CN111036183A - Zirconium sulfate imprinted gel microspheres and preparation method thereof - Google Patents
Zirconium sulfate imprinted gel microspheres and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a zirconium sulfate imprinted gel microsphere and a preparation method thereof, belonging to the field of high-molecular functional materials. The preparation method comprises the following steps: adding a dispersing agent and an organic solvent into a first container, uniformly stirring at a first preset temperature, and simultaneously carrying out argon evacuation treatment to obtain a solvent mixed solution; adding a polymerization monomer, a cross-linking agent, zirconium sulfate and water into a second container, stirring and dissolving at a second preset temperature, then adding an initiator into the second container, and stirring and dissolving uniformly to obtain a solute mixed solution; dropwise adding the solute mixed solution into the solvent mixed solution, performing first water bath heating reaction, adding alkali liquor, adjusting the pH value to a preset value, performing second water bath heating reaction, and filtering to obtain gel microspheres; and (3) placing the gel microspheres in eluent for soaking treatment to remove sulfate radicals, and then performing suction filtration and drying to obtain the zirconium sulfate imprinted gel microspheres. The zirconium sulfate imprinted gel microspheres have good sulfate radical adsorption capacity, and can reduce the amount of regeneration waste liquid.
Description
Technical Field
The invention relates to the field of high molecular functional materials, in particular to a zirconium sulfate imprinted gel microsphere and a preparation method thereof.
Background
In industrial processes such as natural gas purification, sulfur dioxide (SO)2) As a main pollutant emission, the material has great harm to human health and environment. Removal of hydrogen sulphide (H) from natural gas by means of sulphur recovery units is currently carried out2S), but also SO2. SO in the tail gas can be treated by the oxidation absorption tail gas treatment process2The absorption process comprises the following specific steps: to SO2Oxidation combustion treatment to form sulfur trioxide (SO)3) Then spraying the desulfurization solution to absorb SO3，SO3Formation of sulfate radicals (SO) in the desulfurization solution4 2-). But excess SO4 2-Will occupy SO2Absorbing active sites, resulting in a decrease in desulfurization performance of the desulfurization solution. Therefore, in the process of oxidizing and absorbing tail gas treatment, SO in the desulfurization solution needs to be timely treated4 2-The removal is carried out to ensure that the desulfurization solution is in an ideal state.
In the related art, the ion exchange method using ion exchange resin is used to remove SO from the desulfurization solution4 2-。
The inventors found that the related art has at least the following problems:
ion exchange resinAdsorption of SO4 2-Has limited capacity, requires high frequency of regeneration, generates a large amount of regeneration liquid and washes the waste liquid of the regeneration liquid.
Disclosure of Invention
The embodiment of the invention provides a zirconium sulfate imprinted gel microsphere and a preparation method thereof, which can solve the technical problems. The specific technical scheme is as follows:
in one aspect, the embodiment of the present invention provides a preparation method of a zirconium sulfate imprinted gel microsphere, where the preparation method includes:
adding a dispersing agent and an organic solvent into a first container, uniformly stirring at a first preset temperature, and simultaneously carrying out argon evacuation treatment to obtain a solvent mixed solution;
adding a polymerization monomer, a cross-linking agent, zirconium sulfate and water into a second container, stirring and dissolving at a second preset temperature, then adding an initiator into the second container, and stirring and dissolving uniformly to obtain a solute mixed solution;
dropwise adding the solute mixed solution into the solvent mixed solution, performing a first water-bath heating reaction to obtain a mixed solution containing microsphere precipitates, adding an alkali liquor into the mixed solution containing the microsphere precipitates, adjusting the pH value to a preset value, performing a second water-bath heating reaction, and filtering to obtain gel microspheres;
placing the gel microspheres in eluent for soaking treatment, removing sulfate radicals in the gel microspheres, then carrying out suction filtration and drying to obtain the zirconium sulfate imprinted gel microspheres;
wherein the mass ratio of the dispersing agent to the cross-linking agent to the zirconium sulfate to the initiator is 1.5-2:0.2-0.5:0.7-1.5: 0.03-0.08;
the volume ratio of the organic solvent to the polymerized monomer to the water is 38-42:4-5: 6-10.
In one possible design, the dispersant is polyethylene oxide sorbitol monostearate;
the organic solvent is toluene.
In one possible design, the polymerized monomer is acryloyloxyethyltrimethyl ammonium chloride;
the cross-linking agent is hydroxyethyl methacrylate.
In one possible design, the initiator is azobisisobutyronitrile.
In one possible embodiment, the lye is an aqueous NaOH solution and the predetermined value is 8 to 9.
In one possible design, the eluent is a sodium chloride solution with a concentration of 2-3 mol/L.
In one possible design, before the gel microspheres are placed in the eluent for soaking treatment, the preparation method further comprises:
and washing the gel microspheres by adopting toluene and water in sequence.
In one possible design, the first predetermined temperature is 50-60 ℃;
the stirring speed at the first preset temperature is 180-220 rpm;
the time for the argon evacuation treatment is 20-30 min;
the second preset temperature is 50-60 ℃;
the temperature of the first water bath heating is 65-70 ℃;
the temperature of the second water bath heating is 50-55 ℃.
In a possible design, the solute mixed solution is dripped into the solvent mixed solution, mixed solution containing microsphere precipitation is obtained after a first water bath heating reaction, alkali liquor is added into the mixed solution containing microsphere precipitation, the pH value is adjusted to a preset value, and gel microspheres are obtained by filtration after a second water bath heating reaction, which includes:
and dropwise adding the solute mixed solution into the solvent mixed solution, performing water bath heating when the addition amount of the solute mixed solution is 1/3-2/3, continuously dropwise adding the solute mixed solution, performing the first water bath heating reaction for 4-6 hours to obtain a mixed solution containing microsphere precipitates, adding alkali liquor into the mixed solution containing the microsphere precipitates, adjusting the pH value to a preset value, performing the second water bath heating reaction for 7-8 hours, and filtering to obtain the gel microspheres.
In another aspect, the embodiment of the present invention provides a zirconium sulfate imprinted gel microsphere, which is prepared by any one of the above mentioned preparation methods.
The technical scheme provided by the embodiment of the invention has the beneficial effects that at least:
according to the preparation method of the zirconium sulfate imprinted gel microspheres provided by the embodiment of the invention, the solvent mixed solution and the solute mixed solution are prepared, and the solute mixed solution is dropwise added into the solvent mixed solution, so that the uniform reaction of the solute mixed solution in the solvent mixed solution is facilitated to obtain the gel microspheres. Zirconium sulfate is formed in the gel microsphere by adding zirconium sulfate, and sulfate radical elution treatment is carried out on the gel microsphere, so that a binding site and a spatial structure for matching sulfate radical are formed in the gel microsphere, and the prepared gel microsphere can adsorb sulfate radical. The pH value of the mixed solution containing the microsphere precipitate is adjusted to be alkalescent by dropping alkali liquor, so that free zirconium ions can be combined with hydroxide ions to form zirconium hydroxide, the zirconium hydroxide can stably exist in micropores of the microspheres and cannot be washed out by eluent, and the complexing action of zirconium enhances the sulfate radical adsorption capacity of the gel microspheres. The zirconium sulfate imprinted gel microspheres prepared by the preparation method have imprinted cavities with good recognition and memory on sulfate radicals and the ability of complexing sulfate radicals, so that the adsorption ability of the zirconium sulfate imprinted gel microspheres is obviously superior to that of other sulfate imprinted gel microspheres prepared by conventional sulfate radical template molecules and conventional methods, and is more superior to that of ion exchange resins for adsorbing sulfate radicals, the regeneration frequency and the yield of waste liquid are greatly reduced, and energy conservation and consumption reduction are facilitated.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a flow chart of a preparation method of zirconium sulfate imprinted gel microspheres provided by an embodiment of the invention.
Detailed Description
Unless defined otherwise, all technical terms used in the examples of the present invention have the same meaning as commonly understood by one of ordinary skill in the art. Before further detailed description of embodiments of the present invention, definitions are given for some terms used to understand examples of the present invention.
It should be noted that, in the embodiment of the present invention, the print refers to: sites and spatial structures for sulfate binding in gel microspheres. The print and the sulfate radical can be mutually adsorbed.
In the related art, SO in a desulfurization solution is adsorbed by using an ion exchange resin4 2-However, the ion exchange resin has a limited ability to adsorb sulfate, and requires a large amount of treatment with a regenerated solution, thereby generating a large amount of waste liquid. For example, 1m was treated with a commercially available ion exchange resin3The desulfurization solution will yield about 2m3The waste liquid of (2). Therefore, the embodiment of the invention provides a zirconium sulfate imprinted gel microsphere and a preparation method thereof.
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
In one aspect, an embodiment of the present invention provides a preparation method of a zirconium sulfate imprinted gel microsphere, as shown in fig. 1, the preparation method includes:
And 102, adding a polymerization monomer, a cross-linking agent, zirconium sulfate and water into a second container, stirring and dissolving at a second preset temperature, then adding an initiator into the second container, and stirring and dissolving uniformly to obtain a solute mixed solution.
And 103, dropwise adding the solute mixed solution into the solvent mixed solution, performing a first water bath heating reaction to obtain a mixed solution containing the microsphere precipitate, adding alkali liquor into the mixed solution containing the microsphere precipitate, adjusting the pH value to a preset value, performing a second water bath heating reaction, and filtering to obtain the gel microsphere.
And step 104, placing the gel microspheres in eluent for soaking treatment, removing sulfate radicals in the gel microspheres, and then performing suction filtration and drying to obtain the zirconium sulfate imprinted gel microspheres.
Wherein the mass ratio of the dispersing agent to the cross-linking agent to the zirconium sulfate to the initiator is 1.5-2:0.2-0.5:0.7-1.5: 0.03-0.08; the volume ratio of the organic solvent to the polymerized monomer to the water is 38-42:4-5: 6-10.
Note that the solvent mixture can be miscible with the solute mixture.
The mass ratio of the dispersing agent to the cross-linking agent to the zirconium sulfate to the initiator can be 1.5:0.2:0.7:0.03, 1.6:0.3:0.8:0.04, 1.7:0.3:0.9:0.05, 1.8:0.4:1:0.06, 1.9:0.4:1.1:0.07, 1.9:0.5:1.2:0.08, 1.7: 0.5: 0.9:0.07, 1.8:0.4:1.3:0.07, 1.9: 0.3:0.8: 0.06, 1.9:0.5:1.5:0.04, etc.
According to the preparation method of the zirconium sulfate imprinted gel microspheres provided by the embodiment of the invention, the solvent mixed solution and the solute mixed solution are prepared, and the solute mixed solution is dropwise added into the solvent mixed solution, so that the uniform reaction of the solute mixed solution in the solvent mixed solution is facilitated to obtain the gel microspheres. Zirconium sulfate is formed in the gel microspheres by the addition of zirconium sulfate. The gel microspheres are subjected to sulfate radical elution treatment, so that binding sites and spatial structures for matching sulfate radicals are formed in the gel microspheres, and the prepared gel microspheres can adsorb the sulfate radicals. The pH of the mixed solution is adjusted to be alkaline by dropping alkali liquor, so that free zirconium ions can be combined with hydroxide ions to form zirconium hydroxide, the zirconium hydroxide can stably exist in micropores of the gel microsphere and is not easy to be washed out by eluent and washing solution, and the sulfate radical adsorption capacity of the gel microsphere is enhanced by utilizing the complexation of zirconium. The zirconium sulfate imprinted gel microspheres prepared by the preparation method have imprinted cavities with good recognition and memory on sulfate radicals and the ability of complexing sulfate radicals, so that the adsorption ability of the zirconium sulfate imprinted gel microspheres is obviously superior to that of other sulfate imprinted gel microspheres prepared by conventional sulfate radical template molecules and conventional methods, and is more superior to that of ion exchange resins for adsorbing sulfate radicals, the regeneration frequency and the yield of waste liquid are greatly reduced, and energy conservation and consumption reduction are facilitated.
In step 101, a dispersant is added to facilitate uniform mixing of the components added dropwise to the solvent mixture. Among them, the kind of the dispersant has an important influence on whether the monomer, the crosslinking agent, the zirconium sulfate and the initiator can be uniformly mixed. The dispersant may be polyethylene oxide sorbitol monostearate on the premise of good dispersing effect on organic and inorganic molecules.
The organic solvent has an important influence on whether the polymerized monomers, the cross-linking agent, the initiator and the like can be uniformly dissolved with each other, and further influences the component uniformity of the gel microspheres. In an embodiment of the present invention, the organic solvent may be toluene.
Wherein, the toluene is insoluble in water, can be mutually soluble with most organic molecules, has low price and is easy to obtain.
The kind of the polymerized monomer in step 102 has an important influence on the magnitude of the intermolecular force between the prepared zirconium sulfate imprinted gel microsphere and sulfate radical, and in order to make the magnitude of the intermolecular force between the zirconium sulfate imprinted gel microsphere and sulfate radical appropriate, the zirconium sulfate imprinted gel microsphere can easily adsorb and elute the SO4 2-. To this end, in embodiments of the present invention, the polymerized monomer may be acryloyloxyethyltrimethyl ammonium chloride.
The addition of the crosslinking agent allows the polymerization reaction of the polymerizable monomer to proceed easily, and the crosslinking to form a gel. The kind of the cross-linking agent has an important influence on the polymerization effect of the polymerized monomer and the cross-linking reaction, and when the polymerized monomer is acryloyloxyethyl trimethyl ammonium chloride, the cross-linking agent can be hydroxyethyl methacrylate.
The intermolecular forces between different sulfate template molecules and the polymeric monomer or polymer are different, the intermolecular force between zirconium sulfate and the polymeric monomer or polymer is good, and the sulfate is convenient to elute in the later period. However, the experimental test results show that only the SO existing in the imprinted gel microspheres4 2-The matching spatial structure and binding sites still cannot meet the actual production requirements for the improvement of the sulfate radical adsorption capacity. Further experimental research shows that after zirconium sulfate is used as template molecules and zirconium ions are deposited on the imprinted gel microspheres, the zirconium ions and SO are generated4 2-The complexation of the gel microspheres further increases the SO pair of the zirconium sulfate imprinted gel microspheres4 2-The adsorption capacity of (c).
The polymerization of the polymerized monomers generally requires an initiator, which may be azobisisobutyronitrile, in order to allow the polymerized monomers to be sufficiently polymerized.
Considering that the polymerization reaction of the polymerization monomer is very easy to initiate after the initiator is added, the solute mixed solution needs to be rapidly and uniformly stirred after the initiator is added. Further, the solute mixture is added dropwise to the solvent mixture.
In step 103, the alkali solution is an aqueous solution of NaOH, and the preset value is 8-9, such as 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, etc. SO set up, can zirconium ion deposit on the trace gel microballon, and avoid deposit tiny particle to gather into a group, more be favorable to SO4 2-Adsorption of (3).
In the above, by soaking the gel microspheres, sulfate radicals in the gel microspheres can be removed, so that a spatial structure and binding sites for matching with the sulfate radicals are formed in the gel microspheres. In view of the ease with which the sulfate can be removed from the gel microspheres, in the present example the eluent is a sodium chloride solution with a concentration of 2-3 mol/L. For example, the concentration of the eluent can be 2mol/L, 2.1mol/L, 2.2mol/L, 2.3mol/L, 2.4mol/L, 2.5mol/L, 2.6mol/L, 2.7mol/L, 2.8mol/L, 2.9mol/L, 3mol/L, and the like.
The intermolecular force between the sodium chloride and the binding sites in the gel microspheres is greater than the intermolecular force between the sulfate radicals and the binding sites in the gel microspheres, so that the sulfate radicals in the gel microspheres can be easily replaced by the sodium chloride solution, and the preparation of the zirconium sulfate imprinted gel microspheres is facilitated.
In order to prepare pure zirconium sulfate imprinted gel microspheres, before the gel microspheres are placed in an eluent for soaking treatment, the preparation method of the zirconium sulfate imprinted gel microspheres provided by the embodiment of the invention further comprises the following steps: and washing the gel microspheres by adopting toluene and water in sequence.
Toluene is adopted to wash the gel microspheres, which is beneficial to washing organic molecules on the gel microspheres. The gel microspheres are washed by water, so that inorganic molecules on the gel microspheres can be washed conveniently. By the method, pure gel microspheres can be easily prepared.
The number of washing may be plural, and for example, may be 2, 3, 4, 5, or the like.
In the embodiment of the present invention, the first preset temperature may be 50 to 60 ℃, for example, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃ and the like, in consideration of sufficiently uniform dissolution between the dispersant and the organic solvent in step 101.
The stirring speed at the first predetermined temperature may be 180-220rpm, for example, 180rpm, 185rpm, 190rpm, 195rpm, 200rpm, 205rpm, 210rpm, 215rpm, 220rpm, etc.
In order to avoid the active gas in the solvent mixture from affecting the performance of the dispersant, the organic solvent, the polymerized monomer and the zirconium sulfate during the reaction, the time for the argon evacuation treatment may be 20-30min, for example, 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min, 30min, and the like.
The second predetermined temperature may be 50 to 60 ℃ such as 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, 60 ℃ or the like, in order to make the polymerization unit, the crosslinking agent, the zirconium sulfate and the water compatible with each other.
In order to enable the polymerization reaction of the polymerization monomer to be sufficiently performed under the action of the cross-linking agent and the initiator and to enable the zirconium sulfate to have good intermolecular force with the polymerization monomer or the polymer, the temperature of the first water bath heating reaction may be 65 to 70 ℃, for example, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃ or the like. The temperature of the second water bath heating is 50-55 deg.C, such as 50 deg.C, 51 deg.C, 52 deg.C, 53 deg.C, 54 deg.C, 55 deg.C, etc.
Considering that the polymerization reaction can be timely performed among the polymerized monomer, the cross-linking agent, the zirconium sulfate, the initiator and the dispersant, in step 103, the solute mixed solution is dripped into the solvent mixed solution, after the first water bath heating reaction, the mixed solution containing the microsphere precipitate is obtained, then the alkali liquor is added into the mixed solution containing the microsphere precipitate, the pH value is adjusted to the preset value, and after the second water bath heating reaction, the gel microsphere is obtained by filtering, which comprises the following steps:
and (3) dropwise adding the solute mixed solution into the solvent mixed solution, performing water bath heating when the dropwise adding amount of the solute mixed solution is 1/3-2/3, continuously dropwise adding the solute mixed solution, performing first water bath heating reaction for 4-6h to obtain mixed solution containing microsphere precipitate, adding alkali liquor into the mixed solution containing the microsphere precipitate, adjusting the pH value to a preset value, performing second water bath heating reaction for 7-8h, and filtering to obtain the gel microspheres.
It can be understood that the dropping amount of the solute mixed solution is the volume of the solute mixed solution dropping in the total volume. The solute mixture solution may be added dropwise in an amount of 1/3, 1/2, 2/3, or the like.
The speed of dripping the solute mixed solution into the solvent mixed solution is low, so that the solute mixed solution and the solvent mixed solution are fully mixed, and the gel microspheres with uniform components are obtained.
Thus, the solute mixed liquid added dropwise to the solvent mixed liquid can uniformly perform polymerization reaction.
The heating reaction time of the first water bath is 4-6h, for example, 4h, 4.5h, 5h, 5.5h, 6h and the like, which is beneficial for the full reaction of the solute mixed liquor and the solvent mixed liquor. The time for the second water bath heating reaction is 7-8h, and can be 7h, 7.2h, 7.4h, 7.6h, 7.8h, 8h and the like.
In order to deposit zirconium ions on the imprinted gel microspheres, the pH value of the mixed solution is adjusted to 8-9 by using NaOH aqueous solution, and the mixed solution is reacted for 7-8h at 50-55 ℃.
Wherein, the water bath heating can adopt a water bath kettle for heating.
In step 104, in order to sufficiently elute the sulfate on the gel microsphere, the gel microsphere may be stirred while being immersed in the eluent, so as to sufficiently elute the sulfate on the gel microsphere.
In an embodiment of the present invention, the first container may be a four-neck flask with a condenser tube, a stirrer and an air duct. The second container may be a beaker.
As an example, 1.5-2.0g of polyoxyethylene sorbitan monostearate and 40mL of toluene are added into a four-neck flask provided with a condenser tube, a stirrer and an air guide tube, the mixture is heated to 50-60 ℃, the stirring speed is 180-220rpm, and simultaneously argon is evacuated for 20-30min to obtain a solvent mixed solution. 4-5mL of acryloyloxyethyl trimethyl ammonium chloride, 0.2-0.5g of hydroxyethyl methacrylate, 0.7-1.5g of zirconium sulfate and 6-10mL of water are added into a beaker, slowly stirred and dissolved uniformly at 50-60 ℃, then 0.03-0.08g of azobisisobutyronitrile is added into the beaker, and quickly stirred to be dissolved uniformly, thus obtaining solute mixed solution. Placing the solvent mixed solution and the four-neck flask in a water bath kettle, slowly dropwise adding the solute mixed solution into the solvent mixed solution, carrying out a first water bath heating reaction when the dropwise adding volume of the solute mixed solution exceeds 1/3-2/3 of the volume of the solute mixed solution, heating the water bath kettle to 65-70 ℃, and meanwhile, continuously dropwise adding the solute mixed solution. And (3) after the temperature rise is finished, keeping the temperature for reacting for 4-6h, adjusting the pH of the mixed solution to 8-9 by using 0.5-2.0g mol/L NaOH aqueous solution, carrying out a second water bath heating reaction, namely reacting for 7-8h at 50-55 ℃, and filtering while the solution is hot to obtain the gel microspheres. The gel microspheres are washed for a plurality of times by toluene and water with the temperature of 50 ℃. And then soaking the gel microspheres for multiple times by using 3mol/L sodium chloride solution under the stirring state to remove SO 42-in the gel microspheres, and then carrying out suction filtration and vacuum drying to constant weight to obtain the zirconium sulfate imprinted gel microspheres provided by the embodiment.
The volume or the weight of each component is set, so that raw material waste can be avoided, and full reaction among the components is facilitated.
In another aspect, an embodiment of the present invention provides a zirconium sulfate imprinted gel microsphere, which is prepared by any one of the above mentioned preparation methods.
The zirconium sulfate imprinted gel microspheres provided by the embodiment of the invention adsorb SO4 2-The regeneration capacity is good, the regeneration frequency of the zirconium sulfate imprinted gel microspheres can be reduced, the waste liquid used for regeneration is reduced, and the purposes of energy conservation, consumption reduction and environmental protection are achieved. The zirconium sulfate imprinted gel microspheres can effectively ensure that the performance of a desulfurization solution is in an ideal state, and are favorable for solving the problem of SO (sulfur oxide) in the natural gas purification industry2High discharge concentration and wide application prospect.
The present invention will be further described below by way of specific examples.
In the following examples, those whose operations are not subject to the conditions indicated, are carried out according to the conventional conditions or conditions recommended by the manufacturer. The raw materials are conventional products which can be obtained commercially by manufacturers and specifications.
Example 1
The embodiment provides a zirconium sulfate imprinted gel microsphere, which is prepared by the following method: a four-necked flask equipped with a condenser, a stirrer and an air guide tube was charged with 1.8g of polyethylene oxide sorbitan monostearate (span-60) and 40mL of toluene, heated to 55 ℃ and stirred at 200rpm, and purged with argon for 30 minutes to obtain a solvent mixture. 4.3mL of acryloyloxyethyltrimethyl ammonium chloride, 0.230g of hydroxyethyl methacrylate, 0.8043g of zirconium sulfate and 8mL of water are added into a beaker, slowly stirred at 55 ℃ and dissolved uniformly, then 0.043g of azobisisobutyronitrile is added into the beaker, and quickly stirred to be dissolved uniformly, so that solute mixed solution is obtained. And (3) placing the solvent mixed solution and the four-neck flask into a water bath kettle, slowly dropwise adding the solute mixed solution into the solvent mixed solution, and when the dropwise adding volume of the solute mixed solution exceeds half of the volume of the solute mixed solution, heating the water bath kettle to 65 ℃, and meanwhile, continuously dropwise adding the solute mixed solution. And after the temperature rise is finished, keeping the temperature for reaction for 4 hours, dropwise adding 1mol/L sodium hydroxide solution into the mixed solution to adjust the pH of the mixed solution to 8, reacting for 7 hours at 55 ℃, and filtering while the mixed solution is hot to obtain the gel microspheres. Respectively condensing by toluene and water at 50 DEG CThe gel microspheres are washed for multiple times. Then soaking the gel microspheres for multiple times by using 3mol/L sodium chloride solution under the stirring state to remove SO in the gel microspheres4 2-And then carrying out suction filtration and vacuum drying to constant weight to obtain the zirconium sulfate imprinted gel microspheres provided by the embodiment.
Example 2
The embodiment provides an ammonium sulfate imprinted gel microsphere, which is prepared by the following method: a four-necked flask equipped with a condenser, a stirrer and a gas-guide tube was charged with 1.8g of sorbitan monostearate (span-60) and 40mL of cyclohexane, heated to 55 ℃ and stirred at 200rpm, and purged with argon for 30 minutes to obtain a solvent mixture. 4.3mL of acryloyloxyethyltrimethyl ammonium chloride, 0.232g of N, N' -methylene-bisacrylamide, 0.793g of ammonium sulfate and 8mL of water are added into a beaker, slowly stirred at 55 ℃ and dissolved uniformly, then 0.044g of ammonium persulfate is added into the beaker, and quickly stirred to be dissolved uniformly, thus obtaining solute mixed solution. And (3) placing the solvent mixed solution and the four-neck flask into a water bath kettle, slowly dropwise adding the solute mixed solution into the solvent mixed solution, and when the dropwise adding volume of the solute mixed solution exceeds half of the volume of the solute mixed solution, heating the water bath kettle to 65 ℃, and meanwhile, continuously dropwise adding the solute mixed solution. And after the temperature rise is finished, keeping the temperature for reaction for 4 hours, and filtering while the solution is hot to obtain the gel microspheres. The gel microspheres are washed for a plurality of times by cyclohexane, ethanol and water with the temperature of 50 ℃. Then soaking the gel microspheres for multiple times by using 3mol/L sodium chloride solution under the stirring state to remove SO in the gel microspheres4 2-Then, the mixture is filtered by suction and dried in vacuum to constant weight, so as to obtain the ammonium sulfate imprinted gel microspheres provided by the embodiment.
Application examples
In this application example, the zirconium sulfate imprinted gel microspheres provided in example 1 were adsorbed with SO4 2-The ability of (c) was evaluated. The specific evaluation method comprises the following steps: a resin column No. 1 packed with a strongly basic anion exchange resin, a resin column No. 2 packed with the ammonium sulfate imprinted gel microspheres provided in example 2, and a resin No. 3 packed with the zirconium sulfate imprinted gel microspheres provided in example 1 were used, respectivelyThe column purifies the desulfurization solution. Wherein, the inner diameters of the three resin columns are all 25mm, and the volume of the resin column is 50 mL. The purification treatment process comprises the following steps: and leaching the three resin columns by using 200mL of sodium hydroxide solution with the mass concentration of 4%, and leaching by using 100mL of desalted water. Then, the same amount of the desulfurization solution was allowed to flow through three resin columns at a liquid space velocity of 4hr-1, respectively, and the desulfurization solutions flowing out through the three resin columns were collected, respectively, and the sulfate group content in the flowing desulfurization solution was measured. The specific parameters are detailed in table 1.
TABLE 1
As can be seen from Table 1, the residual sulfate content in the desulfurization solution after the treatment of resin column No. 3 (i.e., the zirconium sulfate imprinted gel microspheres provided in example 1) was significantly lower than the residual sulfate content in the desulfurization solution after the treatment of resin column No. 1 (i.e., strongly basic anion exchange resin). It can be calculated from table 1 that the adsorption capacity of the strongly basic anion exchange resin for sulfate is 56.0g/L on average, the adsorption capacity of the ammonium sulfate imprinted gel microspheres provided in example 2 for sulfate is 80.5g/L on average, and the adsorption capacity of the zirconium sulfate imprinted gel microspheres provided in example 1 for sulfate is 123.8g/L on average. Therefore, the adsorption capacity of the zirconium sulfate imprinted gel microspheres provided by the embodiment of the invention to sulfate radicals is obviously higher than that of ion exchange resin to sulfate radicals and that of ammonium sulfate imprinted gel microspheres.
According to the requirement of removing sulfate radicals to 12% in mass percentage, 127mL of desulfurization solution needs to be regenerated after being treated by the strong-base anion exchange resin, the using amount of sodium hydroxide with the mass fraction of 4% is 150mL during regeneration, the using amount of desalted water is 100mL, 250mL of waste liquid is generated in total, and 1.97mL of waste liquid is generated when 1mL of desulfurization solution is treated on average. The ammonium sulfate imprinted gel microspheres provided in example 2 need to be regenerated after treating 183mL of desulfurization solution, the amount of sodium hydroxide with a mass fraction of 4% is 150mL during regeneration, the amount of desalted water is 100mL, 250mL of waste liquid is generated in total, and 1.27mL of waste liquid is generated every 1mL of desulfurization solution is treated on average. The zirconium sulfate imprinted gel microspheres provided in example 1 need to be regenerated after processing 281mL of desulfurization solution, the amount of sodium hydroxide with a mass fraction of 4% is 150mL during regeneration, the amount of desalted water is 100mL, and 250mL of waste liquid is generated in total, 0.89mL of waste liquid is generated when processing 1mL of desulfurization solution on average, and the generation amount of waste liquid is only 45% of that of the strongly basic anion exchange resin and 70% of that of the ammonium sulfate imprinted gel microspheres. Therefore, the zirconium sulfate imprinted gel microspheres provided by the embodiment of the invention have less waste liquid generated during regeneration, and are beneficial to energy conservation, consumption reduction and environmental pollution reduction.
In conclusion, the zirconium sulfate imprinted gel microspheres provided by the embodiment of the invention have good sulfate radical adsorption capacity and a small amount of regenerated waste liquid, so that the desulfurization solution can fully exert the desulfurization effect, and the zirconium sulfate imprinted gel microspheres are beneficial to energy conservation, consumption reduction and environmental pollution reduction.
The above description is only an illustrative embodiment of the present invention, and should not be taken as limiting the scope of the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of zirconium sulfate imprinted gel microspheres is characterized by comprising the following steps:
adding a dispersing agent and an organic solvent into a first container, uniformly stirring at a first preset temperature, and simultaneously carrying out argon evacuation treatment to obtain a solvent mixed solution;
adding a polymerization monomer, a cross-linking agent, zirconium sulfate and water into a second container, stirring and dissolving at a second preset temperature, then adding an initiator into the second container, and stirring and dissolving uniformly to obtain a solute mixed solution;
dropwise adding the solute mixed solution into the solvent mixed solution, performing a first water-bath heating reaction to obtain a mixed solution containing microsphere precipitates, adding an alkali liquor into the mixed solution containing the microsphere precipitates, adjusting the pH value to a preset value, performing a second water-bath heating reaction, and filtering to obtain gel microspheres;
placing the gel microspheres in eluent for soaking treatment, removing sulfate radicals in the gel microspheres, then carrying out suction filtration and drying to obtain the zirconium sulfate imprinted gel microspheres;
wherein the mass ratio of the dispersing agent to the cross-linking agent to the zirconium sulfate to the initiator is 1.5-2:0.2-0.5:0.7-1.5: 0.03-0.08;
the volume ratio of the organic solvent to the polymerized monomer to the water is 38-42:4-5: 6-10.
2. The method for preparing zirconium sulfate imprinted gel microspheres of claim 1, wherein the dispersant is polyethylene oxide sorbitol monostearate;
the organic solvent is toluene.
3. The method for preparing zirconium sulfate imprinted gel microspheres of claim 1, wherein the polymeric monomer is acryloyloxyethyl trimethyl ammonium chloride;
the cross-linking agent is hydroxyethyl methacrylate.
4. The method for preparing zirconium sulfate imprinted gel microspheres of claim 1, wherein the initiator is azobisisobutyronitrile.
5. The method for preparing zirconium sulfate imprinted gel microspheres of claim 1, wherein the alkali solution is an aqueous solution of NaOH, and the preset value is 8-9.
6. The method for preparing the zirconium sulfate imprinted gel microspheres of claim 1, wherein the eluent is a sodium chloride solution with a concentration of 2-3 mol/L.
7. The method for preparing zirconium sulfate imprinted gel microspheres according to claim 1, wherein before the gel microspheres are placed in the eluent for soaking treatment, the method further comprises:
and washing the gel microspheres by adopting toluene and water in sequence.
8. The method for preparing zirconium sulfate imprinted gel microspheres according to any one of claims 1 to 7, wherein the first preset temperature is 50 to 60 ℃;
the stirring speed at the first preset temperature is 180-220 rpm;
the time for the argon evacuation treatment is 20-30 min;
the second preset temperature is 50-60 ℃;
the heating temperature of the first water bath heating is 65-70 ℃;
the temperature of the second water bath heating is 50-55 ℃.
9. The method for preparing zirconium sulfate imprinted gel microspheres of any one of claims 1 to 7, wherein the method comprises the steps of dropwise adding the solute mixed solution into the solvent mixed solution, performing a first water bath heating reaction to obtain a mixed solution containing a microsphere precipitate, adding an alkali solution into the mixed solution containing the microsphere precipitate, adjusting the pH value to a preset value, performing a second water bath heating reaction, and filtering to obtain gel microspheres, and comprises the following steps:
and dropwise adding the solute mixed solution into the solvent mixed solution, performing water bath heating when the addition amount of the solute mixed solution is 1/3-2/3, continuously dropwise adding the solute mixed solution, performing the first water bath heating reaction for 4-6 hours to obtain a mixed solution containing microsphere precipitates, adding alkali liquor into the mixed solution containing the microsphere precipitates, adjusting the pH value to a preset value, performing the second water bath heating reaction for 7-8 hours, and filtering to obtain the gel microspheres.
10. A zirconium sulfate imprinted gel microsphere, which is prepared by the preparation method of any one of claims 1 to 9.
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