CN115382549A - Kaolin-based hydrotalcite composite material and preparation method and application thereof - Google Patents
Kaolin-based hydrotalcite composite material and preparation method and application thereof Download PDFInfo
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- CN115382549A CN115382549A CN202210938427.0A CN202210938427A CN115382549A CN 115382549 A CN115382549 A CN 115382549A CN 202210938427 A CN202210938427 A CN 202210938427A CN 115382549 A CN115382549 A CN 115382549A
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- China
- Prior art keywords
- kaolin
- composite material
- hydrotalcite composite
- based hydrotalcite
- deionized water
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000005995 Aluminium silicate Substances 0.000 title claims abstract description 119
- 235000012211 aluminium silicate Nutrition 0.000 title claims abstract description 119
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 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 title claims abstract description 68
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 68
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 34
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 29
- 238000002386 leaching Methods 0.000 claims abstract description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 238000000967 suction filtration Methods 0.000 claims abstract description 10
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 54
- 239000011259 mixed solution Substances 0.000 claims description 39
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000007790 solid phase Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 16
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims description 14
- 229960001180 norfloxacin Drugs 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000002351 wastewater Substances 0.000 claims description 12
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000004098 Tetracycline Substances 0.000 claims description 2
- 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 2
- 229940012189 methyl orange Drugs 0.000 claims description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 2
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 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 2
- 229940043267 rhodamine b Drugs 0.000 claims description 2
- 229960002180 tetracycline Drugs 0.000 claims description 2
- 229930101283 tetracycline Natural products 0.000 claims description 2
- 235000019364 tetracycline Nutrition 0.000 claims description 2
- 150000003522 tetracyclines Chemical class 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 21
- 238000006731 degradation reaction Methods 0.000 abstract description 21
- 238000000926 separation method Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000010865 sewage Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000001868 cobalt Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 16
- 238000003760 magnetic stirring Methods 0.000 description 11
- 238000001132 ultrasonic dispersion Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical group [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage 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
- 230000036541 health Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal activated persulfate Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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
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- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a kaolin-based hydrotalcite composite material, which comprises the steps of calcining kaolin, and carrying out hydrothermal, suction filtration separation, alkaline leaching modification and other operations on the calcined kaolin, cobalt salt, nickel salt, urea and the like serving as raw materials to obtain the kaolin-based hydrotalcite composite material. In the kaolin-based hydrotalcite composite material, the rod-like hydrotalcite is coated on the surface of the sheet-like kaolin, so that the effect of the kaolin as a carrier is fully exerted. The alkaline leaching modification forms a flaky NiCoAl-LDH structure appearance; in addition, the degradation performance of the prepared kaolin-based hydrotalcite composite material on organic pollutants is further improved. The kaolin hydrotalcite composite material has better catalytic degradation effect on organic pollutants in sewage.
Description
Technical Field
The invention relates to application in the technical field of sewage treatment, in particular to a kaolin-based hydrotalcite material, a preparation method thereof and application thereof in sewage treatment.
Background
The water body pollution situation is increasingly severe, and particularly, the organic pollutants in water have the problems of multiple types, wide sources, great degradation difficulty and the like, so that the health and ecological safety of human beings are directly harmed. The traditional sewage treatment method mainly comprises an adsorption method, a flocculation method, a membrane separation method, an advanced oxidation method and the like, in recent years, the advanced oxidation method represented by a persulfate catalytic degradation technology has the advantages of strong adaptability, good deep degradation effect and the like, and the key of popularization and application of the persulfate catalytic degradation method is how to improve the persulfate catalytic degradation efficiency and reduce the application cost, so that the development of a catalytic material with excellent pollutant capture and degradation capacity becomes an important basic guarantee.
At present, clay minerals with special structures and wide sources show huge potential as adsorbents and catalyst carriers for treating organic pollutants in water. Among them, the ionic layered clay compound hydrotalcite, also called Layered Double Hydroxides (LDHs), is a layered metal hydroxide composed of two or more metal elements, and LDHs have unique structural characteristics, good adsorption properties and redox activities, and have attracted wide attention in applications such as adsorption, catalysis, separation, energy storage, and the like. According to the literature report, the preparation method of the LDHs mainly comprises a coprecipitation method, an ion exchange method, a hydrothermal reaction method of two metal nitrates and the like, and the metal composition raw materials used in the preparation process are mostly chemical reagents of soluble metal salts. How to optimize the preparation process, improve the synthetic raw materials and improve the application performance of the LDHs becomes a leading-edge problem in the research field of the LDHs.
Disclosure of Invention
The invention provides a preparation method of a kaolin-based hydrotalcite composite material, which is novel, the obtained composite material has unique appearance, and the kaolin-based hydrotalcite composite material can be used for treating organic pollutants in wastewater and has good catalytic degradation effect.
In order to achieve the purpose, the technical scheme is as follows:
the invention provides a kaolin-based hydrotalcite composite material, which is prepared by the following method:
uniformly dispersing the calcined kaolin powder into deionized water A, and adding Co (NO) 3 ) 2 ·6H 2 O, nickel salt and urea are uniformly dispersed, the mixture is stirred in a water bath at normal pressure, and the obtained mixed solution is subjected to post-treatment A to obtain the kaolin-based hydrotalcite composite material; the nickel salt is Ni (NO) 3 ) 2 ·6H 2 O or NiCl 2 ·6H 2 O; the conditions of the normal-pressure water bath stirring are as follows: the water bath temperature is 80-100 deg.C, and the time is 18-24h (preferably 90 deg.C, 24 h);
the calcined kaolin powder and Co (NO) 3 ) 2 ·6H 2 The mass ratio of O is 1; said Co (NO) 3 ) 2 ·6H 2 The ratio of the amounts of O, nickel salt and urea is 1:1-2 (preferably 1.
Furthermore, the calcined kaolin powder is obtained by calcining kaolin powder in a muffle furnace at 500-700 ℃ for 1-5h (preferably 700 ℃ for 2 h). The kaolin can be dehydroxylated within the calcination range of 500-700 ℃, so that the activity of the calcined kaolin is enhanced, and the structure of the calcined kaolin is disintegrated in an alkaline environment, so that the Al element is fully exposed and easily leached. The invention recommends a heating rate of 2-10 ℃/min.
Further, the usage ratio of the calcined kaolin powder to the deionized water A is 1g to 30-60mL (preferably 1 g.
Further, the post-treatment A comprises the following steps: and (3) carrying out suction filtration on the mixed solution, leaching the obtained solid phase with deionized water B and ethanol in sequence, drying in vacuum (preferably 60-100 ℃), and grinding to obtain the kaolin-based hydrotalcite composite material.
The invention particularly recommends that the kaolin-based hydrotalcite composite material is further treated as follows:
soaking the kaolin hydrotalcite-like composite material in 1-5mol/L (preferably 3 mol/L) aqueous solution of an alkaline substance, heating in water bath at 60-98 ℃ for 1-5h (preferably 80 ℃ for 3 h), standing for 12-24h (preferably 24 h), and performing aftertreatment B on the obtained dispersion liquid to obtain the kaolin hydrotalcite-like composite material with the silicon-rich molecular sieve structure;
the alkaline substance contained in the aqueous solution of the alkaline substance is sodium hydroxide or potassium hydroxide.
Further, the ratio of the kaolin-based hydrotalcite composite material to the aqueous solution of the alkaline substance is 1g:50-200mL (preferably 1g.
Further, the post-treatment B is: and (3) centrifugally separating the dispersion liquid, washing the obtained solid phase with deionized water and ethanol in sequence, centrifuging, and drying the obtained precipitate to obtain the kaolin-based hydrotalcite composite material containing the silicon-rich molecular sieve structure.
The deionized water A and the deionized water B are both deionized water, and different letters are used for distinguishing the deionized water added in different stages, so that the description is convenient, and no other special meanings exist.
The kaolin presents a sheet structure, and Co (CO) with a rod-shaped structure is loaded on the sheet kaolin obtained through the steps (1) to (3) 3 ) 0.5 (OH)·0.11H 2 O and Ni 2 CO 3 (OH) 2 ·4H 2 The hydrotalcite-like morphology of the O composite phase, the composite material has excellent effect of degrading organic pollutants; the kaolin is subjected to high-temperature calcination treatment, so that the kaolin is dehydroxylated during high-temperature calcination, and a better carrier effect is achieved; when the solid phase after vacuum drying and grinding is dispersed and dipped in the alkali solution, the alkali solution is easier to invadeThe kaolin structure is etched, so that the sheet structure of the kaolin is collapsed, al element is exposed, and a sheet NiCoAl-LDH hydrotalcite-like structure is further formed, meanwhile, si element remained in the kaolin can form a silicon-rich molecular sieve in an alkali liquor environment and is attached to the NiCoAl-LDH hydrotalcite-like structure, and the composite material is more excellent in organic pollutant degradation compared with a composite material before alkaline leaching.
The invention also provides the kaolin hydrotalcite composite material prepared by the preparation method of the kaolin hydrotalcite composite material, and before alkaline leaching, the kaolin hydrotalcite composite material is prepared by loading rod-shaped Co (CO) on kaolin 3 ) 0.5 (OH)·0.11H 2 O and Ni 2 CO 3 (OH) 2 ·4H 2 Hydrotalcite-like morphology of the O composite phase; the flake NiCoAl-LDH structure is shaped after alkaline leaching;
when the kaolin-based hydrotalcite composite material is used for treating organic pollutant wastewater, an advanced oxidation treatment technology represented by transition metal activated persulfate is adopted.
On the other hand, the invention also provides an application of the kaolin-based hydrotalcite composite material in treatment of organic pollutant wastewater, wherein the organic pollutant in the organic pollutant wastewater is one or a mixture of two of norfloxacin, tetracycline, rhodamine B, methyl orange and methylene blue.
Specifically, the application is as follows: dispersing the kaolin-based hydrotalcite composite material into organic pollutant wastewater, and adding persulfate to catalyze and degrade organic pollutants.
Further, the concentration of the organic pollutants in the organic pollutant wastewater is 10-50mg/L. The persulfate is Peroxymonosulfate (PMS) and Peroxydisulfate (PDS). The ratio of the kaolin-based hydrotalcite composite material to the persulfate to the organic pollutant wastewater is 0.2-1g:0.2-1g:1L of the compound.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the kaolin hydrotalcite-based composite material provided by the invention, rod-shaped Co (CO) 3 ) 0.5 (OH)·0.11H 2 O and Ni 2 CO 3 (OH) 2 ·4H 2 The hydrotalcite-like compound of the O composite phase is coated on the surface of the flaky kaolin, so that the effect of the kaolin as a carrier is fully exerted.
(2) The preparation method of the kaolin-based hydrotalcite composite material comprises an alkaline leaching modification step, wherein a flaky NiCoAl-LDH structure morphology is formed after alkaline leaching modification, the kaolin phase morphology disappears, and Al elements in kaolin participate in forming the NiCoAl-LDH flaky structure, meanwhile, si elements remained in the kaolin can form a silicon-rich molecular sieve in an alkaline solution environment and attach to the NiCoAl-LDH hydrotalcite-like structure, so that the degradation performance and the reuse stability of the prepared kaolin-based hydrotalcite composite material on organic pollutants are further improved.
(3) The kaolin hydrotalcite-like composite material provided by the invention has better catalytic degradation effect on organic pollutants in sewage, and the degradation rate on antibiotic norfloxacin can reach 98%.
Drawings
Fig. 1 is an XRD pattern of the kaolin-based hydrotalcite composite material prepared in example 1.
Fig. 2 and 3 are SEM images of the kaolin-based hydrotalcite composite material prepared in example 1 at a low magnification and at a high magnification, respectively.
Fig. 4 is an XRD pattern of the kaolin-based hydrotalcite composite material prepared in example 2.
Fig. 5 is an SEM image of the kaolin-based hydrotalcite composite material prepared in example 2.
Fig. 6 is an EDS analysis of the kaolin-based hydrotalcite composite material prepared in example 2.
FIG. 7 is an XRD pattern of the composite materials prepared in examples 1-2 and comparative examples 1 and 3.
Fig. 8 is a TEM image of the kaolin-based hydrotalcite composite prepared in example 2.
Detailed Description
Example 1
(1) Calcining kaolin powder in a muffle furnace under the following calcining conditions: the calcining temperature is 700 ℃, and the calcining time is 2 hours;
(2) 2g of calcined kaolin is taken to be evenly dispersed in 60mL of deionized water by ultrasonic, and then 2.91g of Co (NO) is added into the solution in sequence 3 ) 2 ·6H 2 O、2.37g NiCl 2 ·6H 2 Performing ultrasonic dispersion on O and 7.2g of urea uniformly to obtain a mixed solution A;
(3) Carrying out water bath magnetic stirring on the mixed solution A at the temperature of 90 ℃ under normal pressure for 24 hours to obtain mixed solution B;
(4) Leaching the mixed solution B while leaching with deionized water and ethanol, separating to obtain a solid phase, vacuum drying at 60 ℃, and grinding to obtain the kaolin-based hydrotalcite composite material;
the XRD and SEM images of the kaolin-based hydrotalcite composite material are shown in figure 1 and figures 2 and 3, and the combination of XRD and SEM analysis shows that the sample shows the Co (CO) with a plurality of rod-shaped morphologies 3 ) 0.5 (OH)·0.11H 2 O and Ni 2 CO 3 (OH) 2 ·4H 2 The O composite phase is loaded on the platy kaolin.
Example 2
(1) Calcining kaolin powder in a muffle furnace under the following calcining conditions: the calcining temperature is 700 ℃, and the calcining time is 2 hours;
(2) 2g of calcined kaolin is taken to be evenly dispersed in 60mL of deionized water by ultrasonic, and then 2.91g of Co (NO) is added into the solution in sequence 3 ) 2 ·6H 2 O、2.37g NiCl 2 ·6H 2 Performing ultrasonic dispersion on O and 7.2g of urea uniformly to obtain a mixed solution A;
(3) Carrying out water bath magnetic stirring on the mixed solution A at the temperature of 90 ℃ under normal pressure for 24 hours to obtain mixed solution B;
(4) Leaching the mixed solution B while leaching with deionized water and ethanol, performing suction filtration and separation to obtain a solid phase, performing vacuum drying at 60 ℃, and grinding;
(5) Uniformly soaking 0.5g of solid phase subjected to vacuum drying and grinding in 100mL of 3mol/L sodium hydroxide alkali solution, heating in a water bath at 80 ℃ for 3 hours, standing for 24 hours, performing centrifugal separation to obtain a solid phase, washing with deionized water and ethanol, centrifuging to obtain a solid phase, and performing vacuum drying and grinding at 60 ℃ to obtain the kaolin-based hydrotalcite composite material;
example 2 compared to example 1, the kaolin-based hydrotalcite composite material prepared in example 1 was subjected to a sodium hydroxide alkaline leaching step of 3 mol/L.
The XRD, SEM, EDS, TEM and XRD of the kaolin-based hydrotalcite composite material are respectively shown in FIG. 4, 5, 6 and 8, and the XRD analysis shows that the composite material is prepared from NiCoAl-LDH and SiO 2 The composition is combined with XRD, SEM and EDS analysis to obtain the appearance presented by the sample table as a flaky NiCoAl-LDH structure, and TEM image analysis shows that the Si element remained in kaolin is converted into a silicon-rich molecular sieve in an alkali solution environment and attached to the flaky NiCoAl-LDH structure besides the flaky NiCoAl-LDH structure.
Example 3
(1) Calcining kaolin powder in a muffle furnace under the following calcining conditions: the calcining temperature is 700 ℃, and the calcining time is 2 hours;
(2) 2g of calcined kaolin is taken to be evenly dispersed in 60mL of deionized water by ultrasonic, and then 2.91g of Co (NO) is added into the solution in sequence 3 ) 2 ·6H 2 O、2.91g Ni(NO 3 ) 2 ·6H 2 Performing ultrasonic dispersion on O and 7.2g of urea uniformly to obtain a mixed solution A;
(3) Carrying out water bath magnetic stirring on the mixed solution A at the temperature of 90 ℃ and normal pressure for 18h to obtain mixed solution B;
(4) Leaching the mixed solution B while leaching with deionized water and ethanol, performing suction filtration and separation to obtain a solid phase, performing vacuum drying at 60 ℃, and grinding to obtain the kaolin-based hydrotalcite composite material;
example 4
(1) Calcining kaolin powder in a muffle furnace under the following calcining conditions: the calcining temperature is 700 ℃, and the calcining time is 2 hours;
(2) 2g of calcined kaolin is taken to be evenly dispersed in 60mL of deionized water by ultrasonic, and then 2.91g of Co (NO) is added into the solution in sequence 3 ) 2 ·6H 2 O、2.37g NiCl 2 ·6H 2 Performing ultrasonic dispersion on O and 7.2g of urea uniformly to obtain a mixed solution A;
(3) Carrying out water bath magnetic stirring on the mixed solution A at the temperature of 90 ℃ under normal pressure for 24 hours to obtain mixed solution B;
(4) Leaching the mixed solution B while leaching with deionized water and ethanol, performing suction filtration and separation to obtain a solid phase, performing vacuum drying at 60 ℃, and grinding;
(5) Uniformly soaking 0.5g of solid phase subjected to vacuum drying and grinding in 100mL 4mol/L sodium hydroxide alkali solution, heating in a water bath at 80 ℃ for 3h, standing for 24h, performing centrifugal separation to obtain a solid phase, washing with deionized water and ethanol, centrifuging to obtain a solid phase, and performing vacuum drying and grinding at 60 ℃ to obtain the kaolin-based hydrotalcite composite material;
example 4 compared with example 1, the kaolin-based hydrotalcite composite material prepared in example 1 was subjected to a sodium hydroxide alkaline leaching step of 4 mol/L.
Example 5
(1) Calcining kaolin powder in a muffle furnace under the following calcining conditions: the calcining temperature is 700 ℃, and the calcining time is 2 hours;
(2) 2g of calcined kaolin is taken to be evenly dispersed in 60mL of deionized water by ultrasonic, and then 2.91g of Co (NO) is added into the solution in sequence 3 ) 2 ·6H 2 O、2.37g NiCl 2 ·6H 2 Performing ultrasonic dispersion on O and 7.2g of urea uniformly to obtain a mixed solution A;
(3) Carrying out water bath magnetic stirring on the mixed solution A at the temperature of 90 ℃ under normal pressure for 24 hours to obtain mixed solution B;
(4) Leaching the mixed solution B while leaching with deionized water and ethanol, performing suction filtration and separation to obtain a solid phase, performing vacuum drying at 60 ℃, and grinding;
(5) Uniformly soaking 0.5g of solid phase subjected to vacuum drying and grinding in 100mL of 2.5mol/L sodium hydroxide alkali solution, heating in a water bath at 80 ℃ for 3h, standing for 24h, performing centrifugal separation to obtain a solid phase, washing with deionized water and ethanol, centrifuging to obtain a solid phase, and performing vacuum drying and grinding at 60 ℃ to obtain the kaolin-based hydrotalcite composite material;
example 5 compared with example 1, the kaolin-based hydrotalcite composite material prepared in example 1 was subjected to a sodium hydroxide alkaline leaching step of 2.5 mol/L.
Comparative example 1
(1) Taking 2g of kaolin to be ultrasonically and uniformly dispersed in 60mL of deionized water, and then sequentially adding 2.91g of Co (NO) into the solution 3 ) 2 ·6H 2 O、2.37g NiCl 2 ·6H 2 Performing ultrasonic dispersion on O and 7.2g of urea uniformly to obtain a mixed solution A;
(2) Carrying out water bath magnetic stirring on the mixed solution A at the temperature of 90 ℃ under normal pressure for 24 hours to obtain mixed solution B;
(3) Leaching the mixed solution B while leaching with deionized water and ethanol, performing suction filtration and separation to obtain a solid phase, performing vacuum drying at 60 ℃, and grinding to obtain the kaolin-based hydrotalcite composite material;
comparative example 1 in comparison to example 1, the kaolin used in comparative example 1 was not subjected to a calcination step.
XRD of the kaolin-based hydrotalcite composite material is shown in figure 7, and the characteristic peak of kaolin in the composite material is stronger according to XRD analysis.
Comparative example 2
(1) Calcining kaolin powder in a muffle furnace under the following calcining conditions: the calcining temperature is 700 ℃, and the calcining time is 2 hours;
(2) Taking 2g of calcined kaolin to be ultrasonically and uniformly dispersed in 30mL of hydrochloric acid solution with the concentration of 1mol/L, carrying out water bath magnetic stirring at the temperature of 90 ℃ and normal pressure for 30min after ultrasonic dispersion is uniform, and then sequentially adding 2.91g of Co (NO) into the solution 3 ) 2 ·6H 2 O、2.37g NiCl 2 ·6H 2 Performing ultrasonic dispersion on O and 30mL of deionized water uniformly to obtain a mixed solution A;
(3) Dropwise adding a sodium hydroxide solution with the concentration of 1mol/L into the mixed solution A to ensure that the pH of the mixed solution A is =7, then adding 0.2g of urea into the solution, and uniformly performing ultrasonic dispersion to obtain a mixed solution B;
(4) Carrying out water bath magnetic stirring on the mixed solution B at the temperature of 90 ℃ under normal pressure for 24 hours to obtain mixed solution C;
(5) Leaching the mixed solution C while leaching with deionized water and ethanol, performing suction filtration separation to obtain a solid phase, performing vacuum drying at 60 ℃, and grinding to obtain composite material powder;
comparative example 2 in comparison to example 1, comparative example 2 was prepared by adding the sodium hydroxide solution and then the urea.
Comparative example 3
(1) Calcining kaolin powder in a muffle furnace under the following calcining conditions: the calcining temperature is 700 ℃, and the calcining time is 2 hours;
(2) 2g of calcined kaolin is taken to be evenly dispersed in 60mL of deionized water by ultrasonic, and then 2.91g of Co (NO) is added into the solution in sequence 3 ) 2 ·6H 2 O、2.91g Ni(NO 3 ) 2 ·6H 2 Performing ultrasonic dispersion on O and 7.2g of urea uniformly to obtain a mixed solution A;
(3) Carrying out water bath magnetic stirring on the mixed solution A at the temperature of 90 ℃ under normal pressure for 8 hours to obtain mixed solution B;
(4) Leaching the mixed solution B while washing with deionized water and ethanol, performing suction filtration and separation to obtain a solid phase, performing vacuum drying at 60 ℃, and grinding to obtain the kaolin-based hydrotalcite composite material;
the XRD of the kaolin-based hydrotalcite composite material is shown in figure 7, and the XRD patterns of the comparative example 1 and the comparative example 3 show that the formation of LDH is influenced by the length of the time of the normal-pressure magnetic stirring at a certain temperature, and the LDH is not formed in the sample when the sample is stirred for 8 hours under the normal-pressure magnetic stirring.
Application example 1
Preparing 50mL of Norfloxacin (NFA) solution with initial concentration of 20mg/L to simulate organic pollutant wastewater, respectively weighing 0.025g of samples prepared in examples 1-5 and comparative examples 1-2, adding the samples into the NFA solution, uniformly stirring by ultrasonic, carrying out dark adsorption for 30min, adding 0.025g of PMS, drawing 3mL of reaction solution into a centrifuge tube every 10min, quenching by methanol, testing the absorbance of the residual NFA in the solution by an ultraviolet spectrophotometer, and calculating the degradation rate of the sample on the NFA. The results of the experiment are shown in table 1:
TABLE 1 degradation rate of organic contaminant norfloxacin molecules by samples
| Sample (I) | Degradation Rate (%) after 30min of reaction |
| Example 1 | 96 |
| Example 2 | 98 |
| Example 3 | 96 |
| Example 4 | 97 |
| Example 5 | 97 |
| Comparative example 1 | 92 |
| Comparative example 2 | 86 |
Application example 2
The samples prepared in example 5 were subjected to repeated use experiments under the same experimental conditions as in application example 1, and the results are shown in table 2:
TABLE 2 degradation and reuse performance of samples on norfloxacin molecules as organic pollutants
| Example 5 sample | Degradation rate (%) after 30min of reaction |
| Number of uses 1 | 97 |
| Number of |
96 |
| Number of uses 3 | 96 |
| Number of |
95 |
1. Examples 1 to 3 show that the composite material prepared by the method for preparing the kaolin-based hydrotalcite composite material provided by the present patent has an efficient degradation effect on organic pollutant norfloxacin.
2. By comparing example 1 with example 2, it is demonstrated that the kaolin hydrotalcite-based composite material prepared in example 1 can be further subjected to alkaline leaching to improve the degradation performance of norfloxacin serving as an organic pollutant.
3. By comparing example 1 with comparative example 1, it is demonstrated that the composite material synthesized by subjecting kaolin to the calcination step and then further to the synthesis step has better degradation performance than the composite material synthesized by directly subjecting kaolin to the synthesis step.
4. By comparing example 1 with comparative example 2, it is shown that the preparation method used in example 1 (the preparation method provided by the patent) has a significant advantage in the performance of degrading norfloxacin, an organic pollutant, compared with the preparation method used in comparative example 2.
5. As can be shown in table 2, the sample prepared in example 5 has excellent reproducibility and stability in degrading norfloxacin, an organic contaminant.
Claims (10)
1. The kaolin-based hydrotalcite composite material is characterized by being prepared by the following method:
uniformly dispersing the calcined kaolin powder into deionized water A, and adding Co (NO) 3 ) 2 〃6H 2 O, nickel salt and urea are uniformly dispersed, the mixture is stirred in a water bath at normal pressure, and the obtained mixed solution is subjected to post-treatment A to obtain the kaolin-based hydrotalcite composite material; the nickel salt is Ni (NO) 3 ) 2 〃6H 2 O or NiCl 2 〃6H 2 O; the conditions of the normal-pressure water bath stirring are as follows: the water bath temperature is 80-100 ℃, and the time is 18-24h;
the calcined kaolin powder and Co (NO) 3 ) 2 〃6H 2 The mass ratio of O is 1; said Co (NO) 3 ) 2 〃6H 2 The ratio of the amounts of O, nickel salt and urea is 1:1-2:10-20.
2. The kaolin-based hydrotalcite composite material according to claim 1, wherein: the calcined kaolin powder is obtained by calcining kaolin powder in a muffle furnace at 500-700 ℃ for 1-5 h.
3. The kaolin-based hydrotalcite composite material according to claim 1, wherein: the dosage ratio of the calcined kaolin powder to the deionized water A is 1g.
4. The kaolin-based hydrotalcite composite according to claim 1, characterized in that the post-treatment a is: and carrying out suction filtration on the mixed solution, sequentially leaching the obtained solid phase with deionized water B and ethanol, carrying out vacuum drying, and grinding to obtain the kaolin-based hydrotalcite composite material.
5. The kaolin-based hydrotalcite composite material according to claims 1 to 4, wherein: the kaolin-based hydrotalcite composite material is further processed as follows to obtain the kaolin-based hydrotalcite composite material with the silicon-rich molecular sieve structure:
soaking the kaolin-based hydrotalcite composite material in 1-5mol/L aqueous solution of an alkaline substance, heating in water bath at 60-98 ℃ for 1-5h, standing for 12-24h, and performing aftertreatment B on the obtained dispersion liquid to obtain the kaolin-based hydrotalcite composite material containing a silicon-rich molecular sieve structure;
the alkaline substance contained in the aqueous solution of the alkaline substance is sodium hydroxide or potassium hydroxide.
6. The kaolin-based hydrotalcite composite material according to claim 5, wherein: the ratio of the kaolin-based hydrotalcite composite material to the aqueous solution of the alkaline substance is 1g:50-200mL.
7. The kaolin-based hydrotalcite composite material according to claim 5, characterized in that the post-treatment B is: and (3) centrifugally separating the dispersion liquid, washing the obtained solid phase with deionized water and ethanol in sequence, centrifuging, and drying the obtained precipitate to obtain the kaolin-based hydrotalcite composite material containing the silicon-rich molecular sieve structure.
8. The kaolin-based hydrotalcite composite material according to claim 1, for use in the treatment of organic pollutant wastewater.
9. The use of claim 8, wherein: the organic pollutant in the organic pollutant wastewater is one or a mixture of two of norfloxacin, tetracycline, rhodamine B, methyl orange and methylene blue.
10. The use according to claim 8, characterized in that said use is: dispersing the kaolin-based hydrotalcite composite material into organic pollutant wastewater, and adding persulfate to catalyze and degrade organic pollutants; the ratio of the kaolin-based hydrotalcite composite material to the persulfate to the organic pollutant wastewater is 0.2-1g:0.2-1g:1L of the compound.
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| CN102674384A (en) * | 2011-03-17 | 2012-09-19 | 华东师范大学 | Hydrotalcite like compound-kaolin composite material and preparation method thereof |
| CN106423044A (en) * | 2016-11-03 | 2017-02-22 | 江苏开放大学 | Method for preparing polymerized nanomaterial with kaolin used as matrix |
| WO2021259317A1 (en) * | 2020-06-23 | 2021-12-30 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method therefor |
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| CN102674384A (en) * | 2011-03-17 | 2012-09-19 | 华东师范大学 | Hydrotalcite like compound-kaolin composite material and preparation method thereof |
| CN106423044A (en) * | 2016-11-03 | 2017-02-22 | 江苏开放大学 | Method for preparing polymerized nanomaterial with kaolin used as matrix |
| WO2021259317A1 (en) * | 2020-06-23 | 2021-12-30 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method therefor |
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