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CN-119750702-B - Manganese-loaded sulfur-rich spartina alterniflora denitrification material and preparation method and application thereof

CN119750702BCN 119750702 BCN119750702 BCN 119750702BCN-119750702-B

Abstract

The invention belongs to the field of sewage treatment. The invention provides a manganese-loaded sulfur-rich spartina alterniflora denitrification material, a preparation method and application thereof, is obtained by loading manganese oxide on alkali modified sulfur-rich spartina alterniflora or alkali modified sulfur-rich spartina alterniflora biochar. The manganese-loaded sulfur-rich spartina alterniflora denitrification material has rich pore channels and large specific surface area, is favorable for adsorption, catalytic oxidation and microbial film formation of nitrogen pollutants, is rich in carbon, sulfur and manganese elements, can directly release an organic carbon source, and can realize high-efficiency denitrification through multiple processes of coupling nitrification, manganese ammoxidation, heterotrophic denitrification, manganese autotrophic denitrification, sulfur autotrophic denitrification and the like. The manganese-loaded sulfur-rich spartina alterniflora denitrification material is fixed on the surfaces of hard aggregates, elastic or soft carriers, and can be widely applied to artificial wetland, biological filter tank, deep denitrification of sewage plants, rural agricultural sewage treatment and initial rainwater purification.

Inventors

  • WANG YIFEI
  • GU YONG
  • ZHAO DONGHUA
  • YIN JIACHUN
  • SONG XINSHAN
  • LI CHENG
  • PENG GUANGMING

Assignees

  • 中交上海航道局有限公司

Dates

Publication Date
20260505
Application Date
20250110

Claims (9)

  1. 1. The manganese-loaded sulfur-rich spartina alterniflora denitrification material is characterized by being prepared by loading manganese oxide on alkali-modified sulfur-rich spartina alterniflora or alkali-modified sulfur-rich spartina alterniflora biochar, wherein the particle size is 20-200 meshes, the atomic percentage of manganese and sulfur elements contained in the manganese-loaded sulfur-rich spartina alterniflora denitrification material exceeds 30%, and the mass percentage of manganese and sulfur elements exceeds 50%.
  2. 2. The manganese-loaded sulfur-rich spartina alterniflora denitrification material according to claim 1, wherein the specific surface area of the denitrification material obtained by loading the alkali-modified sulfur-rich spartina alterniflora with manganese is 20-100m 2 /g, and the specific surface area of the denitrification material obtained by loading the alkali-modified sulfur-rich spartina alterniflora biochar with manganese is 300-500m 2 /g.
  3. 3. The manganese-loaded sulfur-rich spartina alterniflora denitrification material according to claim 2, wherein the manganese-loaded sulfur-rich spartina alterniflora denitrification material is obtained by mixing alkali-modified sulfur-rich spartina alterniflora or alkali-modified sulfur-rich spartina alterniflora biochar with a potassium permanganate solution, and the dosage ratio of the alkali-modified sulfur-rich spartina alterniflora or alkali-modified sulfur-rich spartina alterniflora biochar to the potassium permanganate dry matter is 1g:0.002-0.03mol.
  4. 4. A method for preparing the manganese-loaded sulfur-rich spartina alterniflora denitrification material as claimed in claim 3, which is characterized by comprising the following steps of uniformly mixing alkali-modified sulfur-rich spartina alterniflora or alkali-modified sulfur-rich spartina alterniflora biochar with potassium permanganate solution according to a proportion, oscillating for 20-30 hours at 20-30 ℃, washing with deionized water, drying to obtain the manganese-loaded sulfur-rich spartina alterniflora denitrification material, Wherein the concentration of the potassium permanganate solution is 0.05M-0.3M.
  5. 5. The preparation method according to claim 4, wherein the alkali modified sulfur-rich spartina alterniflora is obtained by immersing sulfur-rich spartina alterniflora in 0.5% -3.0% sodium hydroxide solution for 12-24 hours, washing with deionized water, adjusting pH to 6.5-7.5, and drying at 50-70 ℃.
  6. 6. The preparation method of the alkali modified sulfur-rich spartina alterniflora biochar according to claim 4, wherein the alkali modified sulfur-rich spartina alterniflora biochar is obtained by heating the alkali modified sulfur-rich spartina alterniflora to 290-310 ℃, performing constant-temperature pyrolysis for 1-2 hours, heating to 450-700 ℃ and performing constant-temperature pyrolysis for 1-2 hours, cooling, washing to neutrality, and drying.
  7. 7. The method according to claim 5 or 6, wherein the sulfur-enriched spartina alterniflora is obtained by culturing spartina alterniflora with sulfur enrichment or directly using the sulfur-enriched spartina alterniflora.
  8. 8. The method according to claim 7, wherein the sulfur-rich cultivation comprises the steps of planting spartina alterniflora plants in cotton, immersing root systems in 90-130mM Na 2 S or Na 2 SO 4 solution, and culturing under water culture or under conditions simulating tidal flat silt, wherein the culturing process conditions comprise illumination of a plant light supplementing lamp, humidity of more than 60%, salinity of 0.3-1.0% and temperature of 20-30 ℃.
  9. 9. The application of the manganese-loaded sulfur-enriched spartina alterniflora denitrification material prepared by the preparation method according to any one of claims 1-3 or any one of claims 4-6 or 8, which is characterized in that the manganese-loaded sulfur-enriched spartina alterniflora denitrification material is fixed on the surface of a hard aggregate, an elastic or a soft carrier and is applied to artificial wetland, a biological filter, deep denitrification of a sewage plant, rural agricultural sewage treatment and initial rainwater purification.

Description

Manganese-loaded sulfur-rich spartina alterniflora denitrification material and preparation method and application thereof Technical Field The invention belongs to the field of sewage treatment, and particularly relates to a nitrogen pollution wastewater treatment technology. Background The nitrogen pollution of water is a global environmental problem and mainly comes from agricultural runoff, industrial wastewater, domestic sewage and the like. After the nitrogen pollutants enter the water body, the water body can be eutrophicated, a series of ecological problems such as algal bloom and aquatic organism death are further caused, and the human health is threatened. Therefore, solving the problem of nitrogen pollution in water body has important significance for protecting ecological environment and human health. At present, common denitrification technologies mainly comprise biological denitrification, chemical denitrification, physical denitrification and other methods. The biological denitrification utilizes the nitrification and denitrification of microorganisms to convert ammonia nitrogen into nitrogen, has the advantages of low cost and no secondary pollution, converts nitrogen pollutants into harmless substances through chemical reagents or catalysts, has the characteristics of high reaction speed and simple operation, and mainly removes nitrogen pollutants in water through physical methods such as adsorption, precipitation and the like, and has the advantages of high treatment efficiency and wide application range. Manganese-rich materials have attracted considerable attention in the field of denitrification of water in recent years as an emerging functional material due to their unique physicochemical properties such as high redox potential, good adsorption properties and biocompatibility. The manganese-rich material can effectively remove nitrogen pollutants in water through various ways such as oxidation, adsorption and the like, and simultaneously can provide a proper growth environment for microorganisms to promote the biological denitrification process. However, there are some limitations to the direct use of manganese oxide minerals. The manganese oxide mineral has a small specific surface area, so that the adsorption capacity is limited, the requirement of large-scale water treatment is difficult to meet, the surface activity of the manganese oxide is low, and the manganese oxide mineral is difficult to effectively combine with organic pollutants and microorganisms in water, so that the bioavailability is poor, and the mass transfer efficiency of biochemical reaction is insufficient. If the manganese oxide mineral is loaded on the surface of the carbon material, the application effect of the manganese oxide mineral in denitrification of water can be improved. The carbon material has high specific surface area, excellent mechanical strength and good biocompatibility, and can effectively improve the adsorption capacity and stability of the manganese oxide mineral. Meanwhile, the surface activity of the carbon material is higher, so that the effective combination of the manganese oxide mineral and pollutants and microorganisms in water can be promoted, and the denitrification effect of the manganese oxide mineral is enhanced. For example, patent number CN 113457639B discloses a manganese-loaded loofah sponge fiber for adsorption catalytic denitrification, and preparation and application thereof. Specifically, the loofah sponge with good supporting property, porosity and strong adsorption force is mixed with sodium hydroxide, potassium permanganate and manganese sulfate for modification to prepare the loofah sponge fiber loaded with manganese oxide, and the loofah sponge fiber is applied to ammonia nitrogen adsorption and catalytic degradation. However, the vegetable sponge is supplied as a derivative of agricultural and sideline products, and the demand of vegetable sponge has been greatly increased in recent years, and the situation of supply shortage has been started to appear. The spartina alterniflora is one of invasive plants in the global coastal salt marsh ecosystem, and causes serious threat to the biodiversity maintenance and ecological safety of most coastal beach wetlands. Because of the great difficulty and cost of the spartina alterniflora control, in the spartina alterniflora management, on one hand, control measures are needed to control the diffusion rate of the spartina alterniflora, so that the harm to an ecological system is reduced, and on the other hand, the characteristics of rapid growth, strong stress resistance and the like of the spartina alterniflora are fully utilized, so that the spartina alterniflora is subjected to resource development and utilization. Compared with other plants, the spartina alterniflora has the characteristics of strong environmental adaptability, high oxidation resistance, rapid growth, large biomass, strong reproductive capacity and the like, s