CN113769669A - Ionically-crosslinked clay aerogel material, preparation method and application thereof - Google Patents
Ionically-crosslinked clay aerogel material, preparation method and application thereof Download PDFInfo
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- CN113769669A CN113769669A CN202111156119.4A CN202111156119A CN113769669A CN 113769669 A CN113769669 A CN 113769669A CN 202111156119 A CN202111156119 A CN 202111156119A CN 113769669 A CN113769669 A CN 113769669A
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- 239000004927 clay Substances 0.000 title claims abstract description 312
- 239000004964 aerogel Substances 0.000 title claims abstract description 125
- 239000000463 material Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000009830 intercalation Methods 0.000 claims abstract description 72
- 230000002687 intercalation Effects 0.000 claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000004132 cross linking Methods 0.000 claims abstract description 21
- 239000010865 sewage Substances 0.000 claims abstract description 20
- 239000007791 liquid phase Substances 0.000 claims abstract description 17
- 238000007710 freezing Methods 0.000 claims abstract description 16
- 230000008014 freezing Effects 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 134
- 239000002135 nanosheet Substances 0.000 claims description 115
- 239000012265 solid product Substances 0.000 claims description 105
- 239000006185 dispersion Substances 0.000 claims description 84
- 150000002500 ions Chemical class 0.000 claims description 74
- 239000000203 mixture Substances 0.000 claims description 63
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 55
- 238000002156 mixing Methods 0.000 claims description 47
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- 239000000017 hydrogel Substances 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 37
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 32
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 30
- 238000004108 freeze drying Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 28
- 238000010008 shearing Methods 0.000 claims description 27
- 230000001804 emulsifying effect Effects 0.000 claims description 26
- 229910052902 vermiculite Inorganic materials 0.000 claims description 25
- 239000010455 vermiculite Substances 0.000 claims description 25
- 235000019354 vermiculite Nutrition 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 25
- 238000000967 suction filtration Methods 0.000 claims description 24
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical group [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 23
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 23
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 14
- 238000009775 high-speed stirring Methods 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 13
- 230000001737 promoting effect Effects 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 4
- 229940043267 rhodamine b Drugs 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910052900 illite Inorganic materials 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 3
- 229940012189 methyl orange Drugs 0.000 claims description 3
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229920000554 ionomer Polymers 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract 1
- 238000004299 exfoliation Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 description 42
- 239000010410 layer Substances 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910021389 graphene Inorganic materials 0.000 description 8
- 238000001879 gelation Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 and in the examples Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000006250 one-dimensional material Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- 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
- B01J20/12—Naturally occurring clays or bleaching earth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3071—Washing or leaching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
一种离子交联的粘土气凝胶材料、制备方法及其应用，所述粘土气凝胶材料是以天然粘土为原料，依次经过离子插层、液相剥离、离心浓缩、离子交联及冷冻干燥得到的三维多孔气凝胶；该气凝胶的孔隙率为99.31%‑99.55%，密度为0.0115‑0.0176 g/cm3，所述气凝胶的结构在承重自身1000倍时保持完整，并且在水中或者强酸、强碱溶液中浸泡100 h后也保持完整。本发明粘土气凝胶材料的结构稳定、机械性能好、吸附性能强，其制备方法生产成本低廉、制备工艺简单、反应规模易于扩大化；本发明的粘土气凝胶材料在污水处理领域的应用具有积极的生产意义。An ionically cross-linked clay aerogel material, a preparation method and an application thereof, the clay aerogel material is made of natural clay as raw material, and successively undergoes ion intercalation, liquid phase exfoliation, centrifugal concentration, ion cross-linking and freezing The three-dimensional porous aerogel obtained by drying; the porosity of the aerogel is 99.31%-99.55%, the density is 0.0115-0.0176 g/cm 3 , and the structure of the aerogel remains intact when the load is 1000 times itself, and It also remains intact after being soaked in water or strong acid or alkali solution for 100 h. The clay aerogel material of the invention has stable structure, good mechanical properties and strong adsorption performance, and the preparation method has the advantages of low production cost, simple preparation process and easy expansion of the reaction scale; the application of the clay aerogel material of the invention in the field of sewage treatment have a positive productive meaning.
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 large discharge of industrial wastewater and domestic sewage further causes 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 aerogel has abundant raw material choices, such as dimension division, and comprises one-dimensional material such asCarbon nanotubes, cellulose fibers, two-dimensional materials such as graphene, MXene, three-dimensional materials such as silica, titania; 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/cm3The 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.
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 DEGoHeating 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, 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-55oC. 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+、Ca2+、Mg2+、Al3+、Fe3+Or La3+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 layer, the clay nano-sheet layer is obtained by high-speed shearing stripping after the hydrothermal reaction is adopted for ion intercalation, the production efficiency is high, the reaction condition is mild, the method is green and environment-friendly, and the reaction scale is easy to expand. 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%oHeating for 2 hours under C to enable the mixture of the vermiculite particles and the saturated NaCl solution to carry out hydrothermal reaction; after the hydrothermal reactor is cooled toAt 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 gelled rapidly through ionic crosslinking:
0.5 mol/L AlCl with the volume of 0.8 mL3And 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/cm3The 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%oHeating 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, putting the mixture into a hydrothermal reactor again, heating the mixture for 1 h at the temperature of 100 ℃, separating the solid product after the hydrothermal reaction by a suction filtration or centrifugal separation method again when the hydrothermal reactor is cooled to room temperature to obtain a secondary solid product, and using deionized water to remove ionsAnd washing the secondary solid product for several times by using 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) 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 mL3And 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/cm3. 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 goHeating 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 LiCl solution with the concentration of 3 mol/L and the volume of 100 mL, then placing the mixture in a hydrothermal reactor again, heating the mixture at 120 ℃ for 1 h, 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 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 gelled rapidly through ionic crosslinking:
0.5 mol/L AlCl with the volume of 0.8 mL3And 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/cm3. The structure 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 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, placing in a hydrothermal reactor, and heating to 110%oHeating for 2 hours under C to enable the mixture of the vermiculite particles and the saturated NaCl solution to carry out hydrothermal reaction; the hydrothermal reactor is cooled to roomAt a warm moment, 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 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%oAnd 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 gelled rapidly through ionic crosslinking:
NiCl with the volume of 0.8 mL and the concentration of 0.5 mol/L2And 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/cm3The 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, 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%oHeating 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%oAnd 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 gelled rapidly through ionic crosslinking:
CaCl with the volume of 0.8 mL and the concentration of 0.5 mol/L2And 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/cm3The 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, 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%oHeating 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%oAnd 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. 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.
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/L2And 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/cm3The 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, 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%oHeating 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%oHeating for 2h under C, cooling the hydrothermal reactor to room temperature, and cooling the solid obtained after the hydrothermal reaction againAnd separating the product by suction filtration or centrifugal separation to obtain a secondary solid product, and washing the secondary solid product with deionized water for 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. 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:
FeCl with the volume of 0.8 mL and the concentration of 0.5 mol/L3And 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/cm3The 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 removing device, and methylene blue with the concentration of 10 mg/L is passed through the clay aerogel material at the flow rate of 1mL/min to remove the water-soluble dye methylene blue in the solution. 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%oHeating 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%oAnd 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 gelled rapidly through ionic crosslinking:
LaCl with the volume of 0.8 mL and the concentration of 0.5 mol/L3And 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/cm3The 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%oHeating 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, carrying out suction filtration separation or centrifugal separation on the solid product after the hydrothermal reactionThe method of (1) to obtain a primary solid product, washing the primary solid product with deionized water for several 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 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 mL3And 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:
mixing 1.2 g vermiculite particles with 100 mL saturated NaCl solution, placing in a hydrothermal reactor, and heating to 110%oHeating 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 gelled rapidly through ionic crosslinking:
0.8 mL of AlCl with the concentration of 0.1 mol/L3And 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.
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, performing 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.CoHeating 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 the solid product after the hydrothermal reaction by suction filtration or centrifugal separation to obtain a primary solid product, and usingWashing the primary solid product for several times by 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 mL3And 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 removing device, and methylene blue with the concentration of 10 mg/L is passed through the clay aerogel material at the flow rate of 1mL/min to remove the water-soluble dye methylene blue in the solution. Thereby realizing the removal of the water-soluble dye in the sewage.
The foregoing is a more detailed description of the present invention in connection with specific preferred embodiments and is not intended to limit the practice of the invention to these embodiments. 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 (8)
1. An ion-crosslinked clay aerogel material is characterized in that 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/cm3The 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.
2. The method of preparing an ionically crosslinked clay aerogel material according to claim 1, 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 DEGoHeating 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 the 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 productA 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-55oC. And (5) carrying out freeze drying for 48 hours under 8-15 pa to obtain the clay aerogel material.
3. The method of claim 1 or 2, wherein the natural clay is vermiculite, kaolin, montmorillonite or illite.
4. The method for preparing an ionomer clay aerogel material according to claim 2, wherein the step S1 of separating the solid product of hydrothermal reaction comprises suction filtration or centrifugation.
5. The preparation method of the ionic crosslinked clay aerogel material according to claim 2, wherein the concentration of the high-concentration clay nanosheet dispersion obtained in the step S3 is 6-15 mg/mL.
6. The method of claim 2, wherein the metal salt in the metal salt solution is a solution in which the cation is Ni+、Ca2+、Mg2+、Al3+、Fe3+Or La3+A salt.
7. The application of the ionic crosslinked clay aerogel material according to claim 1, wherein the clay aerogel material is placed in a removing device, and water-soluble dye sewage with the concentration of 10-200 mg/L is passed through the clay aerogel at the flow rate of 1-5 mL/min to remove the water-soluble dye in the sewage.
8. The use of an ionically crosslinked clay aerogel material according to claim 7, wherein said water-soluble dye is methylene blue, methyl orange, or rhodamine B.
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