube dispersion solution, and the mixture was stirred for 0.5 h. Then 12 mL of oil phase liquid paraffin is added into the mixed solution drop by drop under the condition of rapid stirring, and after stirring for 2.0 h, stable O/W PicKering high internal phase emulsion is obtained. The emulsion obtained was transferred to a 25 mL ampoule and polymerized at 40 ℃ for 30 h. And (3) in an oil bath kettle at 70 ℃, performing Soxhlet extraction on the product by acetone for 6 d, removing residual surfactant and oil phase, and drying at 40 ℃ for 26 h to obtain the blocky sulfonic acid type porous adsorbent.
Preparation of sulfonic acid type silver porous adsorbent
10 mg of sulfonic acid type porous adsorbent is put into a centrifuge tube, and AgNO is added3(1.3 mg, 10 mL) solution, nitrogen gas blows the tube mouth and seals, vibrates for 20 h, takes out and immediately puts in boiling NaBH4(20 mg, 20 mL) of the solution was treated at 60 ℃ for 30 min. Washing with deionized water at 70 deg.CAnd drying to obtain the sulfonic acid type silver porous adsorbent.
Through the detection of an instrument, the mass fractions of N, C, H and S in the sulfonic acid type silver porous adsorbent are respectively 3.97%, 30.97%, 3.77% and 3.37%.
Example 3
Preparation of sulfonic acid type porous adsorbent
Firstly, 0.084 g of halloysite nanotube and 0.044 g of surfactant Tween 80 are dispersed into 4.0 mL of deionized water and subjected to ultrasonic treatment for 30 min under the ultrasonic condition; subsequently, 0.72 g of acrylamide monomer, 2.52 g of sodium p-styrenesulfonate monomer, 0.32 g of crosslinking agent N-methylenebisacrylamide and 0.024 g of initiator ammonium persulfate were added to the above halloysite nanotube dispersion solution, and the mixture was stirred for 1.5 hours. Then 20 mL of oil phase liquid paraffin is added into the mixed solution drop by drop under the condition of rapid stirring, and after stirring for 4.0 h, stable O/W PicKering high internal phase emulsion is obtained. The emulsion obtained was transferred to a 25 mL amp bottle and polymerized at 60 ℃ for 20 h. And (3) in an oil bath kettle at 90 ℃, performing Soxhlet extraction on the product by acetone for 4 d, removing residual surfactant and oil phase, and drying at 60 ℃ for 20 h to obtain the blocky sulfonic acid type porous adsorbent.
Preparation of sulfonic acid type silver porous adsorbent
10 mg of sulfonic acid type porous adsorbent is put into a centrifuge tube, and AgNO is added3(1.4 mg, 10 mL) solution, sealing after nitrogen gas blowing, shaking for 26 h, taking out and immediately adding boiling NaBH4(30 mg, 20 mL) of the solution was treated at 90 ℃ for 10 min. Washing with deionized water, and drying at 70 ℃ to obtain the sulfonic acid type silver porous adsorbent.
Through the detection of an instrument, the mass fractions of N, C, H and S in the sulfonic acid type silver porous adsorbent are respectively 4.55%, 39.81%, 4.62% and 3.92%.
Example 4
Preparation of sulfonic acid type porous adsorbent
Firstly, 0.06 g of halloysite nanotube and 0.02 g of surfactant Tween 80 are dispersed into 4.0 mL of deionized water, and ultrasonic treatment is carried out for 30 min under the ultrasonic condition; subsequently, 0.6 g of acrylamide monomer, 2.4 g of sodium p-styrenesulfonate monomer, 0.28 g of crosslinking agent N-methylenebisacrylamide and 0.008 g of initiator ammonium persulfate were added to the above halloysite nanotube dispersion solution, and the mixture was stirred for 0.5 h. Then 10 mL of oil phase liquid paraffin is added into the mixed solution drop by drop under the condition of rapid stirring, and after stirring for 2.0 h, stable O/W PicKering high internal phase emulsion is obtained. The emulsion obtained was transferred to a 25 mL ampoule and polymerized at 40 ℃ for 30 h. And (3) in a 70 ℃ oil bath kettle, performing Soxhlet extraction on the product for 6 d by acetone, removing residual surfactant and oil phase, and drying at 40 ℃ for 26 h to obtain the blocky sulfonic acid type porous adsorbent.
Preparation of sulfonic acid type silver porous adsorbent
Adding 5 mg sulfonic acid type porous adsorbent into a centrifuge tube, and adding AgNO3(0.7 mg, 10 mL) solution, nitrogen gas blows the tube mouth and seals, vibrates for 20 h, takes out and immediately puts in boiling NaBH4(15 mg, 20 mL) of the solution was treated at 60 ℃ for 30 min. Washing with deionized water, and drying at 70 ℃ to obtain the sulfonic acid type silver porous adsorbent.
Through the detection of an instrument, the mass fractions of N, C, H and S in the sulfonic acid type silver porous adsorbent are respectively 3.72%, 26.7%, 3.48% and 2.82%.
Example 5
Preparation of sulfonic acid type porous adsorbent
Firstly, 0.1 g of halloysite nanotube and 0.06 g of surfactant Tween 80 are dispersed into 4.0 mL of deionized water, and ultrasonic treatment is carried out for 30 min under the ultrasonic condition; subsequently, 0.8 g of acrylamide monomer, 2.6 g of sodium p-styrenesulfonate monomer, 0.34 g of crosslinking agent N-methylenebisacrylamide and 0.04 g of initiator ammonium persulfate were added to the above halloysite nanotube dispersion solution, and the mixture was stirred for 1.5 hours. Then 22 mL of oil phase liquid paraffin is added into the mixed solution drop by drop under the condition of rapid stirring, and after stirring for 4.0 h, stable O/W PicKering high internal phase emulsion is obtained. The emulsion obtained was transferred to a 25 mL amp bottle and polymerized at 60 ℃ for 20 h. And (3) in an oil bath kettle at 90 ℃, performing Soxhlet extraction on the product by acetone for 4 d, removing residual surfactant and oil phase, and drying at 60 ℃ for 20 h to obtain the blocky sulfonic acid type porous adsorbent.
Preparation of sulfonic acid type silver porous adsorbent
Adding 15 mg of sulfonic acid type porous adsorbent into a centrifugal tube, and adding AgNO3(2 mg, 10 mL) solution, sealing after nitrogen gas blowing, shaking for 26 h, taking out and immediately adding boiling NaBH4(35 mg, 20 mL) of the solution was treated at 90 ℃ for 10 min. Washing with deionized water, and drying at 70 ℃ to obtain the sulfonic acid type silver porous adsorbent.
Through the detection of an instrument, the mass fractions of N, C, H and S in the sulfonic acid type silver porous adsorbent are respectively 4.86%, 46.9%, 5.32% and 4.89%.
Comparative example 1
10 mg of HIPEs-SS-Ag prepared under the conditions described in example 1 were added to a series of lithium chloride solutions (150 mg/L) having an initial pH of 7 to 11, respectively, and shaken in a water bath at 25 ℃ for 12 hours. And detecting the concentration of the lithium chloride solution after centrifugal separation by using an inductively coupled plasma spectrometer. Experiments were performed in triplicate, adsorption capacity QtCalculated by an equation. Capacity Q of the adsorbent for lithium adsorption at time ttCan be calculated by the following equation:
Qt=（C0-Ct) V/M, wherein: initial concentration of lithium ion is C0(mg/L) and the concentration of lithium ions adsorbed at time t is Ct(mg/L); v is the volume of solution (mL); m is the mass of the adsorbent (mg).
The results showed that the adsorption capacity increased rapidly from pH =7 to pH =9, while pH =10 to pH =11 tended to be gentle, and that the adsorption amount reached a peak of 13.682 mg g at pH 10 of the lithium chloride solution in consideration of the influence of the over-basicity on the environment-1(the results are shown in FIG. 6). This shows that the optimum adsorption condition is pH 10.
Comparative example 2
To measure HIPEs-SS-Ag vs Li+The adsorption performance of the adsorption device is researched and an adsorption balance experiment and an adsorption dynamics experiment are researched. The pH of the lithium chloride solution was adjusted to 10 based on the best adsorption results of the pH experiments. In the kinetic experiment, 10 mL of lithium chloride solution with the initial concentration of 150 mg/L is added into a centrifuge tube, and 10 mg of sulfonic acid type silver ion in example 1 is addedMeasuring with 25 deg.C constant temperature water bath box, taking out at certain time intervals of 10 min, 30 min, 60 min, 120 min, 240 min, 360 min, 480 min, 600 min and 720 min, and measuring adsorbed Li by ICP+The concentration of (c). Through calculation results, the adsorption capacity of HIPEs-SS-Ag is found to increase rapidly in the first 360 min, and then reaches the maximum value of 13.682 mg g at 600 min-1This indicates that HIPEs-SS-Ag is present with Li+The combination of (a) reached a dynamic equilibrium (the results are shown in fig. 7).
In the adsorption equilibrium experiment, 10 mL of lithium chloride (LiCl. H) was taken at initial concentrations of 50 mg/L, 100 mg/L, 150 mg/L, 200 mg/L, 250 mg/L, 300 mg/L, 350 mg/L and 400 mg/L, respectively2O) solution is added into a centrifuge tube, 10 mg of the sulfonic acid type silver porous adsorbent in the embodiment 1 is respectively added, three groups of tests are carried out, the materials are respectively placed in water baths with the temperature of 15 ℃, the temperature of 25 ℃ and the temperature of 35 ℃ for standing for 10 hours, supernatant is collected after centrifugal separation, and Li which is not adsorbed is collected+The concentration was measured by inductively coupled plasma spectrometer, and the adsorption capacity was calculated from the results, and the adsorption isotherm results (as shown in FIG. 8) indicated R at 288K20.9943 for HIPEs-SS-Ag vs Li+The effect is better at low temperature.
Comparative example 3
By comparison with Li+Having a similar molecular structure+，Mg2+And Na+To perform a selectivity test. Potassium chloride (KCl), magnesium nitrate (Mg (NO)3)·6H2O) and sodium chloride (NaCl) were used as competitive adsorption materials, and solutions of the above three compounds were prepared at a concentration of 150 mg/L, respectively. 10 mL of the solution was put into a centrifuge tube, 10 mg of the sulfonic acid type silver porous adsorbent prepared in example 1 was added, and the test solution was placed in a water bath shaker at 25 ℃ for 12 hours, and then centrifuged to obtain a supernatant. The adsorption capacity, adsorbent vs Li, was calculated after ICP measurement+，K+，Mg2+And Na+The final adsorption capacities of the individual solutions were 13.682 mg g, respectively-1、7.205 mg g-1、6.264 mg g-1And 3.307 mg g-1This indicates that HIPEs-SS-Ag is present against Li+The selective adsorption capacity of (2) is outstanding (results are shown in FIG. 9).
The contents of the invention are described and illustrated in detail by the above examples, and the results show that the sulfonic acid type silver ion porous adsorbent prepared by the invention has better stability and is easy to adsorb and separate lithium ions.
Claims (9)
1. A preparation method of a sulfonic acid type silver porous adsorbent for ion adsorption is characterized in that the sulfonic acid type silver porous adsorbent is a massive porous polymer obtained by polymerization through a high internal phase emulsion template method, wherein the mass fractions of N, C, H and S are respectively 3.72-4.86%, 26.7-46.9%, 3.48-5.32% and 2.82-4.89%; the preparation method of the sulfonic acid type silver porous adsorbent comprises the following steps: step 1, dispersing a nanotube and Tween 80 into 4 ml of deionized water, carrying out ultrasonic treatment for 30 min, adding an acrylamide monomer, a sodium p-styrenesulfonate monomer, nitrogen-nitrogen methylene bisacrylamide and ammonium persulfate, and stirring for 0.5-1.5 h to obtain a mixture; step 2, adding 10-22 mL of oil-phase liquid paraffin into the mixture, and stirring for 2.0-4.0 h to obtain a stable O/W Pickering high internal phase emulsion; step 3, transferring the O/W Pickering high internal phase emulsion into an ampere bottle, and polymerizing for 20-30 h in a water bath kettle at the temperature of 40-60 ℃; in an oil bath kettle at 70-90 ℃, soxhlet extraction is carried out on acetone for 4-6 days, and residual surfactant and oil phase are removed; then drying the mixture for 20 to 26 hours in a vacuum oven at the temperature of between 40 and 60 ℃ to obtain the blocky sulfonic acid type porous adsorbent; step 4, placing 5-15 mg of sulfonic acid type porous adsorbent into a centrifuge tube, and adding AgNO3The solution is sealed after being blown by nitrogen, is vibrated for 20 to 26 hours at the temperature of 25 ℃, is taken out and is immediately put into boiling NaBH4Treating the solution at 60-90 ℃ for 10-30 min, washing with deionized water, and drying at 60-80 ℃ to obtain the sulfonic acid type silver porous adsorbent; the AgNO3The solution is 0.7-2 mg AgNO3A solution of said NaBH dissolved in 10 mL of water4The solution of (A) is 15-35 mg NaBH4Dissolved in 20 mL of water.
2. The method for preparing a sulfonic acid type silver porous adsorbent for ion adsorption according to claim 1, wherein the mass fractions of N, C, H and S are 4.25%, 36.1%, 4.22% and 3.74%, respectively.
3. The method for preparing the sulfonic acid type silver porous adsorbent for ion adsorption according to claim 1, wherein in step 1, the stirring time is 1.0 h, and the mass-to-volume ratio of the nanotube, tween 80, acrylamide, sodium p-styrene sulfonate, nitrogen-nitrogen methylene bisacrylamide, ammonium persulfate and deionized water is 15-25 mg: 5-15 mg: 150-200 mg: 600-650 mg: 70-85 mg: 2-10 mg: 1L of the compound.
4. The method for preparing a sulfonic acid type silver porous adsorbent for ion adsorption according to claim 1, wherein the stirring time in step 2 is 3.0 h.
5. The method for preparing a sulfonic acid type silver porous adsorbent for ion adsorption according to claim 1, wherein in step 3, the polymerization temperature is 50 ℃, the polymerization time is 24h, the Soxhlet extraction temperature is 80 ℃, the extraction time is 5 days, and the drying temperature is 50 ℃ and the drying time is 24 h.
6. The method for preparing the sulfonic acid type silver porous adsorbent for ion adsorption according to claim 1, wherein in the step 4, the oscillation time is 24h, and NaBH is added4The reaction temperature of the solution is 70 ℃, the reaction time is 15min, and the drying temperature is 70 ℃.
7. The method for preparing the sulfonic acid type silver porous adsorbent for ion adsorption according to claim 1, wherein the nanotube is a single halloysite nanotube.
8. Use of the sulfonic acid type silver porous adsorbent obtained by the preparation method according to claim 1 in lithium ion extraction in salt lake brine.
9. Use according to claim 8, characterized in that it comprises the following steps: preparing 10 mL of lithium ion solutions with different concentrations, adding 10 mg of sulfonic acid type silver porous adsorbent, oscillating, statically adsorbing at normal temperature, centrifugally separating the solutions adsorbed for different times, taking supernate to measure the residual ion concentration until the adsorption is finished.
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