Zeolite composite material for in-situ repairing black and odorous water body while improving sediment structure

Abstract

The present application relates to the technical field of urban water pollution ecological restoration, in particular to a zeolite composite material for in-situ remediation of black and odorous water body and improvement of sediment structure, which is characterized by the following technical scheme: the zeolite loaded iron-manganese bimetal composite material is prepared by using natural zeolite powder as a carrier, modifying the carrier with ferric chloride and potassium permanganate as Fe source and Mn source, and then performing a centrifugation-washing-drying-pulverizing-calcination process to obtain the composite material.The composite material is applied to black and odorous water body and sediment, which can quickly and effectively remove pollutants in overlying water, improve the oxidation-reduction potential (ORP) and dissolved oxygen (DO) through the principle of micro-battery, improve the living environment of indigenous microorganisms, activate indigenous microorganisms in the water body, gradually restore the integrity of the water body ecosystem, realize the self-activation repair process, and coordinate the removal of pollutants in the water body and sediment with the improvement of the micro-ecological environment to promote the restoration of self-repair function, and fundamentally improve the water body ecosystem.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ecological restoration of urban water pollution, in particular to a zeolite composite material for in-situ remediation of black and odorous water body and improvement of sediment structure. BACKGROUND

[0002] The river in the city is an important fresh water resource reservoir and water cycle path, and also an important part of the urban ecological system. In recent years, with the rapid advancement of industrialization and urbanization, the use of water for urban residents and industrial production has increased, leading to a sharp increase in the discharge of sewage. A large amount of untreated or insufficiently treated domestic sewage and industrial wastewater is directly discharged into the river, causing serious environmental pollution of the river. The excessive pollutants such as nitrogen, phosphorus and organic matter in the river cause damage to the water ecological environment, leading to black and odorous phenomenon of the water body. The black and odorous phenomenon of the water body not only seriously damages the water ecological environment and endangers the nature, but also produces hydrogen sulfide, ammonia and other harmful gases to human health.

[0003] "Black and odorous" is mainly caused by exogenous pollution and endogenous release. With the strengthening of sewage discharge management, the exogenous pollution of black and odorous river has been preliminarily controlled, but the endogenous pollution has caused the vicious problem of river returning to black and odorous again, which has become the main reason for the fundamental remediation of black and odorous water body. This is because the organic matter and nutrients in the sediment are easily decomposed by anaerobic microorganisms, producing a large amount of ammonia nitrogen (NH4 + -N), hydrogen sulfide (H2S) and volatile organic compounds (VOCs) and other malodorous gases, causing the water body to turn black and odorous. These pollutants will again adsorb the exogenous nitrogen, phosphorus and heavy metals, causing a vicious cycle. Therefore, the treatment of sediment pollution is one of the keys to prevent the black and odorous water body from returning to black and odorous.

[0004] At present, the remediation technology of black and odorous river water body and sediment is divided into in-situ and ex-situ, among which ex-situ remediation mainly refers to dredging of sediment and then treatment in another place. The ex-situ remediation technology has fast treatment effect, but due to the large amount of dredged sediment, the relatively complex composition of pollutants, and the secondary pollution of soil and groundwater caused by solidification and landfill technology, the ex-situ remediation technology has the disadvantages of high engineering cost, serious secondary pollution and damage to the ecological system at the bottom of the river. Therefore, the ex-situ remediation technology is not suitable for large-scale popularization and application. In-situ remediation technology emerges as the times require and becomes a common technical means in the process of sediment remediation. In-situ remediation technology refers to the treatment of contaminated sediment in the original place, which degrades the pollutants in the sediment and prevents them from entering the floating water body, cutting off the internal source of river water pollution.

[0005] Therefore, we propose a zeolite composite material for in-situ remediation of black and odorous water body and improvement of sediment structure. SUMMARY

[0006] The zeolite composite material for in-situ repairing black and odorous water body while improving sediment structure is provided to solve the problems in the background art.

[0007] To solve the above technical problems, the present application provides the following technical solutions:

[0008] A zeolite composite material for in-situ repairing black and odorous water body while improving sediment structure, comprising the following steps:

[0009] Step S1: adding natural zeolite powder into ferric chloride solution, fully stirring and mixing, then slowly adding potassium permanganate solution, using sodium hydroxide solution to adjust the system pH to 9.8-10.5, continuously stirring until the reaction is fully completed, to obtain zeolite loaded iron-manganese bimetallic mixed solution;

[0010] Step S2: placing the zeolite loaded iron-manganese bimetallic mixed solution obtained in step S1 into a muffle furnace after centrifugation, washing, drying and crushing, and cooling to room temperature to obtain zeolite loaded iron-manganese bimetallic composite material, i.e. zeolite composite material.

[0011] Further, in step S1, the mass ratio of natural zeolite powder to ferric chloride solution to potassium permanganate solution is 10:(1.3-4.2):(0.8-2.4).

[0012] Further, in step S1, the concentration of ferric chloride solution is 0.1-0.3 mol / L, the concentration of potassium permanganate solution is 0.05-0.15 mol / L, and the concentration of sodium hydroxide solution is 0.5-1.0 mol / L.

[0013] Further, in step S1, the time for continuous stirring is 2-4 h.

[0014] Further, in step S2, the specific steps of centrifugation, washing, drying and crushing are as follows: centrifuging at 2800-3500 rpm for 3-5 min, washing with water, drying in a 40-60℃ electric heating constant temperature air drying oven to constant weight, and then crushing to 500-1000 mesh.

[0015] Further, in step S2, the calcination process conditions are as follows: calcination temperature 200-500℃, heating rate 8-15℃ / min, and calcination time 2-4 h.

[0016] Further, the zeolite composite material takes zeolite as the core and loads iron-manganese bimetal on the surface; the zeolite is natural zeolite powder, and its structural formula is mCaO·xAl2O3·ySiO2·zH2O; the iron-manganese bimetal is industrial grade ferric chloride (FeCl3) and potassium permanganate (KMnO4) respectively.

[0017] Further, the natural zeolite powder is subjected to modification treatment, and the specific modification process is as follows:

[0018] Step (1): under the protection of nitrogen, 4-chloro-allyloxybenzene and dimethyl sulfoxide are uniformly mixed, and then the temperature is raised to 40-50 DEG C, and tetradecyldimethyl tertiary amine is added dropwise, and the dropping is completed in 1-2 hours, and the reaction time is 1-2 hours, and then the temperature is raised to 55-60 DEG C, and the reaction is carried out for 8-10 hours, and then the intermediate is prepared by rotary evaporation; the emulsifier, glycerol and vinyl silicone oil are uniformly mixed, and then emulsification is carried out for 20-40 minutes to prepare emulsified silicone oil; under the protection of nitrogen, the intermediate is heated to 70-80 DEG C, and then 1 / 2 mass fraction of aqueous azobisdimethylammonium hydrochloride solution and emulsified silicone oil are added dropwise in sequence, and the dropping is completed in 1-2 hours, and the reaction is carried out for 10-20 minutes, and then the remaining 1 / 2 mass fraction of aqueous azobisdimethylammonium hydrochloride solution is continuously added dropwise, and the reaction is carried out for 10-12 hours, and then the template agent is prepared by rotary evaporation;

[0019] Step (2): the natural zeolite powder and sodium hydroxide particles are uniformly mixed, and then calcination is carried out at 550-600 DEG C for 2-3 hours, and then deionized water is added after calcination, and the stirring is continuously carried out for 22-24 hours, and then the upper liquid is taken and prepared for use;

[0020] Step (3): the template agent and deionized water are uniformly mixed, and then the upper liquid is added dropwise under the condition of water bath at 35-40 DEG C, and the dropping is completed in 1-2 hours, and then the stirring is carried out for 1-2 hours, and then the pH value of the system is adjusted to 9.5-10.5 by using hydrochloric acid solution, and then the stirring is uniformly carried out, and then the system is moved into a polytetrafluoroethylene-lined reaction kettle, and then the heating is carried out to 110-120 DEG C, and then the reaction is carried out for 24-48 hours, and then the system is cooled to room temperature, and then the system is subjected to filtration, washing and drying, and then the system is heated from room temperature to 550-600 DEG C at a rate of 3-5 DEG C / min, and then the calcination is carried out for 5-6 hours, and then the system is cooled to room temperature to prepare the modified zeolite powder.

[0021] In the above technical scheme, the nucleophilic substitution reaction of 4-chloro-allyloxybenzene and tetradecyldimethyl tertiary amine is carried out, and then the intermediate containing carbon-carbon double bond is formed after the quaternary ammonium treatment of tetradecyldimethyl tertiary amine, and then the intermediate and vinyl silicone oil are used as raw materials, and then the organic silicone quaternary ammonium salt is prepared by the free radical polymerization method with azobisdimethylammonium hydrochloride as initiator to prepare the template agent; the natural zeolite is subjected to alkali activation treatment by using sodium hydroxide, and then the zeolite after calcination is stirred with deionized water to sufficiently leach out silicon and aluminum, and then the upper liquid is used as the silicon and aluminum source, and then the template agent solution is uniformly mixed, and then the template agent is removed by high-temperature calcination to prepare the modified zeolite powder. The modified zeolite powder has large specific surface area and pore volume, ordered pore structure and uniform and adjustable pore size, and can be used as an excellent carrier.

[0022] Further, the mass ratio of 4-chloro-allyloxybenzene to dimethyl sulfoxide in step (1) is 1:(8-10).

[0023] Further, the mass of the tetradecyldimethyl tertiary amine in step (1) is 1:(1.0~1.2) of the mass of 4-chloro-allyloxybenzene.

[0024] Further, the mass ratio of the vinyl silicone oil, the emulsifier and the glycerol in step (1) is 1:(0.10~0.15):(0.4~0.6).

[0025] Further, the emulsifier in step (1) is Tween T-80.

[0026] Further, the mass of the intermediate in step (1) is 4~5 times of the mass of the vinyl silicone oil.

[0027] Further, the total mass of the aqueous solution of azobisdimethylaminoamidine hydrochloride in step (1) is 1.0~1.5% of the total mass of the intermediate and the vinyl silicone oil, and the mass fraction of the aqueous solution of azobisdimethylaminoamidine hydrochloride is 60~65%.

[0028] Further, the mass ratio of the natural zeolite powder and the sodium hydroxide particles in step (2) is 1:(2~3).

[0029] Further, the mass of the deionized water in step (2) is 20~25 times of the total mass of the natural zeolite powder and the sodium hydroxide particles.

[0030] Further, the mass ratio of the template agent and the deionized water in step (3) is 1:(12~14).

[0031] Further, the mass of the upper liquid in step (3) is 20~30 times of the mass of the template agent.

[0032] Further, the concentration of the hydrochloric acid solution in step (3) is 1~2 mol / L.

[0033] Compared with the prior art, the application has the following beneficial effects:

[0034] 1. A zeolite composite material for in-situ repairing black and odorous water bodies and improving sediment structure, the natural zeolite is subjected to alkali activation treatment by using sodium hydroxide, the calcined zeolite is stirred with deionized water to fully leach out silicon and aluminum, the upper liquid is taken as a silicon-aluminum source, and a prepared template agent is introduced, which is helpful to form an ordered pore structure, improve the pore volume and specific surface area of the zeolite, remove the template agent through high-temperature calcination, and prepare modified zeolite powder. The modified zeolite powder has a large specific surface area and pore volume, an ordered pore structure, and a uniform and adjustable pore size, can be used as an excellent carrier, can provide more active sites, and thus increase the adsorption and degradation efficiency of pollutants, and at the same time, the modified zeolite powder can load iron-manganese bimetallic composite material, further improve the efficiency of removing organic matters and improving water quality in black and odorous water bodies, and improve the sediment structure.

[0035] 2. The zeolite supported iron-manganese bimetallic composite material prepared by the present application is applied to black and odorous water bodies. The sulfide metals, H2S, amine substances, ammonia nitrogen and total phosphorus in the overlying water can be quickly eliminated, and at the same time, the organic pollutants can be removed, the form of heavy metals can be changed, the free heavy metals can be chelated and solidified, and the influence of heavy metals can be eliminated, thereby repairing the black and odorous water bodies.

[0036] 3. The zeolite supported iron-manganese bimetallic composite material prepared by the present application is applied to black and odorous water body sediment improvement. The black and odorous sediment suspension is effectively controlled, the degradation of toxic organic matter is promoted, the adsorption and fixation of pollutants are accelerated, the catalytic degradation is cooperated, and the sediment structure characteristics are changed, so that the toxicity of the sediment is weakened. The oxidation reduction potential (ORP) and dissolved oxygen (DO) are improved through the principle of microcell, the survival environment of indigenous microorganisms is improved, the indigenous microorganisms in the water body are activated, the biological chain structure and composition are enriched, the integrity of the water body ecosystem is gradually restored, the self-activation repair process is realized, the removal of pollutants in the water body and the improvement of the microecological environment are coupled and promoted to restore the self-repair function, and the traditional chemical agents, microbial agents or direct microbial addition can be effectively replaced, so that the water body ecosystem is fundamentally improved. BRIEF DESCRIPTION OF DRAWINGS

[0037] The accompanying drawings are included to provide a further understanding of the present application, and constitute a part of the specification, illustrate the present application together with the embodiments thereof, and explain the present application, but do not constitute a limitation of the present application. In the drawings:

[0038] Figure 1 is a flow chart of preparation of the zeolite composite material in examples 1, 2 and 3 in the present application;

[0039] Figure 2 is an effect diagram of removal of ammonia nitrogen, total phosphorus and COD in overlying water by the zeolite composite material prepared in example 1 in the present application in experiment 1;

[0040] Figure 3 is an apparent effect diagram of improvement of black and odorous water bodies and sediments by the zeolite composite material prepared in example 1 in the present application in experiment 1;

[0041] Figure 4 is an effect diagram of removal of total nitrogen and total phosphorus in sediments by the zeolite composite material prepared in example 1 in the present application in experiment 1. DETAILED DESCRIPTION

[0042] With reference to the accompanying drawings on the basis of the embodiments of the present application, the technical solutions in the embodiments of the present application will be described clearly and completely. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments of the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the protection scope of the present application.

[0043] The natural zeolite powder in the embodiment has a SiO2 content of 70 wt%, an Al2O3 content of 18 wt%, a CaO content of 2 wt%, and a particle size of 500 mesh, and is sourced from Dongguan Lihui Mineral Products Co., Ltd.; the emulsifier is Tween T-80, sourced from Jinan Jiuruixi Chemical Co., Ltd.

[0044] Embodiment 1: A zeolite composite material for in-situ remediation of black and odorous water bodies while improving the structure of sediment, comprising the following processes:

[0045] Step S1: 10 g of natural zeolite powder is added to 100 mL of a solution containing 0.3 mol / L of ferric chloride, and after being fully stirred and mixed, 100 mL of a solution containing 0.1 mol / L of potassium permanganate is slowly added, a 1.0 mol / L sodium hydroxide solution is used to adjust the pH of the system to 10, and the stirring is continued for 2 h to ensure that the reaction is fully completed, thereby obtaining a zeolite-loaded iron-manganese bimetallic mixed solution;

[0046] Step S2: The zeolite-loaded iron-manganese bimetallic mixed solution obtained in step S1 is placed in a centrifuge, centrifuged at 3200 rpm for 4.5 min, washed with water, placed in a 50℃ electric heating constant-temperature drying oven for drying to a constant weight, then crushed to 500 mesh, placed in a muffle furnace for calcination (calcination temperature 200℃, heating rate 8℃ / min, calcination time 4 h), and cooled to room temperature, thereby obtaining a zeolite-loaded iron-manganese bimetallic composite material, i.e., a zeolite composite material.

[0047] Embodiment 2: A zeolite composite material for in-situ remediation of black and odorous water bodies while improving the structure of sediment, comprising the following processes:

[0048] Step S1: 10 g of natural zeolite powder is added to 100 mL of a solution containing 0.2 mol / L of ferric chloride, and after being fully stirred and mixed, 100 mL of a solution containing 0.05 mol / L of potassium permanganate is slowly added, a 0.5 mol / L sodium hydroxide solution is used to adjust the pH of the system to 9.8, and the stirring is continued for 3 h to ensure that the reaction is fully completed, thereby obtaining a zeolite-loaded iron-manganese bimetallic mixed solution;

[0049] Step S2: The zeolite loaded iron-manganese bimetallic mixed solution obtained in step S1 is placed in a centrifuge, centrifuged at 2800 rpm for 5 min, washed with water, placed in a 60°C electric heating constant temperature drying oven to dry to constant weight, then crushed to 800 mesh, placed in a muffle furnace to calcine (calcination temperature 300°C, heating rate 10°C / min, calcination time 3h), cooled to room temperature, to obtain a zeolite loaded iron-manganese bimetallic composite material, i.e. a zeolite composite material.

[0050] The natural zeolite powder is subjected to modification treatment, and the specific modification process is as follows:

[0051] Step (1): Under nitrogen protection, 4 g of 4-chloro-allyloxybenzene and 32 g of dimethyl sulfoxide are uniformly mixed, heated to 40°C, and 4 g of tetradecyl dimethyl tertiary amine is added dropwise, 1 h for dropwise addition, the reaction time is 1 h, the temperature is increased to 55°C, and the reaction is kept for 8 h. After rotary evaporation, an intermediate is prepared. 0.1 g of emulsifier, 0.4 g of glycerol, and 1 g of vinyl silicone oil are uniformly mixed and emulsified for 20 min to prepare emulsified silicone oil. Under nitrogen protection, 4 g of the intermediate is heated to 70°C, and 0.025 g of 60 wt% azobisdimethylaminoformamidine hydrochloride aqueous solution and emulsified silicone oil are added dropwise in sequence, 1 h for dropwise addition, reaction for 10 min, and then 0.025 g of 60 wt% azobisdimethylaminoformamidine hydrochloride aqueous solution is continuously added dropwise, reaction for 10 h. After rotary evaporation, a template agent is prepared.

[0052] Step (2): 10 g of natural zeolite powder and 25 g of sodium hydroxide particles are uniformly mixed, calcined at 580°C for 2.5 h, 800 g of deionized water is added after calcination, and stirring is continued for 23 h. The upper liquid is taken and reserved for use.

[0053] Step (3): 4 g of the template agent and 52 g of deionized water are uniformly mixed, 100 g of the upper liquid is added dropwise under the condition of a 38°C water bath, 1.5 h for dropwise addition, stirring for 1.5 h, 1.5 mol / L hydrochloric acid solution is used to adjust the system pH to 10, and after uniform stirring, it is transferred into a polytetrafluoroethylene-lined reaction kettle, heated to 115°C, reacted for 36 h, cooled to room temperature, and after filtration, washing, and drying, it is heated from room temperature to 580°C at a rate of 4°C / min, calcined for 5.5 h, cooled to room temperature, and a modified zeolite powder is prepared.

[0054] Example 3: A zeolite composite material for in-situ remediation of black and odorous water bodies while improving the structure of sediment, comprising the following process:

[0055] Step S1: 10 g of natural zeolite powder is added to 100 mL of 0.1 mol / L ferric chloride solution, stirred and mixed thoroughly, and then 100 mL of 0.15 mol / L potassium permanganate solution is slowly added. 0.8 mol / L sodium hydroxide solution is used to adjust the system pH to 10.5, and stirring is continued for 4 h to ensure complete reaction, to obtain a zeolite loaded iron-manganese bimetallic mixed solution.

[0056] Step S2: The zeolite loaded iron-manganese bimetallic mixed solution obtained in step S1 is placed in a centrifuge, centrifuged at 3500 rpm for 3 min, washed with water, placed in a 40℃ electric heating constant temperature drying oven for drying to constant weight, then crushed to 600 mesh, placed in a muffle furnace for calcination (calcination temperature 500℃, heating rate 15℃ / min, calcination time 2h), cooled to room temperature, to obtain a zeolite loaded iron-manganese bimetallic composite material, i.e. a zeolite composite material.

[0057] The natural zeolite powder is subjected to modification treatment, and the specific modification process is as follows:

[0058] Step (1): Under nitrogen protection, 6g of 4-chloro-allyloxybenzene and 60g of dimethyl sulfoxide are uniformly mixed, heated to 50℃, and 5g of tetradecyl dimethyl tertiary amine is added dropwise, 2h dropwise, the reaction time is 2h, the temperature is increased to 60℃, and the reaction is kept for 10h, then rotary evaporation is performed to prepare an intermediate; 0.15g of emulsifier, 0.6g of glycerol, and 1g of vinyl silicone oil are uniformly mixed and emulsified for 40min to prepare emulsified silicone oil; under nitrogen protection, 5g of the intermediate is heated to 80℃, and 0.045g of 65wt% aqueous azobisdimethylaminoformamide hydrochloride solution and emulsified silicone oil are added dropwise in sequence, 2h dropwise, reaction for 20min, continue to add 0.045g of 65wt% aqueous azobisdimethylaminoformamide hydrochloride solution, keep reaction for 12h, then rotary evaporation is performed to prepare a template;

[0059] Step (2): 10g of natural zeolite powder and 30g of sodium hydroxide particles are uniformly mixed, calcined at 600℃ for 3h, 1000g of deionized water is added after calcination, and stirring is continued for 24h, then the upper liquid is taken and reserved;

[0060] Step (3): 5g of the template and 70g of deionized water are uniformly mixed, 150g of the upper liquid is added dropwise under the condition of 40℃ water bath, 2h dropwise, stirring for 2h, 2mol / L hydrochloric acid solution is used to adjust the system pH to 10.5, after uniform stirring, it is transferred into a polytetrafluoroethylene lined reaction kettle, heated to 120℃, reacted for 48h, cooled to room temperature, then filtered, washed and dried, then heated from room temperature to 600℃ at a rate of 5℃ / min, calcined for 6h, cooled to room temperature, to prepare modified zeolite powder.

[0061] Comparative Example 1: A zeolite composite material for in-situ repair of black and odorous water body and improvement of sediment structure, comprising the following process:

[0062] The natural zeolite powder is subjected to modification treatment, and the specific modification process is as follows:

[0063] Step (1): 1 g of 4-chloro-allyloxybenzene and 50 g of dimethyl sulfoxide were mixed uniformly under nitrogen protection, and 5 g of tetradecyldimethyl tertiary amine was added dropwise at 50 °C for 2 h. The reaction was carried out at 60 °C for 10 h. After rotary evaporation, an intermediate was prepared. 0.15 g of emulsifier, 0.6 g of glycerol, and 1 g of vinyl silicone oil were mixed uniformly and emulsified for 40 min to prepare emulsified silicone oil. 5 g of the intermediate was heated to 80 °C under nitrogen protection, and 0.045 g of 65 wt% aqueous azobisdimethylaminoformamide hydrochloride solution and emulsified silicone oil were added dropwise in sequence for 2 h. The reaction was carried out for 20 min, and then 0.045 g of 65 wt% aqueous azobisdimethylaminoformamide hydrochloride solution was added dropwise. The reaction was carried out for 12 h. After rotary evaporation, a template was prepared.

[0064] Step (2): 10 g of natural zeolite powder and 30 g of sodium hydroxide particles were mixed uniformly and calcined at 600 °C for 3 h. After calcination, 1000 g of deionized water was added, and stirring was continued for 24 h. The upper liquid was taken and reserved.

[0065] Step (3): 5 g of the template and 70 g of deionized water were mixed uniformly. 150 g of the upper liquid was added dropwise under the condition of a 40 °C water bath for 2 h. After stirring for 2 h, the pH of the system was adjusted to 10.5 using 2 mol / L hydrochloric acid solution. After uniform stirring, the system was transferred into a polytetrafluoroethylene-lined reaction kettle, heated to 120 °C, and reacted for 48 h. After cooling to room temperature, the product was filtered, washed, and dried. The product was heated from room temperature to 600 °C at a rate of 5 °C / min and calcined for 6 h. After cooling to room temperature, a modified zeolite powder was prepared.

[0066] In Step (1) of Comparative Example 1, the mass ratio of tetradecyldimethyl tertiary amine to 4-chloro-allyloxybenzene was changed from 5:6 to 5:1, and the other steps were the same as those of Example 3.

[0067] Experiment: The black and odorous water body and the sediment in this experiment were taken from a black and odorous river in Dongguan City, Guangdong Province, and the water quality parameters are shown in the following table:

[0068]

[0069] The zeolite composite materials obtained in Examples 1-3 and Comparative Example 1 were taken to prepare samples, and the performance of the samples was detected and the detection results were recorded.

[0070] Experiment 1: 100 g of black and odorous sediment and 200 mL of black and odorous river overlying water were mixed to prepare a mixed solution. 0.5 g of the zeolite composite material prepared in Examples 1, 2, 3, and Comparative Example 1 was added, and 5 g of the zeolite composite material prepared in Examples 1, 2, 3, and Comparative Example 1 was added. After 7 days, there were obvious experimental data changes and apparent effects.

[0071] Test results:

[0072]

[0073] Based on the data in the table above, the following conclusions can be clearly drawn:

[0074] 1. Experimental data as follows Figure 2 As shown, in Example 1 with an addition of 0.5g, the removal rates of ammonia nitrogen, total phosphorus, and COD in the overlying water reached 15.48%, 15.65%, and 41.53%, respectively, and the dissolved oxygen concentration increased to 2.16 mg / L. In Example 1, with the addition of 5g of zeolite composite material, the removal rates of ammonia nitrogen, total phosphorus, and COD in the overlying water reached 80.30%, 95.29%, and 93.97%, respectively, and the dissolved oxygen concentration increased to 6.23 mg / L. Compared with the control group, the NH4 obtained in Examples 1-3... + The removal efficiency of -N, TP and COD was improved, indicating that the addition of zeolite composite materials can significantly improve water quality.

[0075] 2. Compared with Example 1, the NH4 obtained in Examples 2 and 3 + The removal efficiency of N, TP and COD has been improved, indicating that the present invention improves the adsorption and degradation efficiency of pollutants by modifying zeolite powder to provide more active sites.

[0076] 3. Compared with Examples 1-3, the NH4 obtained in Comparative Example 1 + The removal efficiency of -N, TP and COD decreased, indicating that the intermediate prepared by this invention is affected by the ratio of each reagent in its preparation process. By selecting the mass ratio within the range mentioned above, modified zeolite powder with excellent adsorption and degradation efficiency can be prepared, thereby improving the performance of zeolite composite materials.

[0077] 4. The appearance of the overlying water and bottom sediment in black and odorous water bodies also changes significantly. For example... Figure 3 As shown, the addition of zeolite composite materials effectively controlled the suspension of black and odorous sediment, making the overlying water appear clearer. With increasing material addition, the turbidity of the overlying water decreased more rapidly. In the example with an addition of 5g, a large amount of elemental sulfur appeared at the mud-water interface, odorous substances were essentially removed, the surface sediment ashing effect was significant, the composition of blackening substances in the sediment was significantly improved, and the toxicity of the sediment was significantly reduced. Simultaneously, the addition of zeolite-supported iron-manganese composite materials effectively promoted electron transfer, forming micro-batteries that activated the activity of microorganisms in the sediment; the greater the addition, the more pronounced the effect. Furthermore, total nitrogen and total phosphorus in the sediment were effectively removed, thereby inhibiting the release of N and P into the water body. The removal effect was as follows: Figure 4 As shown, although the degradation rate of pollutants in the sediment is slower than that in the overlying water in a short period of time, the zeolite-supported iron-manganese bimetallic composite material has a significant effect on removing total nitrogen and total phosphorus compared with the control group.

[0078] Experiment 2: 100 g of black and odorous sludge and 200 mL of black and odorous river overlying water were mixed to form a mixture, and three groups of experiments were carried out without adding (control group) and by adding the zeolite composite prepared in Example 1 by surface covering and stirring and mixing the zeolite composite prepared in Example 1, and the amount of addition was 5 g. In the experiment group using the stirring and mixing addition method, it will first be turbid, but then the black and odorous can be basically eliminated after 1 day, and become clear, achieving the effect of more quickly and efficiently improving the ecology of black and odorous water. Although the results of these two processes are quite different, the efficiency of apparent phenomenon changes is different, but their principles of action are the same, and the effects achieved are consistent. Of course, by stirring and adding, the efficiency is improved, but the operating cost required will be higher.

[0079] It should be noted that in this document, relational terms such as first and second and the like can be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises", "comprising", or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0080] Finally, it should be noted that the above descriptions are only preferred embodiments of the present application, and are not used to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent replacements to some technical features. Any modifications, equivalent replacements and improvements within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a zeolite composite material for in-situ remediation of black and odorous water while improving the structure of the sediment, characterized by: Comprise the following steps: Step S1: the natural zeolite powder is added into ferric chloride solution, after mixing with sufficient stirring, then slowly add potassium permanganate solution, using sodium hydroxide solution to adjust the system pH = 9.8-10.5, continue to stir until the reaction is completed, to obtain zeolite loaded iron manganese bimetallic mixed solution; Step S2: the zeolite loaded iron manganese bimetallic mixed solution obtained in step S1 is placed in a muffle furnace after centrifugation, washing, drying and crushing, and is calcined, and is cooled to room temperature to obtain a zeolite loaded iron manganese bimetallic composite material, i.e. a zeolite composite material; The natural zeolite powder is subjected to modification treatment, and the specific modification process is as follows: Step (1): under nitrogen protection, 4-chloro-allyloxybenzene and dimethyl sulfoxide are mixed uniformly, and the temperature is raised to 40-50 DEG C, tetradecyl dimethyl tertiary amine is added dropwise, and the dropping is completed in 1-2 h, the reaction time is 1-2 h, the temperature is raised to 55-60 DEG C, and the reaction is kept for 8-10 h, then the intermediate is prepared by rotary evaporation; the emulsifier, glycerol and vinyl silicone oil are mixed uniformly, and the emulsified silicone oil is prepared by emulsifying for 20-40 min; under nitrogen protection, the intermediate is heated to 70-80 DEG C, and 1 / 2 mass fraction of azobisdimethylaminoformamide hydrochloride aqueous solution and the emulsified silicone oil are added dropwise in sequence, the dropping is completed in 1-2 h, the reaction is carried out for 10-20 min, the remaining 1 / 2 mass fraction of azobisdimethylaminoformamide hydrochloride aqueous solution is continuously added dropwise, the reaction is kept for 10-12 h, and then the template agent is prepared by rotary evaporation; Step (2): the natural zeolite powder and sodium hydroxide particles are mixed uniformly, and are calcined at 550-600 DEG C for 2-3 h, then deionized water is added, and the stirring is kept for 22-24 h, then the upper liquid is taken and is prepared for use; Step (3): the template agent and deionized water are mixed uniformly, the upper liquid is added dropwise under the condition of water bath at 35-40 DEG C, the dropping is completed in 1-2 h, the stirring is carried out for 1-2 h, the system pH is adjusted to 9.5-10.5 by using hydrochloric acid solution, then the system is uniformly stirred, and is transferred into a polytetrafluoroethylene lined reaction kettle, heated to 110-120 DEG C, and reacted for 24-48 h, then the system is cooled to room temperature, and is filtered, washed and dried, then the temperature is raised to 550-600 DEG C from room temperature at a rate of 3-5 DEG C / min, and is calcined for 5-6 h, then the system is cooled to room temperature, and the modified zeolite powder is prepared.

2. The method of claim 1, wherein the method comprises: (a) mixing the zeolite with the water; (b) adding the mixture to the black and odorous water body; and (c) allowing the mixture to react with the black and odorous water body. In step S1, the mass ratio of the natural zeolite powder, the ferric chloride solution and the potassium permanganate solution is 10:(1.3-4.2):(0.8-2.4).

3. The method of claim 1, wherein the method comprises: (a) mixing the zeolite with the water; (b) adding the mixture to the black and odorous water body; and (c) allowing the mixture to react with the black and odorous water body. In step S1, the concentration of the ferric chloride solution is 0.1-0.3 mol / L, the concentration of the potassium permanganate solution is 0.05-0.15 mol / L, and the concentration of the sodium hydroxide solution is 0.5-1.0 mol / L.

4. The method of claim 1, wherein the method comprises: (a) mixing the zeolite with the water; (b) adding the mixture to the black and odorous water body; and (c) allowing the mixture to react with the black and odorous water body. In step S2, the specific steps of centrifugation, washing, drying and crushing are as follows: centrifugation is carried out at 2800-3500 rpm for 3-5 min, washing is carried out with water, the system is dried to constant weight in a 40-60 DEG C electric heating constant temperature air drying oven, and then is crushed to 500-1000 mesh.

5. The method of claim 1, wherein the method comprises: (a) mixing the zeolite with the water; (b) adding the mixture to the black and odorous water body; and (c) allowing the mixture to react with the black and odorous water body. In step S2, the calcination process conditions are as follows: the calcination temperature is 200-500 DEG C, the temperature rising rate is 8-15 DEG C / min, and the calcination time is 2-4 h.

6. The method of claim 1, wherein the method comprises: (a) mixing the zeolite with the water; (b) adding the mixture to the black and odorous water body; and (c) allowing the mixture to react with the black and odorous water body. The mass of the tetradecyldimethyl tertiary amine in step (1) is 1: (1.0-1.2) of the mass of 4-chloro-allyloxybenzene.

7. A zeolite composite material prepared by the method of any one of claims 1-6.

8. The zeolite composite of claim 7, wherein: The zeolite composite material has a zeolite core and an iron-manganese bimetallic coating on the surface; the zeolite is a natural zeolite powder with a structural formula of mCaO·xAl2O3·ySiO2·zH2O; the iron-manganese bimetallic source is ferric chloride and potassium permanganate, respectively.

9. The zeolite composite material of claim 7 is used for in-situ remediation of black and odorous water bodies while improving the structure of the sediment.

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