CN115350685B - Attapulgite composite material rich in ortho-hydroxyl and preparation method and application thereof - Google Patents

Attapulgite composite material rich in ortho-hydroxyl and preparation method and application thereof Download PDF

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CN115350685B
CN115350685B CN202210982598.3A CN202210982598A CN115350685B CN 115350685 B CN115350685 B CN 115350685B CN 202210982598 A CN202210982598 A CN 202210982598A CN 115350685 B CN115350685 B CN 115350685B
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attapulgite
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陈渭
孙哲
王维恩
张明锦
崔香
薛济民
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Qinghai Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • 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
    • 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
    • C02F2101/108—Boron compounds

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Abstract

The invention discloses an attapulgite composite material rich in ortho-hydroxyl, which comprises the following components in parts by weight: 10 parts of attapulgite, 6-15 parts of epoxy silane, 0.2-1.2 parts of amino-rich compound and 0.67-3 parts of glycidol; the invention also discloses a preparation method of the composite material, which comprises the following steps: weighing; preparing epoxy silanized attapulgite; preparing an aminated attapulgite; preparing the attapulgite composite material rich in the ortho-hydroxyl. The attapulgite composite material rich in the ortho-hydroxyl groups, which is prepared by the invention, is used as a boron adsorbent for removing or extracting boron in drinking water, irrigation water, geothermal water, salt lake brine and industrial wastewater, has excellent adsorption effect, and has excellent adsorption effect on HBO under the conditions of pH of 1-14 and temperature of 0-80 DEG C 2 The adsorption capacity of the catalyst can reach more than 130 mg/g.

Description

Attapulgite composite material rich in ortho-hydroxyl and preparation method and application thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to an attapulgite composite material rich in ortho-hydroxyl and a preparation method and application thereof.
Background
Boron and its compounds are widely used in metallurgical, pharmaceutical, glass, ceramic, fertilizer, textile, leather, paint, pigment, military, aerospace and other industries. Since the reserves of high-grade borate ores which are easy to decompose are increasingly reduced with the massive consumption of boron ore resources, the development of boron-containing aqueous solutions in various countries in the world is very important nowadays. In addition, when boron is applied, the discharge of wastewater and mother liquor generated by boron raw material processing also causes environmental pollution, and greatly influences ecological balance. Therefore, the development of boron resources in water and the treatment of boron-containing waste liquid are closely related to national economy and human health.
Attapulgite is a water-containing magnesium-aluminum silicate mineral with a chain layered structure, and has a unique nano pore structure and a large specific surface area, so that the attapulgite is often used for adsorbing and removing heavy metals and cationic pollutants in water. In the natural attapulgite, carbonate cements are filled among attapulgite crystals and in natural pore canals, so that crystal particles are agglomerated, and the pore canal structure, the surface morphology and the crystal stacking state of the natural attapulgite are all in an irregular state, so that the physical and chemical properties of the whole attapulgite are weakened, and the adsorption performance of the attapulgite is influenced. And the attapulgite has excellent colloid stability in a water suspension system, so that the adsorbed and saturated attapulgite is difficult to separate from water, waste of attapulgite resources is caused, and secondary pollution is caused to water. In the separation way of dye wastewater treatment, flocculant is generally added in industrial experiments, so that the problem is that the water treatment cost is increased and a large amount of sludge which is difficult to treat is generated.
In the prior art, a magnesium-aluminum-zirconium composite metal oxide is prepared and can realize H 3 BO 3 The adsorption of (preparation of magnesium aluminum zirconium composite metal oxide and research on boron adsorption performance, hu Anzhuang, etc., university of Qinghai university college), but the adsorption amount is only 34.07mg/g; also disclosed is a magnesium aluminum double hydroxide which achieves adsorption of boron (Adsorption of boron on calcined AlMg layered double hydroxide from aqueous solutions. Solutions and effect of operating conditions, e.d. isaacs-Paez etc.), but which also has a maximum adsorption of boron of only 25mg/g.
Therefore, how to provide an attapulgite composite material rich in ortho-hydroxyl groups, which has excellent adsorption effect and can be used for removing and extracting boron, and a preparation method and application thereof are technical problems to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides an attapulgite composite material rich in ortho-hydroxyl groups, a preparation method and application thereof, and the composite material can be used as a boron adsorbent for removing or extracting boron and has an excellent adsorption effect. The principle is as follows: the attapulgite/acidified attapulgite and the silane coupling agent with epoxy groups are subjected to silanization modification, a large amount of epoxy groups can be endowed to the surface of the attapulgite, the epoxy groups can carry out ring-opening reaction with active hydrogen of an amino-rich compound, so that the amino-rich compound is grafted on the surface of the attapulgite to obtain the aminated attapulgite, and then the aminated attapulgite is subjected to hydroxylation modification by reacting with glycidol, so that the attapulgite composite material rich in ortho-position hydroxyl is obtained.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
an attapulgite composite material rich in ortho-hydroxyl groups comprises the following components in parts by weight:
10 parts of attapulgite/acidified attapulgite, 6-15 parts of epoxy silane, 0.2-1.2 parts of amino-rich compound and 0.67-3 parts of glycidol.
Preferably, the epoxysilane comprises one of 3-glycidoxypropyl trimethoxysilane, triethoxy (3-glycidoxypropyl) silane, 3- [ (2, 3) -glycidoxypropyl ] propyl methyl dimethoxy silane, diethoxy (3-glycidoxypropyl) methylsilane, and 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane.
The beneficial effects brought by the optimization are as follows: the micromolecular organosilane coupling agent with 1 epoxy functional group can be modified by amino compound with active hydrogen after modifying the surface of the attapulgite, thereby endowing the material with special functionality.
Preferably, the amino-rich compound comprises one of ethylenediamine, melamine, diethylenetriamine, triethylenetetramine, phenylenediamine, and polyethyleneimine.
Preferably, the phenylenediamine comprises p-phenylenediamine or m-phenylenediamine;
the polyethylenimine comprises one of PEI300, PEI600, PEI1200, PEI1800, PEI10000, and PEI 70000.
The beneficial effects brought by the optimization are as follows: preferred compounds have a higher content of active hydrogen NH, and can be modified with more propylene oxide to impart a rich ortho-hydroxyl functionality to the material.
Another object of the present invention is to provide a method for preparing the above attapulgite composite material rich in ortho-hydroxyl groups, which comprises the following steps:
(1) Weighing
Weighing the raw materials of the composite material for standby;
(2) Preparation of epoxy silanized attapulgite
Dispersing attapulgite or acidified attapulgite in a first solvent, adding epoxy silane, carrying out reflux reaction at 70-90 ℃ for 6-12h, cooling, centrifuging, dispersing in a second solvent, centrifuging again, repeating for 2-5 times, and drying to obtain epoxy silanized attapulgite;
(3) Preparation of aminated attapulgite
10 parts of epoxy silanized attapulgite is weighed and dispersed in 200-400mL of water, nitrogen is introduced for 20-40min, then an amino-rich compound is added, the reaction is carried out for 6-10h at 30-50 ℃, then the temperature is increased to 60-70 ℃ for 4-8h, the reaction is carried out after the reaction is finished, the mixture is placed in the water for dispersion and centrifugation, and the mixture is dried after repeated 2-5 times, thus obtaining the aminated attapulgite;
(4) Preparation of attapulgite composite material rich in ortho-hydroxyl
10 parts of aminated attapulgite is weighed and dispersed in 200-400mL of water, nitrogen is introduced for 10-40min, glycidol is added, nitrogen is stopped being introduced, stirring is carried out for 5-10h at 20-40 ℃, then heating is carried out to 50-80 ℃, stirring is carried out for 2-8h, centrifugation is carried out after the reaction is finished, then the mixture is placed in water for dispersion, and drying is carried out after repeating for 2-5 times, thus obtaining the attapulgite composite material rich in ortho-hydroxyl groups.
Wherein, the repeating for 2-5 times is the repeating for 2-5 times after dispersing and the repeating for 2-5 times after centrifuging.
Preferably, the acidified attapulgite is prepared by the following method:
dispersing 10 parts of attapulgite in 300-600 parts of hydrochloric acid solution with the concentration of 1.5-3mol/L, refluxing for 1-3 hours at 70-90 ℃, centrifuging, washing with deionized water, repeating for 2-5 times, and drying to obtain the acidified attapulgite.
The beneficial effects brought by the optimization are as follows: the acidified attapulgite has larger specific surface area, and can improve the modification degree of the attapulgite in the later operation, thereby endowing the surface of the attapulgite with more functional groups.
Preferably, the first solvent and the second solvent are respectively one of ethanol, acetonitrile, DMF and DMSO.
Preferably, the centrifugation speed in the steps (2) - (4) is 1000-10000r/min, and the centrifugation time is 3-20min;
the drying in the steps (2) - (4) is drying for 1-6h at 100-200 ℃;
the stirring speed in the step (4) is 200-1000r/min.
The invention also aims to provide the application of the attapulgite composite material rich in the ortho-hydroxyl in removing or extracting boron in drinking water, irrigation water, geothermal water, salt lake brine and industrial wastewater.
Compared with the prior art, the invention has the following beneficial effects:
the attapulgite composite material rich in the ortho-hydroxyl groups, which is prepared by the invention, is used as a boron adsorbent for removing or extracting boron in drinking water, irrigation water, geothermal water, salt lake brine and industrial wastewater, has excellent adsorption effect, and has excellent adsorption effect on HBO under the conditions of pH of 1-14 and temperature of 0-80 DEG C 2 The adsorption capacity of the catalyst can reach more than 130 mg/g.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. 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.
Example 1
(1) Preparation of epoxy silanized attapulgite
10 parts of attapulgite is dispersed with a certain amount of acetonitrile, 12 parts of 3-glycidoxypropyl trimethoxysilane is added, and reflux reaction is carried out for 10 hours at 75 ℃. Cooling, centrifuging, dispersing with a certain amount of acetonitrile, centrifuging, repeating for 3 times, and drying to obtain the epoxy silanized attapulgite.
(2) Preparation of aminated attapulgite
10 parts of epoxy silanized attapulgite is dispersed in 200mL of deionized water, nitrogen is introduced for 20min, 0.6 part of melamine is added, the reaction is carried out for 8h at 40 ℃, and the temperature is raised for 8h at 60 ℃. Dispersing with deionized water after the reaction, centrifuging, repeating for 2 times, and drying to obtain the aminated attapulgite.
(3) Preparation of attapulgite composite material rich in ortho-hydroxyl
10 parts of aminated attapulgite is weighed and dispersed in 250mL of deionized water, nitrogen is introduced for 20min, then 1.8 parts of glycidol is added, the introduction of nitrogen is stopped, stirring is carried out for 9h at 25 ℃, stirring is carried out for 4h at 65 ℃ and then the reaction is stopped, centrifugation and deionized water dispersion are carried out after the reaction is finished, and drying is carried out after 3 times of repetition, thus obtaining the attapulgite composite material rich in ortho-position hydroxyl groups.
The attapulgite composite material rich in the ortho-hydroxyl groups, which is prepared by the method, is used as a boron adsorbent for removing or extracting boron in salt lake brine, has excellent adsorption effect, and has excellent adsorption effect on HBO under the conditions of pH of 9.2 and temperature of 0 DEG C 2 The adsorption capacity of the catalyst can reach 146mg/g.
Example two
(1) Preparation of epoxy silanized attapulgite
10 parts of attapulgite is dispersed with a certain amount of DMF, 8 parts of triethoxy (3-epoxypropyloxypropyl) silane is added, and reflux reaction is carried out for 8 hours at 80 ℃. Cooling, centrifuging, dispersing with a certain amount of DMF, centrifuging, repeating for 4 times, and drying to obtain the epoxy silanized attapulgite.
(2) Preparation of aminated attapulgite
10 parts of epoxy silanized attapulgite is dispersed in 400mL of deionized water, nitrogen is introduced for 35min, 0.2 part of ethylenediamine is added for reaction for 10h at 30 ℃, and the temperature is raised for reaction for 4h at 70 ℃. Dispersing with deionized water after the reaction, centrifuging, repeating the steps, and drying to obtain the aminated attapulgite.
(3) Preparation of attapulgite composite material rich in ortho-hydroxyl
10 parts of aminated attapulgite is weighed and dispersed in 300mL of deionized water, nitrogen is introduced for 20min, then 0.67 part of glycidol is added, the nitrogen introduction is stopped, stirring is performed at 35 ℃ for 6h, stirring is performed at 70 ℃ for 6h, the reaction is stopped, centrifugation and deionized water dispersion are performed after the reaction is finished, and drying is performed after repeating for 2 times, so that the attapulgite composite material rich in ortho-position hydroxyl groups is obtained.
The attapulgite composite material rich in the ortho-hydroxyl groups prepared by the method is used as a boron adsorbent for removing or extracting boron in irrigation water, has excellent adsorption effect, and has excellent adsorption effect on HBO under the conditions of pH of 7.5 and temperature of 25 DEG C 2 The adsorption capacity of the catalyst can reach 133mg/g.
Example III
(1) Preparation of epoxy silanized attapulgite
10 parts of attapulgite are dispersed with a certain amount of ethanol, 6 parts of 3- [ (2, 3) -glycidoxy ] propyl methyl dimethoxy silane are added for reflux reaction for 6 hours at 90 ℃. Cooling, centrifuging, dispersing with a certain amount of ethanol, centrifuging, repeating for 2 times, and drying to obtain the epoxy silanized attapulgite.
(2) Preparation of aminated attapulgite
10 parts of epoxy silanized attapulgite is dispersed in 400mL of deionized water, nitrogen is introduced for 40min, 0.54 part of phenylenediamine is added for reaction for 10h at 35 ℃, and the temperature is raised for 6h at 65 ℃. Dispersing with deionized water after the reaction, centrifuging, repeating for 5 times, and drying to obtain the aminated attapulgite.
(3) Preparation of attapulgite composite material rich in ortho-hydroxyl
10 parts of aminated attapulgite is weighed and dispersed in 200mL of deionized water, nitrogen is introduced for 10min, then 1.2 parts of glycidol is added, the introduction of nitrogen is stopped, stirring is performed for 8h at 30 ℃, stirring is performed for 6h at 60 ℃, the reaction is stopped, centrifugation and deionized water dispersion are performed after the reaction is finished, and drying is performed after repeating for 4 times, so that the attapulgite composite material rich in ortho-position hydroxyl groups is obtained.
The attapulgite composite material rich in the ortho-hydroxyl groups, which is prepared by the method, is used as a boron adsorbent for removing or extracting boron in industrial wastewater, has excellent adsorption effect, and has excellent adsorption effect on HBO under the conditions of pH of 13 and temperature of 80 DEG C 2 The adsorption capacity of the catalyst can reach 135mg/g.
Example IV
(1) Preparation of epoxy silanized attapulgite
Preparation of acidified attapulgite: 10 parts of attapulgite is dispersed in 400 parts of hydrochloric acid solution with the concentration of 2mol/L, the mixture is refluxed for 2 hours at 80 ℃, centrifuged, washed by deionized water and repeated for 3 times, and the acidified attapulgite is obtained after drying.
10 parts of acidified attapulgite are dispersed with a certain amount of DMSO, 9 parts of diethoxy (3-glycidoxypropyl) methylsilane are added and the mixture is refluxed at 85 ℃ for 8 hours. Cooling, centrifuging, dispersing with a certain amount of DMSO, centrifuging, repeating for 5 times, and drying to obtain the epoxy silanized attapulgite.
(2) Preparation of aminated attapulgite
10 parts of epoxy silanized attapulgite is dispersed in 300mL of deionized water, nitrogen is introduced for 30min, 1.2 parts of triethylenetetramine is added for reaction at 50 ℃ for 7h, and the temperature is raised for reaction at 65 ℃ for 6h. Dispersing with deionized water after the reaction, centrifuging, repeating for 3 times, and drying to obtain the aminated attapulgite.
(3) Preparation of attapulgite composite material rich in ortho-hydroxyl
10 parts of aminated attapulgite is weighed and dispersed in 400mL of deionized water, nitrogen is introduced for 40min, 3 parts of glycidol is added, the introduction of nitrogen is stopped, stirring is performed for 5h at 40 ℃, stirring is performed for 8h at 50 ℃, the reaction is stopped, centrifugation is performed after the reaction is finished, deionized water is used for dispersion, and drying is performed after repeating for 5 times, so that the attapulgite composite material rich in ortho-position hydroxyl groups is obtained.
The attapulgite composite material rich in the ortho-hydroxyl groups, which is prepared by the method, is used as a boron adsorbent for removing or extracting boron in industrial wastewater, has excellent adsorption effect, and has excellent adsorption effect on HBO under the conditions of pH of 3 and temperature of 25 DEG C 2 The adsorption capacity of the catalyst can reach 156mg/g.
Example five
(1) Preparation of epoxy silanized attapulgite
Preparation of acidified attapulgite: 10 parts of attapulgite is dispersed in 350 parts of hydrochloric acid solution with the concentration of 1.5mol/L, the mixture is refluxed for 1h at 90 ℃, centrifuged, washed with deionized water and repeated for 2 times, and the acidified attapulgite is obtained after drying.
10 parts of acidified attapulgite is dispersed by a certain amount of ethanol, 15 parts of 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane is added for reflux reaction for 12 hours at 70 ℃. Cooling, centrifuging, dispersing with a certain amount of ethanol, centrifuging, repeating for 5 times, and drying to obtain the epoxy silanized attapulgite.
(2) Preparation of aminated attapulgite
10 parts of epoxy silanized attapulgite is dispersed in 250mL of deionized water, nitrogen is introduced for 25min, 0.48 part of diethylenetriamine is added for reaction for 8h at 40 ℃, and the temperature is raised for reaction for 8h at 60 ℃. Dispersing with deionized water after the reaction, centrifuging, repeating for 3 times, and drying to obtain the aminated attapulgite.
(3) Preparation of attapulgite composite material rich in ortho-hydroxyl
10 parts of aminated attapulgite is weighed and dispersed in 350mL of deionized water, nitrogen is introduced for 30min, then 1.8 parts of glycidol is added, the introduction of nitrogen is stopped, stirring is performed for 10h at 20 ℃, stirring is performed for 2h at 80 ℃, the reaction is stopped, centrifugation and deionized water dispersion are performed after the reaction is finished, and drying is performed after repeating for 3 times, so that the attapulgite composite material rich in ortho-position hydroxyl groups is obtained.
The attapulgite composite material rich in the ortho-hydroxyl groups prepared by the method is used as a boron adsorbent for removing or extracting boron in geothermal water, has excellent adsorption effect, and has excellent adsorption effect on HBO under the conditions of pH of 8.1 and temperature of 60 DEG C 2 The adsorption capacity of the catalyst can reach 176mg/g.
Example six
(1) Preparation of epoxy silanized attapulgite
Preparation of acidified attapulgite: 10 parts of attapulgite is dispersed in 600 parts of hydrochloric acid solution with the concentration of 3mol/L, refluxed for 3 hours at 70 ℃, centrifuged, washed with deionized water, repeated for 5 times, and dried to obtain the acidified attapulgite.
10 parts of acidified attapulgite is dispersed by a certain amount of ethanol, 10 parts of triethoxy (3-epoxypropyloxypropyl) silane is added, and reflux reaction is carried out for 10 hours at 80 ℃. Cooling, centrifuging, dispersing with a certain amount of ethanol, centrifuging, repeating for 3 times, and drying to obtain the epoxy silanized attapulgite.
(2) Preparation of aminated attapulgite
10 parts of epoxy silanized attapulgite is dispersed in 350mL of deionized water, nitrogen is introduced for 35min, 0.88 parts of polyethyleneimine (Mn=1200) is added, the reaction is carried out for 6h at 60 ℃, and the temperature is raised for 65 ℃ for 6h. Dispersing with deionized water after the reaction, centrifuging, repeating for 2 times, and drying to obtain the aminated attapulgite.
(3) Preparation of attapulgite composite material rich in ortho-hydroxyl
10 parts of aminated attapulgite is weighed and dispersed in 300mL of deionized water, nitrogen is introduced for 30min, then 1.52 parts of glycidol is added, the introduction of nitrogen is stopped, stirring is performed for 8h at 30 ℃, stirring is performed for 4h at 75 ℃ after heating, the reaction is stopped, centrifugation and deionized water dispersion are performed after the reaction is finished, and drying is performed after repeating for 4 times, so that the attapulgite composite material rich in ortho-position hydroxyl groups is obtained.
The attapulgite composite material rich in the ortho-hydroxyl groups, which is prepared by the method, is used as a boron adsorbent for removing or extracting boron in salt lake brine, has excellent adsorption effect, and has excellent adsorption effect on HBO under the conditions of pH of 9.2 and temperature of 30 DEG C 2 The adsorption capacity of (C) can reach 163mg/g.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (1)

1. The application of the attapulgite composite material rich in the ortho-hydroxyl groups in removing or extracting boron in drinking water, irrigation water, geothermal water, salt lake brine and industrial wastewater is characterized in that the attapulgite composite material rich in the ortho-hydroxyl groups is prepared by the following steps:
(1) Preparation of epoxy silanized attapulgite
Preparation of acidified attapulgite: dispersing 10 parts of attapulgite in 350 parts of hydrochloric acid solution with the concentration of 1.5mol/L, refluxing for 1h at 90 ℃, centrifuging, washing with deionized water, repeating for 2 times, and drying to obtain acidified attapulgite;
dispersing 10 parts of acidified attapulgite with a certain amount of ethanol, adding 15 parts of 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane, carrying out reflux reaction for 12 hours at 70 ℃, cooling, centrifuging, dispersing with ethanol, centrifuging, repeating for 5 times, and drying to obtain the epoxy silanized attapulgite;
(2) Preparation of aminated attapulgite
Dispersing 10 parts of epoxy silanized attapulgite in 250mL of deionized water, introducing nitrogen for 25min, adding 0.48 part of diethylenetriamine, reacting for 8h at 40 ℃, heating to 60 ℃, reacting for 8h, dispersing with deionized water after the reaction is finished, centrifuging, repeating for 3 times, and drying to obtain the aminated attapulgite;
(3) Preparation of attapulgite composite material rich in ortho-hydroxyl
10 parts of aminated attapulgite is weighed and dispersed in 350mL of deionized water, nitrogen is introduced for 30min, then 1.8 parts of glycidol is added, the introduction of nitrogen is stopped, stirring is performed for 10h at 20 ℃, stirring is performed for 2h at 80 ℃, the reaction is stopped, centrifugation and deionized water dispersion are performed after the reaction is finished, and drying is performed after repeating for 3 times, so that the attapulgite composite material rich in ortho-position hydroxyl groups is obtained.
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