Magnetic zeolite adsorbent composite material and preparation method thereof
Patent Information
- Application Number
- CN202611121321.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-07-27
- Publication Date
- 2026-09-25
AI Technical Summary
[0005]本发明的目的在于提供一种磁性沸石吸附复合材料及其制备方法，以克服现有技术中沸石吸附材料磁种易脱落、无机-有机界面相容性差、固废表面缺乏定向功能化设计、吸附容量与磁分离性能难以兼顾的问题
本发明提供的磁性沸石吸附复合材料的制备方法，通过三元固废协同制备磁性沸石、氯化锌原位沉积形成Zn(OH)2、功能性凝胶网络锚定成型的递进式工艺，构建了磁性分离-化学吸附-物理截留三位一体的功能体系，克服了传统吸附剂高容量与易分离不可兼得的技术矛盾。具体的：在MZA/Zn(OH)2的制备中，以赤泥、煤矸石和粉煤灰三元工业固废为原料，通过赤泥中富含的铁氧化物赋予材料本征磁性，避免了额外负载磁种导致的结合力弱和脱落失效问题，实现了便捷的磁分离回收；引入柠檬酸进行煅烧处理，柠檬酸在煅烧过程中分解产生CO2和H2O，有效提高了赤泥的孔隙率，为染料吸附提供了更多的吸附位点；同时，柠檬酸富含大量的羧基基团，实现了赤泥表面的羧基功能化，显著增强了材料的亲水性；引入氯化锌并调节pH至碱性范围，原位形成Zn(OH)2，该Zn(OH)2能够与羧基功能化的赤泥通过氢键结合，实现分子间的复合，同时，Zn2+可在后续步骤中与丙烯酸的羧基发生配位络合，形成稳定的配位交联点；在复合材料成型步骤中，以丙烯酸和丙三醇为单体、N,N′-亚甲基双丙烯酰胺为交联剂，通过自由基聚合反应将MZA/Zn(OH)2锚定于三维凝胶网络中，聚乙烯吡咯烷酮改善了无机颗粒的分散均匀性，十六烷基三甲基溴化铵诱导了介孔结构的形成，最终产物兼具成型体易分离与粉体高比表面积的双重优势。
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Abstract
Description
Technical Field
[0001] This invention relates to the field of adsorption material preparation technology, specifically to a magnetic zeolite adsorption composite material and its preparation method. Background Technology
[0002] Zeolite-based adsorbents, due to their regular pore structure, large specific surface area, and excellent ion exchange capacity, show promising application prospects in the treatment of dye wastewater. Using industrial solid wastes such as red mud, fly ash, and coal gangue as raw materials to prepare zeolite-based adsorbents enables the resource utilization of solid waste and significantly reduces material costs. In recent years, researchers have used an alkali-fusion-hydrothermal method to convert these solid wastes into adsorbent materials with zeolite structures and have attempted to combine them with magnetic media to achieve magnetic separation and recovery. Meanwhile, organic gel adsorbents have also attracted widespread attention in the water treatment field due to their convenient molding and easy separation. Incorporating zeolite powder into a gel matrix to prepare composite adsorbent materials has become an important research direction that balances adsorption capacity and separation convenience.
[0003] However, existing technologies still have many shortcomings. First, traditional zeolite adsorbents often use single solid waste or pure chemical reagents as silicon-aluminum sources, resulting in large fluctuations in raw material composition and unstable performance of crystallized products. Furthermore, powdered zeolite is prone to loss and difficult to separate and recover in practical applications, usually requiring additional loading of magnetic seeds such as Fe3O4 to achieve magnetic separation. However, the bonding force between the magnetic seeds and the zeolite matrix is weak, leading to easy detachment and failure over long-term use, resulting in a decline in material recycling performance. Second, simply incorporating zeolite powder into a gel matrix relies primarily on physical encapsulation. Poor compatibility between inorganic particles and the organic network interface leads to phase separation and aggregation, resulting in the inactivation of active sites and a significant reduction in adsorption capacity. Third, existing surface modification technologies for industrial solid waste are mostly limited to acid-base impregnation or high-temperature activation, lacking targeted functionalization design of the functional groups on the solid waste surface. This makes it difficult to construct stable chemical bonds and synergistic adsorption mechanisms between the zeolite framework, surface modification layer, and gel network. In addition, although existing gel adsorbents are easy to mold, they have limited adsorption capacity and insufficient mechanical strength, making it difficult to achieve both high adsorption performance and long-term cycle stability in complex wastewater systems.
[0004] Therefore, how to construct zeolite gel adsorption composite materials that combine intrinsic magnetism, high adsorption capacity, and convenient magnetic separation and recovery performance based on the full utilization of diverse industrial solid wastes has become a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention
[0005] The purpose of this invention is to provide a magnetic zeolite adsorption composite material and its preparation method, so as to overcome the problems in the prior art, such as easy detachment of magnetic seeds, poor compatibility of inorganic-organic interfaces, lack of directional functionalization design on solid waste surfaces, and difficulty in balancing adsorption capacity and magnetic separation performance.
[0006] The present invention solves the above-mentioned technical problems through the following technical solution: This invention provides a method for preparing a magnetic zeolite adsorption composite material, comprising the following steps: S1. Add acrylic acid and glycerol to deionized water, stir until homogeneous, add polyvinylpyrrolidone, stir until homogeneous, and obtain gel solution A; S2. Add N,N′-methylenebisacrylamide to gel solution A, and after ultrasonic treatment and stirring, add hexadecyltrimethylammonium bromide and continue stirring to obtain gel solution B. S3. Add MZA / Zn(OH)2 to deionized water, and after ultrasonic treatment and stirring, add gel solution B to it and stir to obtain a composite solution. Add ammonium persulfate to the composite solution, stir, heat to carry out polymerization reaction, and after aging treatment, obtain magnetic zeolite adsorption composite material. MZA / Zn(OH)2 is prepared through the following steps: A1. Red mud, coal gangue and fly ash are dried, mixed and then ground and sieved to obtain calcined composite powder; A2. Sodium hydroxide, sodium bicarbonate and citric acid are added to the calcined composite powder, ground, calcined under a protective atmosphere, and naturally cooled to room temperature to obtain MZA precursor; the MZA precursor is added to deionized water, stirred, heated, washed and dried to obtain MZA; A3. Add MZA to deionized water and perform ultrasonic and stirring treatment. Add zinc chloride and perform ultrasonic and stirring treatment. Add sodium carbonate to adjust the pH value to the alkaline range. After washing and drying, obtain MZA / Zn(OH)2.
[0007] A further improvement of the present invention is that, by weight, in step S1, acrylic acid is 4-7 parts, glycerol is 2-2.5 parts, and polyvinylpyrrolidone is 0.3-0.6 parts; in step S2, N,N′-methylenebisacrylamide is 0.25 parts, and hexadecyltrimethylammonium bromide is 0.4 parts; in step S3, MZA / Zn(OH)2 is 0.3-0.5 parts, and ammonium persulfate is 1.5 parts.
[0008] A further improvement of the present invention is that, in step S2, the ultrasonic treatment time is 15-20 min; in step S3, the heating temperature is 80-100℃, and the polymerization reaction time is 60-90 min.
[0009] A further improvement of the present invention is that, by mass, in step A1, red mud comprises 4-6 parts, coal gangue comprises 3.5-5.5 parts, and fly ash comprises 1.5-2.2 parts; in step A2, sodium hydroxide comprises 9-12 parts, sodium bicarbonate comprises 0.6-0.9 parts, and citric acid comprises 0.4 parts; and in step A3, zinc chloride comprises 0.5-0.8 parts.
[0010] A further improvement of the present invention is that, in step A2, the calcination temperature is 550–750°C and the calcination time is 2–3 hours.
[0011] A further improvement of the present invention is that, in step A2, the protective atmosphere is an argon atmosphere.
[0012] A further improvement of the present invention is that, in step A2, the heating temperature is 90-120°C and the heating time is 12-18 hours; in step A3, the pH value is 8.5-10.5.
[0013] A further improvement of the present invention is that, in step A1, a 200-mesh sieve is used for sieving; and in steps A2 and A3, washing is performed by alternating between deionized water and anhydrous ethanol.
[0014] The present invention also provides a magnetic zeolite adsorption composite material, which is prepared by the method described above for preparing magnetic zeolite adsorption composite materials.
[0015] A further improvement of the present invention is that the magnetic zeolite adsorption composite material comprises a three-dimensional gel network formed by free radical polymerization of acrylic acid, glycerol, ammonium persulfate, polyvinylpyrrolidone, hexadecyltrimethylammonium bromide, MZA / Zn(OH)2 and N,N′-methylenebisacrylamide, wherein MZA / Zn(OH)2 is anchored in the three-dimensional gel network.
[0016] Compared with the prior art, the positive and progressive effects of the present invention are as follows: The method for preparing magnetic zeolite adsorption composite material provided by this invention constructs a three-in-one functional system of magnetic separation, chemical adsorption and physical retention through a progressive process of synergistic preparation of magnetic zeolite from ternary solid waste, in-situ deposition of zinc chloride to form Zn(OH)2, and anchoring and molding of functional gel network. This overcomes the technical contradiction of the traditional adsorbents being unable to simultaneously achieve high capacity and easy separation. Specifically: In the preparation of MZA / Zn(OH)2, red mud, coal gangue, and fly ash, a ternary industrial solid waste, are used as raw materials. The iron oxides abundant in the red mud impart intrinsic magnetism to the material, avoiding the problems of weak bonding and detachment caused by additional magnetic seeds, thus achieving convenient magnetic separation and recycling. Citric acid is introduced for calcination treatment. During calcination, citric acid decomposes to produce CO2 and H2O, effectively increasing the porosity of the red mud and providing more adsorption sites for dye adsorption. Simultaneously, citric acid is rich in carboxyl groups, achieving carboxyl functionalization of the red mud surface and significantly enhancing the hydrophilicity of the material. Zinc chloride is introduced and the pH is adjusted to an alkaline range to form Zn(OH)2 in situ. This Zn(OH)2 can bind with the carboxyl-functionalized red mud through hydrogen bonds, achieving intermolecular complexation. Furthermore, Zn… 2+ In subsequent steps, it can coordinate with the carboxyl groups of acrylic acid to form stable coordination crosslinking points. In the composite material molding step, acrylic acid and glycerol are used as monomers, and N,N′-methylenebisacrylamide is used as a crosslinking agent. MZA / Zn(OH)2 is anchored in the three-dimensional gel network through free radical polymerization. Polyvinylpyrrolidone improves the dispersion uniformity of inorganic particles, and hexadecyltrimethylammonium bromide induces the formation of mesoporous structures. The final product has the dual advantages of easy separation of the molded body and high specific surface area of the powder.
[0017] Furthermore, the coordinated ratio of organic monomers, crosslinking agents, initiators, and inorganic fillers can form a stable three-dimensional network structure with fully exposed adsorption sites. This ensures the mechanical strength of the composite material while avoiding the embedding of active sites caused by the agglomeration of inorganic particles, thus achieving the optimal balance of adsorption performance.
[0018] Furthermore, the ultrasonic treatment time, polymerization reaction temperature, and reaction time were optimized and limited. Ammonium persulfate can effectively initiate free radical polymerization, allowing the gel network to fully cross-link and form, while avoiding the problems of excessive shrinkage of the gel network and reduction of specific surface area caused by excessive temperature or time.
[0019] The magnetic zeolite adsorption composite material provided by this invention possesses intrinsic magnetism, enabling convenient magnetic separation and recovery without the need for external magnetic seeds. Simultaneously, MZA / Zn(OH)2 is uniformly anchored in a three-dimensional gel network, fully exposing active adsorption sites. It combines the advantages of easy handling of gel molded bodies and high specific surface area of powder materials, achieving convenient magnetic separation and recovery while maintaining high adsorption capacity. Attached Figure Description
[0020] The accompanying drawings are provided to further understand the invention and constitute a part of this invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.
[0021] Figure 1 A simplified diagram of the preparation method of the magnetic zeolite adsorption composite material proposed in this application; Figure 2 The image shows the magnetic adsorption test results of MZA / Zn(OH)2 dispersed in water as shown in Example 2. Figure 3 The image shows the SEM test results of MZA / Zn(OH)2 prepared in Example 2. Figure 4 Figure 1 shows the Congo red adsorption test results of the magnetic zeolite adsorption composite materials prepared in the examples and comparative examples. Detailed Implementation To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.
[0022] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.
[0023] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values (including integers and fractions) within those ranges.
[0024] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”
[0025] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.
[0026] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.
[0027] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under standard conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications in the art, unless otherwise stated.
[0028] This invention provides a method for preparing a magnetic zeolite adsorption composite material, the overall process of which can be found in [reference needed]. Figure 1 Specifically, it includes the following steps S1 to S3.
[0029] Step S1: Prepare gel solution A.
[0030] Acrylic acid and glycerol were added to deionized water and stirred until homogeneous, allowing the acrylic acid monomer and glycerol to fully dissolve and form a uniform solution. Then, polyvinylpyrrolidone (PVP) was added to the solution, and stirring was continued until homogeneous, yielding gel solution A. PVP, acting as a steric stabilizer, improves the dispersion uniformity of subsequently added inorganic particles in the organic system, preventing sedimentation or aggregation, thus laying the foundation for constructing a homogeneous organic-inorganic composite network.
[0031] Step S2: Prepare gel solution B.
[0032] The crosslinking agent N,N′-methylenebisacrylamide was added to gel solution A obtained in step S1. The mixture was first sonicated and then stirred to ensure that the crosslinking agent was fully dissolved and uniformly dispersed in gel solution A. Then, hexadecyltrimethylammonium bromide (CTAB) was added to the mixture, and stirring continued to obtain gel solution B. CTAB, as a pore-forming template agent, can induce the formation of mesoporous structures during subsequent polymerization, which helps to improve the material transport channels and specific surface area within the final composite material.
[0033] Step S3: Composite and polymerization reaction.
[0034] MZA / Zn(OH)₂ powder was added to deionized water and subjected to ultrasonic treatment followed by stirring to fully disperse the powder in the water, obtaining a dispersion. Then, the gel solution B obtained in step S2 was added to this dispersion, and the mixture was continuously stirred to ensure thorough mixing of the organic gel component and the inorganic MZA / Zn(OH)₂ powder, resulting in a composite solution. Next, ammonium persulfate initiator was added to the composite solution and stirred to ensure uniform dispersion. The system was then heated to the polymerization temperature to initiate the polymerization reaction, allowing the acrylic monomers to undergo free radical polymerization in the presence of a crosslinking agent, forming a three-dimensional gel network. After the reaction, a curing treatment was performed to further refine and stabilize the gel network, ultimately yielding a magnetic zeolite adsorption composite material.
[0035] The preparation process of MZA / Zn(OH)2 follows steps A1 to A3. This process first utilizes multi-component solid waste to synergistically prepare a zeolite matrix (MZA) with intrinsic magnetic properties, and then deposits a Zn(OH)2 modification layer on its surface in situ.
[0036] Step A1: Raw material pretreatment.
[0037] Red mud, coal gangue, and fly ash, three industrial solid waste raw materials, were dried separately to remove free water. The dried raw materials were then mixed in a predetermined ratio, followed by grinding and sieving to obtain a calcined composite powder with uniform particle size and composition.
[0038] Step A2: Prepare magnetic zeolite matrix (MZA).
[0039] Sodium hydroxide, sodium bicarbonate, and citric acid were added to the calcined composite powder obtained in step A1, and the mixture was ground again to ensure thorough and uniform mixing of the alkali flux and additives with the powder. The mixed powder was then calcined at high temperature under a protective atmosphere. During calcination, the gas generated by the decomposition of citric acid acts as a pore-forming agent, and its carboxyl groups can functionalize the surface of solid waste. Simultaneously, the alkali flux promotes the recombination of aluminosilicate phases and the formation of zeolite crystal nuclei. After calcination, the mixture was naturally cooled to room temperature to obtain the MZA precursor. Subsequently, the MZA precursor was added to deionized water and subjected to stirring and heating. Through a hydrothermal crystallization reaction, zeolite crystals grew fully, forming a complete porous structure. After washing and drying, the reaction product yielded a zeolite matrix with intrinsic magnetic properties, denoted as MZA.
[0040] Step A3: In-situ deposition of Zn(OH)2 modified layer.
[0041] The MZA obtained in step A2 was added to deionized water and first subjected to ultrasonic and stirring treatment to ensure uniform dispersion. Then, zinc chloride was added to the dispersion, and ultrasonic and stirring treatment was performed again to allow zinc ions to be fully adsorbed and enriched on the surface and in the pores of the MZA. Subsequently, an aqueous sodium carbonate solution was added to adjust the pH of the system to the alkaline range, so that the adsorbed zinc ions were converted into Zn(OH)2 in situ and uniformly deposited on the MZA surface. After washing and drying, the product yielded magnetic zeolite powder with a Zn(OH)2 modified surface, namely MZA / Zn(OH)2.
[0042] Through the above steps, this invention uses three types of industrial solid waste as initial raw materials and utilizes the iron oxides inherent in red mud to impart intrinsic magnetism to the material, solving the problems of weak bonding force and easy detachment of external magnetic seeds with the matrix. The Zn(OH)2 modification layer formed in situ on the surface of MZA not only provides abundant surface hydroxyl groups, but also establishes a strong chemical connection with the organic gel network through hydrogen bonds and coordination bonds in subsequent steps, overcoming the technical defects of poor compatibility of inorganic-organic phase interface and easy embedding and deactivation of active sites caused by traditional physical embedding.
[0043] Example 1 A magnetic zeolite adsorption composite material, comprising the following materials in parts by weight: 4 parts acrylic acid, 2 parts glycerol, 1.5 parts ammonium persulfate, 0.3 parts PVP, 0.4 parts CTAB, 0.3 parts MZA / Zn(OH)2, and 0.25 parts N'N-methylenebisacrylamide; The preparation method of MZA / Zn(OH)2 includes the following steps: A1. Weigh 4 parts red mud, 3.5 parts coal gangue and 1.5 parts fly ash and dry them at 65℃ for 24 hours. After mixing, grind them for 20 minutes and then sieve them using a 200-mesh screen to obtain calcined composite powder. A2. Weigh 9 parts of sodium hydroxide, 0.6 parts of sodium bicarbonate and 0.4 parts of citric acid and add them to the calcined composite powder obtained in step A1. Grind for 30 min, then calcine at 550℃ for 2 h at a heating rate of 3℃ / min, and introduce argon gas at a flow rate of 100 mL / min. Allow to cool naturally to room temperature to obtain MZA precursor. Add 50 parts of deionized water to the obtained MZA precursor and stir at 500 r / min for 30 min. Then heat at 90℃ for 12 h, wash with deionized water and anhydrous ethanol three times each, and dry at 70℃ for 24 h to obtain MZA. A3. Add the MZA obtained in step A2 to 200 parts of deionized water, sonicate at a frequency of 30 kHz for 15 min, stir at a speed of 500 r / min for 30 min, weigh out 0.5 parts of zinc chloride and add it to the mixture, sonicate at a frequency of 30 kHz for 15 min, continue stirring at the above speed for 30 min, weigh out sodium carbonate and add it to adjust the pH to 8.5, wash with deionized water and anhydrous ethanol alternately 3 times each, and dry at a temperature of 70℃ for 24 h to obtain MZA / Zn(OH)2.
[0044] This embodiment also provides a method for preparing a magnetic zeolite adsorption composite material, comprising the following steps: S1. Weigh 4 parts of acrylic acid and 2 parts of glycerol and add them to 30 parts of deionized water. Stir at 500 r / min for 60 min. Weigh 0.3 parts of PVP and add them to the mixture to obtain gel solution A. S2. Weigh 0.25 parts of N'N methylenebisacrylamide and add it to the gel solution A obtained in step S1. Sonicate at a frequency of 30 kHz for 15 min, then stir at a speed of 500 r / min for 60 min. Weigh 0.4 parts of CTAB and add it to the gel solution A. Continue stirring at the speed mentioned above for 60 min to obtain gel solution B. S3. Weigh 0.3 parts of MZA / Zn(OH)2 and add it to 1.5 parts of deionized water. Sonicate at 30 kHz for 15 min and stir at 500 r / min for 60 min. Add the gel solution B obtained in step S2 and continue stirring at the above speed for 60 min to obtain a composite solution. Weigh 1.5 parts of ammonium persulfate and add it to the composite solution. Continue stirring at the above speed for 60 min and heat at 80℃ for 60 min. Then, cure at 10℃ for 24 h to obtain the magnetic zeolite adsorption composite material.
[0045] Example 2 A magnetic zeolite adsorption composite material, comprising the following materials in parts by weight: 5.5 parts acrylic acid, 2.3 parts glycerol, 1.5 parts ammonium persulfate, 0.5 parts PVP, 0.4 parts CTAB, 0.4 parts MZA / Zn(OH)2, and 0.25 parts N'N-methylenebisacrylamide; The preparation method of MZA / Zn(OH)2 includes the following steps: A1. Weigh 5 parts red mud, 4.5 parts coal gangue and 1.8 parts fly ash and dry them at 65℃ for 24 hours. After mixing, grind them for 20 minutes and then sieve them using a 200-mesh screen to obtain calcined composite powder. A2. Weigh 10.5 parts of sodium hydroxide, 0.8 parts of sodium bicarbonate and 0.4 parts of citric acid and add them to the calcined composite powder obtained in step A1. Grind for 30 min, then calcine at 650℃ for 2-3 h at a heating rate of 3℃ / min, and introduce argon gas at a flow rate of 100 mL / min. Allow to cool naturally to room temperature to obtain MZA precursor. Add 60 parts of deionized water to the obtained MZA precursor and stir at 500 r / min for 30 min. Then heat at 110℃ for 15 h, wash with deionized water and anhydrous ethanol three times each, and dry at 70℃ for 24 h to obtain MZA. A3. Add the MZA obtained in step A2 to 200 parts of deionized water, sonicate at a frequency of 30 kHz for 15 min, stir at a speed of 500 r / min for 30 min, weigh out 0.65 parts of zinc chloride and add it to the mixture, sonicate at a frequency of 30 kHz for 15 min, continue stirring at the above speed for 30 min, weigh out sodium carbonate and add it to adjust the pH to 9.5, wash with deionized water and anhydrous ethanol alternately 3 times each, and dry at a temperature of 70℃ for 24 h to obtain MZA / Zn(OH)2.
[0046] This embodiment also provides a method for preparing a magnetic zeolite adsorption composite material, comprising the following steps: S1. Weigh 5.5 parts of acrylic acid and 2.3 parts of glycerol and add them to 40 parts of deionized water. Stir at 500 r / min for 60 min. Weigh 0.5 parts of PVP and add them to the mixture to obtain gel solution A. S2. Weigh 0.25 parts of N'N methylenebisacrylamide and add it to the gel solution A obtained in step S1. Sonicate at a frequency of 30 kHz for 18 min, then stir at a speed of 500 r / min for 60 min. Weigh 0.4 parts of CTAB and add it to the gel solution A. Continue stirring at the above speed for 60 min to obtain gel solution B. S3. Weigh 0.4 parts of MZA / Zn(OH)2 and add it to 1.8 parts of deionized water. Sonicate at 30 kHz for 15 min and stir at 500 r / min for 60 min. Add the gel solution B obtained in step S2 and continue stirring at the above speed for 60 min to obtain a composite solution. Weigh 1.5 parts of ammonium persulfate and add it to the composite solution. Continue stirring at the above speed for 60 min and heat at 90℃ for 80 min. Then, cure at 10℃ for 24 h to obtain the magnetic zeolite adsorption composite material.
[0047] Example 3 A magnetic zeolite adsorption composite material, comprising the following materials in parts by weight: 7 parts acrylic acid, 2.5 parts glycerol, 1.5 parts ammonium persulfate, 0.6 parts PVP, 0.4 parts CTAB, 0.5 parts MZA / Zn(OH)2, and 0.25 parts N'N-methylenebisacrylamide; The preparation method of MZA / Zn(OH)2 includes the following steps: A1. Weigh 6 parts red mud, 5.5 parts coal gangue and 2.2 parts fly ash and dry them at 65℃ for 24 hours. After mixing, grind them for 20 minutes and then sieve them using a 200-mesh screen to obtain calcined composite powder. A2. Weigh 12 parts of sodium hydroxide, 0.9 parts of sodium bicarbonate and 0.4 parts of citric acid and add them to the calcined composite powder obtained in step A1. Grind for 30 min, then calcine at 750℃ for 3 h with a heating rate of 3℃ / min and argon gas with a flow rate of 100 mL / min. Cool naturally to room temperature to obtain MZA precursor. Add 70 parts of deionized water to the obtained MZA precursor and stir at 500 r / min for 30 min. Then heat at 120℃ for 18 h, wash with deionized water and anhydrous ethanol three times each, and dry at 70℃ for 24 h to obtain MZA. A3. Add the MZA obtained in step A2 to 200 parts of deionized water, sonicate at a frequency of 30 kHz for 15 min, stir at a speed of 500 r / min for 30 min, weigh out 0.8 parts of zinc chloride and add it to the mixture, sonicate at a frequency of 30 kHz for 15 min, continue stirring at the above speed for 30 min, weigh out sodium carbonate and add it to adjust the pH to 10.5, wash with deionized water and anhydrous ethanol alternately 3 times each, and dry at a temperature of 70℃ for 24 h to obtain MZA / Zn(OH)2.
[0048] This embodiment also provides a method for preparing a magnetic zeolite adsorption composite material, comprising the following steps: S1. Weigh 7 parts of acrylic acid and 2.5 parts of glycerol and add them to 50 parts of deionized water. Stir at 500 r / min for 60 min. Weigh 0.6 parts of PVP and add them to obtain gel solution A. S2. Weigh 0.25 parts of N'N methylenebisacrylamide and add it to the gel solution A obtained in step S1. Sonicate at a frequency of 30 kHz for 20 min, then stir at a speed of 500 r / min for 60 min. Weigh 0.4 parts of CTAB and add it to the gel solution A. Continue stirring at the above speed for 60 min to obtain gel solution B. S3. Weigh 0.5 parts of MZA / Zn(OH)2 and add it to 2 parts of deionized water. Sonicate at 30 kHz for 15 min and stir at 500 r / min for 60 min. Add the gel solution B obtained in step S2 and continue stirring at the above speed for 60 min to obtain a composite solution. Weigh 1.5 parts of ammonium persulfate and add it to the composite solution. Continue stirring at the above speed for 60 min and heat at 100℃ for 90 min. Then, cure at 10℃ for 24 h to obtain the magnetic zeolite adsorption composite material.
[0049] Comparative example: The difference between Comparative Example 1 and Example 2 is that zinc chloride was not added; otherwise, they are the same as Example 2. The difference between Comparative Example 2 and Example 2 is that fly ash and citric acid were not added; otherwise, they are the same as Example 2. The difference between Comparative Example 3 and Example 2 is that no coal gangue was added; otherwise, they are the same as Example 2. Comparative Example 4 is MZA / Zn(OH)2; Comparative Example 5 is MZA.
[0050] The magnetic properties of the above materials were tested, and the results showed that: After MZA / Zn(OH)2 powder is dispersed in deionized water, it can be completely adsorbed and recovered by a magnet without powder residue. This proves that the composite material prepared in this application has excellent magnetic separation and recovery performance, enabling rapid solid-liquid separation and solving the problems of difficult recovery and easy loss of traditional powder adsorbents. Specifically: See Figure 2For Example 2, 0.5 g of MZA / Zn(OH)2 was weighed and dispersed in 5 mL of deionized water. After sonication for 10 min and stirring at 500 r / min for 30 min, the sample was adsorbed by a magnet. The test results show that all the prepared MZA / Zn(OH)2 was adsorbed on the sample tube wall with the magnet, indicating that the prepared MZA / Zn(OH)2 has the advantage of being recyclable. Figure 3 The image shows the SEM results of the MZA / Zn(OH)2 prepared in Example 2. It can be seen that there are many pores on the surface, indicating that it can provide more adsorption sites for dye adsorption. Figure 4 The figures show the adsorption test results of Congo red prepared in the examples and comparative examples. The adsorption performance of the composite materials prepared in the three examples of this application is significantly better than that of the five comparative examples, which proves that the synergistic effect of ternary solid waste compounding, citric acid pore-forming modification, zinc hydroxide functionalization modification and organic gel crosslinking network can greatly improve the adsorption capacity and adsorption stability of the material. Each technical feature is indispensable.
[0051] Finally, it should be noted that the embodiments listed above are merely one or more specific manifestations of the technical solution of this invention. Their purpose is to clearly illustrate the concept, principle, and application of this invention through specific examples, and is by no means intended to limit the scope of protection of this invention to these specific embodiments. In fact, the true value of this invention lies in its proposed technical ideas and innovations, rather than its manifestations or implementation methods.
[0052] For those skilled in the art, after thoroughly reading and understanding the technical solution of this invention, they are fully capable of making various changes, modifications, or equivalent substitutions to the specific implementation of the invention based on their own professional knowledge and skills. These changes may include, but are not limited to: adjusting the range of technical parameters, optimizing the algorithm flow to improve efficiency, and replacing some technical components to achieve better compatibility or reduce costs. As long as these modified technical solutions substantially retain the technical features claimed by the original invention, that is, they can still achieve the core functions and effects of this invention, then these changes should be considered to fall within the scope of protection of the pending claims of this invention.
[0053] Furthermore, with the continuous progress and development of technology, new technical means and methods are constantly emerging, which provides ample space for further improvement and perfection of this invention. Therefore, the scope of protection of this invention should also include reasonable and foresightful improvements and extensions based on existing technology. As long as these improvements and extensions do not depart from the basic principles and core concepts of this invention, they should be considered equivalents of this invention and are equally protected by patent rights.
Claims
1. A method for preparing a magnetic zeolite adsorption composite material, characterized in that, Includes the following steps: S1. Add acrylic acid and glycerol to deionized water, stir until homogeneous, add polyvinylpyrrolidone, stir until homogeneous, and obtain gel solution A; S2. Add N,N′-methylenebisacrylamide to gel solution A, and after ultrasonic treatment and stirring, add hexadecyltrimethylammonium bromide and continue stirring to obtain gel solution B. S3. Add MZA / Zn(OH)2 to deionized water, and after ultrasonic treatment and stirring, add gel solution B to it and stir to obtain a composite solution. Add ammonium persulfate to the composite solution, stir, heat to carry out polymerization reaction, and after aging treatment, obtain magnetic zeolite adsorption composite material. MZA / Zn(OH)2 is prepared through the following steps: A1. Red mud, coal gangue and fly ash are dried, mixed and then ground and sieved to obtain calcined composite powder; A2. Sodium hydroxide, sodium bicarbonate and citric acid are added to the calcined composite powder, ground, calcined under a protective atmosphere, and naturally cooled to room temperature to obtain MZA precursor; the MZA precursor is added to deionized water, stirred, heated, washed and dried to obtain MZA; A3. Add MZA to deionized water and perform ultrasonic and stirring treatment. Add zinc chloride and perform ultrasonic and stirring treatment. Add sodium carbonate to adjust the pH value to the alkaline range. After washing and drying, obtain MZA / Zn(OH)2.
2. The method for preparing a magnetic zeolite adsorption composite material according to claim 1, characterized in that, By weight, in step S1, acrylic acid comprises 4-7 parts, glycerol comprises 2-2.5 parts, and polyvinylpyrrolidone comprises 0.3-0.6 parts; in step S2, N,N′-methylenebisacrylamide comprises 0.25 parts, and hexadecyltrimethylammonium bromide comprises 0.4 parts; in step S3, MZA / Zn(OH)2 comprises 0.3-0.5 parts, and ammonium persulfate comprises 1.5 parts.
3. The method for preparing a magnetic zeolite adsorption composite material according to claim 1, characterized in that, In step S2, the ultrasonic treatment time is 15-20 min; in step S3, the heating temperature is 80-100℃, and the polymerization reaction time is 60-90 min.
4. The method for preparing a magnetic zeolite adsorption composite material according to claim 1, characterized in that, By mass, in step A1, red mud comprises 4-6 parts, coal gangue comprises 3.5-5.5 parts, and fly ash comprises 1.5-2.2 parts; in step A2, sodium hydroxide comprises 9-12 parts, sodium bicarbonate comprises 0.6-0.9 parts, and citric acid comprises 0.4 parts; in step A3, zinc chloride comprises 0.5-0.8 parts.
5. The method for preparing a magnetic zeolite adsorption composite material according to claim 1, characterized in that, In step A2, the calcination temperature is 550–750°C, and the calcination time is 2–3 hours.
6. The method for preparing a magnetic zeolite adsorption composite material according to claim 1, characterized in that, In step A2, the protective atmosphere is an argon atmosphere.
7. The method for preparing a magnetic zeolite adsorption composite material according to claim 1, characterized in that, In step A2, the heating temperature is 90–120°C and the heating time is 12–18 h; in step A3, the pH value is 8.5–10.
5.
8. The method for preparing a magnetic zeolite adsorption composite material according to claim 1, characterized in that, In step A1, a 200-mesh sieve is used for sieving; in steps A2 and A3, washing is performed by alternating between deionized water and anhydrous ethanol.
9. A magnetic zeolite adsorption composite material, characterized in that, The magnetic zeolite adsorption composite material was prepared using the method described in any one of claims 1 to 8.
10. The magnetic zeolite adsorption composite material according to claim 9, characterized in that, The magnetic zeolite adsorption composite material comprises a three-dimensional gel network formed by free radical polymerization of acrylic acid, glycerol, ammonium persulfate, polyvinylpyrrolidone, hexadecyltrimethylammonium bromide, MZA / Zn(OH)2 and N,N′-methylenebisacrylamide, wherein MZA / Zn(OH)2 is anchored in the three-dimensional gel network.