CN116371352A - Calcium-containing hydrotalcite-vermiculite composite material and preparation method and application thereof - Google Patents
Calcium-containing hydrotalcite-vermiculite composite material and preparation method and application thereof Download PDFInfo
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- CN116371352A CN116371352A CN202310331781.1A CN202310331781A CN116371352A CN 116371352 A CN116371352 A CN 116371352A CN 202310331781 A CN202310331781 A CN 202310331781A CN 116371352 A CN116371352 A CN 116371352A
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- vermiculite
- calcium
- hydrotalcite
- composite material
- alooh
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- 239000010455 vermiculite Substances 0.000 title claims abstract description 149
- 229910052902 vermiculite Inorganic materials 0.000 title claims abstract description 149
- 239000011575 calcium Substances 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 91
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910002706 AlOOH Inorganic materials 0.000 claims abstract description 60
- 239000012266 salt solution Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 36
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 35
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 35
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004202 carbamide Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 17
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 13
- 229910001593 boehmite Inorganic materials 0.000 claims description 31
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 27
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 230000007246 mechanism Effects 0.000 abstract description 2
- 239000002344 surface layer Substances 0.000 abstract description 2
- 239000008279 sol Substances 0.000 description 28
- 239000008367 deionised water Substances 0.000 description 27
- 229910021641 deionized water Inorganic materials 0.000 description 27
- 238000003756 stirring Methods 0.000 description 23
- 238000005406 washing Methods 0.000 description 21
- 238000001816 cooling Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000011777 magnesium Substances 0.000 description 13
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 12
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to the technical field of inorganic composite functional materials, in particular to a calcium-containing hydrotalcite-vermiculite composite material, and a preparation method and application thereof. According to the invention, the AlOOH/vermiculite and the mixed metal salt solution containing calcium ions, magnesium ions and urea are subjected to hydrothermal reaction by utilizing the in-situ growth mechanism of hydrotalcite, and the advantages of large expansion volume of the vermiculite and easiness in negatively charging a surface layer plate are utilized, so that the hydrotalcite uniformly grows on the surface of the expanded vermiculite in situ, and the defects of easiness in agglomeration and high loss of the traditional hydrotalcite material in flowing water are overcome. In addition, the calcium ions in the calcium-containing hydrotalcite-vermiculite composite material prepared by the method can have lattice substitution effect with nickel ions, so that the selective adsorption performance of the nickel ions is greatly improved, and the calcium-containing hydrotalcite-vermiculite composite material has obvious advantages in particular to the selective adsorption of low-concentration nickel ions; meanwhile, the expanded vermiculite has certain nickel ion adsorption capacity, so that the nickel ion adsorption performance of hydrotalcite is improved.
Description
Technical Field
The invention relates to the technical field of inorganic composite functional materials, in particular to a calcium-containing hydrotalcite-vermiculite composite material, and a preparation method and application thereof.
Background
With the development of human society, human activities cause non-negligible pollution to the natural environment. Petroleum is an industrial "blood" and the modern industry is not separated from petroleum. However, a large amount of wastewater containing pollutants is generated in the petroleum exploitation process, and the wastewater generated in the petroleum exploitation causes considerable environmental problems. In general, the main compounds found in petroleum-produced water consist of compounds dissolved and dispersed in water, such as hydrocarbons (benzene, toluene, ethylbenzene and xylenes) and various contaminants such as nickel ions. The significant amount of wastewater and petroleum produced water discharged into the environment will cause irreversible damage and pollution to human health and other biological organisms and the entire biosphere, and how to reduce the pollution of wastewater to the environment has become a serious concern.
Hydrotalcite has the characteristics of positively charged laminate structure, exchangeable anions between laminates and the like, and has good application prospect in sewage treatment. However, hydrotalcite is easy to agglomerate and lost with water flow in practical use, which limits the application of hydrotalcite in industry. The hydrotalcite is loaded on vermiculite, so that the agglomeration and loss problems of the hydrotalcite can be solved. For example, chinese patent CN113877519a discloses a method for preparing hydrotalcite/vermiculite composite material, in which divalent metal ions (Mg 2+ ) Trivalent metal ion (Al) 3+ Or Fe (Fe) 3+ ) Mixing urea and water to obtain a mixed salt solution; and mixing the expanded vermiculite with the mixed salt solution, and performing hydrothermal reaction to obtain the hydrotalcite/vermiculite composite material, wherein the hydrotalcite/vermiculite composite material prepared by the hydrotalcite/vermiculite composite material directionally grows between laminates of the expanded vermiculite. However, the hydrotalcite/vermiculite composite material prepared by the method has poor performance of adsorbing nickel ions.
Disclosure of Invention
In view of the above, the invention aims to provide a calcium-containing hydrotalcite-vermiculite composite material, a preparation method and application thereof, and the calcium-containing hydrotalcite-vermiculite composite material prepared by the invention is free from agglomeration and difficult to run off in the application process and has excellent selective adsorption performance on nickel ions.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a calcium-containing hydrotalcite-vermiculite composite material, which comprises the following steps:
(1) Soaking the expanded vermiculite in AlOOH sol, and drying to obtain AlOOH/vermiculite;
(2) Mixing calcium ions, magnesium ions, urea and water to obtain a mixed metal salt solution;
(3) Mixing the AlOOH/vermiculite with the mixed metal salt solution, and performing hydrothermal reaction to obtain a calcium-containing hydrotalcite-vermiculite composite material;
the steps (1) and (2) have no time sequence.
Preferably, the expanded vermiculite has a particle size of 15-20 mesh;
the ratio of the mass of the expanded vermiculite to the volume of the AlOOH sol is 1g: 40-80 mL.
Preferably, the number of repetitions of the impregnation and drying is 5 to 10.
Preferably, the total concentration of calcium ions and magnesium ions in the mixed metal salt solution is 0.02-0.04 mol/L, and the concentration of urea is 1-5 mol/L;
the molar ratio of the calcium ions to the magnesium ions is 1:4 to 7;
the ratio of the mass of AlOOH/vermiculite to the volume of the mixed metal salt solution is 1g: 40-70 mL.
Preferably, the temperature of the hydrothermal reaction is 90-110 ℃ and the time is 12-24 h.
Preferably, the preparation method of the AlOOH sol comprises the following steps:
mixing aluminum isopropoxide with water, regulating the pH value to 3-4, and hydrolyzing to obtain boehmite;
mixing the boehmite with water and dilute acid to obtain AlOOH sol.
Preferably, the temperature of the hydrolysis is 85-95 ℃ and the time is 2-3 h.
Preferably, the ratio of the mass of boehmite to the volume of water is 1g: 20-25 mL;
the dilute acid comprises dilute nitric acid and/or dilute acetic acid;
the mass ratio of boehmite to the amount of acid species in dilute acid was 1g:2 to 2.5mmol.
The invention provides a calcium-containing hydrotalcite-vermiculite composite material prepared by the preparation method in the technical scheme, which comprises expanded vermiculite and calcium-containing hydrotalcite growing on the surface of the expanded vermiculite.
The invention provides application of the calcium-containing hydrotalcite-vermiculite composite material in removing nickel ions.
The invention provides a preparation method of a calcium-containing hydrotalcite-vermiculite composite material, which comprises the following steps: (1) Soaking the expanded vermiculite in AlOOH sol, and drying to obtain AlOOH/vermiculite; (2) Mixing calcium ions, magnesium ions, urea and water to obtain a mixed metal salt solution; (3) Mixing the AlOOH/vermiculite with the mixed metal salt solution, and performing hydrothermal reaction to obtain a calcium-containing hydrotalcite-vermiculite composite material; the steps (1) and (2) have no time sequence. According to the invention, the expanded vermiculite is immersed in the AlOOH sol and then dried, so that the expanded vermiculite is provided with aluminum, the AlOOH/vermiculite and the mixed metal salt solution are subjected to hydrothermal reaction by utilizing the in-situ growth mechanism of hydrotalcite, and the advantages of large expansion volume of the vermiculite and easiness in negatively charging a surface layer plate are utilized, so that the hydrotalcite is easy to self-assemble with the surface of the expanded vermiculite material in the growth process, and the hydrotalcite uniformly grows on the surface of the expanded vermiculite in situ, thereby preparing the novel composite material, and solving the defects of easiness in agglomeration and high loss of the traditional hydrotalcite material in flowing water bodies. In addition, the calcium ions in the calcium-containing hydrotalcite-vermiculite composite material prepared by the method can have lattice substitution effect with nickel ions, so that the selective adsorption performance of the nickel ions is greatly improved, and the calcium-containing hydrotalcite-vermiculite composite material has obvious advantages in particular to the selective adsorption of low-concentration nickel ions; meanwhile, the expanded vermiculite has certain nickel ion adsorption capacity, so that the nickel ion adsorption performance of hydrotalcite is improved. The calcium ions in the calcium-containing hydrotalcite-vermiculite composite material prepared by the method have wide application prospects in the fields of sewage treatment (especially petroleum sewage treatment), soil remediation and the like. In addition, the preparation method provided by the invention is simple to operate, low in cost, environment-friendly and suitable for industrial production.
Drawings
FIG. 1 is an XRD pattern of calcium-containing hydrotalcite-vermiculite composite material prepared in example 1 and example 3 and calcium-containing hydrotalcite prepared in comparative example 1;
FIG. 2 is an SEM image of a calcium-containing hydrotalcite-vermiculite composite prepared according to example 1;
FIG. 3 is an SEM image of a calcium-containing hydrotalcite-vermiculite composite prepared according to example 2;
FIG. 4 is an SEM image of a calcium-containing hydrotalcite-vermiculite composite prepared according to example 3;
fig. 5 is an SEM image of the calcium-containing hydrotalcite-vermiculite composite material prepared in example 4.
Detailed Description
The invention provides a preparation method of a calcium-containing hydrotalcite-vermiculite composite material, which comprises the following steps:
(1) Soaking the expanded vermiculite in AlOOH sol, and drying to obtain AlOOH/vermiculite;
(2) Mixing calcium ions, magnesium ions, urea and water to obtain a mixed metal salt solution;
(3) Mixing the AlOOH/vermiculite with the mixed metal salt solution, and performing hydrothermal reaction to obtain a calcium-containing hydrotalcite-vermiculite composite material;
the steps (1) and (2) have no time sequence.
In the present invention, all raw material components are commercially available products well known to those skilled in the art unless specified otherwise.
The invention is characterized in that the expanded vermiculite is immersed in AlOOH sol and then dried, thus obtaining AlOOH/vermiculite. In the present invention, the expanded vermiculite preferably has a particle size of 15 to 20 mesh. In the present invention, the ratio of the mass of the exfoliated vermiculite to the volume of the AlOOH sol is preferably 1g:40 to 80mL, more preferably 1g:50 to 80mL, more preferably 1g: 60-70 mL. In the present invention, the temperature of the impregnation is preferably room temperature, and the time of the impregnation is preferably 10 to 30 minutes, more preferably 20 to 30 minutes. In the present invention, the drying temperature is preferably 60 to 80 ℃, more preferably 60 to 70 ℃, and the drying time is not particularly limited, and the drying time is required to be constant. In the present invention, the number of repetitions of the impregnation and drying is preferably 5 to 10, more preferably 5 to 8.
In the present invention, the preparation method of the AlOOH sol preferably includes the steps of: mixing aluminum isopropoxide with water, regulating the pH value to 3-4, and hydrolyzing to obtain boehmite; mixing the boehmite with water and dilute acid to obtain AlOOH sol.
According to the invention, aluminum isopropoxide and water are mixed, the pH value is regulated to 3-4, and hydrolysis is carried out, so that boehmite is obtained. In the present invention, the ratio of the mass of aluminum isopropoxide to the volume of water is preferably 10 to 12 g/100 mL, more preferably 10.5 to 11.5 g/100 mL. In the present invention, the temperature of the mixing is preferably 85 to 90 ℃, more preferably 86 to 88 ℃; the mixing time is preferably 20 to 30 minutes, more preferably 25 minutes. In the present invention, the acid used for the adjustment of the pH value preferably includes dilute nitric acid or dilute acetic acid, and the concentration of the dilute nitric acid and the dilute hydrochloric acid is independently preferably 0.8 to 1mol/L, more preferably 0.9 to 1mol/L; the acid is preferably added dropwise; more preferably, the pH is adjusted to 3.5. In the present invention, the temperature of the hydrolysis is preferably 85 to 95 ℃, more preferably 85 to 90 ℃; the time of the hydrolysis is preferably 2 to 3 hours, more preferably 2.5 hours. After the hydrolysis is completed, the invention preferably further comprises the steps of sequentially concentrating the obtained hydrolysis reaction liquid to constant weight, cooling to room temperature and crushing to obtain boehmite (powder); the concentration is not particularly limited, and a concentration mode well known to those skilled in the art, such as evaporation to dryness, is adopted; the cooling method is not particularly limited, and a cooling mode well known to those skilled in the art, such as natural cooling, is adopted; the crushing method is not particularly limited, and a crushing method well known to those skilled in the art, such as grinding, is adopted; the particle size of the boehmite is preferably 20 to 40 mesh.
After boehmite is obtained, the boehmite is mixed with water and dilute acid to obtain AlOOH sol. In the present invention, the mass to volume ratio of boehmite to water is preferably 1g:20 to 25mL, more preferably 1g:20 to 23mL, more preferably 1g: 20-21 mL. In the present invention, the ratio of the mass of boehmite to the amount of acid in the dilute acid is preferably 1g:2 to 2.5mmol, more preferably 1g:2 to 2.4mmol, more preferably 1g:2 to 2.2mmol; the dilute acid preferably comprises dilute nitric acid and/or dilute acetic acid, the concentration of the dilute acid is preferably 0.8-1 mol/L, more preferably 0.9-1 mol/L, boehmite is unevenly dispersed in water, and stable AlOOH sol can be obtained by adding the dilute acid. In the present invention, the temperature of the mixing is preferably 85 to 90 ℃, more preferably 86 to 88 ℃; the order of mixing is preferably: premixing boehmite and water, then dripping nitric acid, and then mixing; the premixing time is preferably 1 to 2 hours, more preferably 1 to 1.5 hours; the time for the remixing is preferably 5 to 6 hours, more preferably 5.5 to 6 hours. After the mixing is completed, the invention preferably further comprises cooling to room temperature to obtain AlOOH sol; the cooling method is not particularly limited, and a cooling method well known to those skilled in the art, such as natural cooling, may be used.
The invention mixes calcium ion, magnesium ion, urea and water to obtain mixed metal salt solution. In the present invention, the total concentration of calcium ions and magnesium ions in the mixed metal salt solution is preferably 0.02 to 0.04mol/L, more preferably 0.02 to 0.03mol/L; the molar ratio of calcium ions to magnesium ions is preferably 1:4 to 7, particularly preferably 1:4, 1:5, 1:6 or 1:7; the concentration of urea in the mixed metal salt solution is preferably 1 to 5mol/L, more preferably 1 to 3mol/L. In the present invention, the calcium ions are preferably derived from water-soluble calcium salts, which preferably include calcium chloride and/or calcium nitrate. In the present invention, the magnesium ion is preferably derived from water-soluble calcium magnesium, which preferably includes magnesium chloride and/or magnesium nitrate. The present invention is not particularly limited, and the raw materials may be completely dissolved in water, and specifically, the raw materials may be mixed by stirring.
After AlOOH/vermiculite and mixed metal salt solution are obtained, the AlOOH/vermiculite and the mixed metal salt solution are mixed and subjected to hydrothermal reaction to obtain the calcium-containing hydrotalcite-vermiculite composite material. In the present invention, the ratio of the mass of the AlOOH/vermiculite to the volume of the mixed metal salt solution is preferably 1g:40 to 70mL, more preferably 1g:40 to 60mL, more preferably 1g: 40-50 mL. The present invention is not particularly limited to the above-mentioned mixing, and the raw materials may be uniformly mixed, specifically, stirring and mixing. In the present invention, the temperature of the hydrothermal reaction is preferably 90 to 110 ℃, more preferably 100 to 110 ℃; the time of the hydrothermal reaction is preferably 12 to 24 hours, more preferably 12 to 15 hours; the hydrothermal reaction is preferably carried out in a polytetrafluoroethylene autoclave. After the hydrothermal reaction is finished, the method preferably further comprises the steps of sequentially washing, washing and drying the obtained hydrothermal reaction product with an organic solvent to obtain the calcium-containing hydrotalcite-vermiculite composite material; the organic solvent wash organic solvent preferably comprises ethanol and/or acetone; the organic solvent washing is preferably organic solvent centrifugal washing; the number of times of washing with the organic solvent is preferably 3 to 5 times, more preferably 4 to 5 times; the washing is preferably water centrifugal washing, and the number of times of washing is preferably 3 to 5 times, more preferably 4 to 5 times. In the present invention, the drying temperature is preferably 60 to 70 ℃, more preferably 60 to 65 ℃; the drying time is preferably 6 to 12 hours, more preferably 10 to 12 hours.
The invention provides a calcium-containing hydrotalcite-vermiculite composite material prepared by the preparation method in the technical scheme, which comprises expanded vermiculite and calcium-containing hydrotalcite growing on the surface of the expanded vermiculite.
The invention provides application of the calcium-containing hydrotalcite-vermiculite composite material in removing nickel ions.
In the present invention, the method of application preferably comprises the steps of: and placing the calcium-containing hydrotalcite-vermiculite composite material in a nickel ion-containing water body or nickel ion-containing soil, and performing adsorption removal. In the present invention, the concentration of nickel ions in the nickel ion-containing water body and the nickel ion-containing soil is independently 10 to 30mg/L, more preferably 10 to 20mg/L; the ratio of the mass of the calcium-containing hydrotalcite-vermiculite composite material to the nickel element to the volume of the water body containing nickel ions is preferably 1g:100 to 150mL, more preferably 1g: 100-120 mL. In the present invention, the adsorption removal is preferably performed under stirring conditions; the stirring speed is not particularly limited, and stirring speeds well known to those skilled in the art are adopted; the temperature of the adsorption removal is preferably room temperature; the time for the adsorption removal is preferably 1 to 120 minutes, more preferably 50 to 80 minutes.
According to the calcium-containing hydrotalcite-vermiculite composite material provided by the invention, hydrotalcite is loaded on the surface of vermiculite, so that the problems of easy agglomeration and high loss of hydrotalcite in the adsorption process are solved radically, and the vermiculite has certain nickel ion adsorption capacity, so that the adsorption performance of hydrotalcite on nickel ions is improved; in addition, the calcium ions in the calcium-containing hydrotalcite-vermiculite composite material prepared by the method can perform lattice substitution with nickel ions, so that the selective adsorption performance of nickel ions is greatly improved, and the calcium-containing hydrotalcite-vermiculite composite material has obvious advantages in the fields of sewage treatment (especially petroleum sewage treatment), soil remediation and the like, and can meet the requirements of practical application.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The expanded vermiculite used in the following examples and comparative examples: commercially available expanded vermiculite is screened with a 20 mesh screen to give expanded Vermiculite (VMT) having a particle size of 15 to 20 mesh.
Example 1
Putting aluminum isopropoxide into deionized water, stirring for 20min at 85 ℃, slowly dripping 1mol/L dilute nitric acid into the solution until the pH value is 3, stirring for 2h at 85 ℃, evaporating to dryness, cooling to room temperature, and grinding to 20 meshes to obtain boehmite; wherein, the dosage ratio of the aluminum isopropoxide to the deionized water is 11.3g:100mL.
Adding boehmite into deionized water, stirring for 1h at 90 ℃, then dropwise adding 1mol/L dilute nitric acid, continuously stirring for 6h, and cooling to room temperature to obtain AlOOH sol; wherein, the dosage ratio of boehmite, deionized water and dilute nitric acid is 5g:100mL:10mmol.
Soaking expanded vermiculite in AlOOH sol at room temperature for 30min, taking out, drying in a 60 ℃ oven, repeating the soaking-drying steps for 5 times to obtain AlOOH/vermiculite; wherein, the dosage ratio of the expanded vermiculite to the AlOOH sol is 1g:50mL.
Mixing magnesium nitrate, calcium nitrate, urea and water to obtain a mixed metal salt solution; wherein Mg is 2+ And Ca 2+ The total concentration is 0.02M, ca 2+ /Mg 2+ Molar ratio = 1:4, urea concentration 1M.
Simultaneously and rapidly transferring AlOOH/vermiculite and mixed metal salt solution into a polytetrafluoroethylene autoclave, carrying out hydrothermal reaction for 12 hours at 110 ℃, sequentially centrifugally washing the obtained product with ethanol for 5 times, centrifugally washing with deionized water to obtain supernatant which is clear liquid, and drying in a baking oven at 60 ℃ for 6 hours to obtain the calcium-containing hydrotalcite-vermiculite composite material; wherein, the dosage ratio of AlOOH/vermiculite to mixed metal salt solution is 1g:70mL.
Example 2
Dissolving aluminum isopropoxide in deionized water, stirring for 30min at 90 ℃, slowly dripping 1mol/L dilute nitric acid into the solution until the pH value is 3, stirring for 3h at 90 ℃, evaporating to dryness, cooling to room temperature, and grinding to 30 meshes to obtain boehmite; wherein, the dosage ratio of the aluminum isopropoxide to the deionized water is 10g:100mL.
Adding boehmite into deionized water, stirring for 1h at 90 ℃, then dropwise adding 1mol/L nitric acid, continuously stirring for 6h, and cooling to room temperature to obtain AlOOH sol; wherein, the dosage ratio of boehmite, deionized water and dilute nitric acid is 4.8g:100mL:10mmol.
Soaking expanded vermiculite in AlOOH sol at room temperature for 20min, taking out, drying in a 60 ℃ oven, repeating the soaking-drying steps 5 times to obtain AlOOH/vermiculite; wherein, the dosage ratio of the expanded vermiculite to the AlOOH sol is 1g:40mL.
Mixing magnesium nitrate, calcium nitrate, urea and water to obtain a mixed metal salt solution; wherein Mg is 2+ And Ca 2+ The total concentration is 0.03M, ca 2+ /Mg 2+ Molar ratio = 1:5, urea concentration 1M.
Simultaneously and rapidly transferring AlOOH/vermiculite and mixed metal salt solution into a polytetrafluoroethylene autoclave, carrying out hydrothermal reaction for 24 hours at 110 ℃, centrifugally washing the obtained product with ethanol and deionized water for 5 times in sequence until the supernatant fluid of the centrifugal washing value of the deionized water is clear liquid, and then drying for 6 hours in a baking oven at 70 ℃ to obtain the calcium-containing hydrotalcite-vermiculite composite material; wherein, the dosage ratio of AlOOH/vermiculite to mixed metal salt solution is 1g:60mL.
Example 3
Commercially available expanded vermiculite is sieved with a 20 mesh screen to obtain expanded Vermiculite (VMT) with a particle size of 15-20 mesh.
Dissolving aluminum isopropoxide in deionized water, stirring for 30min at 85 ℃, slowly dripping 1mol/L dilute nitric acid into the solution until the pH value is 4, stirring for 2h at 85 ℃, evaporating to dryness, cooling to room temperature, and grinding to reach the granularity of 40 meshes to obtain boehmite; wherein, the dosage ratio of the aluminum isopropoxide to the deionized water is 10.5g:100mL.
Adding boehmite into deionized water, stirring for 1h at 85 ℃, then dropwise adding 1mol/L nitric acid, continuously stirring for 6h, and cooling to room temperature to obtain AlOOH sol; wherein, the dosage ratio of boehmite, deionized water and dilute nitric acid is 4.6g:100mL:9mmol.
Soaking expanded vermiculite in AlOOH sol at room temperature for 10min, taking out, drying in a 60 ℃ oven, repeating the soaking-drying steps for 6 times to obtain AlOOH/vermiculite; wherein, the volume ratio of the expanded vermiculite to the AlOOH sol is 1g:60mL.
Mixing magnesium nitrate, calcium nitrate, urea and water to obtain a mixed metal salt solution; wherein Mg is 2+ And Ca 2+ The total concentration is 0.035M, ca 2+ /Mg 2+ Molar ratio = 1:6, urea concentration 1.5M.
Simultaneously and rapidly transferring AlOOH/vermiculite and mixed metal salt solution into a polytetrafluoroethylene autoclave, carrying out hydrothermal reaction for 24 hours at 110 ℃, centrifugally washing the obtained product with ethanol and deionized water for 5 times in sequence until the supernatant fluid of the centrifugal washing value of the deionized water is clear liquid, and then drying in a baking oven at 60 ℃ for 12 hours to obtain the calcium-containing hydrotalcite-vermiculite composite material; wherein, the dosage ratio of AlOOH/vermiculite to mixed metal salt solution is 1g:40mL.
Example 4
Commercially available expanded vermiculite is sieved with a 20 mesh screen to obtain expanded Vermiculite (VMT) with a particle size of 15-20 mesh.
Dissolving aluminum isopropoxide in deionized water, stirring for 20-30 min at 85-90 ℃, slowly dripping 1mol/L dilute nitric acid into the solution until the pH value is 3-4, stirring for 2-3 h at 85-90 ℃, evaporating, cooling to room temperature, and grinding to 20 meshes to obtain boehmite; wherein, the dosage ratio of the aluminum isopropoxide to the deionized water is 10.3g:100mL.
Adding boehmite into deionized water, stirring for 1h at 86 ℃, then dropwise adding 1mol/L nitric acid, continuously stirring for 6h, and cooling to room temperature to obtain AlOOH sol; wherein, the dosage ratio of boehmite, deionized water and dilute nitric acid is 4g:100mL:9mmol.
Soaking expanded vermiculite in AlOOH sol at room temperature for 20min, taking out, drying in a 60 ℃ oven, repeating the soaking-drying steps for 7 times to obtain AlOOH/vermiculite; wherein, the dosage ratio of the expanded vermiculite to the AlOOH sol is 1g:50mL.
Mixing magnesium nitrate, calcium nitrate, urea and water to obtain a mixed metal salt solution; wherein Mg is 2+ And Ca 2+ The total concentration is 0.02M, ca 2+ /Mg 2+ Molar ratio = 1:7, urea concentration 1.25M.
Simultaneously and rapidly transferring AlOOH/vermiculite and mixed metal salt solution into a polytetrafluoroethylene autoclave, carrying out hydrothermal reaction for 12 hours at 100 ℃, centrifugally washing the obtained product with ethanol and deionized water for 3 times in sequence until the supernatant fluid of the centrifugal washing value of the deionized water is clear liquid, and then drying for 6 hours in a 60 ℃ oven to obtain the calcium-containing hydrotalcite-vermiculite composite material; wherein, the dosage ratio of AlOOH/vermiculite to mixed metal salt solution is 1g:50mL.
Comparative example 1
Simultaneously and rapidly transferring the mixed metal salt solution prepared in the example 1 and the AlOOH sol prepared in the example 1 into a polytetrafluoroethylene autoclave, carrying out hydrothermal reaction for 12 hours at 90 ℃, centrifugally washing the obtained product with ethanol and deionized water for 5 times in sequence until the supernatant fluid of the centrifugal washing value of the deionized water is clear liquid, and then drying in a baking oven at 60 ℃ for 6 hours to obtain calcium-containing hydrotalcite (CaMgAl-LDH); wherein, the dosage ratio of the AlOOH sol to the mixed metal salt solution is 1g:70mL.
Fig. 1 shows XRD patterns of the calcium-containing hydrotalcite-vermiculite composites prepared in example 1 and example 3 and the calcium-containing hydrotalcite prepared in comparative example 1, and as can be seen from fig. 1, the calcium-containing hydrotalcite-vermiculite composites with different Ca/Mg molar ratios show characteristic peaks of the calcium-containing hydrotalcite (denoted as CaMgAl-LDH) and characteristic peaks of the vermiculite, demonstrating that the calcium-containing hydrotalcite is successfully compounded on the expanded vermiculite.
Fig. 2 is an SEM image of the calcium-containing hydrotalcite-vermiculite composite material prepared in example 1, fig. 3 is an SEM image of the calcium-containing hydrotalcite-vermiculite composite material prepared in example 2, fig. 4 is an SEM image of the calcium-containing hydrotalcite-vermiculite composite material prepared in example 3, and fig. 5 is an SEM image of the calcium-containing hydrotalcite-vermiculite composite material prepared in example 4. As can be seen from fig. 2 to 5, the calcium-containing hydrotalcite-vermiculite composite materials with different Ca/Mg molar ratios all show uniform terra silicate layers, have good two-dimensional lamellar structures, and prove that the calcium-containing hydrotalcite grows well on the surface of the expanded vermiculite.
Comparative example 2
Hydrotalcite/vermiculite composites were prepared according to example 5 in CN113877519 a.
Comparative example 3
Mixing magnesium nitrate, calcium nitrate, urea and water to obtain a mixed metal salt solution; wherein Mg is 2+ And Ca 2+ The total concentration is 0.02M, ca 2+ /Mg 2+ Molar ratio = 1:4, urea concentration 1M.
Simultaneously and rapidly transferring the expanded vermiculite and the mixed metal salt solution into a polytetrafluoroethylene autoclave, carrying out hydrothermal reaction for 12 hours at the temperature of 110 ℃, sequentially centrifugally washing the obtained product with ethanol for 5 times, centrifugally washing with deionized water for 5 times, centrifugally washing the supernatant with deionized water to obtain clear liquid, and drying in a baking oven at the temperature of 60 ℃ for 6 hours to obtain the calcium-containing hydrotalcite-vermiculite composite material; wherein, the dosage ratio of vermiculite to mixed metal salt solution is 1g:70mL.
Test example 1
Test of adsorption Performance of calcium-containing hydrotalcite-vermiculite composite Material prepared in examples 1 to 4 and comparative example 3 on Metal ions by hydrotalcite/vermiculite composite Material prepared in comparative example 2
1g of the calcium-containing hydrotalcite-vermiculite composite material prepared in examples 1 to 4 and comparative example 3, and the hydrotalcite/vermiculite composite material prepared in comparative example 2 were added to 100mL of nickel chloride solution (12 mg/L, pH=7), lithium nitrate solution (30 mg/L, pH=7) and zinc nitrate (30 mg/L, pH=7) solutions, respectively, and adsorption was performed under uniform stirring, the contents of Ni (II), li (I) and Zn (II) in the water body after adsorption were sampled and tested at regular intervals, and the adsorption capacity for Ni (II), and the adsorption rates for Ni (II), li (I) and Zn (II) were calculated, and the adsorption test results are shown in Table 1.
TABLE 1 adsorption Effect of composite materials on Ni (II), li (I) and Zn (II)
Note that: "-" indicates no test.
As can be seen from Table 1, the adsorption capacity of the calcium-containing hydrotalcite-vermiculite composite material prepared by the invention is more than 8.89mg/g and the adsorption rate is more than 74.1% after the calcium-containing hydrotalcite-vermiculite composite material adsorbs low-concentration Ni (II) for 80 min; the adsorption capacity to Li (I) is below 9.7mg/g, and the adsorption rate is below 32.3%; the adsorption capacity to Zn (II) is below 4.94mg/g, the adsorption rate is below 16.5%, and the calcium-containing hydrotalcite-vermiculite composite material prepared by the method has good selective adsorption performance to low-concentration Ni (II), and the higher the ratio of Ca to the Ni (II), the better the adsorption effect to Ni (II).
Test example 2
Test of adsorption Performance of calcium-containing hydrotalcite-vermiculite composite Material prepared in examples 1-4 and comparative example 3 on higher concentration of Nickel ions by hydrotalcite/vermiculite composite Material prepared in comparative example 2
1g of the calcium-containing hydrotalcite-vermiculite composite material prepared in examples 1 to 4 and comparative example 3, and the hydrotalcite/vermiculite composite material prepared in comparative example 2 were respectively added to 100mL of nickel chloride solution (80 mg/L, pH=7), and adsorption was performed under uniform stirring, the content of Ni (II) in the water body after adsorption was sampled and tested at regular intervals, and the adsorption capacity for Ni (II) was calculated, and the test results are shown in Table 2.
TABLE 2 adsorption Effect of composite materials on Ni (II)
As can be seen from a comparison of tables 1 and 2, the calcium-containing hydrotalcite-vermiculite composite materials prepared in examples 1 to 4 of the present invention had adsorption capacities of 6.04mg/g, 5.56mg/g, 5.36mg/g and 4.05mg/g for high concentration (80 mg/L) of Ni (II), respectively, while the adsorption capacities of 10.12mg/g, 10.02mg/g, 9.80mg/g and 8.89mg/g for low concentration (12 mg/L) of Ni (II) were increased by 67.55%, 80.22%, 82.84% and 119.51%, respectively, while the adsorption capacities of the composite materials prepared in comparative examples 2 and 3 had decreased by 94.21% and 41.32%, respectively, for low concentration of Ni (II), respectively, at the same adsorption time (80 min). The calcium-containing hydrotalcite-vermiculite composite material prepared by the invention has excellent adsorption effect on low-concentration Ni (II).
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the calcium-containing hydrotalcite-vermiculite composite material is characterized by comprising the following steps of:
(1) Soaking the expanded vermiculite in AlOOH sol, and drying to obtain AlOOH/vermiculite;
(2) Mixing calcium ions, magnesium ions, urea and water to obtain a mixed metal salt solution;
(3) Mixing the AlOOH/vermiculite with the mixed metal salt solution, and performing hydrothermal reaction to obtain a calcium-containing hydrotalcite-vermiculite composite material;
the steps (1) and (2) have no time sequence.
2. The method of claim 1, wherein the expanded vermiculite has a particle size of 15 to 20 mesh;
the ratio of the mass of the expanded vermiculite to the volume of the AlOOH sol is 1g: 40-80 mL.
3. The method according to claim 1 or 2, wherein the number of repetitions of the impregnation and drying is 5 to 10.
4. The preparation method according to claim 1, wherein the total concentration of calcium ions and magnesium ions in the mixed metal salt solution is 0.02 to 0.04mol/L, and the concentration of urea is 1 to 5mol/L;
the molar ratio of the calcium ions to the magnesium ions is 1:4 to 7;
the ratio of the mass of AlOOH/vermiculite to the volume of the mixed metal salt solution is 1g: 40-70 mL.
5. The method according to claim 1 or 4, wherein the hydrothermal reaction is carried out at a temperature of 90 to 110 ℃ for a time of 12 to 24 hours.
6. The preparation method according to claim 1 or 2, wherein the preparation method of AlOOH sol comprises the steps of:
mixing aluminum isopropoxide with water, regulating the pH value to 3-4, and hydrolyzing to obtain boehmite;
mixing the boehmite with water and dilute acid to obtain AlOOH sol.
7. The method according to claim 6, wherein the hydrolysis is carried out at a temperature of 85 to 95℃for a period of 2 to 3 hours.
8. The method of claim 6, wherein the mass to water volume ratio of boehmite is 1g: 20-25 mL;
the dilute acid comprises dilute nitric acid and/or dilute acetic acid;
the mass ratio of boehmite to the amount of acid species in dilute acid was 1g:2 to 2.5mmol.
9. A calcium-containing hydrotalcite-vermiculite composite material according to any one of claims 1 to 8, comprising expanded vermiculite and calcium-containing hydrotalcite grown on the surface of the expanded vermiculite.
10. Use of the calcium-containing hydrotalcite-vermiculite composite material according to claim 9 for removing nickel ions.
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