Graphene composite adsorbent and preparation method thereof

Abstract

The invention discloses a graphene composite adsorbent and a preparation method thereof, and the graphene composite adsorbent comprises a graphene raw material, a waste catalyst, an acid aqueous solution, polyether sulfone, N, N-dimethylacetamide, polyallylamine hydrochloride and a modified glucose mixed solution. The waste catalyst comprises one or more of a waste Z-5 molecular sieve catalyst, a waste MTO catalyst, a waste molecular sieve adsorbent, fly ash, a waste FCC catalyst and a waste VOC adsorbent, the acid aqueous solution comprises a sulfurous acid solution and / or a phosphoric acid aqueous solution, the molar concentration of the acid aqueous solution is 1.5-2.5 mol / L, the graphene mixed powder is calcined, washed and dried to obtain pretreated powder, and the pretreated powder is dispersed in water; the preparation method comprises the following steps: adding polyether sulfone into N, N-dimethylacetamide, and fully dissolving to obtain a solution A; the graphene composite gel adsorbent obtained by the invention has very strong stability, can be repeatedly used, cannot reduce the adsorption effect due to repeated use, and can be used under various environmental conditions.

Description

Technical Field

[0001] The present invention relates to the technical field of adsorbents, and in particular to a graphene composite adsorbent and a preparation method thereof. Background Art

[0002] The main methods for treating organic pollutants in aqueous solutions include physical methods, chemical reduction methods, advanced oxidation methods and biological methods. More than 90% of them use chemical methods. The main chemical methods include: chemical precipitation, membrane separation, ion exchange, electrolysis, electrodialysis, activated carbon adsorption, etc.

[0003] Since graphene was first developed, it has received widespread attention in the fields of chemical power sources, optoelectronic devices and heterogeneous catalysis due to its excellent physical and chemical properties, such as large specific surface area, excellent mechanical strength, high electrical conductivity and thermal conductivity.

[0004] However, graphene materials are rarely used in the environment. Graphene can remove pollutants such as organic pollutants, but the agglomeration of graphene not only reduces the specific surface area of ​​graphene, but is also not conducive to dispersion in the solution, which limits its application in the removal of pollutants in aqueous solutions. Traditional graphene adsorbents also have the problem that the adsorption performance and compressive resistance cannot be further improved. Therefore, how to improve the shortcomings of traditional graphene adsorbents is a problem to be solved. Summary of the invention

[0005] Based on the technical problems existing in the background technology, the present invention proposes a graphene composite adsorbent and a preparation method thereof.

[0006] The invention provides a graphene composite adsorbent, which comprises a graphene raw material, a waste catalyst, an acid aqueous solution, polyethersulfone, N,N-dimethylacetamide, polyhydrochloride and a modified glucose mixed solution.

[0007] Preferably, the spent catalyst comprises one or more of spent Z-5 molecular sieve catalyst, spent MTO catalyst, spent molecular sieve adsorbent, fly ash, spent FCC catalyst and spent VOC adsorbent.

[0008] Preferably, the acid aqueous solution includes sulfurous acid solution and / or phosphoric acid aqueous solution, and the molar concentration is 1.5-2.5 mol / L.

[0009] Preferably, the steps include: S1: calcining, washing and drying the graphene mixed powder to obtain pretreated powder, and dispersing the pretreated powder in water; S2: Add polyethersulfone into N,N-dimethylacetamide and fully dissolve it to prepare solution A; S3: adding polyethersulfone and graphene oxide to N,N-dimethylacetamide and uniformly dispersing them to prepare solution B; S4: Mixing solution A with solution B to obtain a graphene oxide suspension; S5: mixing the graphene oxide suspension and polyallylamine hydrochloride in a mass ratio of 8:1 to 10:1, adding an iron ion mixture in an amount of 0.2 to 0.5 times the mass of the pretreated powder dispersion, stirring and mixing to obtain a modified powder dispersion; S6: dissolving aluminum on the waste catalyst to obtain aluminum-rich liquid, and mixing the aluminum-rich liquid to obtain a gel mother liquid; S7: mixing the gel mother liquid and the modified powder dispersion in a ratio of 1:8 to 1:10, adding an alkaline aqueous solution, adjusting the pH to 10.0 to 11, soaking, stirring and reacting, filtering, and obtaining a pretreated graphene composite gel adsorbent; S8: mixing the pretreated graphene composite gel adsorbent and the modified glucose mixed solution at a mass ratio of 1:5 to 1:8, and adding 0.1 to 0.2 times the mass of the pretreated graphene composite gel adsorbent aminosilicon dioxide and 0.1 to 0.2 times the mass of the pretreated graphene composite gel adsorbent sodium borohydride, stirring for reaction, filtering, drying, and calcining at high temperature to obtain a graphene composite gel adsorbent blank; S5: Pressing, cutting and packaging the graphene composite gel adsorbent blank.

[0010] Preferably, the aluminum dissolving comprises: mixing the waste catalyst with NaCO3, calcining at 550-800°C for 60-120min, then dissolving the calcined product with a monobasic acid having a mass concentration of 10-35%, filtering, and obtaining aluminum-rich liquid and aluminum-dissolving filter residue.

[0011] Preferably, the drying conditions are: drying at 100-120°C for 10-14 hours; the calcination conditions of step one are: calcination at 600-750°C for 4-6 hours; the calcination conditions of step two are: calcination at 600-800°C for 2-4 hours.

[0012] The beneficial effects of the present invention are: 1. Add polyethersulfone to N,N-dimethylacetamide and fully dissolve it to obtain solution A; add polyethersulfone and graphene oxide to N,N-dimethylacetamide and evenly disperse them to obtain solution B; mix solution A with solution B to obtain graphene oxide suspension, catalyze the obtained graphene oxide suspension with waste catalyst, dissolve aluminum with the waste catalyst to obtain aluminum-rich liquid, mix the aluminum-rich liquid to obtain a gel-like mother liquid, and the obtained graphene composite gel adsorbent has strong stability, can be reused, and will not reduce the adsorption effect due to repeated use, and can be used under various environmental conditions.

[0013] 2. It can effectively utilize waste catalyst resources, has low preparation cost, and has excellent physical and chemical properties and environmental adaptability. It is suitable for environmental protection applications in multiple fields, especially industrial emissions and indoor air purification, providing an efficient and environmentally friendly solution. DETAILED DESCRIPTION

[0014] The technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0015] A graphene composite adsorbent comprises a graphene raw material, a waste catalyst, an acid aqueous solution, polyethersulfone, N,N-dimethylacetamide, polyolefin hydrochloride and a modified glucose mixed solution.

[0016] Further, the spent catalyst includes one or more of spent Z-5 molecular sieve catalyst, spent MTO catalyst, spent molecular sieve adsorbent, fly ash, spent FCC catalyst and spent VOC adsorbent.

[0017] Furthermore, the acid aqueous solution includes a sulfurous acid solution and / or a phosphoric acid aqueous solution, and the molar concentration is 1.5 to 2.5 mol / L.

[0018] Further, the following steps are included: S1: calcining, washing and drying the graphene mixed powder to obtain pretreated powder, and dispersing the pretreated powder in water; S2: Add polyethersulfone into N,N-dimethylacetamide and fully dissolve it to prepare solution A; S3: adding polyethersulfone and graphene oxide to N,N-dimethylacetamide and uniformly dispersing them to prepare solution B; S4: Mixing solution A with solution B to obtain a graphene oxide suspension; S5: mixing the graphene oxide suspension and polyallylamine hydrochloride in a mass ratio of 8:1 to 10:1, adding an iron ion mixture in an amount of 0.2 to 0.5 times the mass of the pretreated powder dispersion, stirring and mixing to obtain a modified powder dispersion; S6: dissolving the waste catalyst with aluminum to obtain aluminum-rich liquid, and mixing the aluminum-rich liquid to obtain a gel mother liquid; S7: mixing the gel mother liquid and the modified powder dispersion in a ratio of 1:8 to 1:10, adding an alkaline aqueous solution, adjusting the pH to 10.0 to 11, soaking, stirring and reacting, filtering, and obtaining a pretreated graphene composite gel adsorbent; S8: mixing the pretreated graphene composite gel adsorbent and the modified glucose mixed solution at a mass ratio of 1:5 to 1:8, and adding 0.1 to 0.2 times the mass of the pretreated graphene composite gel adsorbent aminosilicon dioxide and 0.1 to 0.2 times the mass of the pretreated graphene composite gel adsorbent sodium borohydride, stirring for reaction, filtering, drying, and calcining at high temperature to obtain a graphene composite gel adsorbent blank; S5: Pressing, cutting and packaging the graphene composite gel adsorbent blank.

[0019] Furthermore, the aluminum dissolving includes: mixing the waste catalyst with NaCO3, calcining at 550-800°C for 60-120min, then dissolving the calcined product with a monobasic acid having a mass concentration of 10-35%, filtering, and obtaining aluminum-rich liquid and aluminum-dissolving filter residue.

[0020] Furthermore, the drying conditions are: drying at 100-120°C for 10-14 hours; the calcination conditions of step one are: calcination at 600-750°C for 4-6 hours; the calcination conditions of step two are: calcination at 600-800°C for 2-4 hours.

[0021] In the present invention, polyethersulfone is added to N,N-dimethylacetamide and fully dissolved to obtain solution A; polyethersulfone and graphene oxide are added to N,N-dimethylacetamide and uniformly dispersed to obtain solution B; solution A is mixed with solution B to obtain graphene oxide suspension, the obtained graphene oxide suspension is catalyzed by waste catalyst, aluminum is dissolved by the waste catalyst to obtain aluminum-rich liquid, the aluminum-rich liquid is mixed to obtain gel mother liquid, and the obtained graphene composite gel adsorbent has strong stability, can be reused, and the adsorption effect will not be reduced due to repeated use, and can be used under various environmental conditions.

[0022] The present invention can effectively utilize waste catalyst resources, has low preparation cost, and has excellent physical and chemical properties and environmental adaptability. It is suitable for environmental protection applications in multiple fields, especially industrial emissions and indoor air purification, and provides an efficient and environmentally friendly solution.

[0023] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A graphene composite adsorbent, characterized in that: The invention comprises graphene raw materials, waste catalysts, acid aqueous solution, polyethersulfone, N,N-dimethylacetamide, polyallylamine hydrochloride and modified glucose mixed solution.

2. A graphene composite adsorbent according to claim 1, characterized in that: The waste catalyst includes one or more of a waste Z-5 molecular sieve catalyst, a waste MTO catalyst, a waste molecular sieve adsorbent, fly ash, a waste FCC catalyst and a waste VOC adsorbent.

3. A graphene composite adsorbent according to claim 1, characterized in that: The acid aqueous solution includes a sulfurous acid solution and / or a phosphoric acid aqueous solution, and the molar concentration is 1.5 to 2.5 mol / L.

4. The method for preparing a graphene composite adsorbent according to claim 1, characterized in that: The following steps are involved: S1: calcining, washing and drying the graphene mixed powder to obtain pretreated powder, and dispersing the pretreated powder in water; S2: Add polyethersulfone into N,N-dimethylacetamide and fully dissolve it to prepare solution A; S3: adding polyethersulfone and graphene oxide to N,N-dimethylacetamide and uniformly dispersing them to prepare solution B; S4: Mixing solution A with solution B to obtain a graphene oxide suspension; S5: mixing the graphene oxide suspension and polyallylamine hydrochloride in a mass ratio of 8:1 to 10:1, adding an iron ion mixture in an amount of 0.2 to 0.5 times the mass of the pretreated powder dispersion, stirring and mixing to obtain a modified powder dispersion; S6: dissolving aluminum on the waste catalyst to obtain aluminum-rich liquid, and mixing the aluminum-rich liquid to obtain a gel mother liquid; S7: mixing the gel mother liquid and the modified powder dispersion in a ratio of 1:8 to 1:10, adding an alkaline aqueous solution, adjusting the pH to 10.0 to 11, soaking, stirring and reacting, filtering, and obtaining a pretreated graphene composite gel adsorbent; S8: mixing the pretreated graphene composite gel adsorbent and the modified glucose mixed solution at a mass ratio of 1:5 to 1:8, and adding 0.1 to 0.2 times the mass of the pretreated graphene composite gel adsorbent aminosilicon dioxide and 0.1 to 0.2 times the mass of the pretreated graphene composite gel adsorbent sodium borohydride, stirring for reaction, filtering, drying, and calcining at high temperature to obtain a graphene composite gel adsorbent blank; S5: Pressing, cutting and packaging the graphene composite gel adsorbent blank.

5. The method for preparing a graphene composite adsorbent according to claim 4, characterized in that: The aluminum dissolving process comprises: mixing the waste catalyst with NaCO3, calcining at 550-800°C for 60-120min, then dissolving the calcined product with a monobasic acid having a mass concentration of 10-35%, filtering, and obtaining aluminum-rich liquid and aluminum-dissolving filter residue.

6. A graphene composite adsorbent and a preparation method thereof according to claim 4, characterized in that: The drying conditions are: drying at 100-120°C for 10-14 hours; the calcination conditions of step one are: calcination at 600-750°C for 4-6 hours; the calcination conditions of step two are: calcination at 600-800°C for 2-4 hours.