CN110898796A - Preparation method of magnetic layered double hydroxide, magnetic layered double hydroxide and application thereof - Google Patents

Preparation method of magnetic layered double hydroxide, magnetic layered double hydroxide and application thereof Download PDF

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CN110898796A
CN110898796A CN201911185036.0A CN201911185036A CN110898796A CN 110898796 A CN110898796 A CN 110898796A CN 201911185036 A CN201911185036 A CN 201911185036A CN 110898796 A CN110898796 A CN 110898796A
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layered double
double hydroxide
intercalated
magnetic
betaine
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管运涛
张立勋
毛伟
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Shenzhen International Graduate School of Tsinghua University
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Abstract

The invention provides a preparation method of a magnetic layered double hydroxide, the magnetic layered double hydroxide and application thereof. The betaine intercalated magnetic layered double hydroxide material has the advantages of abundant and easily-obtained synthetic raw materials, simple synthetic process, easy operation, conventional required equipment, low production cost, green and nontoxic adsorption material, and suitability for large-scale popularization and application; can realize the simultaneous removal of heavy metals in the form of anions and cations in a short time, and can reduce the water quality of surface water to be below the limit value, thereby showing great application potential in the aspect of heavy metal pollution of water bodies. Meanwhile, the magnetic material can realize high-efficiency recovery due to the magnetism, and has good practical application value in the treatment of heavy metal pollution of water bodies.

Description

Preparation method of magnetic layered double hydroxide, magnetic layered double hydroxide and application thereof
Technical Field
The invention relates to the technical field of layered double hydroxides, in particular to a preparation method of a magnetic layered double hydroxide, the magnetic layered double hydroxide and application thereof.
Background
With the progress of activities such as industrial production, automobile exhaust emission and the like, a large amount of heavy metals are discharged into water, and the ecological safety and the human health are seriously threatened. Heavy metals in water often have two forms of anions and cations, and the different electrical characteristics greatly increase the treatment difficulty of the actual water. Research and development of an adsorption material capable of adsorbing heavy metals in anion and cation forms simultaneously can quickly reduce the heavy metals in the water body to the state-related water quality limit value (such as that Cr (VI) is 0.05mg/L, and Cu limit value is 1mg/L), and is of great importance for guaranteeing ecological safety and human health.
The layered double hydroxide is an inorganic adsorption material with low cost, excellent performance, environmental friendliness and chemical stability, has certain adsorption capacity for heavy metals, has the defects of low adsorption rate, poor selectivity, difficulty in simultaneous adsorption of cationic and anionic heavy metals and the like, and is greatly limited in the actual use process. The betaine is a natural or artificially synthesized quaternary ammonium base, contains functional groups such as carboxyl, amino and the like, shows good chelating capacity for heavy metals, and can greatly improve the adsorption performance of the layered double hydroxide for the heavy metals if the betaine can be intercalated into the layered double hydroxide by virtue of a hydration reconstruction mode. In addition, the layered double hydroxide and the ferroferric oxide are compounded to have magnetic characteristics, so that the recovery of materials and the water purification reach the standard conveniently, and the practical applicability of the layered double hydroxide and the ferroferric oxide is improved.
At present, no study has been made on the intercalation of betaine into layered double hydroxides as an interlayer anion. The research screens and prepares a novel betaine intercalated magnetic layered double hydroxide functional material in a pyrolysis-hydration reconstruction mode, and the material is used for repairing and treating heavy metal polluted water bodies in anion and cation forms.
Disclosure of Invention
The invention provides a preparation method of a magnetic layered double hydroxide, the magnetic layered double hydroxide and application thereof, aiming at solving the existing problems.
In order to solve the above problems, the technical solution adopted by the present invention is as follows:
a preparation method of a magnetic layered double hydroxide is characterized in that the betaine intercalated layered double hydroxide is prepared by a pyrolysis-hydration reconstruction mode, and then the betaine intercalated layered double hydroxide is prepared by compounding with ferroferric oxide powder.
Preferably, the method comprises the following steps: s1: preparing carbonate intercalated layered double hydroxide; s2: pyrolyzing the layered double hydroxide to obtain a double metal oxide; s3: and adding the bimetal oxide into a solution containing betaine monomers to carry out hydration reconstruction in a nitrogen atmosphere, and adding ferroferric oxide powder after aging to obtain the betaine intercalated magnetic layered double hydroxide.
Preferably, the preparation of the carbonate intercalated layered double hydroxide comprises the steps of: s11: the divalent metal cation and the trivalent metal cation form a first mixed solution, and 1-2mol/L of NaOH and 1-1.5mol/L of Na2CO3The second mixed solution is added dropwise and simultaneously into deionized water with the pH value of 9.5-10.5, and stirring is continued for at least 1 hour, so that a third mixed solution is obtained, wherein the sum of the concentrations of the divalent metal cations and the trivalent metal cations in the first mixed solution is 1 mol/L; s12: aging the third mixed solution at 70-80 ℃ for 24 hours to obtain carbonate intercalated layered double hydroxide; s13: washing the layered double hydroxide of the carbonate intercalation with degassed deionized water, and centrifuging until the conductivity of the washing liquid is less than 1000 mus/cm; s14: and drying the centrifugally dehydrated carbonate intercalated layered double hydroxide at the temperature of 70-80 ℃ to constant weight, grinding and crushing the dried carbonate intercalated layered double hydroxide through a 0.149-0.45mm sieve to obtain the final carbonate intercalated layered double hydroxide.
Preferably, the divalent metal cation is Mg2+Or Ca2+(ii) a The trivalent metal cation is Al3+OrFe3 +。
Preferably, the concentration of the divalent metal cation is 3 to 5 times that of the trivalent metal cation.
Preferably, the carbonate intercalated layered double hydroxide is treated in a muffle furnace at 450-500 ℃ for 2-4 hours and cooled to obtain the double hydroxide.
Preferably, the process for obtaining betaine-intercalated magnetic layered double hydroxides comprises the steps of: s31: putting 0.5-1g of the bimetal oxide into a solution containing 50-100ml of 0.1-0.2mol/L betaine, uniformly stirring, and fully reacting for 2-3 days under the conditions of nitrogen atmosphere and 70-80 ℃ to obtain a first reaction solution; s32: adding 0.05-0.1g of ferroferric oxide powder into the first reaction solution, and uniformly stirring in a nitrogen atmosphere to obtain the magnetic layered double hydroxide; s33: washing and centrifuging the magnetic layered double hydroxide by using degassed deionized water and absolute ethyl alcohol in sequence; s34: drying the magnetic layered double hydroxide after centrifugal ethanol removal at 70-80 ℃ to constant weight, grinding and crushing, and sieving by a sieve of 0.149-0.45mm to obtain the betaine intercalated magnetic layered double hydroxide material.
The invention also provides a layered double hydroxide, which is the organic sulfur functional monomer intercalated layered double hydroxide taking the organic sulfur functional monomer containing sulfydryl as interlayer anions and prepared by adopting any one of the methods.
The invention further provides the application of the layered double hydroxide, which comprises the application of the layered double hydroxide according to claim 9 in the water body or soil pollution remediation treatment for simultaneously removing heavy metals in the form of anions and cations.
Preferably, the heavy metal in anionic and cationic forms comprises Cr2O7 2-And Cu2+。
The invention has the beneficial effects that: the betaine intercalated layered double hydroxide is prepared by a pyrolysis-hydration reconstruction mode and then compounded with ferroferric oxide to prepare the betaine intercalated magnetic layered double hydroxide. The method has the following advantages:
(1) the betaine intercalated magnetic layered double hydroxide material has the advantages of abundant and easily-obtained synthetic raw materials, simple synthetic process, easy operation, conventional required equipment, low production cost, green and nontoxic adsorption material and suitability for large-scale popularization and application.
(2) The betaine intercalated magnetic layered double hydroxide material can remove heavy metals in negative and positive ion forms in a short time, can be reduced to be below the water quality limit value of surface water, and shows great application potential in the aspect of heavy metal pollution of water bodies.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a magnetic layered double hydroxide in an embodiment of the present invention.
FIG. 2 shows an embodiment of the present invention
FIG. 3 shows an embodiment of the present invention
FIG. 4 is an XRD pattern of a betaine intercalated magnetic layered double hydroxide of the MgAl type.
FIG. 5 is an XRD pattern of a betaine intercalated magnetic layered double hydroxide of the MgFe type.
FIG. 6 is an XRD pattern of a CaAl type betaine intercalated magnetic layered double hydroxide.
FIG. 7(a) shows the MgAl type of betaine intercalated magnetic layered double hydroxide for Cr2O7 2-Kinetic results of adsorption are shown schematically.
FIG. 7(b) shows the MgAl type of betaine intercalated magnetic layered double hydroxide for Cr2O7 2-The kinetic results of adsorption are shown schematically in the enlarged view within 60 minutes.
FIG. 8(a) is a representation of a betaine intercalated magnetic layered double hydroxide of MgAl type vs. Cu2+Kinetic results of adsorption are shown schematically.
FIG. 8(b) shows the MgAl type of betaine intercalated magnetic layered double hydroxide for Cu2+The kinetic results of adsorption are shown schematically in the enlarged scale over 10 minutes.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the embodiments of the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It will be understood that when an element is referred to as being "secured to" or "disposed on" another element, it can be directly on the other element or be indirectly on the other element. When an element is referred to as being "connected to" another element, it can be directly connected to the other element or be indirectly connected to the other element. In addition, the connection may be for either a fixing function or a circuit connection function.
It is to be understood that the terms "length," "width," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in an orientation or positional relationship indicated in the drawings for convenience in describing the embodiments of the present invention and to simplify the description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed in a particular orientation, and be in any way limiting of the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the embodiments of the present invention, "a plurality" means two or more unless specifically limited otherwise.
Example 1
A preparation method of a magnetic layered double hydroxide is characterized in that the betaine intercalated layered double hydroxide is prepared by a pyrolysis-hydration reconstruction mode, and then the betaine intercalated layered double hydroxide is prepared by compounding with ferroferric oxide powder.
The invention aims to provide a betaine intercalated magnetic layered double hydroxide material by taking betaine as an interlayer anion to be inserted between layered double hydroxide layers in a pyrolysis-hydration reconstruction mode and compounding with ferroferric oxide. By means of the strong affinity of carboxyl and amino functional groups in betaine to heavy metals, anionic heavy metals (such as Cr) in water are realized2O7 2-) And heavy metals in cationic state (Cu)2+) In addition, the solid-liquid rapid separation can be realized by compounding with ferroferric oxide by means of magnetic characteristics, and the water body purification effect is efficiently achieved. The method disclosed by the invention shows huge application potential in the aspect of quickly and simultaneously removing heavy metals in the forms of anions and cations in the water body, and is significant for guaranteeing ecological safety and human health.
As shown in fig. 1, the preparation method of the magnetic layered double hydroxide of the present invention comprises the steps of:
s1: preparing carbonate intercalated layered double hydroxide;
s2: pyrolyzing the layered double hydroxide to obtain a double metal oxide;
s3: and adding the bimetal oxide into a solution containing betaine monomers to carry out hydration reconstruction in a nitrogen atmosphere, and adding ferroferric oxide powder after aging to obtain the betaine intercalated magnetic layered double hydroxide.
As shown in fig. 2, the preparation of the carbonate intercalated layered double hydroxide comprises the steps of:
s11: the divalent metal cation and the trivalent metal cation form a first mixed solution, and 1-2mol/L of NaOH and 1-1.5mol/L of Na2CO3The second mixed solution is added dropwise and simultaneously into deionized water with the pH value of 9.5-10.5, and stirring is continued for at least 1 hour, so that a third mixed solution is obtained, wherein the sum of the concentrations of the divalent metal cations and the trivalent metal cations in the first mixed solution is 1 mol/L;
s12: aging the third mixed solution at 70-80 ℃ for 24 hours to obtain carbonate intercalated layered double hydroxide;
the aim here is to allow the crystals to develop fully.
S13: washing the layered double hydroxide of the carbonate intercalation with degassed deionized water, and centrifuging until the conductivity of the washing liquid is less than 1000 mus/cm;
in this case, impurities such as excess salts are removed.
S14: and drying the centrifugally dehydrated carbonate intercalated layered double hydroxide at the temperature of 70-80 ℃ to constant weight, grinding and crushing the dried carbonate intercalated layered double hydroxide through a 0.149-0.45mm sieve to obtain the final carbonate intercalated layered double hydroxide.
In one embodiment of the invention, the divalent metal cation is Mg2+Or Ca2+(ii) a The trivalent metal cation being Al3 +Or Fe3+. The concentration of the divalent metal cation is 3 to 5 times that of the trivalent metal cation.
Further, the carbonate intercalated layered double hydroxide is treated in a muffle furnace at the temperature of 450-500 ℃ for 2-4 hours and cooled to obtain the double hydroxide.
As shown in fig. 3, the method for obtaining betaine-intercalated magnetic layered double hydroxide comprises the following steps:
s31: putting 0.5-1g of the bimetal oxide into a solution containing 50-100ml of 0.1-0.2mol/L betaine, uniformly stirring, and fully reacting for 2-3 days under the conditions of nitrogen atmosphere and 70-80 ℃ to obtain a first reaction solution;
s32: adding 0.05-0.1g of ferroferric oxide powder into the first reaction solution, and uniformly stirring in a nitrogen atmosphere to obtain the magnetic layered double hydroxide;
s33: washing and centrifuging the magnetic layered double hydroxide by using degassed deionized water and absolute ethyl alcohol in sequence;
s34: drying the magnetic layered double hydroxide after centrifugal ethanol removal at 70-80 ℃ to constant weight, grinding and crushing, and sieving by a sieve of 0.149-0.45mm to obtain the betaine intercalated magnetic layered double hydroxide material.
Example 2
The layered double hydroxide is MgAl type betaine intercalated magnetic layered double hydroxide prepared by the method, and the specific steps and synthesis parameters are as follows:
(1)0.75mol/L Mg2+and 0.25mol/L Al3+The first mixed solution is composed of 1.5mol/L NaOH and 1mol/L Na2CO3The composed second mixed solution was added dropwise while adding to deionized water at pH 10, and stirring was continued for at least 1 hour to obtain a third mixed solution.
(2) The mixed solution was aged at 75 ℃ for 24 hours to allow the crystals to fully develop.
(3) And washing the synthesized material with degassed deionized water, and centrifuging until the conductivity of the mixed solution is about 1000 mus/cm to remove impurities such as redundant salt.
(4) And (3) putting the centrifugally dehydrated material into a common drying oven, drying at 75 ℃ to constant weight, grinding and crushing the material, and sieving by a 0.149mm sieve to obtain the carbonate intercalated layered double hydroxide material.
(5) And putting the obtained carbonate intercalated layered double hydroxide material into a muffle furnace at 500 ℃, carrying out pyrolysis treatment for 2 hours, and cooling to obtain the double metal oxide material.
(6) 0.5 g of the bimetallic oxide material is weighed into a solution containing 50ml of 0.15mol/L betaine, the mixture is stirred evenly by magnetic force, and the mixture is fully reacted for 2 days under the condition of nitrogen atmosphere and 75 ℃.
(7) And (3) adding 0.05g of ferroferric oxide into the solution obtained in the step (6), and magnetically stirring for 30 minutes under the nitrogen atmosphere to fully and uniformly mix the ferroferric oxide and the solution.
(8) The synthesized material is washed and centrifuged for several times in sequence by using degassed deionized water and absolute ethyl alcohol to remove impurities such as redundant salt and the like.
(9) And (3) putting the material subjected to centrifugal de-ethanol in a vacuum drying oven, drying at 75 ℃ to constant weight, grinding and crushing the material, and sieving by using a 0.149mm sieve to obtain the MgAl type betaine intercalated magnetic layered double hydroxide material.
As shown in FIG. 4, it is an XRD pattern of the betaine-intercalated magnetic layered double hydroxide of MgAl type according to the present invention. The synthesized MgAl type betaine intercalated magnetic layered double hydroxide has characteristic diffraction peaks of a series of layered double hydroxides such as (003) and (006), and simultaneously has diffraction peaks related to ferroferric oxide, thereby proving that the MgAl type betaine intercalated magnetic layered double hydroxide adsorbing material is successfully synthesized.
Example 3
The layered double hydroxide is MgFe type betaine intercalated magnetic layered double hydroxide prepared by the method, and the specific steps and the synthesis parameters are as follows:
(1)0.83mol/L Mg2+and 0.17mol/L Fe3+Is composed of a first mixed solution, 1mol/L NaOH and 1.5mol/L Na2CO3The composed second mixed solution was added dropwise while adding to deionized water at pH 10.5, and stirring was continued for at least 1 hour to obtain a third mixed solution.
(2) The mixed solution was aged at 80 ℃ for 24 hours to allow the crystals to fully develop.
(3) And washing the synthesized material with degassed deionized water, and centrifuging until the conductivity of the mixed solution is about 1000 mus/cm to remove impurities such as redundant salt.
(4) And (3) putting the centrifugally dehydrated material into a common drying oven, drying at 80 ℃ to constant weight, grinding and crushing the material, and sieving by a 0.25mm sieve to obtain the carbonate intercalated layered double hydroxide material.
(5) And putting the obtained carbonate intercalated layered double hydroxide material into a muffle furnace at 450 ℃, performing pyrolysis treatment for 3 hours, and cooling to obtain the double metal oxide material.
(6) 0.75 g of the bimetal oxide material is weighed and put into a solution containing 100ml of 0.1mol/L betaine, the mixture is stirred evenly by magnetic force, and the mixture is fully reacted for 2.5 days under the condition of nitrogen atmosphere and 80 ℃.
(7) And (3) adding 0.05g of ferroferric oxide into the solution obtained in the step (6), and magnetically stirring for 30 minutes under the nitrogen atmosphere to fully and uniformly mix the ferroferric oxide and the solution.
(8) The synthesized material is washed and centrifuged for several times in sequence by using degassed deionized water and absolute ethyl alcohol to remove impurities such as redundant salt and the like.
(9) And (3) putting the material subjected to centrifugal de-ethanol in a vacuum drying oven, drying at 80 ℃ to constant weight, grinding and crushing the material, and sieving by using a 0.25mm sieve to obtain the MgFe type betaine intercalated magnetic layered double hydroxide material.
As shown in FIG. 5, it is an XRD pattern of the betaine-intercalated magnetic layered double hydroxide of the MgFe type of the present invention. The synthesized MgFe type betaine intercalated magnetic layered double hydroxide has characteristic diffraction peaks of a series of layered double hydroxides such as (003) and (006), and simultaneously has diffraction peaks related to ferroferric oxide. Compared with fig. 4, the diffraction peak noise of the MgFe type betaine intercalated magnetic layered double hydroxide is less, which indicates that the MgFe type betaine intercalated magnetic layered double hydroxide has a better crystal morphology.
Example 4
A layered double hydroxide is a CaAl type betaine intercalated magnetic layered double hydroxide prepared by the method, and the specific steps and synthesis parameters are as follows:
(1)0.80mol/L Ca2+and 0.20mol/L Al3+The first mixed solution is composed of 2.0mol/L NaOH and 1.2mol/L Na2CO3The composed second mixed solution was added dropwise while adding to deionized water at pH 9.5, and stirring was continued for at least 1 hour to obtain a third mixed solution.
(2) The mixed solution was aged at 70 ℃ for 24 hours to allow the crystals to fully develop.
(3) And washing the synthesized material with degassed deionized water, and centrifuging until the conductivity of the mixed solution is about 1000 mus/cm to remove impurities such as redundant salt.
(4) And (3) putting the centrifugally dehydrated material into a common drying oven, drying at 70 ℃ to constant weight, grinding and crushing the material, and sieving by a 0.45mm sieve to obtain the carbonate intercalated layered double hydroxide material.
(5) And putting the obtained carbonate intercalated layered double hydroxide material into a muffle furnace at 480 ℃, performing pyrolysis treatment for 4 hours, and cooling to obtain the double metal oxide material.
(6) Weighing 1.0 g of bimetallic oxide material, putting the bimetallic oxide material into a solution containing 75ml of 0.2mol/L thiomalic acid, uniformly stirring by magnetic force, and fully reacting for 3 days under the condition of nitrogen atmosphere and 70 ℃.
(7) And (3) adding 0.05g of ferroferric oxide into the solution obtained in the step (6), and magnetically stirring for 30 minutes under the nitrogen atmosphere to fully and uniformly mix the ferroferric oxide and the solution.
(8) The synthesized material is washed and centrifuged for several times in sequence by using degassed deionized water and absolute ethyl alcohol to remove impurities such as redundant salt and the like.
(9) And (3) putting the material subjected to centrifugal de-ethanol in a vacuum drying oven, drying at 70 ℃ to constant weight, grinding and crushing the material, and sieving by using a 0.45mm sieve to obtain the CaAl type betaine intercalated magnetic layered double hydroxide material.
FIG. 6 shows the XRD pattern of the CaAl-type betaine-intercalated magnetic layered double hydroxide of the present invention. The synthesized CaAl type betaine intercalated magnetic layered double hydroxide has characteristic diffraction peaks of a series of layered double hydroxides such as (003) and (006), and simultaneously has diffraction peaks related to ferroferric oxide, which indicates that the CaAl type betaine intercalated magnetic layered double hydroxide is successfully synthesized.
Example 5
The application of the layered double hydroxide comprises the application of the layered double hydroxide in simultaneously removing heavy metals in the form of anions and cations in the water body or soil pollution remediation treatment. The layered double hydroxide is the MgAl type betaine intercalated magnetic layered double hydroxide synthesized in example 2.
MgAl type betaine intercalated magnetic layered double hydroxide pair single Cr2O7 2-Cu alone2+And mixed Cr2O7 2-And Cu2+The adsorption performance of (2):
when Cu is not present, as shown in FIGS. 7(a) and 7(b)2+Magnetic layer of MgAl type betaine intercalation when ionizedThe double hydroxide can react Cr within 10 min2O7 2-The concentration of (B) is reduced from 10mg/L to less than 0.05mg/L, and Cu is co-present2+Increase of the content (from 0 to 10mg/L to 20mg/L), Cr2O7 2-The removal rate of (A) is lowered to some extent, and it is presumed that this is likely to be accompanied by Cu2+Competition for adsorption sites in the organofunctional groups.
As shown in FIGS. 8(a) and 8(b), betaine-intercalated magnetic layered double hydroxides of MgAl type are used for Cu2+Exhibits strong adsorption performance, and can adsorb Cu within 30 seconds2+The concentration of the water is reduced from 10mg/L to below 1mg/L, and the water reaches the national II-class water quality standard of surface water; with coexistence of Cr2O7 2-The content is increased from 0 to 10mg/L to 20mg/L, Cu2+The removal rate of (A) is obviously increased, which shows that the Cr is removed2O7 2-And Cu2+Coexistence can promote Cu2+Possibly with Cr2O7 2-The adsorption to the surface of the material can reduce the positive charge density of the surface of the material, thereby reducing the Cu resistance of the material2+Electrostatic repulsion of (1). In general, the layered double hydroxides of the invention are useful for heavy metals (Cr) in the anionic state2O7 2-) And the cationic heavy metal show good adsorption capacity, greatly reduce the operation flow and treatment cost in the treatment of the multiple heavy metal composite polluted water body, and show strong practical application potential.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several equivalent substitutions or obvious modifications can be made without departing from the spirit of the invention, and all the properties or uses are considered to be within the scope of the invention.

Claims (10)

1. A preparation method of a magnetic layered double hydroxide is characterized in that the betaine intercalated layered double hydroxide is prepared by a pyrolysis-hydration reconstruction mode, and then the betaine intercalated layered double hydroxide is prepared by compounding with ferroferric oxide powder.
2. The process for the preparation of a magnetic layered double hydroxide according to claim 1, comprising the steps of:
s1: preparing carbonate intercalated layered double hydroxide;
s2: pyrolyzing the layered double hydroxide to obtain a double metal oxide;
s3: and adding the bimetal oxide into a solution containing betaine monomers to carry out hydration reconstruction in a nitrogen atmosphere, and adding ferroferric oxide powder after aging to obtain the betaine intercalated magnetic layered double hydroxide.
3. The process for preparing a magnetic layered double hydroxide according to claim 2, wherein the preparation of the carbonate intercalated layered double hydroxide comprises the steps of:
s11: the divalent metal cation and the trivalent metal cation form a first mixed solution, and 1-2mol/L of NaOH and 1-1.5mol/L of Na2CO3The second mixed solution is added dropwise and simultaneously into deionized water with the pH value of 9.5-10.5, and stirring is continued for at least 1 hour, so that a third mixed solution is obtained, wherein the sum of the concentrations of the divalent metal cations and the trivalent metal cations in the first mixed solution is 1 mol/L;
s12: aging the third mixed solution at 70-80 ℃ for 24 hours to obtain carbonate intercalated layered double hydroxide;
s13: washing the layered double hydroxide of the carbonate intercalation with degassed deionized water, and centrifuging until the conductivity of the washing liquid is less than 1000 mus/cm;
s14: and drying the centrifugally dehydrated carbonate intercalated layered double hydroxide at the temperature of 70-80 ℃ to constant weight, grinding and crushing the dried carbonate intercalated layered double hydroxide through a 0.149-0.45mm sieve to obtain the final carbonate intercalated layered double hydroxide.
4. Such as rightThe process for producing a magnetic layered double hydroxide according to claim 3, wherein the divalent metal cation is Mg2+Or Ca2+(ii) a The trivalent metal cation is Al3+Or Fe3+。
5. The method of preparing a magnetic layered double hydroxide according to claim 3 wherein the concentration of the divalent metal cation is 3 to 5 times the concentration of the trivalent metal cation.
6. The method for preparing a magnetic layered double hydroxide as claimed in claim 2, wherein the carbonate intercalated layered double hydroxide is treated in a muffle furnace at 450-500 ℃ for 2-4 hours and cooled to obtain the double metal oxide.
7. The process for preparing a magnetic layered double hydroxide according to claim 2, wherein the process for obtaining a betaine-intercalated magnetic layered double hydroxide comprises the steps of:
s31: putting 0.5-1g of the bimetal oxide into a solution containing 50-100ml of 0.1-0.2mol/L betaine, uniformly stirring, and fully reacting for 2-3 days under the conditions of nitrogen atmosphere and 70-80 ℃ to obtain a first reaction solution;
s32: adding 0.05-0.1g of ferroferric oxide powder into the first reaction solution, and uniformly stirring in a nitrogen atmosphere to obtain the magnetic layered double hydroxide;
s33: washing and centrifuging the magnetic layered double hydroxide by using degassed deionized water and absolute ethyl alcohol in sequence;
s34: drying the magnetic layered double hydroxide after centrifugal ethanol removal at 70-80 ℃ to constant weight, grinding and crushing, and sieving by a sieve of 0.149-0.45mm to obtain the betaine intercalated magnetic layered double hydroxide material.
8. A layered double hydroxide, characterized in that it is a layered double hydroxide intercalated with an organic sulfur functional monomer having a mercapto group-containing organic sulfur functional monomer as an interlayer anion, prepared by the method of any one of claims 1 to 7.
9. Use of a layered double hydroxide according to claim 8 for the simultaneous removal of heavy metals in anionic and cationic form in the remediation of water or soil contamination.
10. Use of a layered double hydroxide according to claim 9 wherein the heavy metals in anionic and cationic form comprise Cr2O7 2-And Cu2+。
CN201911185036.0A 2019-11-27 2019-11-27 Preparation method of magnetic layered double hydroxide, magnetic layered double hydroxide and application thereof Pending CN110898796A (en)

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