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CN-122006511-A - Efficient catalytic composite membrane for advanced sewage treatment and preparation method and application thereof

CN122006511ACN 122006511 ACN122006511 ACN 122006511ACN-122006511-A

Abstract

The invention discloses a high-efficiency catalytic composite membrane for sewage deep treatment, and a preparation method and application thereof, belonging to the technical field of sewage treatment and membrane separation, and comprising a membrane separation matrix and a multi-element metal composite oxide active layer loaded on the surface of the matrix and/or in a pore canal; the metal element in the multi-metal composite oxide active layer comprises three or more combinations of Mn, co, cu, fe, ni, cr, al, zn, la, ce, ti. The composite membrane provided by the invention forms an efficient and stable catalysis-separation integrated water treatment material by constructing the multi-element metal catalytic active layer distributed in a gradient manner on the porous separation membrane matrix. Can efficiently activate various common oxidants for water treatment such as persulfates, hydrogen peroxide, ozone and the like under mild conditions without additional energy input (such as light, electricity and heat), and realize synchronous degradation of various characteristic pollutants.

Inventors

  • CHEN JIAPING
  • Jin Tenghui
  • QU WEI

Assignees

  • 深圳大学

Dates

Publication Date
20260512
Application Date
20251230

Claims (10)

  1. 1. The high-efficiency catalytic composite membrane for advanced sewage treatment is characterized by comprising a membrane separation matrix and a multi-element metal composite oxide active layer loaded on the surface of the matrix and/or in a pore canal; The metal element in the multi-metal composite oxide active layer comprises three or more combinations of Mn, co, cu, fe, ni, cr, al, zn, la, ce, ti.
  2. 2. The high-efficiency catalytic composite membrane for advanced wastewater treatment according to claim 1, wherein said metal element comprises at least one flocculating metal element of which metal is an oxide or hydroxide easily forming low solubility; the flocculation metal element comprises one or more of Mn, fe and Al.
  3. 3. A high efficiency catalytic composite membrane for advanced wastewater treatment according to claim 1 or 2, wherein said combination of metallic elements comprises one of Mn-Fe-Al、Mn-Co-Cu、Fe-Ni-Cr、MnCoFeAl、FeNiCrAl、MnCoFeAlTi、CoCuFeNiZnLa、CoCuFeNiZn、CoCuFeNiLa、CoCuFeZnLa、CoCuNiZnLa、CoFeNiZnLa、CuFeNiZnLa、CoCuMnAlLaCr、CuMnAlLaCr、CoCuMnAlCr、CoCuAlLaCr、CoCuMnAlLa、CoCuMnAlLaCe or CoCuMnLaCr.
  4. 4. The high-efficiency catalytic composite membrane for advanced wastewater treatment according to claim 1, wherein the membrane separation matrix is a polymer micro-filtration membrane or an ultrafiltration membrane with a membrane pore size of 10-500 nm, and the polymer micro-filtration membrane or the ultrafiltration membrane comprises one of polyvinylidene fluoride, polyethersulfone, polyacrylonitrile, polysulfone and modified materials thereof; Or alternatively, the first and second heat exchangers may be, The membrane separation matrix is an alpha-Al 2 O 3 ceramic flat membrane with a gamma-Al 2 O 3 transition layer arranged on the surface and/or the inner wall of the pore canal, and the average pore diameter of the membrane is 10-50 nm.
  5. 5. A method of preparing a high efficiency catalytic composite membrane for water treatment as claimed in any one of claims 1 to 4, comprising the steps of: And (3) carrying out hydrophilic treatment on the membrane matrix, then soaking the membrane matrix in dispersion liquid of the multi-metal composite oxide powder, carrying out heat treatment after the soaking is finished, and circulating the soaking and heat treatment steps to ensure that the multi-metal composite oxide forms gradient distribution from outside to inside on the surface layer of the membrane matrix and the inner wall of the pore canal, thus obtaining the high-efficiency catalytic composite membrane.
  6. 6. The method for preparing a high efficiency catalytic composite membrane for water treatment according to claim 5, wherein the time of the impregnation is 10-30min; the temperature of the heat treatment is 120-180 ℃ and the time is 10-30min.
  7. 7. The method for preparing a high efficiency catalytic composite membrane for water treatment according to claim 5, wherein the number of cycles is 3-8.
  8. 8. The method for preparing a high efficiency catalytic composite membrane for water treatment according to claim 5, wherein the method for preparing the multi-metal composite oxide powder comprises the steps of: and weighing corresponding metal hydrated salt raw materials, dissolving the raw materials in a mixed solution of a complexing agent and absolute ethyl alcohol to obtain a precursor solution, and carrying out pyrolysis, drying, grinding and calcination on the obtained precursor solution to obtain the multi-element metal composite oxide powder.
  9. 9. The method for preparing a high efficiency catalytic composite membrane for water treatment according to claim 8, wherein the complexing agent is citric acid; the pyrolysis temperature is 90 ℃ and the pyrolysis time is 0.5-1h; the calcination temperature is 800-1100 ℃ and the calcination time is 3-5h.
  10. 10. Use of a high-efficiency catalytic composite membrane for water treatment according to any one of claims 1-4 in wastewater treatment.

Description

Efficient catalytic composite membrane for advanced sewage treatment and preparation method and application thereof Technical Field The invention belongs to the technical field of sewage treatment and membrane separation, and particularly relates to a high-efficiency catalytic composite membrane for sewage deep treatment, and a preparation method and application thereof. Background With the diversification of industrial production and the large-scale use of chemicals, the environmental risk brought by the difficult degradation of emerging pollutants in the water body is increasingly serious. Such contaminants (e.g., pharmaceuticals and Personal Care Products (PPCPs), endocrine Disrupting Compounds (EDCs), perfluoro and polyfluoroalkyl substances (PFAS), persistent organic contaminants, toxic industrial chemicals, etc.) generally have the characteristics of stable structure, strong toxicity, difficult biodegradation, etc., and have limited removal efficiency in conventional sewage treatment processes (e.g., conventional biological treatment, activated carbon adsorption, coagulating sedimentation), and easy penetration of the treatment system into the environment. The problem of pollution of refractory organic matters is particularly remarkable in various special water bodies and industrial wastewater, such as water bodies, wherein the water bodies comprise high-concentration antibiotics, synthetic intermediates, hormone medicines and the like in pharmaceutical and chemical wastewater, dyeing and textile wastewater comprises complex structural colorants such as azo dyes, anthraquinone dyes and the like and auxiliary agents, landfill leachate and part of agrochemicals wastewater comprise high-concentration pesticides, halogenated organic matters and humus macromolecules, petrochemical and coking wastewater comprises characteristic pollutants such as benzene series, phenols, polycyclic aromatic hydrocarbon and the like, and polluted surface water and underground water are subjected to long-term diffusion pollution by industrial or living sources and comprise low-concentration and various persistent organic matters. Advanced oxidation technologies (AOPs) are one of the key technologies for advanced treatment and water quality upgrading because they can generate strong oxidative free radicals and can effectively decompose the refractory organic substances. The technology is characterized in that oxidizing agents such as peroxymonosulfate, peroxydisulfate, hydrogen peroxide, ozone and the like are activated to generate high-activity species such as hydroxyl free radicals (OH), sulfate free radicals (SO 4-), superoxide anion free radicals (O 2-), singlet oxygen (1O2) and the like. The existing oxidant activation modes comprise thermal activation, alkali activation, radiation activation, transition metal activation, carbon-based material activation, electrochemical activation and the like. Among the various activation modes, heterogeneous catalytic activation is attracting attention due to mild conditions and high efficiency. In recent years, multi-principal or high entropy materials with multi-active site synergy have demonstrated potential in the catalytic field. The high-entropy material is a novel multi-principal element material which is composed of a plurality of main elements in a nearly equimolar way, has the characteristics of high configuration entropy, obvious lattice distortion effect, delayed diffusion effect, cocktail effect and the like, and can introduce rich local chemical environment and active sites into a single solid solution or multiphase structure. Research has shown that multiphase high entropy oxide powder can be used for activating PMS to degrade atrazine and other pollutants, and the oxidation-coagulation integrated treatment is realized by utilizing MnO 2 flocs formed in the reaction process. However, the system has obvious limitations that (1) the catalyst exists in a powder form, is easy to agglomerate, settle and run away along with effluent, is difficult to stably run for a long time and efficiently recover under engineering conditions, (2) the system is mainly verified for single or few organic pollutants, has limited synergistic removal capability for organic pollutants with various structures and different ionization potentials, and (3) the oxidation-coagulation process is difficult to be deeply coupled with the membrane separation process on the same interface, and the risks of metal overflow control and secondary pollution are still to be reduced. Meanwhile, when the existing catalytic system is directly used for the special wastewater or advanced treatment scene, the problems of difficult separation and recovery of the catalyst, contradiction between activity and stability, low process integration level and energy consumption and universality are still faced. Therefore, how to provide a novel and engineering-applicable high-efficiency catalysis-separation integrated technology a