CN112275264A - Modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent and preparation method and application thereof - Google Patents
Modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent and preparation method and application thereof Download PDFInfo
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- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
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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 relates to the technical field of catalytic materials, and provides a preparation method of a modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent, which comprises the following steps: mixing attapulgite with a hydrochloric acid solution for acid modification to obtain acid-modified attapulgite; mixing the obtained acid modified attapulgite with water, magnesium sulfate solution and ammonia water in sequence, and carrying out double decomposition reaction to obtain a precursor; calcining the precursor to obtain a magnesium oxide/attapulgite composite material; mixing the obtained magnesium oxide/attapulgite composite material with water, polyvinyl alcohol and sodium alginate to obtain a mixed solution; and sequentially molding and curing the mixed solution to obtain the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent. According to the preparation method provided by the invention, the attapulgite is modified, so that the adsorbability of the composite adsorbent can be improved; the composite adsorbent has excellent mechanical performance after molding and curing, and the reuse rate of the composite adsorbent is improved.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a cobalt metal organic framework material and a preparation method and application thereof.
Background
Soil is an important component of the earth's biosphere and the foundation of agricultural and natural ecosystems. Soil is used as a living dynamic resource, is a base for producing grains, fibers and the like, is a buffer for forming, attenuating and degrading harmful compounds in the environment, has the functions of balancing regions and global ecosystems, and plays an important role in maintaining the environmental quality of regions. Heavy metal pollution has the characteristics of concealment, hysteresis, form diversity, accumulation and difficult elimination, excessive heavy metals in soil and water bodies can be ingested by animals and plants in an ecological system, and the heavy metals enter human bodies through an amplification effect generated by a food chain, so that the health of residents is influenced, and serious harm is caused to the ecological system. Therefore, the removal of heavy metals in water and soil and the restoration of the environment polluted by the heavy metals become ecological problems which need to be solved urgently.
For removing heavy metal ions in soil and water, the adsorption technology has low cost, simple operation method and high removal effect, so the method becomes an ecological environment restoration means with a wide application prospect. In recent years, attapulgite is widely researched as an adsorbent, which is mainly used for removing organic pollutants and heavy metal ions in water and polluted soil, and the attapulgite is mainly used for adsorbing heavy metals in a mode of ion exchange, surface coordination and surface coordination. (1) Ion exchange: the phyllosilicate topology of the attapulgite clay may undergo isomorphous substitution to generate a topology charge, thereby adsorbing a large number of cations to neutralize these structural charges. (2) Surface matching: the surface sites of the attapulgite can be transformed into surface hydroxyls which can perform coordination reactions with heavy metal ions. (3) Surface coordination: the surface hydroxyl position of the silicate mineral can be electrostatically coordinated with heavy metal ions so as to adsorb the heavy metal ions. However, the natural attapulgite contains a large amount of impurities, has low adsorption capacity and poor adsorption selectivity, so that the problem that the environment restoration field is urgently solved by finding the efficient, cheap and green modified attapulgite conforming to the adsorption material through a modification method.
In recent years, the attapulgite is modified to improve the adsorption performance of the attapulgite, so that the attapulgite can attract wide attention, the high-temperature modification can effectively remove pore channels inside the attapulgite and water molecules on the surface of the structure, and Si-O-M bonds can be broken, so that the adsorption capacity of heavy metal ions is enhanced. The attapulgite is subjected to proper acid treatment to activate pore channels and generate more adsorption points, so that the adsorption capacity of the attapulgite is enhanced. Research shows that the floatable porous foam adsorbent formed by embedding Attapulgite (ATP) in Sodium Alginate (SA) is prepared by a freeze-drying crosslinking method. Research also finds that the attapulgite clay-carbon nano composite adsorbent is prepared by a one-pot hydrothermal method, and the research on removing toxic metal ions in water is carried out on the attapulgite clay-carbon nano composite adsorbent, so that the novel ATP @ C nano composite material has higher adsorption capacity on Cr (VI) ions and Pb (II) ions. Therefore, the organic functional groups on the surface of the attapulgite can be increased by carrying out surface modification on the attapulgite, and the adsorption capacity of the attapulgite on heavy metals in water is improved.
Although the adsorption capacity of the adsorption material can be improved by modifying the attapulgite in multiple aspects, the adsorption material prepared in the prior art still has the defects of low adsorption performance and low reuse rate.
Disclosure of Invention
The invention aims to provide a modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent with strong adsorption performance and high reuse rate, and a preparation method and application thereof.
The invention provides a preparation method of a modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent, which comprises the following steps:
(1) mixing attapulgite with a hydrochloric acid solution for acid modification to obtain acid-modified attapulgite;
(2) mixing the acid-modified attapulgite obtained in the step (1) with water, a magnesium sulfate solution and ammonia water in sequence, and carrying out double decomposition reaction to obtain a precursor; calcining the precursor to obtain a magnesium oxide/attapulgite composite material;
(3) mixing the magnesium oxide/attapulgite composite material obtained in the step (2) with water, polyvinyl alcohol and sodium alginate to obtain a mixed solution; and sequentially molding and curing the mixed solution to obtain the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent.
Preferably, the concentration of the hydrochloric acid solution in the step (1) is 0.5-2.0 mol/L.
Preferably, the volume ratio of the mass of the attapulgite to the hydrochloric acid solution in the step (1) is 50-100 g/L.
Preferably, the concentration of the magnesium sulfate solution in the step (2) is 100-120 g/L.
Preferably, the volume ratio of the mass of the acid-modified attapulgite to the magnesium sulfate solution and the water in the step (2) is 1g (2-2.5) mL (40-50) mL.
Preferably, the volume ratio of the mass of the acid-modified attapulgite to the ammonia water in the step (2) is 1g (2-2.5) mL.
Preferably, the calcining temperature in the step (2) is 400-420 ℃, and the calcining time is 2-3 h.
Preferably, the mass ratio of the magnesium oxide/attapulgite composite material, the polyvinyl alcohol and the sodium alginate in the step (3) is 1: (2-2.5): (2-2.5).
The invention also provides the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent prepared by the preparation method in the technical scheme.
The invention also provides application of the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent in the technical scheme in removing heavy metal ions in soil or water.
Has the advantages that:
the invention provides a preparation method of a modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent, which comprises the following steps: mixing attapulgite with a hydrochloric acid solution for acid modification to obtain acid-modified attapulgite; mixing the obtained acid modified attapulgite with water, magnesium sulfate solution and ammonia water in sequence, and carrying out double decomposition reaction to obtain a precursor; calcining the precursor to obtain a magnesium oxide/attapulgite composite material; and mixing the obtained magnesium oxide/attapulgite composite material with water, polyvinyl alcohol and sodium alginate, and then sequentially molding and curing to obtain the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent. According to the invention, the attapulgite is subjected to acid modification by hydrochloric acid, so that the charges and adsorption active sites on the surface of the attapulgite are changed, and the adsorption and purification performance of the attapulgite is improved; then, chemically modifying to load magnesium oxide on the acid-modified attapulgite, so as to improve the adsorption active sites of the attapulgite; and the chemically modified attapulgite is molded through molding and curing, so that the mechanical property of the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent is improved, and the composite adsorbent can be repeatedly utilized and still has excellent adsorption effect. Experimental results show that the composite adsorbent prepared by the preparation method provided by the invention has a rapid adsorption effect within 60 minutes, and basically reaches adsorption balance within 6 hours, wherein the adsorption capacity to Zn is 45.0mg/g, and the adsorption capacity to Cd is 54.6 mg/g; and when the attapulgite which is not treated by the preparation method is used for 1 hour, the adsorption capacity of the attapulgite on Zn is only 5.82mg/g, the adsorption capacity of the attapulgite on Cd is 4.93mg/g, the adsorption balance is realized, the adsorption capacity of the attapulgite on Zn is 7.50mg/g, and the adsorption capacity of the attapulgite on Cd is 6.61 mg/g.
Drawings
FIG. 1 is a flow chart of the preparation of the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent in examples 1 to 3 of the present invention.
Detailed Description
The invention provides a preparation method of a modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent, which comprises the following steps:
(1) mixing attapulgite with a hydrochloric acid solution for acid modification to obtain acid-modified attapulgite;
(2) mixing the acid-modified attapulgite obtained in the step (1) with water, a magnesium sulfate solution and ammonia water in sequence, and carrying out double decomposition reaction to obtain a precursor; calcining the precursor to obtain a magnesium oxide/attapulgite composite material;
(3) mixing the magnesium oxide/attapulgite composite material obtained in the step (2) with water, polyvinyl alcohol and sodium alginate to obtain a mixed solution; and sequentially molding and curing the mixed solution to obtain the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent.
The invention mixes the attapulgite with hydrochloric acid solution for acid modification to obtain the acid modified attapulgite.
In the present invention, the particle size of the attapulgite is preferably 75 to 150 μm, and more preferably 150 μm. The source of the attapulgite in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used. In the present invention, when the particle size of the attapulgite is in the above range, it is more advantageous to obtain a composite adsorbent having good adsorption performance.
In the invention, the concentration of the hydrochloric acid solution is preferably 0.5-2.0 mol/L, and more preferably 0.8-1.5 mol/L. The source of the hydrochloric acid solution is not particularly limited in the present invention, and a commercially available product well known to those skilled in the art may be used. In the present invention, when the concentration of the hydrochloric acid solution is within the above range, the electric charge and the adsorption active site on the surface of the attapulgite can be changed, and the adsorption purification performance of the attapulgite can be further improved.
In the invention, the volume ratio of the mass of the attapulgite to the hydrochloric acid solution is preferably 50-100 g/L, more preferably 60-80 g/L, and most preferably 50-70 g/L. In the present invention, when the ratio of the mass of the attapulgite to the volume of the hydrochloric acid solution is in the above range, the acid modification of the charge on the surface of the attapulgite is facilitated, and the adsorption purification performance of the attapulgite is further improved.
The operation of the mixing is not particularly limited, and the attapulgite and the hydrochloric acid solution can be mixed by adopting a solid-liquid mixing mode well known to those skilled in the art.
In the present invention, the acid modification is preferably performed under mechanical stirring. In the present invention, the mechanical stirring device is preferably a shaker. In the present invention, the process of the acid modification is preferably: placing the mixed solution obtained after mixing the attapulgite and the hydrochloric acid solution in a shaking table for oscillation, wherein the oscillation rotating speed is preferably 150-200 rpm, and more preferably 160-180 rpm; the oscillation time is preferably 45-60 min, and more preferably 50-55 min. In the present invention, when the acid modification process is the above case, it is more advantageous to promote the modification of attapulgite with hydrochloric acid.
After the acid modification is finished, the invention preferably carries out solid-liquid separation, washing and drying on the product after the acid modification in sequence to obtain the acid-modified attapulgite. The operation of the solid-liquid separation, washing and drying in the present invention is not particularly limited, and the operation of the solid-liquid separation, washing and drying known to those skilled in the art may be employed. In the invention, the solid-liquid separation is preferably centrifugation, and the rotation speed of the centrifugation is preferably 3000-6000 rpm, more preferably 4000-5000 rpm; the time for centrifugation is preferably 10-30 min, and more preferably 15-20 min. In the present invention, the washed solvent is preferably deionized water; the washing is preferably: and washing the centrifuged solid for 3-5 times by using deionized water. In the invention, the drying temperature is preferably 70-80 ℃, and more preferably 75-80 ℃; the drying time is preferably 18-30 h, and more preferably 24 h.
In the present invention, the particle size of the acid-modified attapulgite is preferably 100 to 200 mesh, and more preferably 100 mesh. When the particle size of the acid-modified attapulgite is not in the above range, the present invention preferably screens the dried product. In the present invention, the sieving enables the agglomerated particles to be separated.
After the acid-modified attapulgite is obtained, the acid-modified attapulgite is mixed with water, magnesium sulfate solution and ammonia water in sequence, and double decomposition reaction is carried out to obtain a precursor.
In the invention, the concentration of the magnesium sulfate solution is preferably 100-120 g/L, and more preferably 110-120 g/L. In the invention, the volume ratio of the mass of the attapulgite to the magnesium sulfate solution and the water is preferably 1g (2-2.5) mL (40-50) mL, and more preferably 1g (2.2-2.4) mL to 45 mL. In the present invention, when the concentration of the magnesium sulfate solution is within the above range, sufficient magnesium groups can be supported on the attapulgite, active sites on the surface of the modified attapulgite can be further increased, and the adsorption performance of the composite adsorbent can be further improved. The source of the magnesium sulfate solution is not particularly limited in the present invention, and the magnesium sulfate solution may be prepared in the above concentration range by a method for preparing a solution, which is well known to those skilled in the art, using a commercially available product well known to those skilled in the art.
In the present invention, the concentration of the ammonia water is preferably 20 to 28%, and more preferably 28%. In the present invention, the volume ratio of the mass of the acid-modified attapulgite to the ammonia water is preferably 1g (2 to 2.5) mL, and more preferably 1g (2.2 to 2.4) mL. The source of the ammonia water is not particularly limited in the present invention, and the ammonia water can be prepared into the above concentration range by using a commercially available product well known to those skilled in the art. In the present invention, when the concentration of the aqueous ammonia is within the above range, the double decomposition reaction with magnesium sulfate is more favorably carried out.
In the present invention, the mixing of the acid-modified attapulgite with water, a magnesium sulfate solution and ammonia water is preferably: placing the acid-modified attapulgite, water and magnesium sulfate solution in a shaking table for first oscillation to form suspension, adding ammonia water into the suspension, and performing second oscillation. In the invention, the rotation speed of the first oscillation is preferably 150-200 rpm, and more preferably 150 rpm; the time of the first oscillation is preferably 15-20 min, and more preferably 15-18 min. In the invention, the rotation speed of the second oscillation is preferably 150-180 rpm, and more preferably 160-170 rpm; the time of the second oscillation is preferably 30-45 min, and more preferably 35 min. In the present invention, when the mixing is performed in the above manner, the magnesium hydroxide generated by the metathesis reaction can be more favorably dispersed uniformly in the attapulgite, and more magnesium hydroxide can be supported on the attapulgite, which is favorable for increasing the supporting amount of magnesium hydroxide on the attapulgite.
After the double decomposition reaction is finished, the invention preferably carries out solid-liquid separation, washing and drying on the product after the double decomposition reaction in sequence to obtain the precursor. The operation of the solid-liquid separation, washing and drying in the present invention is not particularly limited, and the operation of the solid-liquid separation, washing and drying known to those skilled in the art may be employed. In the invention, the solid-liquid separation is preferably centrifugation, and the rotation speed of the centrifugation is preferably 3000-6000 rpm, more preferably 4000-5000 rpm; the time for centrifugation is preferably 10-30 min, and more preferably 15-20 min. In the present invention, the washed solvent is preferably deionized water; the washing is preferably: and washing the centrifuged solid with deionized water until the pH of the supernatant reaches 6-7. In the invention, the drying temperature is preferably 70-80 ℃, and more preferably 75-80 ℃; the drying time is preferably 4-6 h, and more preferably 5-6 h.
After the precursor is obtained, the invention calcines the precursor to obtain the magnesium oxide/attapulgite composite material.
In the invention, the calcining temperature is preferably 400-420 ℃, and more preferably 410-420 ℃; the calcination time is preferably 2-3 h, and more preferably 2.5 h; the heating rate for heating to the calcination temperature is preferably 10-20 ℃/min, and more preferably 10 ℃/min. In the present invention, when the calcination parameter is in the above range, the magnesium hydroxide supported on the surface of the attapulgite can be sufficiently converted into magnesium oxide, and the adsorption property of the composite adsorbent can be further improved. The calcination apparatus used in the present invention is not particularly limited, and any calcination apparatus known to those skilled in the art may be used. In the present invention, the calcination apparatus is preferably a muffle furnace.
After the magnesium oxide/attapulgite composite material is obtained, the magnesium oxide/attapulgite composite material is mixed with water, polyvinyl alcohol and sodium alginate to obtain a mixed solution; and sequentially molding and curing the mixed solution to obtain the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent.
In the invention, the mass-to-water volume ratio of the magnesium oxide/attapulgite composite material is preferably 1g (100-120) mL, and more preferably 1g (110-115) mL. In the invention, when the mass-to-water volume ratio of the magnesium oxide/attapulgite composite material is in the above range, a uniform suspension can be formed after adding polyvinyl alcohol and sodium alginate, which is more beneficial to the proceeding of a crosslinking reaction and the solidification of a composite adsorbent.
In the invention, the mass ratio of the magnesium oxide/attapulgite composite material to the polyvinyl alcohol to the sodium alginate is preferably 1: (2-2.5): (2 to 2.5), more preferably 1: (2.2-2.5): (2.2-2.5). The source of the polyvinyl alcohol and sodium alginate in the present invention is not particularly limited, and commercially available products well known to those skilled in the art may be used. In the invention, when the mass ratio of the magnesium oxide/attapulgite composite material to the polyvinyl alcohol to the sodium alginate is within the above range, the cured composite adsorbent can be ensured to have better mechanical properties, and the reuse rate of the composite adsorbent can be further improved.
In the present invention, the mixing of the magnesium oxide/attapulgite composite material with water, polyvinyl alcohol and sodium alginate is preferably: mixing the magnesium oxide/attapulgite composite material with water to form a first suspension, mixing the first suspension with polyvinyl alcohol to obtain a second suspension, and mixing the second suspension with sodium alginate to obtain a mixed solution.
In the invention, the magnesium oxide/attapulgite composite material and water are preferably mixed by shaking in a shaking table, the shaking rate is preferably 150-180 rpm, and the shaking time is preferably 30-60 min.
In the invention, the mixing temperature of the first suspension and the polyvinyl alcohol is preferably 85-95 ℃, and more preferably 90-95 ℃; the mixing time of the first suspension and the polyvinyl alcohol is preferably 2-4 h, and more preferably 3-4 h. In the present invention, when the mixing parameter of the first suspension and the polyvinyl alcohol is within the above range, the polyvinyl alcohol can be promoted to be fully dissolved in the first suspension, and a uniformly mixed second suspension can be formed.
In the invention, the mixing mode of the second suspension and sodium alginate is preferably mechanical stirring, and the speed of the mechanical stirring is preferably 400-600 rpm, and more preferably 450-550 rpm; the mechanical stirring time is preferably 1-2 hours, and more preferably 1.5-2 hours. In the invention, when the manner of mixing the second suspension with the sodium alginate is the above-mentioned case, the sodium alginate and the second suspension can be fully mixed to form a uniformly mixed solution.
In the present invention, the molding is preferably performed by injecting the mixed solution into a mold having a desired shape and drying the mixture. The shape of the mold is not particularly limited, and the mold can be selected according to the required shape.
In the present invention, the drying is preferably freeze-drying. In the present invention, the freeze-drying is preferably performed by freezing the mold filled with the mixed solution, thawing the mold at room temperature, and repeating the freeze-thawing for 3 times. In the present invention, the temperature of the freeze-drying is preferably-20 to-30 ℃, more preferably-25 to-30 ℃; the freeze drying time is preferably 20-24 hours, and more preferably 22-24 hours; the time for thawing at room temperature is preferably 4-5 h. In the present invention, when the freeze-drying parameter is within the above range, water in the mixed solution can be sufficiently removed, and the molded product can have a rich pore structure.
In the present invention, the curing is preferably carried out by immersing the molded product in a curing agent to carry out a crosslinking reaction. In the invention, the time for soaking the molded product in the curing agent is preferably 60-120 min. In the invention, the curing agent is preferably a calcium chloride solution with the mass concentration of 5-10%. In the invention, when the curing parameter is in the above range, polyvinyl alcohol can be fully crosslinked, the strength of the composite adsorbent is improved, and the reuse rate of the composite adsorbent can be further improved.
In an embodiment of the present invention, as shown in fig. 1, a flowchart of a method for preparing the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent is preferably shown, and the method includes performing acid modification on attapulgite to obtain acidified Attapulgite (ATP), performing chemical modification on the acidified ATP, calcining the acidified ATP to obtain a magnesium oxide/attapulgite composite material (MgO/ATP composite), mixing the MgO/ATP composite material with water, polyvinyl alcohol (PVA) and Sodium Alginate (SA) to obtain a mixed solution, and sequentially performing molding and cross-linking curing on the mixed solution to obtain the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent.
According to the preparation method of the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent, the attapulgite is subjected to acid modification by hydrochloric acid, so that the charges on the surface of the attapulgite and adsorption active sites are changed, and the adsorption and purification performance of the attapulgite is improved; then, chemically modifying to load magnesium oxide on the acid-modified attapulgite, so as to improve the adsorption active sites of the attapulgite; and the chemically modified attapulgite is molded through molding and curing, so that the mechanical property of the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent is improved, and the composite adsorbent can be repeatedly utilized and still has excellent adsorption effect.
The invention also provides the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent prepared by the preparation method in the technical scheme.
The modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent provided by the invention has good adsorption performance, can be repeatedly used for many times, and has good reuse rate.
The invention also provides application of the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent in the technical scheme in removing heavy metal ions in soil or water. The application method of the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent in removing the heavy metal ions in the soil or the water body is not particularly limited, and the method for removing the heavy metal ions in the soil or the water body by using the composite adsorbent known by the technical personnel in the field can be adopted.
The modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent provided by the invention has good adsorption performance, can be repeatedly used for many times, has good reuse rate, and can be used for removing heavy metal ions in soil or water.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Mixing 5g of ATP with the particle size of 150 mu m and 75mL of hydrochloric acid solution with the concentration of 1mol/L, placing the obtained mixed solution in a shaking table, shaking for 60min at the speed of 180rpm, and then centrifuging for 20min at the speed of 4000 rpm; and washing the precipitate obtained by centrifugation for 3 times by using deionized water, placing the washed precipitate in an oven at 75 ℃ for 24 hours, and then sieving the dried solid by using a 100-mesh sieve to obtain the acid modified ATP.
(2) Placing 5g of mixed solution obtained by the acid modified ATP obtained in the step (1) and 200mL of deionized water and 12mL of magnesium sulfate solution with the concentration of 100g/L in a shaking table, shaking for 15min at the speed of 150rpm to form suspension, adding 10mL of 28% ammonia water into the suspension, and shaking for 45min at the speed of 180 rpm; and (3) separating a solid product from the vibrated product under the centrifugal condition of 4000rpm, fully washing the solid product by using deionized water, drying the washed solid product in an oven at 80 ℃ for 4h to obtain a precursor when the pH of a supernatant reaches 7, calcining the precursor in a muffle furnace at 400 ℃ for 2h at the heating rate of 10 ℃/min to obtain the MgO/ATP composite material.
(3) Stirring 0.25g of the MgO/ATP composite material obtained in the step (2) and 25mL of deionized water at the speed of 180rpm for 35min to obtain a first suspension, adding 0.5g of PVP into the first suspension, and heating at 95 ℃ for 2h to fully dissolve the PVP to obtain a second suspension; adding 0.5g of SA into the second suspension, and stirring for 90min at the speed of 500rpm to obtain a mixed solution; injecting the obtained mixed solution into a PVC mould (1cm multiplied by 1cm) through an injector, freezing for 20h at the temperature of minus 20 ℃, then unfreezing for 4h at the room temperature, repeatedly freezing and thawing for 3 times, then freeze-drying, taking out and immersing in 5% wt calcium chloride solution to fully crosslink, thus obtaining the modified ATP/PVP/SA composite adsorbent.
Example 2
(1) Mixing 5g ATP with the particle size of 100 μm and 50mL hydrochloric acid solution with the concentration of 0.5mol/L, placing the obtained mixed solution in a shaking table, shaking for 45min at the speed of 150rpm, and then centrifuging for 20min at the speed of 4500 rpm; and washing the precipitate obtained by centrifugation for 3 times by using deionized water, placing the washed precipitate in an oven at 70 ℃ for 24 hours, and then sieving the dried solid by using a 100-mesh sieve to obtain the acid modified ATP.
(2) Placing 5g of mixed solution obtained by the acid modified ATP obtained in the step (1) and 200mL of deionized water and 10mL of magnesium sulfate solution with the concentration of 110g/L in a shaking table, shaking for 20min at the speed of 150rpm to form suspension, adding 12mL of 28% ammonia water into the suspension, and shaking for 30min at the speed of 150 rpm; and (3) separating a solid product from the vibrated product under the centrifugal condition of 4500rpm, fully washing the solid product with deionized water, drying the washed solid product in an oven at 80 ℃ for 4h to obtain a precursor when the pH of a supernatant reaches 7, calcining the precursor in a muffle furnace at 400 ℃ for 2h at the heating rate of 10 ℃/min to obtain the MgO/ATP composite material.
(3) Stirring 0.25g of the MgO/ATP composite material obtained in the step (2) and 20mL of deionized water at the speed of 180rpm for 15min to obtain a first suspension, adding 0.55g of PVP into the first suspension, and heating at 95 ℃ for 2.5h to fully dissolve the PVP to obtain a second suspension; adding 0.55g of SA into the second suspension, and stirring for 30min at the speed of 160rpm to obtain a mixed solution; injecting the obtained mixed solution into a PVC mould (1cm multiplied by 1cm) through an injector, freezing for 24h at minus 25 ℃, then unfreezing for 5h at room temperature, repeatedly freezing and thawing for 3 times, then freeze-drying, taking out and immersing in 8% wt calcium chloride solution to fully crosslink, thus obtaining the modified ATP/PVP/SA composite adsorbent.
Example 3
(1) Mixing 5g of ATP with the particle size of 100 mu m and 100mL of hydrochloric acid solution with the concentration of 2mol/L, placing the obtained mixed solution in a shaking table, shaking for 50min at the speed of 200rpm, and then centrifuging for 20min at the speed of 6000 rpm; and washing the precipitate obtained by centrifugation for 3 times by using deionized water, placing the washed precipitate in an oven at 80 ℃ for 24 hours, and then sieving the dried solid by using a 100-mesh sieve to obtain the acid modified ATP.
(2) Placing 5g of mixed solution obtained by the acid modified ATP obtained in the step (1) and 250mL of deionized water and 10mL of magnesium sulfate solution with the concentration of 120g/L in a shaking table, shaking for 40min at the speed of 150rpm to form suspension, adding 10mL of 28% ammonia water into the suspension, and shaking for 35min at the speed of 160 rpm; and (3) separating a solid product from the vibrated product under the centrifugal condition of 5000rpm, fully washing the solid product by using deionized water, drying the washed solid product in an oven at 80 ℃ for 4h to obtain a precursor when the pH of a supernatant reaches 6, calcining the precursor in a muffle furnace at 400 ℃ for 2h at the heating rate of 10 ℃/min to obtain the MgO/ATP composite material.
(3) Stirring 0.25g of the MgO/ATP composite material obtained in the step (2) and 30mL of deionized water at the speed of 180rpm for 18min to obtain a first suspension, adding 0.6g of PVP into the first suspension, and heating at 95 ℃ for 3h to fully dissolve the PVP to obtain a second suspension; adding 0.6g of SA into the second suspension, and stirring for 30min at the speed of 170rpm to obtain a mixed solution; injecting the obtained mixed solution into a PVC mould (1cm multiplied by 1cm) through an injector, freezing for 20h at minus 30 ℃, then unfreezing for 4.5h at room temperature, repeatedly freezing and thawing for 3 times, then freeze-drying, taking out and immersing in 10% wt calcium chloride solution to fully crosslink, thus obtaining the modified ATP/PVP/SA composite adsorbent.
Comparative example 1
Stirring 0.25g of ordinary commercially available ATP and 25mL of deionized water at the speed of 180rpm for 18min to obtain a first suspension, adding 0.5g of PVP into the first suspension, and heating at 95 ℃ for 3h to fully dissolve the PVP to obtain a second suspension; adding 0.5g of SA into the second suspension, and stirring for 30min at the speed of 170rpm to obtain a mixed solution; injecting the obtained mixed solution into a PVC mould (1cm multiplied by 1cm) through an injector, freezing for 20h at the temperature of minus 20 ℃, then unfreezing for 4h at the room temperature, repeatedly freezing and thawing for 3 times, then freeze-drying, taking out and immersing in 5% wt calcium chloride solution to fully crosslink, thus obtaining the ATP/PVP/SA composite adsorbent.
Application example 1
0.5g of the modified ATP/PVP/SA complex adsorbent prepared in example 1 was added to 100mL of a zinc-containing ion (Zn)2+) In an aqueous solution having a concentration of 200mg/L, magnetic stirring was carried out at 100rpm and 25 ℃. The experimental period is 4 hours, samples are taken at 10 minutes, 20 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, 3 hours and 4 hours to determine the heavy metal content, each sample is 3mL, and the test results are shown in Table 1.
0.5g of the modified ATP/PVP/SA composite adsorbent prepared in example 1 was added to 100mL of cadmium-containing ion (Cd)2+) In an aqueous solution having a concentration of 200mg/L, magnetic stirring was carried out at 100rpm and 25 ℃. The experimental period was 4 hours, and sampling was performed at 10 minutes, 20 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, 3 hours, and 4 hoursThe content of heavy metal is determined, 3mL of heavy metal is sampled every time, and the test result is shown in Table 2.
0.5g of ATP/PVP/SA composite adsorbent prepared in comparative example 1 was added to 100mL of Zn-containing solution2+In an aqueous solution having a concentration of 200mg/L, magnetic stirring was carried out at 100rpm and 25 ℃. The experimental period is 4 hours, samples are taken at 10 minutes, 20 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, 3 hours and 4 hours to determine the heavy metal content, each sample is 3mL, and the test results are shown in Table 1.
0.5g of ATP/PVP/SA composite adsorbent prepared in comparative example 1 was added to 100mL of Cd-containing adsorbent2+In an aqueous solution having a concentration of 200mg/L, magnetic stirring was carried out at 100rpm and 25 ℃. The experimental period is 4 hours, samples are taken at 10 minutes, 20 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, 3 hours and 4 hours to determine the heavy metal content, each sample is 3mL, and the test results are shown in Table 2.
In this application example, the material adsorption amount in the experiment was calculated using the following formula:
wherein q (ti) -the adsorption amount of the material after the ith sampling, mg/g;
C0-initial heavy metal concentration in solution, mg/L;
V0-initial solution volume, L;
Ci-the concentration of heavy metals in the solution sampled at the ith time, mg/L;
v-volume sampled at a time, L;
n-mass of added adsorbing material, g.
Table 1 adsorption amount of the composite adsorbents prepared in example 1 and comparative example 1 to the Zn-containing aqueous solution
As a result of the experiment, it was found that the composite adsorbent prepared in example 1 was adsorbedThe adsorption time of the agent is fast within 60 minutes, and Zn is adsorbed within 1 hour2+The amount of adsorbed was 25.2 mg/g. The adsorbent reaches adsorption equilibrium at 6h basically, and then Zn is treated2+The amount of adsorption of (A) was 45.0 mg/g. While the composite adsorbent prepared in comparative example 1 can adsorb Zn for 1h2+The amount of adsorption of (A) was only 5.8 mg/g. The adsorbent reaches adsorption equilibrium at 6h basically, and then Zn is treated2+The amount of adsorbed was 7.5 mg/g. It can be seen that the composite adsorbent prepared in the examples provided by the invention has a Zn content in an aqueous solution higher than that of the composite adsorbent prepared from commercially available attapulgite2+Has excellent adsorption effect.
TABLE 2 adsorption capacity of the composite adsorbents prepared in example 1 and comparative example 1 for Cd-containing aqueous solution
Experimental results show that the adsorption time of the composite adsorbent prepared in example 1 is fast in 60 minutes, and Cd is adsorbed for 1h2+The amount of adsorbed was 53.4 mg/g. The adsorbent reaches adsorption equilibrium at 6h basically, and then Cd is treated2+The amount of adsorbed was 54.6 mg/g. For Cd at 1h in the composite adsorbent prepared in comparative example 12+The amount of adsorbed was 4.9 mg/g. The adsorbent reaches adsorption equilibrium at 6h basically, and then Cd is treated2+The amount of adsorbed was 6.6 mg/g. Therefore, compared with the composite adsorbent prepared from the commercially available attapulgite, the composite adsorbent prepared by the embodiment provided by the invention has the advantages that the Cd in the aqueous solution is adsorbed by the composite adsorbent2+Has excellent adsorption effect.
Application example 2
The modified ATP/PVP/SA composite adsorbent prepared in example 1 was immersed in 100mL of a 1mol/L HCl solution and magnetically stirred for 2h to perform a desorption experiment. The material after completion of desorption was subjected to an adsorption experiment as in application example 1. The 5 cycles are circulated, according to the previous research, the adsorption time has a rapid adsorption effect after 60 minutes, so the 60-minute adsorption performance of the material after each adsorption and desorption is directly measured. After 5 times of adsorption and desorption cycles, the adsorption performance of the SA/PVA/MgO/ATP material on Zn and Cd can still reach 85% and 90% of that of the first time.
TABLE 3 adsorption capacity of Zn-containing aqueous solution by using the composite adsorbents prepared in example 2 and comparative example
The ATP/PVP/SA composite adsorbent charge prepared in comparative example 1 was immersed in 100mL of a 1mol/L HCl solution and magnetically stirred for 2h for desorption experiments. The material after completion of desorption was subjected to the adsorption experiment as described above. The cycle is repeated for 5 periods, and the adsorption performance of the material at the 60 th minute after each adsorption and desorption is also measured. After 5 adsorption and desorption cycles, Zn is adsorbed and desorbed by common commercial attapulgite2+And Cd2+The adsorption performance of the adsorbent can only reach about 20 percent of that of the first time.
TABLE 4 adsorption capacity of composite adsorbent prepared in application example 2 and comparative example for Cd-containing aqueous solution
The recycling performance is an important index for representing the economic performance of the material, so that after the adsorption is finished, a recycling experiment is carried out on the material. The data of the application example 2 can show that the material not only has good adsorption performance, but also has the potential of being recycled, and has the application prospect of the heavy metal adsorbent in water treatment.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent comprises the following steps:
(1) mixing attapulgite with a hydrochloric acid solution for acid modification to obtain acid-modified attapulgite;
(2) mixing the acid-modified attapulgite obtained in the step (1) with water, a magnesium sulfate solution and ammonia water in sequence, and carrying out double decomposition reaction to obtain a precursor; calcining the precursor to obtain a magnesium oxide/attapulgite composite material;
(3) mixing the magnesium oxide/attapulgite composite material obtained in the step (2) with water, polyvinyl alcohol and sodium alginate to obtain a mixed solution; and sequentially molding and curing the mixed solution to obtain the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent.
2. The method according to claim 1, wherein the concentration of the hydrochloric acid solution in the step (1) is 0.5 to 2.0 mol/L.
3. The method according to claim 2, wherein the ratio of the mass of the attapulgite to the volume of the hydrochloric acid solution in the step (1) is 50 to 100 g/L.
4. The preparation method according to claim 1, wherein the concentration of the magnesium sulfate solution in the step (2) is 100-120 g/L.
5. The preparation method according to claim 4, wherein the volume ratio of the mass of the acid-modified attapulgite to the magnesium sulfate solution and the water in the step (2) is 1g (2-2.5) mL (40-50) mL.
6. The method according to claim 1, wherein the volume ratio of the mass of the acid-modified attapulgite to the ammonia water in the step (2) is 1g (2-2.5) mL.
7. The preparation method according to claim 1, wherein the calcining temperature in the step (2) is 400-420 ℃, and the calcining time is 2-3 h.
8. The preparation method according to claim 1, wherein the mass ratio of the magnesium oxide/attapulgite composite material, the polyvinyl alcohol and the sodium alginate in the step (3) is 1: (2-2.5): (2-2.5).
9. The modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent prepared by the preparation method of any one of claims 1 to 8.
10. The use of the modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent of claim 9 in the removal of heavy metal ions in soil or water.
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