CN113769669B - Ionic crosslinked clay aerogel material, preparation method and application thereof - Google Patents
Ionic crosslinked clay aerogel material, preparation method and application thereof Download PDFInfo
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Abstract
An ion-crosslinked clay aerogel material, a preparation method and application thereof, wherein the clay aerogel material is a three-dimensional porous aerogel obtained by sequentially carrying out ion intercalation, liquid phase stripping, centrifugal concentration, ion crosslinking and freeze drying on natural clay serving as a raw material; the aerogel has a porosity of 99.31-99.55% and a density of 0.0115-0.0176 g/cm 3 The structure of the aerogel keeps intact when bearing 1000 times of the weight of the aerogel, and also keeps intact after being soaked in water or strong acid and strong alkali solution for 100 hours. The clay aerogel material has the advantages of stable structure, good mechanical property and strong adsorption property, and the preparation method has low production cost, simple preparation process and easy enlargement of reaction scale; the application of the clay aerogel material in the field of sewage treatment has positive production significance.
Description
Technical Field
The invention relates to the field of preparation processes of aerogel materials, in particular to an ionic crosslinked clay aerogel material, a preparation method and application thereof.
Background
Energy crisis and water resource shortage are global problems that severely restrict the development of human society, and the demand for drinking water sources is remarkably increased due to the increasing number of the world population; in addition, environmental pollution caused by the discharge of large amounts of industrial wastewater and domestic sewage further results in the shortage of clean water resources. The purification of seawater and sewage by proper water purification technology to obtain clean water is considered as an effective means for solving the shortage of water resources, but the traditional methods such as distillation, rectification, membrane separation, chemical flocculation and the like have high energy consumption and high cost, are not beneficial to the sustainable development of the society, and efficient, economic and green water purification means and technology are urgently needed to be developed.
The aerogel has a high specific surface area (600-1200 m) 2 g -1 ) Solid materials with high porosity (over 90%) and three-dimensional network structure, gas or liquid can penetrate through the whole material without being bound in the pores due to the interconnected pore structure, and the surface has good adsorption property, so the aerogel can be used as an ideal material for efficiently treating pollutants in water. The raw materials for assembling the aerogel are very rich in selection, for example, the raw materials are divided according to the dimensionality, and comprise one-dimensional materials such as carbon nano tubes and cellulose fibers, two-dimensional materials such as graphene and MXene, and three-dimensional materials such as silicon dioxide and titanium dioxide; particularly, the problem of excessive stacking of nanosheets is effectively avoided by the aerogel assembled by a two-dimensional material, so that the advantages of more open single-layer nanosheet structure, rapid mass transfer, capability of providing more adsorption sites and the like are well maintained.
At present, abundant research is carried out on aerogel assembled by using a two-dimensional material, and in a preparation method of magnetic graphene aerogel (CN 107140620A), graphite oxide is used as a raw material, ultrasonic dispersion is carried out to obtain a graphene oxide nanosheet layer, then the graphene oxide nanosheet layer is compounded with dopamine and iron salt under a hydrothermal reaction to carry out gelation, and freeze drying is carried out to obtain the graphene aerogel; wanxianbao et al in ' an MXene and graphene oxide composite aerogel and its preparation method and application ' (CN 110090603A) ', MXene and graphene oxide nanosheets are obtained by using MAX powder and graphite powder as raw materials through chemical stripping, then mixed with sodium alginate dispersion liquid for gelation, freeze-dried to obtain composite aerogel, and then cross-linked with a cross-linking agent to enhance the overall mechanical properties of the aerogel; wu Xiao Chi et al in "a preparation method of a high temperature resistant light BN aerogel material" (CN 110104619A) use phenol, aldehyde, alcohol, silicon source, urea and boron source as raw materials, and obtain BN aerogel by combining a sol-gel method with a supercritical drying technology. However, the above method for assembling the aerogel uses expensive raw materials, the assembly process is complicated, and some reagents also cause environmental pollution, thus being low in economical efficiency and not environment-friendly; in addition, the cross-linking process for assembling aerogels generally takes a long time, further increasing economic costs.
Disclosure of Invention
The invention aims to provide an ionic crosslinking clay aerogel material, a preparation method and application thereof aiming at the defects in the prior art. The clay aerogel material has the advantages of stable structure, good mechanical property and strong adsorption property, and the preparation method has low production cost, simple preparation process and easy enlargement of reaction scale; the application of the clay aerogel material in the field of sewage treatment has positive production significance.
The invention solves the technical problems in the prior art by adopting the following technical scheme:
the clay aerogel material is three-dimensional porous aerogel which is prepared by taking natural clay as a raw material and sequentially carrying out ion intercalation, liquid phase stripping, centrifugal concentration, ion crosslinking and freeze drying; the aerogel has a porosity of 99.31-99.55% and a density of 0.0115-0.0176 g/cm 3 The structure of the aerogel remains intact when bearing 1000 times its own weight, and also remains intact after 100 h of immersion in water or strong acid, strong base solutions.
A method of preparing an ionically crosslinked clay aerogel material, comprising the steps of:
s1, performing ion intercalation through hydrothermal reaction:
mixing natural clay and saturated NaCl solution according to the mass-volume ratio of 0.3 g to 100 mL-1.2 g to 100 mL, placing the mixture in a hydrothermal reactor, and reacting the mixture in the hydrothermal reactor at the temperature of 100-120 DEG o Heating for 1-3 h under C to make the mixture of natural clay and saturated NaCl solution undergo hydrothermal reactionThe preparation method comprises the following steps of; when the hydrothermal reactor is cooled to room temperature, separating out a solid product after the hydrothermal reaction to obtain a primary solid product, and washing the primary solid product with deionized water to obtain a washed primary solid product; mixing the washed primary solid product with a LiCl solution, then placing the mixture in a hydrothermal reactor again, heating the mixture for 1-3 hours at 100-120 ℃, separating the solid product after the hydrothermal reaction again when the hydrothermal reactor is cooled to room temperature to obtain a secondary solid product, and washing the secondary solid product with deionized water to obtain clay after ion intercalation; the concentration of the LiCl solution is 1-3 mol/L, and the volume of the LiCl solution is the same as that of a saturated NaCl solution;
s2, liquid phase stripping is assisted by high-speed stirring:
mixing the clay subjected to ion intercalation obtained in the step S1 with deionized water to form clay mixed solution subjected to ion intercalation, wherein the volume of the deionized water in the clay mixed solution subjected to ion intercalation is 80% of the volume of saturated NaCl solution; placing the clay mixed solution after the ion intercalation into a high-speed shearing emulsifying machine, and stirring and stripping for 5-15 min at the rotating speed of 15000-25000 rpm in the high-speed shearing emulsifying machine to form a mixture containing clay nano-sheet layers; centrifuging the mixture in a high-speed centrifuge at the rotating speed of 300 rpm for 1 h to remove particles which are not completely stripped and impurities to obtain clay nanosheet dispersion liquid;
s3, obtaining a high concentration dispersion by centrifugal concentration:
centrifuging and concentrating the clay nanosheet dispersion obtained in the step S2 in a high-speed centrifuge at the rotating speed of 6000-10000 rpm for 20-60 min to obtain a clay nanosheet concentrated solution, removing the supernatant of the clay nanosheet concentrated solution, and performing ultrasonic dispersion on the precipitate of the clay nanosheet concentrated solution to obtain a high-concentration clay nanosheet dispersion;
s4, promoting the dispersion to be gelled rapidly through ionic crosslinking:
mixing a metal salt solution with the concentration of 0.1-0.5 mol/L and the high-concentration clay nanosheet dispersion liquid according to the volume ratio of 2:25 to obtain a clay hydrogel;
s5, freeze drying:
freezing the clay hydrogel obtained in the step S4 at-30 ℃ for 2h, and then carrying out freezing at-45 to-55 o C. And (5) carrying out freeze drying for 48 hours under 8-15 pa to obtain the clay aerogel material.
The natural clay is vermiculite, kaolin, montmorillonite or illite.
The method for separating the solid product in the hydrothermal reaction in step S1 includes suction filtration or centrifugation.
The concentration of the high-concentration clay nanosheet dispersion obtained in the step S3 is 6-15 mg/mL.
The metal salt in the metal salt solution is Ni as a cation + 、Ca 2+ 、Mg 2+ 、Al 3+ 、Fe 3+ Or La 3+ A salt.
The application of the ionic crosslinked clay aerogel material is characterized in that the clay aerogel material is placed in a removing device, water-soluble dye sewage with the concentration of 10-200 mg/L passes through the clay aerogel at the flow speed of 1-5 mL/min, and water-soluble dye in the sewage is removed.
The water-soluble dye is methylene blue, methyl orange or rhodamine B.
The invention has the beneficial effects that: the invention uses natural mineral clay particles with a layered structure as a raw material, obtains two-dimensional clay nano-sheets by an ion intercalation auxiliary liquid phase stripping method, and promotes the rapid gelation of dispersion liquid by combining an ion crosslinking method, thereby obtaining the clay aerogel with the advantages of stable structure, good mechanical property, strong adsorption property and the like. For the selection of raw materials, the natural clay particles have rich reserves, low price, easy availability, safety and stability, and have higher economical efficiency compared with two-dimensional materials such as graphene, MXene and the like. For the stripping method of the clay nano-sheet, the clay nano-sheet is obtained by carrying out ion intercalation by adopting hydrothermal reaction and then carrying out high-speed shearing stripping, and the method has the advantages of high production efficiency, mild reaction conditions, environmental friendliness and easiness in enlarging the reaction scale. For the crosslinking method of the clay nano-sheet layer, the rapid gelation of the dispersion liquid is promoted by directly mixing the metal ion solution and the high-concentration dispersion liquid, and the ionic crosslinking method is more efficient, safe and simple to operate and saves time and cost. The ionic crosslinked clay aerogel material provided by the invention has a remarkable application effect in the fields of sewage treatment and the like.
Detailed Description
The invention is illustrated but not limited by the following examples in which:
the natural clay used in the present invention is vermiculite, kaolin, montmorillonite or illite, and in the examples, vermiculite particles and montmorillonite powder are used as examples, but not limited thereto.
Example 1:
a method of preparing an ionically crosslinked clay aerogel material comprising the steps of:
s1, performing ion intercalation through hydrothermal reaction:
1.2 g vermiculite particles mixed with 100 mL saturated NaCl solution in hydrothermal reactor at 110% o Heating for 2 hours under C to enable the mixture of the vermiculite particles and the saturated NaCl solution to carry out hydrothermal reaction; when the hydrothermal reactor is cooled to room temperature, separating a solid product after the hydrothermal reaction by a suction filtration separation or centrifugal separation method to obtain a primary solid product, and washing the primary solid product with deionized water for a plurality of times to obtain a washed primary solid product; mixing the washed primary solid product with LiCl solution with the concentration of 2 mol/L and the volume of 100 mL, then placing the mixture in a hydrothermal reactor again, heating the mixture for 2 hours at 110 ℃, separating the solid product after the hydrothermal reaction again by a suction filtration separation or centrifugal separation method when the hydrothermal reactor is cooled to room temperature to obtain a secondary solid product, and washing the secondary solid product for a plurality of times by deionized water to obtain the clay after ion intercalation.
S2, liquid phase stripping is assisted by high-speed stirring:
and (4) mixing the clay subjected to ion intercalation obtained in the step (S1) with 80 mL of deionized water to form a clay mixed solution subjected to ion intercalation. Placing the clay mixed solution after ion intercalation in a high-speed shearing emulsifying machine, and stirring and stripping for 10 min in the high-speed shearing emulsifying machine at the rotating speed of 20000 rpm to form a mixture containing clay nano-sheet layers; and then centrifuging the mixture in a high-speed centrifuge at the rotating speed of 300 rpm for 1 h to remove incompletely stripped particles and impurities to obtain the clay nanosheet dispersion.
S3, obtaining a high-concentration dispersion by centrifugal concentration:
and (4) carrying out centrifugal concentration on the clay nanosheet dispersion liquid obtained in the step (S2) in a high-speed centrifuge at the rotating speed of 6000 rpm for 60 min to obtain a clay nanosheet concentrated solution, removing part of supernatant of the clay nanosheet concentrated solution, and carrying out ultrasonic dispersion on the precipitate at the bottom of the clay nanosheet concentrated solution to obtain the high-concentration clay nanosheet dispersion liquid.
S4, promoting the dispersion to be quickly gelled through ionic crosslinking:
0.5 mol/L AlCl with the volume of 0.8 mL 3 And mixing the solution with a high-concentration clay nanosheet dispersion liquid with the volume of 10 mL and the concentration of 12mg/mL to obtain the clay hydrogel.
S5, freeze drying:
and (4) freezing the clay hydrogel obtained in the step S4 at-30 ℃ for 2h to completely freeze the clay hydrogel, and then carrying out freeze drying at-45 ℃ for 48 h at 8 pa to obtain the clay aerogel material.
The clay aerogel material obtained in example 1 was determined to have a porosity of 99.45% and an apparent density of 0.0139 g/cm 3 The structure of the clay aerogel material remained intact when bearing 1000 times itself and after soaking in water and a solution of strong acid (pH = 1), strong base (pH = 14) for 100 h.
Use of the clay aerogel material obtained in example 1: the clay aerogel material obtained in example 1 is placed in a removing device, and methylene blue with the concentration of 10 mg/L can be removed from the water-soluble dye in the solution by passing the clay aerogel material through the methylene blue solution with the flow rate of 1 mL/min. It was determined that when 500 mL of methylene blue solution was dye stripped using the clay aerogel material of example 1: the removal rate of the methylene blue is up to 93.92 percent, and the absorption amount of the methylene blue is up to 54.5 mg/g. Thereby realizing the removal of the water-soluble dye in the sewage.
Example 2:
a method of preparing an ionically crosslinked clay aerogel material comprising the steps of:
s1, performing ion intercalation through hydrothermal reaction:
mixing vermiculite particles with a mass of 0.3 g with saturated NaCl solution with a volume of 100 mL, placing the mixture in a hydrothermal reactor, and placing the reactor in a temperature range of 100% o Heating for 1 h under C to enable the mixture of the vermiculite particles and the saturated NaCl solution to carry out hydrothermal reaction; when the hydrothermal reactor is cooled to room temperature, separating a solid product after the hydrothermal reaction by a suction filtration separation or centrifugal separation method to obtain a primary solid product, and washing the primary solid product for a plurality of times by using deionized water to obtain a washed primary solid product; mixing the washed primary solid product with a LiCl solution with the concentration of 1 mol/L and the volume of 100 mL, then placing the mixture in a hydrothermal reactor again, heating the mixture for 1 h at 100 ℃, separating the solid product after the hydrothermal reaction again by a suction filtration separation or centrifugal separation method when the hydrothermal reactor is cooled to room temperature to obtain a secondary solid product, and washing the secondary solid product for a plurality of times by deionized water to obtain the clay after ion intercalation.
S2, liquid phase stripping is assisted by high-speed stirring:
and (4) mixing the clay subjected to ion intercalation obtained in the step (S1) with 80 mL of deionized water to form a clay mixed solution subjected to ion intercalation. Placing the clay mixed solution after ion intercalation in a high-speed shearing emulsifying machine, and stirring and stripping for 5 min in the high-speed shearing emulsifying machine at the rotating speed of 15000 rpm to form a mixture containing clay nano-sheet layers; and then centrifuging the mixture in a high-speed centrifuge at the rotating speed of 300 rpm for 1 h to remove incompletely stripped particles and impurities to obtain the clay nanosheet dispersion.
S3, obtaining a high concentration dispersion by centrifugal concentration:
and (4) performing centrifugal concentration on the clay nanosheet dispersion liquid obtained in the step S2 in a high-speed centrifuge at the rotating speed of 6000 rpm for 60 min to obtain a clay nanosheet concentrated solution. And removing part of supernatant of the clay nano-sheet concentrated solution, and performing ultrasonic dispersion on the precipitate at the bottom of the clay nano-sheet concentrated solution to obtain the high-concentration clay nano-sheet dispersion solution.
S4, promoting the dispersion to be gelled rapidly through ionic crosslinking:
0.5 mol/L AlCl with the volume of 0.8 mL 3 And mixing the solution with a high-concentration clay nanosheet dispersion liquid with the volume of 10 mL and the concentration of 15 mg/mL to obtain the clay hydrogel.
S5, freeze drying:
and (4) freezing the clay hydrogel obtained in the step S4 at-30 ℃ for 2h to completely freeze the clay hydrogel, and then carrying out freeze drying at-55 ℃ for 48 h at 15 pa to obtain the clay aerogel material.
The clay aerogel material obtained in example 2 was determined to have a porosity of 99.31% and an apparent density of 0.0176 g/cm 3 . The structure of the clay aerogel material remained intact when bearing 1000 times itself and after soaking in water and a solution of strong acid (pH = 1), strong base (pH = 14) for 100 h.
Use of the clay aerogel material obtained in example 2: the clay aerogel material obtained in example 2 is placed in a removing device, and methyl orange solution with the concentration of 200 mg/L is passed through the clay aerogel material at the flow rate of 5 mL/min to remove the water-soluble dye methyl orange in the solution. Thereby realizing the removal of the water-soluble dye in the sewage.
Example 3:
a method of preparing an ionically crosslinked clay aerogel material comprising the steps of:
s1, performing ion intercalation through hydrothermal reaction:
mixing vermiculite particles with a mass of 0.6 g with saturated NaCl solution with a volume of 100 mL, placing the mixture in a hydrothermal reactor, and placing the mixture in the hydrothermal reactor for 120 g o Heating for 1 h under C to enable the mixture of the vermiculite particles and the saturated NaCl solution to carry out hydrothermal reaction; when the hydrothermal reactor is cooled to room temperature, separating the solid product after the hydrothermal reaction by a suction filtration separation or centrifugal separation method to obtain a primary solid product, and washing the primary solid product for a plurality of times by using deionized water to obtain the productA washed primary solid product; mixing the washed primary solid product with a LiCl solution with the concentration of 3 mol/L and the volume of 100 mL, putting the mixture into a hydrothermal reactor again, heating the mixture for 1 h at 120 ℃, separating the solid product after the hydrothermal reaction by a suction filtration separation or centrifugal separation method again when the hydrothermal reactor is cooled to room temperature to obtain a secondary solid product, and washing the secondary solid product with deionized water for a plurality of times to obtain the clay after ion intercalation.
S2, liquid phase stripping is assisted by high-speed stirring:
and (4) mixing the clay subjected to ion intercalation obtained in the step (S1) with 80 mL of deionized water to form a clay mixed solution subjected to ion intercalation. Placing the clay mixed solution after ion intercalation in a high-speed shearing emulsifying machine, and stirring and stripping for 15 min in the high-speed shearing emulsifying machine at the rotating speed of 20000 rpm to form a mixture containing clay nano-sheet layers; and then centrifuging the mixture in a high-speed centrifuge at the rotating speed of 300 rpm for 1 h to remove incompletely stripped particles and impurities to obtain the clay nanosheet dispersion.
S3, obtaining a high concentration dispersion by centrifugal concentration:
and (4) carrying out centrifugal concentration on the clay nano sheet dispersion liquid obtained in the step (S2) in a high-speed centrifuge at the rotating speed of 6000 rpm for 60 min to obtain a clay nano sheet concentrated solution. And removing part of supernatant of the clay nano-sheet concentrated solution, and performing ultrasonic dispersion on the precipitate at the bottom of the clay nano-sheet concentrated solution to obtain the high-concentration clay nano-sheet dispersion solution.
S4, promoting the dispersion to be quickly gelled through ionic crosslinking:
0.5 mol/L AlCl with the volume of 0.8 mL 3 And mixing the solution with a high-concentration clay nanosheet dispersion liquid with the volume of 10 mL and the concentration of 6 mg/mL to obtain the clay hydrogel.
S5, freeze drying:
and (3) freezing the clay hydrogel obtained in the step S4 at-30 ℃ for 2h to completely freeze the clay hydrogel, and then carrying out freeze drying at-50 ℃ for 48 h at 10 pa to obtain the clay aerogel material.
The clay aerogel material obtained in example 3 was determined to have a porosity of 99.55% and an apparent density of 0.0115 g/cm 3 . The structure remained intact when bearing 1000 times its own weight and after soaking in water and a solution of strong acid (pH = 1), strong base (pH = 14) for 100 h.
Use of the clay aerogel material obtained in example 3: the clay aerogel material obtained in the example 3 is placed in a removing device, and rhodamine B solution with the concentration of 50 mg/L passes through the clay aerogel material at the flow rate of 3 mL/min, so that the water-soluble dye rhodamine B in the solution can be removed. Thereby realizing the removal of the water-soluble dye in the sewage.
Example 4:
a method of preparing an ionically crosslinked clay aerogel material comprising the steps of:
s1, performing ion intercalation through hydrothermal reaction:
mixing 1.2 g vermiculite particles with 100 mL saturated NaCl solution, heating in a hydrothermal reactor at 110% o Heating for 2 hours under C to ensure that the mixture of the vermiculite particles and the saturated NaCl solution carries out hydrothermal reaction; when the hydrothermal reactor is cooled to room temperature, separating a solid product after the hydrothermal reaction by a suction filtration separation or centrifugal separation method to obtain a primary solid product, and washing the primary solid product for a plurality of times by using deionized water to obtain a washed primary solid product; the washed primary solid product was mixed with LiCl solution of 2 mol/L concentration and 100 mL volume and then placed in the hydrothermal reactor again at 110% o And C, heating for 2 hours, separating the solid product after the hydrothermal reaction by a suction filtration separation or centrifugal separation method when the hydrothermal reactor is cooled to room temperature to obtain a secondary solid product, and washing the secondary solid product for a plurality of times by deionized water to obtain the clay after ion intercalation.
S2, liquid phase stripping is assisted by high-speed stirring:
and (5) mixing the clay subjected to ion intercalation obtained in the step (S1) with 80 mL of deionized water to form a clay mixed solution subjected to ion intercalation. Placing the clay mixed solution after ion intercalation in a high-speed shearing emulsifying machine, and stirring and stripping for 10 min at the rotating speed of 20000 rpm in the high-speed shearing emulsifying machine to form a mixture containing clay nano-sheet layers; and then centrifuging the mixture in a high-speed centrifuge at the rotating speed of 300 rpm for 1 h to remove incompletely stripped particles and impurities to obtain the clay nanosheet dispersion.
S3, obtaining a high concentration dispersion by centrifugal concentration:
and (4) carrying out centrifugal concentration on the clay nano sheet dispersion liquid obtained in the step (S2) in a high-speed centrifuge at the rotating speed of 6000 rpm for 60 min to obtain a clay nano sheet concentrated solution. And removing part of supernatant of the clay nano-sheet concentrated solution, and performing ultrasonic dispersion on the precipitate at the bottom of the clay nano-sheet concentrated solution to obtain the high-concentration clay nano-sheet dispersion solution.
S4, promoting the dispersion to be gelled rapidly through ionic crosslinking:
NiCl with the volume of 0.8 mL and the concentration of 0.5 mol/L 2 And mixing the solution with a high-concentration clay nanosheet dispersion liquid with the volume of 10 mL and the concentration of 12mg/mL to obtain the clay hydrogel.
S5, freeze drying:
and (4) freezing the clay hydrogel obtained in the step S4 at-30 ℃ for 2h to completely freeze the clay hydrogel, and then carrying out freeze drying at-45 ℃ for 48 h at 8 pa to obtain the clay aerogel material.
The clay aerogel material obtained in example 4 was determined to have a porosity of 99.35% and an apparent density of 0.0167 g/cm 3 The clay aerogel material remains intact after being soaked in water for 100 hours.
Use of the clay aerogel material obtained in example 4: the clay aerogel material obtained in example 4 is placed in a removing device, and methylene blue solution with the concentration of 10 mg/L is passed through the clay aerogel material at the flow rate of 1mL/min, so that methylene blue which is a water-soluble dye in the solution can be removed. Thereby realizing the removal of the water-soluble dye in the sewage.
Example 5:
a method of preparing an ionically crosslinked clay aerogel material, comprising the steps of:
s1, carrying out ion intercalation through hydrothermal reaction:
mixing 1.2 g vermiculite particles with 100 mL saturated NaCl solution, placing in a hydrothermal reactor, and heating to 110% o Heating for 2 hours under C to enable the mixture of the vermiculite particles and the saturated NaCl solution to carry out hydrothermal reaction; when the hydrothermal reactor is cooled to room temperature, separating a solid product after the hydrothermal reaction by a suction filtration separation or centrifugal separation method to obtain a primary solid product, and washing the primary solid product for a plurality of times by using deionized water to obtain a washed primary solid product; the washed primary solid product was mixed with LiCl solution of 2 mol/L concentration and 100 mL volume and then placed in the hydrothermal reactor again at 110% o And C, heating for 2 hours, separating the solid product after the hydrothermal reaction by a suction filtration separation or centrifugal separation method when the hydrothermal reactor is cooled to room temperature to obtain a secondary solid product, and washing the secondary solid product for a plurality of times by deionized water to obtain the clay after ion intercalation.
S2, liquid phase stripping is assisted by high-speed stirring:
and (4) mixing the clay subjected to ion intercalation obtained in the step (S1) with 80 mL of deionized water to form a clay mixed solution subjected to ion intercalation. Placing the clay mixed solution after ion intercalation in a high-speed shearing emulsifying machine, and stirring and stripping for 10 min at the rotating speed of 20000 rpm in the high-speed shearing emulsifying machine to form a mixture containing clay nano-sheet layers; and then centrifuging the mixture in a high-speed centrifuge at the rotating speed of 300 rpm for 1 h to remove incompletely stripped particles and impurities to obtain the clay nanosheet dispersion liquid.
S3, obtaining a high concentration dispersion by centrifugal concentration:
and (4) carrying out centrifugal concentration on the clay nano sheet dispersion liquid obtained in the step (S2) in a high-speed centrifuge at the rotating speed of 6000 rpm for 60 min to obtain a clay nano sheet concentrated solution. And removing part of supernatant of the clay nano-sheet concentrated solution, and performing ultrasonic dispersion on the precipitate at the bottom of the clay nano-sheet concentrated solution to obtain the high-concentration clay nano-sheet dispersion solution.
S4, promoting the dispersion to be gelled rapidly through ionic crosslinking:
CaCl with the volume of 0.8 mL and the concentration of 0.5 mol/L 2 And mixing the solution with a high-concentration clay nanosheet dispersion liquid with the volume of 10 mL and the concentration of 12mg/mL to obtain the clay hydrogel.
S5, freeze drying:
and (4) freezing the clay hydrogel obtained in the step S4 at-30 ℃ for 2h to completely freeze the clay hydrogel, and then carrying out freeze drying at-45 ℃ for 48 h at 8 pa to obtain the clay aerogel material.
The clay aerogel material obtained in example 5 was determined to have a porosity of 99.32% and an apparent density of 0.0172g/cm 3 The clay aerogel material remains intact after being soaked in water for 100 hours.
Use of the clay aerogel material obtained in example 5: the clay aerogel material obtained in example 4 is placed in a removing device, and methylene blue with the concentration of 10 mg/L can be removed from the water-soluble dye in the solution by passing the clay aerogel material through the methylene blue solution with the flow rate of 1 mL/min. Thereby realizing the removal of the water-soluble dye in the sewage.
Example 6:
a method of preparing an ionically crosslinked clay aerogel material comprising the steps of:
s1, carrying out ion intercalation through hydrothermal reaction:
mixing 1.2 g vermiculite particles with 100 mL saturated NaCl solution, placing in a hydrothermal reactor, and heating to 110% o Heating for 2 hours under C to ensure that the mixture of the vermiculite particles and the saturated NaCl solution carries out hydrothermal reaction; when the hydrothermal reactor is cooled to room temperature, separating a solid product after the hydrothermal reaction by a suction filtration separation or centrifugal separation method to obtain a primary solid product, and washing the primary solid product for a plurality of times by using deionized water to obtain a washed primary solid product; the washed primary solid product was mixed with LiCl solution having a concentration of 2 mol/L and a volume of 100 mL, and then placed again in the hydrothermal reactor at 110% o Heating for 2h under C, cooling the hydrothermal reactor to room temperature, and separating the solid product after hydrothermal reaction by suction filtrationOr separating by centrifugal separation to obtain secondary solid product, and washing the secondary solid product with deionized water several times to obtain the clay after ion intercalation.
S2, liquid phase stripping is assisted by high-speed stirring:
and (4) mixing the clay subjected to ion intercalation obtained in the step (S1) with 80 mL of deionized water to form a clay mixed solution subjected to ion intercalation. And (3) placing the clay mixed solution after ion intercalation in a high-speed shearing emulsifying machine, and stirring and stripping for 10 min at the rotating speed of 20000 rpm in the high-speed shearing emulsifying machine to form a mixture containing clay nano-sheet layers. And then centrifuging the mixture in a high-speed centrifuge at the rotating speed of 300 rpm for 1 h to remove incompletely stripped particles and impurities to obtain the clay nanosheet dispersion liquid.
S3, obtaining a high concentration dispersion by centrifugal concentration:
and (4) carrying out centrifugal concentration on the clay nano sheet dispersion liquid obtained in the step (S2) in a high-speed centrifuge at the rotating speed of 6000 rpm for 60 min to obtain a clay nano sheet concentrated solution. And removing part of supernatant of the clay nano-sheet concentrated solution, and performing ultrasonic dispersion on the precipitate at the bottom of the clay nano-sheet concentrated solution to obtain the high-concentration clay nano-sheet dispersion solution.
S4, promoting the dispersion to be gelled rapidly through ionic crosslinking:
MgCl with the volume of 0.8 mL and the concentration of 0.5 mol/L 2 And mixing the solution with a high-concentration clay nanosheet dispersion liquid with the volume of 10 mL and the concentration of 12mg/mL to obtain the clay hydrogel.
S5, freeze drying:
and (4) freezing the clay hydrogel obtained in the step S4 at-30 ℃ for 2h to completely freeze the clay hydrogel, and then carrying out freeze drying at-45 ℃ for 48 h at 8 pa to obtain the clay aerogel material.
The clay aerogel material obtained in example 6 was determined to have a porosity of 99.37% and an apparent density of 0.0161 g/cm 3 The clay aerogel material remains intact after being soaked in water for 100 hours.
Use of the clay aerogel material obtained in example 6: the clay aerogel material obtained in example 6 is placed in a removing device, and methylene blue with the concentration of 10 mg/L can be removed from the water-soluble dye in the solution by passing the clay aerogel material through the methylene blue solution with the flow rate of 1 mL/min. Thereby realizing the removal of the water-soluble dye in the sewage.
Example 7:
a method of preparing an ionically crosslinked clay aerogel material comprising the steps of:
s1, carrying out ion intercalation through hydrothermal reaction:
mixing 1.2 g vermiculite particles with 100 mL saturated NaCl solution, placing in a hydrothermal reactor, and heating to 110% o Heating for 2 hours under C to enable the mixture of the vermiculite particles and the saturated NaCl solution to carry out hydrothermal reaction; when the hydrothermal reactor is cooled to room temperature, separating a solid product after the hydrothermal reaction by a suction filtration separation or centrifugal separation method to obtain a primary solid product, and washing the primary solid product for a plurality of times by using deionized water to obtain a washed primary solid product; the washed primary solid product was mixed with LiCl solution of 2 mol/L concentration and 100 mL volume and then placed in the hydrothermal reactor again at 110% o And C, heating for 2 hours, separating the solid product after the hydrothermal reaction by a suction filtration separation or centrifugal separation method when the hydrothermal reactor is cooled to room temperature to obtain a secondary solid product, and washing the secondary solid product for a plurality of times by deionized water to obtain the clay after ion intercalation.
S2, liquid phase stripping is assisted by high-speed stirring:
and (4) mixing the clay subjected to ion intercalation obtained in the step (S1) with 80 mL of deionized water to form a clay mixed solution subjected to ion intercalation. Placing the clay mixed solution after ion intercalation in a high-speed shearing emulsifying machine, and stirring and stripping for 10 min at the rotating speed of 20000 rpm in the high-speed shearing emulsifying machine to form a mixture containing clay nano-sheet layers; and then centrifuging the mixture in a high-speed centrifuge at the rotating speed of 300 rpm for 1 h to remove incompletely stripped particles and impurities to obtain the clay nanosheet dispersion.
S3, obtaining a high concentration dispersion by centrifugal concentration:
and (4) carrying out centrifugal concentration on the clay nano sheet dispersion liquid obtained in the step (S2) in a high-speed centrifuge at the rotating speed of 6000 rpm for 60 min to obtain a clay nano sheet concentrated solution. And removing part of supernatant of the clay nano-sheet concentrated solution, and performing ultrasonic dispersion on the precipitate at the bottom of the clay nano-sheet concentrated solution to obtain the high-concentration clay nano-sheet dispersion solution.
S4, promoting the dispersion to be quickly gelled through ionic crosslinking:
FeCl with the volume of 0.8 mL and the concentration of 0.5 mol/L 3 And mixing the solution with a high-concentration clay nanosheet dispersion liquid with the volume of 10 mL and the concentration of 12mg/mL to obtain the clay hydrogel.
S5, freeze drying:
and (4) freezing the clay hydrogel obtained in the step S4 at-30 ℃ for 2h to completely freeze the clay hydrogel, and then carrying out freeze drying at-45 ℃ for 48 h at 8 pa to obtain the clay aerogel material.
The clay aerogel material obtained in example 7 was determined to have a porosity of 99.33% and an apparent density of 0.0161 g/cm 3 The clay aerogel material remains intact after being soaked in water for 100 hours.
Use of the clay aerogel material obtained in example 7: the clay aerogel material obtained in example 7 is placed in a removal device, and methylene blue with the water-soluble dye in the solution can be removed by passing a methylene blue solution with the concentration of 10 mg/L through the clay aerogel material at the flow rate of 1 mL/min. Thereby realizing the removal of the water-soluble dye in the sewage.
Example 8:
a method of preparing an ionically crosslinked clay aerogel material comprising the steps of:
s1, performing ion intercalation through hydrothermal reaction:
mixing 1.2 g vermiculite particles with 100 mL saturated NaCl solution, placing in a hydrothermal reactor, and heating to 110% o Heating for 2 hours under C to enable the mixture of the vermiculite particles and the saturated NaCl solution to carry out hydrothermal reaction; when the hydrothermal reactor is cooled to room temperature, introducing a solid product obtained after the hydrothermal reactionSeparating by suction filtration separation or centrifugal separation to obtain a primary solid product, and washing the primary solid product with deionized water for several times to obtain a washed primary solid product; the washed primary solid product was mixed with LiCl solution of 2 mol/L concentration and 100 mL volume and then placed in the hydrothermal reactor again at 110% o And C, heating for 2 hours, separating the solid product after the hydrothermal reaction by a suction filtration separation or centrifugal separation method when the hydrothermal reactor is cooled to room temperature to obtain a secondary solid product, and washing the secondary solid product for a plurality of times by deionized water to obtain the clay after ion intercalation.
S2, liquid phase stripping is assisted by high-speed stirring:
and (5) mixing the clay subjected to ion intercalation obtained in the step (S1) with 80 mL of deionized water to form a clay mixed solution subjected to ion intercalation. Placing the clay mixed solution after ion intercalation in a high-speed shearing emulsifying machine, and stirring and stripping for 10 min at the rotating speed of 20000 rpm in the high-speed shearing emulsifying machine to form a mixture containing clay nano-sheet layers; and then centrifuging the mixture in a high-speed centrifuge at the rotating speed of 300 rpm for 1 h to remove incompletely stripped particles and impurities to obtain the clay nanosheet dispersion.
S3, obtaining a high-concentration dispersion by centrifugal concentration:
and (4) carrying out centrifugal concentration on the clay nano sheet dispersion liquid obtained in the step (S2) in a high-speed centrifuge at the rotating speed of 6000 rpm for 60 min to obtain a clay nano sheet concentrated solution. And removing part of supernatant of the clay nanosheet concentrated solution, and performing ultrasonic dispersion on the precipitate at the bottom of the clay nanosheet concentrated solution to obtain a high-concentration clay nanosheet dispersion solution.
S4, promoting the dispersion to be gelled rapidly through ionic crosslinking:
LaCl with the volume of 0.8 mL and the concentration of 0.5 mol/L 3 And mixing the solution with a high-concentration clay nanosheet dispersion liquid with the volume of 10 mL and the concentration of 12mg/mL to obtain the clay hydrogel.
S5, freeze drying:
and (4) freezing the clay hydrogel obtained in the step S4 at-30 ℃ for 2h to completely freeze the clay hydrogel, and then carrying out freeze drying at-45 ℃ for 48 h at 8 pa to obtain the clay aerogel material.
The clay aerogel material obtained in example 8 was determined to have a porosity of 99.45% and an apparent density of 0.0138 g/cm 3 The clay aerogel material remains intact after being soaked in water for 100 hours.
Use of the clay aerogel material obtained in example 8: the clay aerogel material obtained in example 8 is placed in a removing device, and methylene blue with the concentration of 10 mg/L can be removed from the water-soluble dye in the solution by passing the clay aerogel material through the methylene blue solution with the flow rate of 1 mL/min. Thereby realizing the removal of the water-soluble dye in the sewage.
Example 9:
a method of preparing an ionically crosslinked clay aerogel material comprising the steps of:
s1, performing ion intercalation through hydrothermal reaction:
mixing vermiculite particles with a mass of 0.9 g with saturated NaCl solution with a volume of 100 mL, placing the mixture in a hydrothermal reactor, and placing the reactor in a temperature range of 100% o Heating for 3 hours under C to enable the mixture of the vermiculite particles and the saturated NaCl solution to carry out hydrothermal reaction; when the hydrothermal reactor is cooled to room temperature, separating a solid product after the hydrothermal reaction by a suction filtration separation or centrifugal separation method to obtain a primary solid product, and washing the primary solid product for a plurality of times by using deionized water to obtain a washed primary solid product; mixing the washed primary solid product with LiCl solution with the concentration of 2 mol/L and the volume of 100 mL, then placing the mixture in a hydrothermal reactor again, heating the mixture for 3 hours at the temperature of 100 ℃, separating the solid product after the hydrothermal reaction again by a suction filtration separation or centrifugal separation method when the hydrothermal reactor is cooled to the room temperature to obtain a secondary solid product, and washing the secondary solid product for a plurality of times by deionized water to obtain the clay after ion intercalation.
S2, liquid phase stripping is assisted by high-speed stirring:
and (4) mixing the clay subjected to ion intercalation obtained in the step (S1) with 80 mL of deionized water to form a clay mixed solution subjected to ion intercalation. Placing the clay mixed solution after the ion intercalation into a high-speed shearing emulsifying machine, and stirring and stripping for 10 min at 25000 rpm in the high-speed shearing emulsifying machine to form a mixture containing clay nano-sheet layers; and then centrifuging the mixture in a high-speed centrifuge at the rotating speed of 300 rpm for 1 h to remove incompletely stripped particles and impurities to obtain the clay nanosheet dispersion.
S3, obtaining a high concentration dispersion by centrifugal concentration:
and (4) carrying out centrifugal concentration on the clay nano sheet dispersion liquid obtained in the step (S2) in a high-speed centrifuge at the rotation speed of 10000 rpm for 20 min to obtain a clay nano sheet concentrated solution. And removing part of supernatant of the clay nano-sheet concentrated solution, and performing ultrasonic dispersion on the precipitate at the bottom of the clay nano-sheet concentrated solution to obtain the high-concentration clay nano-sheet dispersion solution.
S4, promoting the dispersion to be gelled rapidly through ionic crosslinking:
0.3 mol/L AlCl with the volume of 0.8 mL 3 And mixing the solution with a high-concentration clay nanosheet dispersion liquid with the volume of 10 mL and the concentration of 9 mg/mL to obtain the clay hydrogel.
S5, freeze drying:
and (4) freezing the clay hydrogel obtained in the step S4 at-30 ℃ for 2h to completely freeze the clay hydrogel, and then carrying out freeze drying at-45 ℃ for 48 h at 8 pa to obtain the clay aerogel material.
Use of the clay aerogel material obtained in example 9: the clay aerogel material obtained in example 9 is placed in a removing device, and methylene blue with the concentration of 100 mg/L can be removed from the water-soluble dye in the solution by passing the methylene blue solution through the clay aerogel material at the flow rate of 1 mL/min. Thereby realizing the removal of the water-soluble dye in the sewage.
Example 10:
a method of preparing an ionically crosslinked clay aerogel material comprising the steps of:
s1, performing ion intercalation through hydrothermal reaction:
1.2 g of vermiculite particles are dissolved in 100 mL of saturated NaClThe liquids are mixed and placed in a hydrothermal reactor, 110 o Heating for 3 hours under C to enable the mixture of the vermiculite particles and the saturated NaCl solution to carry out hydrothermal reaction; when the hydrothermal reactor is cooled to room temperature, separating a solid product after the hydrothermal reaction by a suction filtration separation or centrifugal separation method to obtain a primary solid product, and washing the primary solid product for a plurality of times by using deionized water to obtain a washed primary solid product; mixing the washed primary solid product with LiCl solution with the concentration of 2 mol/L and the volume of 100 mL, then placing the mixture in a hydrothermal reactor again, heating the mixture for 3 hours at 110 ℃, separating the solid product after the hydrothermal reaction again by a suction filtration separation or centrifugal separation method when the hydrothermal reactor is cooled to room temperature to obtain a secondary solid product, and washing the secondary solid product for a plurality of times by deionized water to obtain the clay after ion intercalation.
S2, liquid phase stripping is assisted by high-speed stirring:
and (4) mixing the clay subjected to ion intercalation obtained in the step (S1) with 80 mL of deionized water to form a clay mixed solution subjected to ion intercalation. Placing the clay mixed solution after ion intercalation in a high-speed shearing emulsifying machine, and stirring and stripping for 10 min at the rotating speed of 20000 rpm in the high-speed shearing emulsifying machine to form a mixture containing clay nano-sheet layers; and then centrifuging the mixture in a high-speed centrifuge at the rotating speed of 300 rpm for 1 h to remove incompletely stripped particles and impurities to obtain the clay nanosheet dispersion.
S3, obtaining a high-concentration dispersion by centrifugal concentration:
and (4) carrying out centrifugal concentration on the clay nano sheet dispersion liquid obtained in the step (S2) in a high-speed centrifuge at the rotating speed of 8000 rpm for 40 min to obtain a clay nano sheet concentrated solution. And removing part of supernatant of the clay nano-sheet concentrated solution, and performing ultrasonic dispersion on the precipitate at the bottom of the clay nano-sheet concentrated solution to obtain the high-concentration clay nano-sheet dispersion solution.
S4, promoting the dispersion to be quickly gelled through ionic crosslinking:
0.8 mL of AlCl with the concentration of 0.1 mol/L 3 The solution is mixed with high-concentration clay sodium with the volume of 10 mL and the concentration of 12mg/mLAnd mixing the rice flake dispersion liquid to obtain the clay hydrogel.
S5, freeze drying:
and (4) freezing the clay hydrogel obtained in the step S4 at-30 ℃ for 2h to completely freeze the clay hydrogel, and then carrying out freeze drying at-45 ℃ for 48 h at 8 pa to obtain the clay aerogel material.
Use of the clay aerogel material obtained in example 10: the clay aerogel material obtained in example 10 is placed in a removing device, and methylene blue with the concentration of 150 mg/L can be removed from the water-soluble dye in the solution by passing the clay aerogel material through the methylene blue solution with the flow rate of 1 mL/min. Thereby realizing the removal of the water-soluble dye in the sewage.
Example 11:
a method of preparing an ionically crosslinked clay aerogel material comprising the steps of:
s1, carrying out ion intercalation through hydrothermal reaction:
mixing montmorillonite powder 1.2 g with saturated NaCl solution 100 mL, placing in hydrothermal reactor, and heating to 110 deg.C o Heating for 2 hours under C to enable the mixture of the vermiculite particles and the saturated NaCl solution to carry out hydrothermal reaction; when the hydrothermal reactor is cooled to room temperature, separating a solid product after the hydrothermal reaction by a suction filtration separation or centrifugal separation method to obtain a primary solid product, and washing the primary solid product for a plurality of times by using deionized water to obtain a washed primary solid product; mixing the washed primary solid product with LiCl solution with the concentration of 2 mol/L and the volume of 100 mL, then placing the mixture in a hydrothermal reactor again, heating the mixture for 2 hours at 110 ℃, separating the solid product after the hydrothermal reaction again by a suction filtration separation or centrifugal separation method when the hydrothermal reactor is cooled to room temperature to obtain a secondary solid product, and washing the secondary solid product for a plurality of times by deionized water to obtain the clay after ion intercalation.
S2, liquid phase stripping is assisted by high-speed stirring:
and (4) mixing the clay subjected to ion intercalation obtained in the step (S1) with 80 mL of deionized water to form a clay mixed solution subjected to ion intercalation. Placing the clay mixed solution after ion intercalation in a high-speed shearing emulsifying machine, and stirring and stripping for 10 min at the rotating speed of 20000 rpm in the high-speed shearing emulsifying machine to form a mixture containing clay nano-sheet layers; and then centrifuging the mixture in a high-speed centrifuge at the rotating speed of 300 rpm for 1 h to remove incompletely stripped particles and impurities to obtain the clay nanosheet dispersion.
S3, obtaining a high concentration dispersion by centrifugal concentration:
and (4) carrying out centrifugal concentration on the clay nano sheet dispersion liquid obtained in the step (S2) in a high-speed centrifuge at the rotating speed of 6000 rpm for 60 min to obtain a clay nano sheet concentrated solution. And removing part of supernatant of the clay nano-sheet concentrated solution, and performing ultrasonic dispersion on the precipitate at the bottom of the clay nano-sheet concentrated solution to obtain the high-concentration clay nano-sheet dispersion solution.
S4, promoting the dispersion to be gelled rapidly through ionic crosslinking:
0.5 mol/L AlCl with the volume of 0.8 mL 3 And mixing the solution with a high-concentration clay nanosheet dispersion liquid with the volume of 10 mL and the concentration of 15 mg/mL to obtain the clay hydrogel.
S5, freeze drying:
and (4) freezing the clay hydrogel obtained in the step S4 at-30 ℃ for 2h to completely freeze the clay hydrogel, and then carrying out freeze drying at-45 ℃ for 48 h at 8 pa to obtain the clay aerogel material.
Use of the clay aerogel material obtained in example 11: the clay aerogel material obtained in example 11 is placed in a removal device, and methylene blue with a concentration of 10 mg/L is passed through the clay aerogel material at a flow rate of 1mL/min to remove methylene blue, a water-soluble dye, from the solution. Thereby realizing the removal of the water-soluble dye in the sewage.
The foregoing is a further detailed description of the present invention in connection with specific preferred embodiments thereof, and it is not intended to limit the invention to the specific embodiments thereof. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (5)
1. A method for preparing an ionically crosslinked clay aerogel material, comprising the steps of:
s1, performing ion intercalation through hydrothermal reaction:
mixing natural clay and saturated NaCl solution according to the mass-volume ratio of 0.3 g to 100 mL-1.2 g to 100 mL, placing the mixture in a hydrothermal reactor, and reacting the mixture in the hydrothermal reactor at the temperature of 100-120 DEG o Heating for 1-3 h under C to enable the mixture of the natural clay and the saturated NaCl solution to carry out hydrothermal reaction; when the hydrothermal reactor is cooled to room temperature, separating out a solid product after the hydrothermal reaction to obtain a primary solid product, and washing the primary solid product with deionized water to obtain a washed primary solid product; mixing the washed primary solid product with a LiCl solution, putting the mixture into a hydrothermal reactor again, heating the mixture for 1-3 hours at 100-120 ℃, separating the solid product after the hydrothermal reaction again when the hydrothermal reactor is cooled to room temperature to obtain a secondary solid product, and washing the secondary solid product with deionized water to obtain clay after ion intercalation; the concentration of the LiCl solution is 1-3 mol/L, and the volume of the LiCl solution is the same as that of a saturated NaCl solution;
s2, liquid phase stripping is assisted by high-speed stirring:
mixing the clay subjected to ion intercalation obtained in the step S1 with deionized water to form clay mixed solution subjected to ion intercalation, wherein the volume of the deionized water in the clay mixed solution subjected to ion intercalation is 80% of the volume of saturated NaCl solution; placing the clay mixed solution after the ion intercalation into a high-speed shearing emulsifying machine, and stirring and stripping for 5-15 min at the rotating speed of 15000-25000 rpm in the high-speed shearing emulsifying machine to form a mixture containing clay nano-sheet layers; then centrifuging the mixture in a high-speed centrifuge at the rotating speed of 300 rpm for 1 h to remove incompletely stripped particles and impurities to obtain clay nanosheet dispersion liquid;
s3, obtaining a high concentration dispersion by centrifugal concentration:
centrifuging and concentrating the clay nanosheet dispersion obtained in the step S2 in a high-speed centrifuge at the rotating speed of 6000-10000 rpm for 20-60 min to obtain a clay nanosheet concentrated solution, removing the supernatant of the clay nanosheet concentrated solution, and performing ultrasonic dispersion on the precipitate of the clay nanosheet concentrated solution to obtain a high-concentration clay nanosheet dispersion;
s4, promoting the dispersion to be gelled rapidly through ionic crosslinking:
mixing a metal salt solution with the concentration of 0.1-0.5 mol/L and the high-concentration clay nanosheet dispersion liquid according to the volume ratio of 2:25 to obtain a clay hydrogel;
s5, freeze drying:
freezing the clay hydrogel obtained in the step S4 at-30 ℃ for 2h, and then carrying out freezing at-45 to-55 o C. Freeze-drying for 48 hours under 8-15 pa to obtain the clay aerogel material, wherein the porosity of the clay aerogel material is 99.31-99.55%, and the density of the clay aerogel material is 0.0115-0.0176 g/cm 3 The structure of the aerogel remains intact when bearing 1000 times its own weight, and also remains intact after 100 h of immersion in water or strong acid, strong base solutions.
2. The method of claim 1, wherein the natural clay is vermiculite, kaolin, montmorillonite or illite.
3. The method for preparing an ionomer clay aerogel material according to claim 1, wherein the step S1 of separating the solid product of hydrothermal reaction comprises suction filtration or centrifugation.
4. The method for preparing an ionic crosslinked clay aerogel material according to claim 1, wherein the concentration of the high-concentration clay nanosheet dispersion obtained in step S3 is 6-15 mg/mL.
5. The method of claim 1, wherein the metal salt of the metal salt solution is cationicSeed is Ni + 、Ca 2+ 、Mg 2+ 、Al 3+ 、Fe 3+ Or La 3+ A salt.
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