CN113019325A - Magnetic adsorption material and preparation method thereof - Google Patents

Magnetic adsorption material and preparation method thereof Download PDF

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CN113019325A
CN113019325A CN202110277235.5A CN202110277235A CN113019325A CN 113019325 A CN113019325 A CN 113019325A CN 202110277235 A CN202110277235 A CN 202110277235A CN 113019325 A CN113019325 A CN 113019325A
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magnetic
preparing
polymer precursor
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fluorine
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CN113019325B (en
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杨瑞洪
马裕华
钱琛
单丹
孙昕
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Yangzhou Shouda Environmental Protection Technology Co ltd
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Yangzhou Polytechnic Institute
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
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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
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/08—Ferroso-ferric oxide [Fe3O4]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols

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Abstract

The scheme relates to a magnetic adsorption material and a preparation method thereof, wherein free radicals are carried out on a fluorine-containing methacrylate monomer and a quinoline derivative with double bonds at the tail endPolymerizing to obtain a polymer precursor; preparing rare earth metal complex by using 8-hydroxyquinoline as initial raw material, and reacting the rare earth metal complex with Fe3O4Mixing according to the mass ratio of 1:10 to obtain a magnetic donor additive; adding the polymer precursor and the magnetic donor auxiliary agent into a reaction bottle, hydrothermally preparing a blended sphere, and then carbonizing to obtain the magnetic adsorption material. The preparation method can prepare the magnetic activated carbon material with the mesopore content of about 80 percent, the mesopore occupancy ratio is high, the carbonization yield is more than 50 percent, the adsorption performance is good, and the adsorption capacity to phenol can reach 130 mg/g; the material has uniform size, good fluidity and excellent regeneration performance, can be used independently and can be better applied to equipment such as a fluidized bed and the like.

Description

Magnetic adsorption material and preparation method thereof
Technical Field
The invention belongs to the technical field of wastewater adsorbent preparation, and particularly relates to a magnetic adsorption material and a preparation method thereof.
Background
The industrial wastewater contains a large amount of harmful substances, has high organic matter concentration and deep color, and can be discharged into rivers after being treated. The industrial wastewater treatment method comprises an oxidation-reduction method, an ion exchange method, an ultrafiltration membrane method, a biological decolorization method, an adsorption method, a flocculation precipitation method and the like. Among them, the adsorption method is considered to be an efficient, simple and convenient method for solving the environmental pollution of the water body, and is most widely applied.
With the rapid development of modern society and economy, the common activated carbon adsorbent cannot meet the industrial requirements, and the magnetic carbon adsorbent is produced at the same time. The magnetic carbon adsorption material has strong adsorption capacity on environmental pollutants, good adsorption performance, high adsorption efficiency, low energy consumption and repeated utilization, and is widely researched in recent years. Most of magnetic carbon adsorption materials are prepared by taking commercial activated carbon as a raw material and combining a magnetic material (precursor) and the activated carbon in a physical-mechanical mode, and although the method meets the requirement of the activated carbon on magnetism to a certain extent, the strength is low and the magnetic durability is poor. In the preparation process, the prepared activated carbon has more macropores due to the performance of the precursor and the metal additive, so that the activated carbon is easy to block, and the adsorption quantity is reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a novel precursor and a magnetic donor additive, when the precursor and the magnetic donor additive are used for preparing a magnetic activated carbon adsorption material, the prepared material has a mesopore diameter and strong adsorption capacity.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a magnetic adsorption material comprises the following steps:
preparation of a Polymer precursor
The fluorine-containing methacrylate monomer and quinoline derivative with double bond at the tail end are subjected to free radical polymerization to obtain the fluorine-containing methacrylate monomer;
secondly, preparing the magnetic donor auxiliary agent
Preparing rare earth metal complex by using 8-hydroxyquinoline as initial raw material, and reacting the rare earth metal complex with Fe3O4Mixing according to the mass ratio of 1:10 to obtain the magnetic donor additive;
third, pretreatment before carbonization
Adding the polymer precursor and the magnetic donor additive into a reaction bottle, adding urotropine, polyethylene glycol and ethanol, mixing at 55-60 ℃ for 60min, then drying under reduced pressure, crushing the obtained solid, screening, adding the crushed solid and a sodium dodecyl sulfate aqueous solution into an autoclave, and heating to 120 ℃ to obtain a blending sphere;
fourthly, charring
And (3) placing the blended spheres in a tube furnace, heating to 800 ℃ at the speed of 4 ℃/min in the nitrogen atmosphere, carbonizing for 30min at a constant temperature, and introducing distilled water for activation to obtain the magnetic adsorption material.
Further, the specific steps of preparing the polymer precursor are as follows:
1) preparing a fluorine-containing methacrylate monomer by using glycidyl methacrylate and hexafluoroisopropanol as raw materials;
2) taking 6-aminoquinoline as a raw material, firstly carrying out substitution reaction with 6-chloro-1-hexanol, and then carrying out esterification reaction with methacryloyl chloride to obtain a quinoline derivative with a double bond at the tail end;
3) placing the fluorine-containing methacrylate monomer and quinoline derivative in a reaction bottle, adding an initiator AIBN and a solvent DMF, introducing nitrogen/vacuumizing for three times, placing the reaction bottle at the temperature of 60-70 ℃ for polymerization reaction for 2-3h, precipitating and separating out a polymer in methanol after the reaction is finished, and performing suction filtration and drying to obtain a polymer precursor.
Further, the ratio of the fluorine-containing methacrylate monomer to the quinoline derivative to the initiator AIBN is 50-150: 100: 1.
Further, the rare earth metal complex has the following formula:
Figure BDA0002977140800000031
wherein n is a positive integer; m is selected from one of La, Ce, Nd, Eu or Yb.
Further, the mass ratio of the polymer precursor to the magnetic donor auxiliary agent to the urotropine to the polyethylene glycol to the ethanol is 100: 2-10: 12:15: 200.
The invention provides a magnetic adsorption material prepared by the preparation method.
In three pores of the activated carbon, micropores (the diameter is 0.4-2nm, and the volume is 0.15-0.9ml/g) play a leading role in adsorbing gas, mesopores (the diameter is 2-50nm, and the volume is 0.02-0.1ml/g) can assist an adsorbing substance to pass through the micropores, and in liquid phase adsorption, the mesopores can adsorb the adsorbing substance with large molecular diameter to a great extent, so that a coloring aqueous solution is well treated; macropores (diameter >50nm) do not have a large effect on the adsorption capacity, and larger pore diameters can even cause the deposition of the catalyst, block the pore channels and cause the reduction of the adsorption efficiency.
The invention has the beneficial effects that: the preparation method can prepare the magnetic activated carbon material with the mesopore content of about 80 percent, the mesopore occupancy ratio is high, the carbonization yield is more than 50 percent, the adsorption performance is good, and the adsorption capacity to phenol can reach 130 mg/g; the material has uniform size, good fluidity and excellent regeneration performance, can be used independently and can be better applied to equipment such as a fluidized bed and the like.
The polymer precursor is different from conventional phenolic resin or styrene resin and the like, the invention carries out free radical polymerization on a newly synthesized fluorine-containing acrylate monomer and a polymerizable quinoline derivative to obtain a macromolecular copolymer, and the chain structure and the conjugated ring structure in the polymer are mutually wound and connected together, so that the polymer has the characteristics of high strength and high hardness, and simultaneously can still keep low density and high porosity during high-temperature treatment, and the active carbon obtained by carbonization also has high porosity; the abundant nitrogen element also provides more adsorption sites for the activated carbon during adsorption.
Iron materials are generally used for magnetizing activated carbon, and in addition, iron plays a role in catalyzing and reaming during the activation stage of activated carbon preparation, but active points formed on the surface of a carbon-containing raw material by iron excessively reduce the reaction activation energy of carbon and water vapor, so that the oxidation reaction speed of carbon and water vapor is high and is difficult to control, and the addition amount of iron has a large influence on the pore structure.
The proposal tries to introduce a small amount of rare earth metal into the conventional iron-based material to be blended to form the magnetic donor auxiliary agent, and the rare earth metal is combined with quinoline with a structure similar to that of the polymer precursor. During pretreatment before carbonization, because the structure of the rare earth metal ligand is similar to that of the polymer precursor, the interface energy between molecules is reduced during blending, and meanwhile, sulfonic groups in the structure of the rare earth metal ligand, hydroxyl groups in the polymer precursor and the like are beneficial to increasing certain hydrophilicity, the rare earth metal ligand is more uniformly dispersed in a water phase, and the obtained blended spheres are uniform in size and more beneficial to the subsequent carbonization process. When the composite bimetal magnetic donor assistant is used in carbonization, nearly half of micropores can be promoted to develop into mesopores, the number of the mesopores is gradually increased along with the increase of the addition amount, and when the usage amount of the magnetic donor assistant is 4.5 percent in the scheme, the mesopores account for 81 percent of the total pores, and the adsorption efficiency is the best.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
A preparation method of a magnetic adsorption material comprises the following steps:
preparation of a Polymer precursor
1) Preparing a fluorine-containing methacrylate monomer by using glycidyl methacrylate and hexafluoroisopropanol as raw materials;
Figure BDA0002977140800000051
2) taking 6-aminoquinoline as a raw material, firstly carrying out substitution reaction with 6-chloro-1-hexanol, and then carrying out esterification reaction with methacryloyl chloride to obtain a quinoline derivative with a double bond at the tail end;
Figure BDA0002977140800000052
3) placing 5mmol of the fluorine-containing methacrylate monomer and 10mmol of quinoline derivative in a reaction bottle, adding 0.1mmol of initiator AIBN and solvent DMF, introducing nitrogen/vacuumizing for three times, placing the mixture at the temperature of 60-70 ℃ for polymerization reaction for 2-3h, precipitating and separating out a polymer in methanol after the reaction is finished, and performing suction filtration and drying to obtain a polymer precursor.
Figure BDA0002977140800000053
Secondly, preparing the magnetic donor auxiliary agent
Preparing a target compound (A) from 8-hydroxyquinoline according to the following synthesis steps;
Figure BDA0002977140800000054
under the initiation of AIBN, a target compound (A) is polymerized to form macromolecules, 1mmol of polymer and 20mmol of 5-sulfonic acid-8-hydroxyquinoline are dissolved in a proper amount of THF (tetrahydrofuran) by taking the polymerization degree n as 10 and M as La as an example, lanthanum acetate is dissolved in a proper amount of THF at the same time, a lanthanum acetate solution is dropwise added into the THF solution, heating and refluxing are carried out for 2 hours, the solution is poured into a large amount of ethanol for precipitation and filtration, then the ethanol is used for washing for a plurality of times, and drying is carried out to obtain an organic rare earth complex; then with Fe3O4And mixing according to the mass ratio of 1:10 to obtain the magnetic donor additive.
Figure BDA0002977140800000061
Adding the polymer precursor and the magnetic donor auxiliary agent into a reaction bottle, adding urotropine, polyethylene glycol and ethanol, mixing for 60min at 55-60 ℃, then drying under reduced pressure, crushing the obtained solid, adding the crushed solid and a sodium dodecyl sulfate aqueous solution into an autoclave, and heating to 120 ℃ to obtain a blending sphere;
and (3) placing the blended spheres in a tube furnace, heating to 800 ℃ at the speed of 4 ℃/min in the nitrogen atmosphere, carbonizing for 30min at constant temperature, and introducing distilled water for activation to obtain the magnetic adsorption material.
In the reaction, the mass ratio of the polymer precursor to the magnetic donor auxiliary agent to the urotropine to the polyethylene glycol to the ethanol is 100: 2-10: 12:15:200, and the following specific examples are obtained according to different proportions.
The pore structure of the prepared activated carbon was characterized and the adsorption performance of each activated carbon to phenol was tested, with the results recorded in table 1, using the amount of the magnetic donor additive as 0, 2%, 4.5%, 7.5%, 10% of the polymer precursor, as one hundred parts of the charged amount of the polymer precursor.
TABLE 1
Figure BDA0002977140800000062
Figure BDA0002977140800000071
It can be seen from the table that when a small amount of the magnetic donor additive is added, the mesopore proportion can be increased to more than 50%, when the addition amount is 4.5%, the mesopore proportion is 80.8%, the carbonization yield is higher than 50%, and the adsorption amount to phenol is large; when the dosage of the auxiliary agent is continuously increased to 7.5 percent or 10 percent, all micropores cannot be promoted to develop into mesopores, but the mesopores cannot be caused to continue to develop into macropores, which may be that under the condition of high temperature, iron and rare earth metal form a dinuclear or polynuclear structure, the catalytic activity of iron is inhibited to a certain extent, the oxidation reaction rate of carbon and water vapor is stabilized, and macropores are not easy to generate even under the condition that the number of active points is increased; the excessive using amount of the auxiliary agent has little significance on the adsorption amount of the activated carbon and causes waste of raw materials, so the scheme of the embodiment 3 in the scheme is optimal.
Further, the magnetic performance and effect of the activated carbon of example 3 were measured, and the specific saturation magnetization was 24.32 A.m based on VSM2And kg, which shows that the activated carbon has stronger magnetism.
For comparison, the following tests were simultaneously performed:
comparative example 1: on the basis of the examples 3 and 5, the organic rare earth complex in the magnetic donor auxiliary is removed. When the additive amount is 4.5%, the mesopore ratio of the obtained activated carbon material is 71.2%, and the phenol adsorption amount is 113.87 mg/g; when the amount of the additive was 10%, the mesopore ratio of the obtained activated carbon material was 65.8%, and the phenol adsorption amount was 98.7 mg/g. That is, in this case, the iron-based material can obtain activated carbon having a high mesopore ratio at 4.5%, but the mesopore ratio is rather decreased when the amount of the iron-based material is increased, and the adsorption amount is smaller than that of the activated carbon.
Comparative example 2: on the basis of the examples 3 and 5, the organic rare earth complex in the magnetic donor auxiliary agent is replaced by a conventional organic rare earth complex, such as lanthanum 2-ethylhexanoate. When the dosage of the additive is 4.5 percent, the mesopore ratio of the obtained activated carbon material is 70.1 percent, and the phenol adsorption capacity is 108.48 mg/g; when the amount of the additive was 10%, the obtained activated carbon material had a mesopore ratio of 67.9% and a phenol adsorption amount of 100.56 mg/g. Comparative example 2 shows that the use of the rare earth metal-containing bimetallic composite magnetic donor additive is beneficial to inhibiting the catalytic activity of iron to a certain extent, and does not cause great reduction of the mesopore rate under the condition of increasing the use amount, but the adsorption performance of the prepared activated carbon material is still not ideal due to poor dispersibility during blending.
From the two sets of data in comparative examples 1 and 2, it can be seen that the expected effect of the present case can not be achieved when no rare earth metal complex is used in the metal additive or the organic ligand used is independent of the polymer structure.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.

Claims (6)

1. The preparation method of the magnetic adsorption material is characterized by comprising the following steps of:
preparation of a Polymer precursor
The fluorine-containing methacrylate monomer and quinoline derivative with double bond at the tail end are subjected to free radical polymerization to obtain the fluorine-containing methacrylate monomer;
secondly, preparing the magnetic donor auxiliary agent
Preparing rare earth metal complex by using 8-hydroxyquinoline as initial raw material, and reacting the rare earth metal complex with Fe3O4Mixing according to the mass ratio of 1:10 to obtain the magnetic donor additive;
third, pretreatment before carbonization
Adding the polymer precursor and the magnetic donor additive into a reaction bottle, adding urotropine, polyethylene glycol and ethanol, mixing at 55-60 ℃ for 60min, then drying under reduced pressure, crushing the obtained solid, screening, adding the crushed solid and a sodium dodecyl sulfate aqueous solution into an autoclave, and heating to 120 ℃ to obtain a blending sphere;
fourthly, charring
And (3) placing the blended spheres in a tube furnace, heating to 800 ℃ at the speed of 4 ℃/min in the nitrogen atmosphere, carbonizing for 30min at a constant temperature, and introducing distilled water for activation to obtain the magnetic adsorption material.
2. The method for preparing a magnetic adsorbent material according to claim 1, wherein the first step of preparing the polymer precursor comprises the following steps:
1) preparing a fluorine-containing methacrylate monomer by using glycidyl methacrylate and hexafluoroisopropanol as raw materials;
2) taking 6-aminoquinoline as a raw material, firstly carrying out substitution reaction with 6-chloro-1-hexanol, and then carrying out esterification reaction with methacryloyl chloride to obtain a quinoline derivative with a double bond at the tail end;
3) placing the fluorine-containing methacrylate monomer and quinoline derivative in a reaction bottle, adding an initiator AIBN and a solvent DMF, introducing nitrogen/vacuumizing for three times, placing the reaction bottle at the temperature of 60-70 ℃ for polymerization reaction for 2-3h, precipitating and separating out a polymer in methanol after the reaction is finished, and performing suction filtration and drying to obtain a polymer precursor.
3. The method for preparing a magnetic adsorption material according to claim 2, wherein the ratio of the fluorine-containing methacrylate monomer to the quinoline derivative to the initiator AIBN is 50-150: 100: 1.
4. The method of preparing a magnetic adsorbent material according to claim 1, wherein the rare earth metal complex has the following formula:
Figure FDA0002977140790000021
wherein n is a positive integer; m is selected from one of La, Ce, Nd, Eu or Yb.
5. The preparation method of the magnetic adsorption material according to claim 1, wherein the mass ratio of the polymer precursor to the magnetic donor auxiliary agent to the urotropin to the polyethylene glycol to the ethanol is 100: 2-10: 12:15: 200.
6. A magnetic adsorbent material produced by the production method according to any one of claims 1 to 5.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115138346A (en) * 2022-07-22 2022-10-04 扬州工业职业技术学院 Magnetic zeolite composite material, preparation method thereof and application of magnetic zeolite composite material in treatment of printing and dyeing wastewater

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CN103965835A (en) * 2014-05-13 2014-08-06 西南石油大学 Ultra-light magnetic oil absorption material and preparation method thereof
CN104907042A (en) * 2015-05-14 2015-09-16 河南师范大学 Preparation method for carbon-Fe3O4 magnetic active carbon
CN112250783A (en) * 2020-10-23 2021-01-22 中国科学院长春应用化学研究所 Copolymer of alpha-olefin and 2, 3-dimethyl-1, 3-butadiene, preparation method thereof and rare earth metal complex

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Publication number Priority date Publication date Assignee Title
DE2105515A1 (en) * 1970-02-05 1971-09-30 Osaka Soda Co. Ltd., Osaka-(Japan) Process for removing metals and means therefor
CN101284223A (en) * 2007-04-13 2008-10-15 中国科学院金属研究所 Magnetic porous carbon adsorbent and preparation method thereof
CN101531360A (en) * 2009-04-28 2009-09-16 湖南理工学院 Method for preparing mesoporous carbon material
CN103965835A (en) * 2014-05-13 2014-08-06 西南石油大学 Ultra-light magnetic oil absorption material and preparation method thereof
CN104907042A (en) * 2015-05-14 2015-09-16 河南师范大学 Preparation method for carbon-Fe3O4 magnetic active carbon
CN112250783A (en) * 2020-10-23 2021-01-22 中国科学院长春应用化学研究所 Copolymer of alpha-olefin and 2, 3-dimethyl-1, 3-butadiene, preparation method thereof and rare earth metal complex

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115138346A (en) * 2022-07-22 2022-10-04 扬州工业职业技术学院 Magnetic zeolite composite material, preparation method thereof and application of magnetic zeolite composite material in treatment of printing and dyeing wastewater

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