CN113184867B - Method for preparing magnetic super-hydrophobic clay mineral composite material and application - Google Patents

Method for preparing magnetic super-hydrophobic clay mineral composite material and application Download PDF

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CN113184867B
CN113184867B CN202110467558.0A CN202110467558A CN113184867B CN 113184867 B CN113184867 B CN 113184867B CN 202110467558 A CN202110467558 A CN 202110467558A CN 113184867 B CN113184867 B CN 113184867B
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clay mineral
composite material
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hydrophobic
ferric
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CN113184867A (en
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王彦斌
庞少峰
李一京
李吉海
田雨
苏琼
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Northwest Minzu University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/40—Clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—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
    • B01J20/28009—Magnetic 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
    • 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
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds

Abstract

The invention relates to the technical field of clay mineral modification, and discloses a simple method for preparing a magnetic super-hydrophobic clay mineral composite material by taking a clay mineral as a framework and application of the magnetic super-hydrophobic clay mineral composite material. The clay mineral with hydroxyl functional groups is used as a raw material, the magnetic functionalized clay mineral is prepared by an in-situ magnetic doping method, and then the magnetic clay mineral is wrapped by a mercaptosilane polymer, so that the obtained magnetic super-hydrophobic clay mineral solves the problem that magnetic particles of a magnetic composite material are lost in the using and recycling processes for the first time, the adsorption effect of the clay mineral on organic molecules in water is improved through modification, the hydrophobicity of the clay mineral is enhanced, and the clay mineral can be used for oil-water separation. The invention has the advantages of low cost of raw materials, convenient operation, low requirement on conditions, multifunction of the clay mineral composite material and the like.

Description

Method for preparing magnetic super-hydrophobic clay mineral composite material and application
Technical Field
The invention relates to the field of clay mineral modification, in particular to a preparation method of a magnetic super-hydrophobic clay mineral composite material; also relates to the application of the magnetic super-hydrophobic clay mineral composite material.
Background
The organic synthesis industry is rapidly developed, which causes the emission of a large amount of organic wastewater, thereby causing the aggravation of environmental pollution. In order to purify industrial wastewater of organic pollutants, the composite material with low preparation cost, high removal rate and high practicability is particularly important.
The clay mineral composite material with magnetic separation performance is the first choice material for sewage treatment due to good recyclability,usually Fe 2+ And Fe 3+ Preparation of Fe by coprecipitation 3 O 4 The nano particles are covered on the surface structure of the clay mineral. Although the prepared materials have the advantages of the magnetic clay mineral composite materials, they have limitations in that the magnetic particles in the materials have a large size and the magnetic separation ability is gradually reduced due to the loss of the magnetic particles during the recovery process. Therefore, it is necessary to prepare a highly recycled magnetic clay mineral composite material, which can avoid the loss of magnetic particles in the separation process in the real sense.
Disclosure of Invention
In the process of preparing the magnetic super-hydrophobic clay mineral composite material, the invention aims to solve the technical problems of avoiding the loss of magnetic particles in the separation process, improving the treatment effect of the clay mineral on organic pollutants and reducing the overall cost in the reaction process. The invention provides a preparation method of a magnetic super-hydrophobic clay mineral composite material, which has the advantages of low cost, mild reaction conditions, simple preparation process, low equipment requirement and the like.
In order to solve the technical problem, the invention adopts the following technical scheme:
the preparation method of the magnetic super-hydrophobic clay mineral composite material comprises the steps of taking clay minerals, iron (III) compounds and mercaptosilane coupling agents as raw materials, carrying out in-situ magnetic doping on the raw materials under a hydrogen condition, and modifying the magnetic functionalized clay minerals by using the mercaptosilane coupling agents to prepare the magnetic clay mineral composite material with super-strong hydrophobicity.
Preferably, the method comprises the following steps,
a: and (3) calcining the clay mineral in a muffle furnace, cooling to room temperature, dispersing the clay mineral in an iron (III) compound solution, and adsorbing at room temperature until the clay mineral is saturated. The suspension was centrifuged and the supernatant removed and placed in an oven for drying.
B: the sample adsorbed with iron (iii) was ground into powder with a mortar and reduced at a reduction temperature of 300-400 ℃ under a hydrogen atmosphere.
C: soaking the clay mineral with magnetic functionalization in 0.5mol/L hydrochloric acid water solution for 1h, and washing to be neutral. Then, an ethanol/hydrochloric acid solution with PH =3 was added, and the resulting suspension was transferred to a hydrothermal kettle, subjected to hydrothermal reaction at 120 ℃ for 24 hours, and then taken out. The precipitate was separated with a magnet, washed and dried.
D: after drying, the mixture was placed in a reaction flask, a methanol/deionized water mixture at a volume ratio of 2. And after the reaction, separating the solid by using a magnet, washing to be neutral, and drying in vacuum to obtain the magnetic super-hydrophobic clay mineral composite material.
Preferably, the clay mineral is one or more of attapulgite, bentonite, kaolinite, illite, activated clay and sepiolite clay.
Preferably, the clay mineral is roasted in a muffle furnace at the temperature of 150-250 ℃ for 1-3h.
Preferably, the iron (III) -containing compound is one or more of ferric nitrate, ferric chloride, ferric sulfate, ferric bromide and ferric perchlorate.
Preferably, the amount of ferric ionic species in the solution of iron (III) compound is 0.10 to 0.12mol.
Preferably, in step B, the reduction is carried out at a reduction temperature of 360 ℃ in a hydrogen atmosphere.
Preferably, the mercaptosilane coupling agent is one or more of mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane and mercaptopropylmethyldimethoxysilane.
Preferably, 1-2mg of clay mineral is contained in 1ml of methanol/deionized water mixed solution of the mercaptosilane coupling agent; the amount of mercaptosilane coupling agent species is from 0.25 to 3mmol.
The application of the magnetic super-hydrophobic clay mineral composite material takes the magnetic super-hydrophobic clay mineral composite material as a raw material and can be used for adsorption of organic molecules; the preparation method comprises the following steps of (1) taking a magnetic super-hydrophobic clay mineral composite material as a raw material, and preparing a super-hydrophobic coating by using a silicone resin curing agent; the magnetic super-hydrophobic clay mineral composite material is used as a raw material for oil-water separation.
According to the invention, the clay mineral with hydroxyl functional groups is used as a raw material, firstly, the magnetic functionalized clay mineral is prepared by an in-situ magnetic doping method, and then, the magnetic clay mineral is wrapped by a mercaptosilane polymer, so that the obtained magnetic super-hydrophobic clay mineral firstly solves the problem of magnetic particle loss in the using and recycling processes of the magnetic composite material, and simultaneously, the adsorption effect of the clay mineral on organic molecules in water is improved through modification, the hydrophobicity of the clay mineral is enhanced, and the clay mineral can also be used for oil-water separation. The invention has the advantages of low cost of raw materials, convenient operation, low requirement on conditions, multiple functions and the like.
Compared with the existing preparation method of the magnetic super-hydrophobic clay mineral composite material, the preparation method has the beneficial effects that:
(1) The raw materials for preparing the composite material are cheap and easily available, and the cost of the whole preparation process is low.
(2) The clay mineral is used as a framework, and the method of in-situ magnetic doping and mercaptosilane polymer coating is adopted, so that the problem of magnetic particle loss in the using and recycling processes of the magnetic composite material is solved for the first time.
(3) The composite material can be used for adsorbing organic molecules in water, and can also be used for preparing a super-hydrophobic coating and separating oil from water.
(4) Can be repeatedly used for a plurality of times, and has certain economic benefit.
(5) The composite material has practical application value in the field of organic wastewater treatment.
Drawings
FIG. 1 is a schematic diagram of the preparation of the magnetic super-hydrophobic clay mineral composite according to the present invention;
fig. 2 is an application schematic diagram of the magnetic super-hydrophobic clay mineral composite material.
Detailed Description
The present invention will be described in further detail with reference to examples.
1. The method for preparing the magnetic super-hydrophobic clay mineral composite material is characterized by comprising the following steps: the magnetic super-hydrophobic clay mineral composite material is synthesized by taking clay minerals, iron (III) containing compounds and mercapto silane coupling agents as raw materials through in-situ reduction and in-situ cross-linking polymerization of the silane coupling agents.
2. The method of claim 1, wherein the method comprises the following steps: the method comprises the steps of firstly adsorbing ferric ions by the pretreated clay mineral, and then reducing the pretreated clay mineral in a hydrogen atmosphere.
3. The method for preparing a magnetic superhydrophobic clay mineral composite material according to claim 2, wherein the amount of ferric iron ion substance in the iron (iii) compound solution is 0.10-0.12mol; the reduction was carried out at a reduction temperature of 360 ℃ in a hydrogen atmosphere.
4. The method of claim 1, wherein the method comprises the following steps: the mercapto silane coupling agent is used for modifying the magnetic functionalized clay mineral, and the magnetic super-hydrophobic clay mineral composite material is obtained by an in-situ cross-linking polymerization method.
5. The method of claim 4, wherein the method comprises the following steps: 1-2mg of clay mineral is contained in 1ml of methanol/deionized water mixed solution of the mercaptosilane coupling agent; the amount of mercaptosilane coupling agent species is from 0.25 to 3mmol.
6. The method of claim 1, wherein the method comprises the following steps: the clay mineral is one or more of attapulgite, bentonite, kaolin, illite, activated clay and sepiolite clay; the iron (III) -containing compound is one or more of ferric nitrate, ferric chloride, ferric sulfate, ferric bromide and ferric perchlorate; the mercapto silane coupling agent is one or more of mercaptopropyl trimethoxysilane, mercaptopropyl triethoxysilane and mercaptopropyl methyldimethoxysilane.
7. The method of claim 1, wherein the method comprises the following steps: the pretreatment of the clay mineral is to roast in a muffle furnace at the roasting temperature of 150-250 ℃ for 1-3 hours;
8. use of a magnetic superhydrophobic clay-mineral composite material obtained by the method of any one of claims 1-7, characterized in that: the magnetic super-hydrophobic clay mineral composite material can be used for adsorbing organic molecules; can be used for preparing super-hydrophobic coatings; can be used for oil-water separation.
Example 1
The clay mineral is attapulgite, the iron (III) compound is ferric nitrate, and the mercapto silane coupling agent is mercaptopropyl trimethoxysilane. Modifying the clay mineral by hydrogen in-situ reduction and silane coupling agent in-situ cross-linking polymerization to obtain the magnetic super-hydrophobic clay mineral composite material. The method comprises the following steps:
a: putting the clay mineral into a muffle furnace, calcining for 2h at the temperature of 200 ℃, cooling to room temperature, dispersing the clay mineral into an iron (III) compound solution with the amount of ferric ion substances of 0.10mol, and adsorbing to saturation at the room temperature. The suspension was centrifuged and the precipitate was dried in an oven.
B: the iron (iii) adsorbed sample was ground into powder with a mortar and reduced by a reduction temperature of 360 ℃ under a hydrogen atmosphere.
C: soaking the magnetic clay mineral in 0.5mol/L hydrochloric acid water solution for 1h, and washing to neutrality. Then, an ethanol/hydrochloric acid solution having PH =3 was added, and the resulting suspension was transferred to a hydrothermal kettle, subjected to hydrothermal reaction at a temperature of 120 ℃ for 24 hours, and then taken out. The precipitate was separated with a magnet, washed and dried.
D: after drying, the mixture was placed in a reaction flask, a methanol/deionized water mixed solution having a volume ratio of 2. After the reaction, the solid was separated with a magnet and washed to neutrality. And (5) drying in vacuum to obtain the magnetic super-hydrophobic clay mineral composite material.
Then, the composite material is subjected to an adsorption performance test, and the result shows that: the highest adsorption rate of the paranitrobenzene reaches 96.97 percent; the composite material is subjected to hydrophobic property test and water connectionThe feeler angle reaches 161 degrees, and the sliding angle is 2 degrees; in CH 2 Cl 2 In the water system mixture system, the oil-water separation efficiency reaches 99.4 percent.
Example 2
The clay mineral is sepiolite clay, the iron (III) -containing compound is ferric chloride, and the mercapto silane coupling agent is mercaptopropyl trimethoxy silane. Modifying the clay mineral by a high-temperature in-situ reduction method and a silane coupling agent in-situ cross-linking polymerization method to obtain the magnetic super-hydrophobic clay mineral composite material. The method comprises the following steps:
a: placing clay mineral in a muffle furnace, roasting at 150 ℃ for 3h, cooling to room temperature, dispersing the clay mineral in an iron (III) compound solution with the amount of ferric ion substances of 0.10mol, and adsorbing at room temperature until the clay mineral is saturated. The suspension was then centrifuged and placed in an oven to dry.
B: the dried sample was pulverized into powder with a mortar and reduced at 360 ℃ in a hydrogen atmosphere.
C: soaking the magnetic clay mineral in 0.5mol/L hydrochloric acid aqueous solution for 1h, and washing with water to neutrality. Then, an ethanol/hydrochloric acid solution with PH =3 was added, and the resulting suspension was transferred to a hydrothermal kettle, and the temperature was adjusted to 120 ℃, and the hydrothermal reaction was carried out for 24 hours. The precipitate was separated with a magnet, washed and dried.
D: after drying, the mixture was placed in a reaction flask, a methanol/deionized water mixed solution in a volume ratio of 2. After the reaction, the solid was separated with a magnet and washed to neutrality. And (5) drying in vacuum to obtain the magnetic super-hydrophobic clay mineral composite material.
The composite material is subjected to an adsorption performance test, and the result shows that: the highest adsorption rate of the paranitrobenzene reaches 95.42 percent; the composite material is subjected to hydrophobic property test, the water contact angle reaches 157 degrees, and the sliding angle is 3 degrees; in CH 2 Cl 2 In the water system mixture system, the oil-water separation efficiency reaches 99.1 percent.
Example 3
The clay mineral is kaolin, the iron (III) containing compound is ferric sulfate, and the mercapto silane coupling agent is mercaptopropyl triethoxysilane. Modifying the clay mineral by a high-temperature in-situ reduction method and a silane coupling agent in-situ cross-linking polymerization method to obtain the magnetic super-hydrophobic clay mineral composite material. The method comprises the following steps:
a: placing clay mineral in a muffle furnace, roasting at 180 ℃ for 2h, cooling to room temperature, dispersing the clay mineral into an iron (III) compound solution with the amount of ferric ion substances of 0.12mol, and adsorbing at room temperature until the clay mineral is saturated. The suspension was then centrifuged and placed in an oven to dry.
B: the dried sample was ground into powder in a mortar and reduced at 360 ℃ in a hydrogen atmosphere.
C: soaking the clay mineral with magnetism in 0.5mol/L hydrochloric acid water solution for 1h, and washing with water to neutrality. Then, an ethanol/hydrochloric acid solution with pH =3 was added, and the obtained suspension was transferred to a hydrothermal kettle and subjected to hydrothermal reaction at 120 ℃ for 24 hours, and then taken out. The precipitate was separated with a magnet, washed and dried.
D: after drying, the mixture was placed in a reaction flask, a methanol/deionized water mixed solution in a volume ratio of 2. After the reaction, the solid was separated with a magnet and washed to neutrality. And (5) drying in vacuum to obtain the magnetic super-hydrophobic clay mineral composite material.
The composite material is subjected to an adsorption performance test, and the result shows that: the highest adsorption rate of the paranitrobenzene reaches 95.73 percent; performing hydrophobic property test on the composite material, wherein the water contact angle reaches 158 degrees, and the sliding angle is 3 degrees; in CH 2 Cl 2 In the water system mixture system, the oil-water separation efficiency reaches 99.1 percent.
Example 4
The clay mineral is activated clay, the iron (III) compound is ferric bromide, and the mercapto silane coupling agent is mercaptopropyl trimethoxy silane. Modifying the clay mineral by a high-temperature in-situ reduction method and a silane coupling agent in-situ cross-linking polymerization method to obtain the magnetic super-hydrophobic clay mineral composite material. The method comprises the following steps:
a: placing clay mineral in a muffle furnace, roasting at 220 deg.C for 2h, cooling to room temperature, dispersing into 0.10mol ferric ion substance of iron (III) compound solution, and adsorbing at room temperature to saturation. The suspension was then centrifuged and placed in an oven to dry.
B: the dried sample was pulverized into powder with a mortar and reduced at 360 ℃ in a hydrogen atmosphere.
C: soaking the clay mineral with magnetism in 0.5mol/L hydrochloric acid water solution for 1h, and washing with water to neutrality. Then adding an ethanol/hydrochloric acid solution with the pH =3, transferring the obtained suspension into a hydrothermal kettle, controlling the temperature at 120 ℃, and taking out after 24 hours of hydrothermal reaction. The precipitate was separated with a magnet, washed and dried.
D: after drying, the mixture was placed in a reaction flask, a methanol/deionized water mixed solution in a volume ratio of 2. After the reaction, the solid was separated with a magnet and washed to neutrality. And (5) drying in vacuum to obtain the magnetic super-hydrophobic clay mineral composite material.
The composite material is subjected to an adsorption performance test, and the result shows that: the highest adsorption rate of the p-nitrobenzene reaches 96.36 percent; the hydrophobic performance test is carried out on the composite material, the water contact angle reaches 160 degrees, and the sliding angle is 3 degrees; in CH 2 Cl 2 In the water system mixture system, the oil-water separation efficiency reaches 99.3 percent.
Example 5
The clay mineral is illite, the iron (III) containing compound is ferric chloride, and the mercapto silane coupling agent is mercaptopropyl methyldimethoxysilane. Modifying the clay mineral by a high-temperature in-situ reduction method and a silane coupling agent in-situ cross-linking polymerization method to obtain the magnetic super-hydrophobic clay mineral composite material. The method comprises the following steps:
a: placing clay mineral in a muffle furnace, roasting at 200 ℃ for 2.5h, cooling to room temperature, dispersing the clay mineral into an iron (III) compound solution with the amount of ferric ion substances of 0.12mol, and adsorbing at room temperature until the clay mineral is saturated. The suspension was then centrifuged and placed in an oven to dry.
B: the dried sample was pulverized into powder with a mortar and reduced at 360 ℃ in a hydrogen atmosphere.
C: soaking the clay mineral with magnetism in 0.5mol/L hydrochloric acid water solution for 1h, and washing with water to neutrality. Then, an ethanol/hydrochloric acid solution with pH =3 is added, the obtained suspension is transferred to a hydrothermal kettle, and the hydrothermal reaction is carried out for 24 hours at 120 ℃ and then the suspension is taken out. The precipitate was separated with a magnet, washed and dried.
D: after drying, the mixture was placed in a reaction flask, a methanol/deionized water mixed solution at a volume ratio of 2. After the reaction, the solid was separated with a magnet and washed to neutrality. And (5) drying in vacuum to obtain the magnetic super-hydrophobic clay mineral composite material.
The composite material is subjected to an adsorption performance test, and the result shows that: the highest adsorption rate of the paranitrobenzene reaches 95.71 percent; the hydrophobic performance test is carried out on the composite material, the water contact angle reaches 158 degrees, and the sliding angle is 3 degrees; in CH 2 Cl 2 In a water system mixture system, the oil-water separation efficiency reaches 99.2 percent.
Example 6
The clay mineral is bentonite, the iron (III) containing compound is ferric nitrate, and the mercapto silane coupling agent is mercaptopropyl methyldimethoxysilane. Modifying the clay mineral by a high-temperature in-situ reduction method and a silane coupling agent in-situ cross-linking polymerization method to obtain the magnetic super-hydrophobic clay mineral composite material. The method comprises the following steps:
a: placing clay mineral in a muffle furnace, roasting at 250 ℃ for 1.5h, cooling to room temperature, dispersing into 0.10mol of iron (III) compound solution containing ferric ion substances, and adsorbing at room temperature to saturation. The suspension was then centrifuged and placed in an oven to dry.
B: the dried sample was pulverized into powder with a mortar and reduced at 360 ℃ in a hydrogen atmosphere.
C: soaking the magnetic clay mineral in 0.5mol/L hydrochloric acid aqueous solution for 1h, and washing with water to neutrality. Then, an ethanol/hydrochloric acid solution with pH =3 was added, the obtained suspension was transferred to a hydrothermal kettle, and hydrothermal reaction was carried out at 120 ℃ for 24 hours and then taken out. The precipitate was separated with a magnet, washed and dried.
D: after drying, the mixture was placed in a reaction flask, a methanol/deionized water mixed solution at a volume ratio of 2. After the reaction, the solid was separated with a magnet and washed to neutrality. And (5) drying in vacuum to obtain the magnetic super-hydrophobic clay mineral composite material.
The composite material is subjected to an adsorption performance test, and the result shows that: the highest adsorption rate of the p-nitrobenzene reaches 96.42 percent; the composite material is subjected to hydrophobic property test, the water contact angle reaches 160 degrees, and the sliding angle is 2 degrees; in CH 2 Cl 2 In a water system mixture system, the oil-water separation efficiency reaches 99.4 percent.
Example 7
The clay mineral is bentonite, the iron (III) compound is ferric perchlorate, and the mercapto silane coupling agent is a mixture of mercaptopropyl trimethoxy silane and mercaptopropyl triethoxy silane. Modifying the clay mineral by a high-temperature in-situ reduction method and a silane coupling agent in-situ cross-linking polymerization method to obtain the magnetic super-hydrophobic clay mineral composite material. The method comprises the following steps:
a: placing clay mineral in a muffle furnace, roasting at 200 ℃ for 2h, cooling to room temperature, dispersing into 0.12mol of iron (III) compound solution of ferric ion substances, and adsorbing at room temperature to saturation. The suspension was then centrifuged and placed in an oven to dry.
B: the dried sample was pulverized into powder with a mortar and reduced at 360 ℃ in a hydrogen atmosphere.
C: soaking the magnetic clay mineral in 0.5mol/L hydrochloric acid aqueous solution for 1h, and washing with water to neutrality. Then, an ethanol/hydrochloric acid solution with pH =3 was added, and the obtained suspension was transferred to a hydrothermal kettle and subjected to hydrothermal reaction at 120 ℃ for 24 hours, and then taken out. The precipitate was separated with a magnet, washed and dried.
D: after drying, the mixture was placed in a reaction flask, a methanol/deionized water mixed solution in a volume ratio of 2. After the reaction, the solid was separated with a magnet and washed to neutrality. And (5) drying in vacuum to obtain the magnetic super-hydrophobic clay mineral composite material.
The composite material is subjected to an adsorption performance test, and the result shows that: the highest adsorption rate of the paranitrobenzene reaches 96.22 percent; the hydrophobic performance test is carried out on the composite material, the water contact angle reaches 159 degrees, and the sliding angle is 3 degrees; in CH 2 Cl 2 In the water system mixture system, the oil-water separation efficiency reaches 99.3 percent.
Example 8
The clay mineral is attapulgite, the iron (III) compound is ferric perchlorate, and the mercapto silane coupling agent is mercaptopropyl methyldimethoxysilane. Modifying the clay mineral by a high-temperature in-situ reduction method and a silane coupling agent in-situ cross-linking polymerization method to obtain the magnetic super-hydrophobic clay mineral composite material. The method comprises the following steps:
a: placing clay mineral in a muffle furnace, roasting at 200 ℃ for 2h, cooling to room temperature, dispersing the clay mineral into an iron (III) compound solution with the amount of ferric ion substances of 0.12mol, and adsorbing at room temperature until the clay mineral is saturated. The suspension was then centrifuged and placed in an oven to dry.
B: the dried sample was ground into powder in a mortar and reduced at 360 ℃ in a hydrogen atmosphere.
C: soaking the magnetic clay mineral in 0.5mol/L hydrochloric acid aqueous solution for 1h, and washing with water to neutrality. Then, an ethanol/hydrochloric acid solution with pH =3 was added, and the obtained suspension was transferred to a hydrothermal kettle and subjected to hydrothermal reaction at 120 ℃ for 24 hours, and then taken out. The precipitate was separated with a magnet, washed and dried.
D: after drying, the mixture was placed in a reaction flask, a methanol/deionized water mixed solution having a volume ratio of 2. After the reaction, the solid was separated with a magnet and washed to neutrality. And (5) drying in vacuum to obtain the magnetic super-hydrophobic clay mineral composite material.
The composite material is subjected to an adsorption performance test, and the result shows that: the highest adsorption rate of the paranitrobenzene reaches 95.52 percent; the composite material is subjected to hydrophobic property test, the water contact angle reaches 157 degrees, and the sliding angle is 4 degrees; in CH 2 Cl 2 In the water system mixture system, the oil-water separation efficiency reaches 99.2 percent.
Example 9
The clay mineral is a mixture of attapulgite, bentonite, kaolinite, illite, activated clay and sepiolite clay, the iron (III) containing compound is ferric nitrate, and the mercaptosilane coupling agent is a mixture of mercaptopropyl trimethoxysilane and mercaptopropyl triethoxysilane. Modifying the clay mineral by a high-temperature in-situ reduction method and a silane coupling agent in-situ cross-linking polymerization method to obtain the magnetic super-hydrophobic clay mineral composite material. The method comprises the following steps:
a: placing clay mineral in a muffle furnace, roasting at 250 ℃ for 3h, cooling to room temperature, dispersing the clay mineral in an iron (III) compound solution with the amount of ferric ion substances of 0.10mol, and adsorbing at room temperature until the clay mineral is saturated. The suspension was then centrifuged and placed in an oven to dry.
B: the dried sample was pulverized into powder with a mortar and reduced at 360 ℃ in a hydrogen atmosphere.
C: soaking the clay mineral with magnetism in 0.5mol/L hydrochloric acid water solution for 1h, and washing with water to neutrality. Then, an ethanol/hydrochloric acid solution having PH =3 was added, and the resulting suspension was transferred to a hydrothermal kettle, subjected to hydrothermal reaction at 120 ℃ for 24 hours, and then taken out. The precipitate was separated with a magnet, washed and dried.
D: after drying, the mixture was placed in a reaction flask, a methanol/deionized water mixed solution having a volume ratio of 2. After the reaction, the solid was separated with a magnet and washed to neutrality. And (5) drying in vacuum to obtain the magnetic super-hydrophobic clay mineral composite material.
The composite material is subjected to an adsorption performance test, and the result shows that: the highest adsorption rate of the paranitrobenzene reaches 96.14 percent; performing hydrophobic property test on the composite material, wherein the water contact angle reaches 158 degrees, and the sliding angle is 4 degrees; in CH 2 Cl 2 In the water system mixture system, the oil-water separation efficiency reaches 99.3 percent.
Example 10
The clay mineral is sepiolite clay, the iron (III) -containing compound is a mixture of ferric nitrate, ferric chloride, ferric sulfate, ferric bromide and ferric perchlorate, and the mercapto silane coupling agent is mercaptopropyl triethoxysilane. Modifying the clay mineral by a high-temperature in-situ reduction method and a silane coupling agent in-situ cross-linking polymerization method to obtain the magnetic super-hydrophobic clay mineral composite material.
The method comprises the following steps:
a: placing clay mineral in a muffle furnace, roasting at 160 ℃ for 2.5h, cooling to room temperature, dispersing the clay mineral into an iron (III) compound solution with the amount of ferric ion substances of 0.10mol, and adsorbing at room temperature until the clay mineral is saturated. The suspension was then centrifuged and placed in an oven to dry.
B: the dried sample was ground into powder in a mortar and reduced at 360 ℃ in a hydrogen atmosphere.
C: soaking the magnetic clay mineral in 0.5mol/L hydrochloric acid aqueous solution for 1h, and washing with water to neutrality. Then, an ethanol/hydrochloric acid solution with pH =3 was added, and the resulting suspension was transferred to a hydrothermal kettle and subjected to hydrothermal reaction at 120 ℃ for 24 hours, and then taken out. The precipitate was separated with a magnet, washed and dried.
D: after drying, the mixture was placed in a reaction flask, a methanol/deionized water mixed solution having a volume ratio of 2. After the reaction, the solid was separated with a magnet and washed to neutrality. And (5) drying in vacuum to obtain the magnetic super-hydrophobic clay mineral composite material.
The composite material is subjected to an adsorption performance test, and the result shows that: the highest adsorption rate of the paranitrobenzene reaches 96.34 percent; the hydrophobic performance test is carried out on the composite material, the water contact angle reaches 160 degrees, and the sliding angle is 3 degrees; in CH 2 Cl 2 In a water system mixture system, the oil-water separation efficiency reaches 99.4 percent.
Example 11
The clay mineral is bentonite, the iron (III) compound is ferric sulfate, and the mercapto silane coupling agent is a mixture of mercaptopropyl trimethoxy silane, mercaptopropyl triethoxy silane and mercaptopropyl methyl dimethoxy silane. Modifying the clay mineral by a high-temperature in-situ reduction method and a silane coupling agent in-situ cross-linking polymerization method to obtain the magnetic super-hydrophobic clay mineral composite material. The method comprises the following steps:
a: placing clay mineral in a muffle furnace, roasting at 250 ℃ for 1.5h, cooling to room temperature, dispersing into 0.10mol of iron (III) compound solution containing ferric ion substances, and adsorbing at room temperature to saturation. The suspension was then centrifuged and placed in an oven to dry.
B: the dried sample was pulverized into powder with a mortar and reduced at 360 ℃ in a hydrogen atmosphere.
C: soaking the magnetic clay mineral in 0.5mol/L hydrochloric acid aqueous solution for 1h, and washing with water to neutrality. Then, an ethanol/hydrochloric acid solution with pH =3 was added, and the obtained suspension was transferred to a hydrothermal kettle and subjected to hydrothermal reaction at 120 ℃ for 24 hours, and then taken out. The precipitate was separated with a magnet, washed and dried.
D: after drying, the mixture was placed in a reaction flask, a methanol/deionized water mixed solution in a volume ratio of 2. After the reaction, the solid was separated with a magnet and washed to neutrality. And (5) drying in vacuum to obtain the magnetic super-hydrophobic clay mineral composite material.
The composite material is subjected to an adsorption performance test, and the result shows that: the highest adsorption rate of the paranitrobenzene reaches 95.67 percent; the hydrophobic performance test is carried out on the composite material, the water contact angle reaches 156 degrees, and the sliding angle is 4 degrees; in CH 2 Cl 2 In the water system mixture system, the oil-water separation efficiency reaches 99.2 percent.
According to the invention, the clay mineral is used as a raw material, and is modified by a hydrogen in-situ reduction method and a silane coupling agent in-situ crosslinking polymerization method, so that the loss of magnetic particles is better prevented, and the clay mineral has high affinity to organic molecules in a water phase and has multiple functional applications. The magnetic super-hydrophobic clay mineral composite material obtained by the invention has stronger hydrophobicity and good magnetic responsiveness, and can be used for adsorption of nitrobenzene, preparation of super-hydrophobic coatings and oil-water separation application.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (4)

1. The method for preparing the magnetic super-hydrophobic clay mineral composite material is characterized by comprising the following steps: synthesizing a magnetic super-hydrophobic clay mineral composite material by taking clay mineral, an iron (III) compound and a mercapto-containing silane coupling agent as raw materials through an in-situ reduction and silane coupling agent in-situ cross-linking polymerization method;
carrying out in-situ reduction on the pretreated clay mineral to obtain a magnetic functionalized clay mineral, wherein the pretreated clay mineral firstly adsorbs ferric ions and then is reduced in a hydrogen atmosphere; wherein the amount of ferric ion substance in the iron (III) compound solution is 0.10-0.12mol; reducing at a reduction temperature of 360 ℃ in a hydrogen atmosphere;
modifying the magnetic functionalized clay mineral by using a mercapto silane coupling agent, and obtaining a magnetic super-hydrophobic clay mineral composite material by using an in-situ cross-linking polymerization method; wherein, 1-2mg of clay mineral is contained in 1ml of methanol/deionized water mixed solution of the mercaptosilane coupling agent; the amount of mercaptosilane coupling agent substance is 0.25-3mmol;
specifically, the method comprises the following steps:
step A: calcining clay mineral in a muffle furnace, cooling to room temperature, dispersing the clay mineral in an iron (III) compound solution, adsorbing at room temperature until the clay mineral is saturated, centrifuging the suspension, removing supernatant, and drying in an oven;
and B: grinding the sample adsorbing iron (III) into powder by using a mortar, and reducing at a reduction temperature of 360 ℃ in a hydrogen atmosphere;
and C: soaking the clay mineral with magnetic function in 0.5mol/L hydrochloric acid aqueous solution for 1h, washing to be neutral, then adding ethanol/hydrochloric acid solution with PH =3, transferring the obtained suspension into a hydrothermal kettle, carrying out hydrothermal reaction at 120 ℃ for 24h, then taking out, separating the precipitate by using a magnet, washing the precipitate and drying;
step D: and drying, then placing in a reaction flask, adding a methanol/deionized water mixed solution with the volume ratio of 2.
2. The method of claim 1, wherein the method comprises the following steps: the clay mineral is one or more of attapulgite, bentonite, kaolin, illite, activated clay and sepiolite clay; the iron (III) -containing compound is one or more of ferric nitrate, ferric chloride, ferric sulfate, ferric bromide and ferric perchlorate; the mercapto silane coupling agent is one or more of mercaptopropyl trimethoxysilane, mercaptopropyl triethoxysilane and mercaptopropyl methyldimethoxysilane.
3. The method of claim 1, wherein the method comprises the following steps: in the step A, the pretreatment of the clay mineral is to roast in a muffle furnace at the roasting temperature of 150-250 ℃ for 1-3 hours.
4. Use of a magnetic superhydrophobic clay-mineral composite material obtained by the method of any one of claims 1-3, characterized in that: the magnetic super-hydrophobic clay mineral composite material is used for adsorbing organic molecules; the method is used for preparing the super-hydrophobic coating; used for oil-water separation.
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