Renewable adsorption material for sewage treatment and preparation method thereof

Abstract

The invention belongs to the technical field of sewage treatment, and particularly relates to a renewable adsorption material for sewage treatment and a preparation method of the renewable adsorption material. 20 to 50 parts of a fluxing agent; 10 to 20 parts of a pore forming agent; 3 to 10 parts of a binder; the renewable adsorption material for sewage treatment has the advantages of being wide in raw material source, low in preparation cost, high in mechanical strength, high in specific surface area, good in adsorption performance and renewable.

Description

Technical Field

[0001] The invention belongs to the technical field of sewage treatment, and in particular relates to a renewable adsorption material for sewage treatment and a preparation method thereof. Background Art

[0002] With the development of modern society, the discharge of industrial and domestic sewage is increasing, and the pollutants contained in the sewage are also increasing. Among them, organic pollutants have great harm to the environment and human health. The sewage must be deeply purified before discharge to avoid environmental pollution.

[0003] At present, there are many methods for treating organic polluted wastewater, such as common biological methods, physical methods, chemical methods, etc. Among them, the biological method is a method of using the metabolic activities of microorganisms to decompose organic pollutants in wastewater, mainly including aerobic biological treatment, anaerobic biological treatment, biochemical method, biosorption method, bioflocculation method, etc.; the microorganisms that play a key role in the biological method are very susceptible to toxic and harmful organic pollutants, resulting in wastewater treatment that cannot meet satisfactory standards. Therefore, the operation and management process is relatively complicated and requires professional technicians to conduct continuous monitoring and maintenance. If it is poorly managed or improperly operated, it may lead to a decrease in treatment effect or system collapse, and the application is difficult. The chemical method is a method of using chemical reagents for oxidation treatment, and it is also treated by precipitation technology. The chemical method usually requires the introduction of new chemical agents. It is often difficult to avoid the formation of new chemical pollution during the generation of these chemical agents, and the price of chemical agents is usually more expensive. Physical treatment is a method of removing or transforming organic matter in wastewater by physical means, such as adsorption method, membrane separation technology, etc. Among them, adsorption method is a method of using porous solid adsorbents to adsorb one or several pollutants in sewage to recover or remove these pollutants, thereby purifying sewage. Adsorption method has the advantages of good treatment effect, high effluent quality, stable operation, simple operation, convenient management, simple process, wide application range, etc. It is one of the most widely used water treatment technologies at present. However, at the same time, adsorption method also has the problems of high adsorbent cost and difficulty in regeneration, and the pollutants adsorbed by the adsorbent still need to be properly treated, otherwise it may cause secondary pollution.

[0004] In order to reduce the manufacturing cost of porous adsorbents for treating sewage by adsorption, technicians in this field have tried many methods, such as the Chinese patents with publication (announcement) numbers CN112979275B and CN112279243B, which use low-cost materials or industrial waste such as sludge, garbage incineration ash, blast furnace slag, steel slag, river sand, waste glass, coal gangue, etc. to prepare porous adsorbents with low cost and good adsorption effect. Among them, the method of preparing porous adsorbents by sludge carbonization can not only treat sludge, reduce sludge storage and transportation costs, but also obtain solid carbides with stable biological and chemical properties. Sludge carbides are mainly composed of elements such as carbon, hydrogen, oxygen, and nitrogen, and contain minerals such as aluminum, iron, potassium, sodium, magnesium, and calcium. They contain rich microporous structures, large specific surface area and adsorption characteristics, good water permeability and air permeability, and good adsorption of heavy metal ions, organic pollutants, etc. At present, sludge carbides have been widely used as porous adsorbents for wastewater and waste gas treatment. However, the source of fixed carbon in sludge carbonization is the pyrolysis of organic matter in the sludge. In addition to organic matter, the sludge also contains a large amount of non-carbonizable inorganic matter, heavy metal ions, soil and other components, which leads to the specific surface area and adsorption performance of sludge carbonization being significantly worse than those of activated carbon. In addition, the strength of sludge carbonization is low, and the sludge carbonization is easy to break and pulverize under the long-term erosion of water flow, which is also one of the factors limiting its circulation and application.

[0005] In this context, finding new and more cost-effective porous adsorbents for sewage treatment has become one of the long-term research directions of technicians in this field. We found that: At present, people's consumption of plastic products remains high. For example, China's production and consumption of plastic products are among the highest in the world, but the recycling rate of plastic waste is generally low worldwide. A large amount of plastic waste is not effectively recycled and reused, but is landfilled or incinerated. If plastic waste can be used to prepare porous adsorbents for sewage treatment, then while achieving plastic waste treatment, it can also reduce the preparation cost of porous adsorbents, providing a new way to prepare porous adsorbents.

[0006] In view of this, the present invention provides an adsorbent material for sewage treatment based on waste plastics, which has low preparation cost, good adsorption effect, high mechanical strength, is not prone to secondary pollution, and is renewable. Summary of the invention

[0007] The purpose of the present invention is to provide a new type of renewable adsorption material for sewage treatment in view of the above-mentioned technical problems.

[0008] In view of this, the present invention provides a method for preparing a renewable adsorbent material for sewage treatment, wherein the renewable adsorbent material for sewage treatment comprises the following raw materials in parts by weight: Aggregate 70~120 parts; 20~50 parts of flux; 10-20 parts of pore-forming agent; 3~10 parts of binder; 30~90 parts of plastic particles.

[0009] Furthermore, the renewable adsorbent material for sewage treatment also includes 3 to 15 parts by weight of reinforcing fibers, and the fire-resistant temperature of the reinforcing fibers is ≥ 1100°C.

[0010] Furthermore, the aggregate includes inorganic particles of three sizes: large, medium and small, wherein the average particle size of the large-sized inorganic particles is 0.5-1 mm, the average particle size of the medium-sized inorganic particles is 100-300 um, and the average particle size of the small-sized inorganic particles is <100 um. The aggregate is a mixture of natural inorganic minerals and industrial inorganic solid waste, wherein the industrial inorganic solid waste accounts for 20-40 wt% of the total aggregate.

[0011] Furthermore, the binder is an inorganic sol, and the solid content of the inorganic sol is 5-20wt%.

[0012] Furthermore, the particle size of the plastic particles is 0.5-1 mm, and the plastic particles are selected from one or more of polyethylene, polypropylene, and polystyrene.

[0013] Furthermore, the method for preparing the renewable adsorbent material for sewage treatment comprises the steps of: S1, prepare aggregate: (1) First, the natural inorganic mineral particles and the industrial inorganic solid waste particles are screened to obtain natural inorganic mineral particles and industrial inorganic solid waste particles with an average particle size of 0.5-1 mm, natural inorganic mineral particles and industrial inorganic solid waste particles with an average particle size of 100-300 μm, and natural inorganic mineral particles and industrial inorganic solid waste particles with an average particle size of less than 100 μm; (2) Then, according to the weight ratio of large, medium and small inorganic particles in the aggregate, natural inorganic mineral particles or industrial inorganic solid waste particles of corresponding particle sizes are selected to prepare the aggregate, wherein the aggregate is a mixture of natural inorganic minerals and industrial inorganic solid waste, and the industrial inorganic solid waste accounts for 20-40wt% of the total amount of the aggregate; (3) Then, the selected industrial inorganic solid waste particles are dispersed in an alkaline solution, and after sufficient stirring, an alkaline suspension of the industrial inorganic solid waste particles is obtained, and the suspension is heated to 50-90° C., kept warm for 1-3 hours, filtered, and dried to obtain pretreated industrial inorganic solid waste particles; (4) mixing and stirring the pretreated industrial inorganic solid waste particles and natural inorganic mineral particles to obtain aggregate; S2, uniformly mixing the aggregate prepared in step S1 with a flux, a pore former and a binder in a prescribed amount to obtain a mixture I; S3, mixing the formulated amount of plastic particles with the mixture I uniformly to obtain a mixture II; S4, shaping the mixture II to obtain a profile III; S5, placing the profile III in a high-temperature carbonization furnace for calcination and carbonization, and then naturally cooling to room temperature to obtain the carbonized profile IV, which is the renewable adsorption material for sewage treatment.

[0014] Furthermore, in step S5, a staged carbonization process or a one-stage carbonization process is used to perform high-temperature carbonization treatment on the profile III: Among them, the segmented carbonization process is: (1) Pre-oxidation treatment: First, place profile III in a high-temperature furnace at 300-500°C for pre-oxidation treatment in an air atmosphere for 20-60 minutes; (2) Carbonization treatment: placing the pre-oxidized profile III in a high-temperature carbonization furnace, calcining and carbonizing it at 600-1000° C. for 2-4 hours under the protection of an inert atmosphere, and then naturally cooling it to room temperature to obtain the renewable adsorption material for sewage treatment; The one-stage carbonization process is as follows: placing the profile III in a high-temperature carbonization furnace, calcining and carbonizing it at 600-1000°C for 3-5 hours under the protection of an inert atmosphere, and then naturally cooling it to room temperature to obtain the renewable adsorption material for sewage treatment.

[0015] Furthermore, after obtaining the adsorption material through step S5, the adsorption material obtained in step S5 is post-processed by a physical activation or plasma etching process, wherein: The physical activation process is as follows: firstly, the carbonized profile IV is placed in an argon atmosphere furnace, and then water vapor is loaded into the atmosphere furnace through argon as an activating agent, wherein the total flow rate of argon and water vapor is 50-80 mL / min, and the volume ratio of argon and water vapor is 1:(1.2-1.8); and the furnace temperature in the atmosphere furnace is raised to 500-800°C at a rate of 5-10°C / min, and then kept warm for 0.5-1.5h, and then naturally cooled to obtain the post-treated renewable adsorption material for sewage treatment; The plasma etching process is as follows: using hydrogen fluoride as etching gas, the renewable adsorbent material for sewage treatment is subjected to plasma etching at an etching pressure of 40-60 Pa, a gas flow rate of 40-80 sccm, and a power of 50-60 W. During the plasma etching process, it should be ensured that the surface of the adsorbent material is evenly exposed to the plasma. The etching time is 20-60 min. After the etching is completed, the adsorbent material is washed with water and dried at a low temperature of 40-80° C. to obtain the renewable adsorbent material for sewage treatment after post-treatment.

[0016] Furthermore, the regeneration process of the regenerable adsorbent material for sewage treatment comprises the steps of: P1, placing the adsorbent saturated material in a high-temperature carbonization furnace, calcining and carbonizing at 600-1000°C for 1-2 hours under the protection of argon atmosphere; P2, then water vapor is loaded into the atmosphere furnace as an activating agent through argon gas, wherein the total flow rate of argon gas and water vapor is 30~50mL / min, and the volume ratio of argon gas to water vapor is 1:(1.2~1.8); and the furnace temperature in the atmosphere furnace is increased to 500~800℃ at a rate of 10~15℃ / min, and then kept warm for 10~30min, and the regenerated adsorption material is obtained after natural cooling.

[0017] A renewable adsorption material for sewage treatment, wherein the renewable adsorption material for sewage treatment is the adsorption material prepared by the above-mentioned preparation method.

[0018] The beneficial effects of the present invention are: The renewable adsorption material for sewage treatment of the present invention has the advantages of wide raw material sources, low preparation cost, high mechanical strength, high specific surface area, good adsorption performance and renewability. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 is a flow chart for preparing the regenerable adsorbent material for sewage treatment according to the present invention; Figure 2 This is a physical cross-sectional view of the renewable adsorbent material for sewage treatment prepared by the present invention; Figure 3 It is a graph showing the variation trend of the adsorption performance of the regenerable adsorbent material for sewage treatment according to the present invention with the number of regeneration times. DETAILED DESCRIPTION

[0020] The following will be combined with the drawings in the embodiments of the present application to clearly describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments in the present application belong to the scope of protection of this application.

[0021] It should be noted that, in the present application, the terms "comprise", "include" or any other variant thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, an element defined by the sentence "comprises one..." does not exclude the presence of other identical elements in the process, method, article or device including the element. In addition, it should be noted that the scope of the method and device in the embodiment of the present application is not limited to performing functions in the order shown or discussed, and may also include performing functions in a substantially simultaneous manner or in reverse order according to the functions involved, for example, the described method may be performed in an order different from that described, and various steps may also be added, omitted, or combined. In addition, the features described with reference to certain examples may be combined in other examples.

[0022] A method for preparing a renewable adsorbent material for sewage treatment, the renewable adsorbent material for sewage treatment comprising the following raw materials in parts by weight: Aggregate 70~120 parts; 20~50 parts of flux; 10-20 parts of pore-forming agent; 3~10 parts of binder; 30~90 parts of plastic particles.

[0023] Furthermore, the renewable adsorbent material for sewage treatment also includes 3 to 15 parts by weight of reinforcing fibers.

[0024] Preferably, the reinforcing fiber is a high temperature resistant fiber, and the fire resistant temperature of the reinforcing fiber is ≥1100°C.

[0025] As some examples of the present invention, the reinforcing fiber is selected from one or more of asbestos fiber, aluminum silicate fiber, zirconium dioxide fiber, mullite refractory fiber, silicon carbide fiber and the like.

[0026] The provision of the reinforcing fibers can improve the skeleton structure of the prepared renewable adsorbent material product for sewage treatment, help form more open pores, improve its porosity, structural strength and toughness, and thus increase its regeneration and recycling times. At the same time, by adding the reinforcing fibers, it can be used as a bridge for stress conduction during high-temperature treatment, reduce the accumulation of internal stress, and avoid cracking caused by stress accumulation caused by temperature gradient during high-temperature treatment.

[0027] Preferably, the aggregate includes inorganic particles of large, medium and small particle sizes, wherein the average particle size of the large-sized inorganic particles is 0.5-1 mm, the average particle size of the medium-sized inorganic particles is 100-300 um, and the average particle size of the small-sized inorganic particles is <100 um.

[0028] More preferably, in the aggregate, the weight ratio of the large-size inorganic particles, the medium-size inorganic particles and the small-size inorganic particles is (1-3): (4-6): (2-3).

[0029] In the present invention, inorganic particles with large, medium and small particle sizes are used as aggregates. The large-diameter inorganic particles can form the skeleton of the adsorption material, ensure the mechanical strength of the adsorption material, and provide a larger flow channel for the fluid, which is beneficial to the rapid diffusion and transmission of the substance; the medium-diameter inorganic particles mainly play a connecting role, filling the gaps between the large-diameter inorganic particles, improving the strength of the adsorption material, and maintaining a certain porosity; the small-diameter inorganic particles are filled in the pores, mainly playing the role of increasing the specific surface area, providing more adsorption sites, and improving the adsorption efficiency. In this way, through the compounding of large, medium and small-diameter inorganic particles, the pore size distribution can be optimized, which is helpful to form a multi-level pore structure with good connectivity. This is beneficial to the rapid transmission of substances and provides a large number of adsorption sites, thereby improving the permeability, selectivity, adsorption capacity and adsorption efficiency of the adsorbent.

[0030] As some examples of the present invention, the aggregate is selected from one or more natural inorganic minerals such as mica, potassium feldspar, sodium feldspar, quartz sand, talc, wollastonite, river sand, etc. In addition, the aggregate can also be selected from one or more industrial inorganic solid wastes such as blast furnace slag, steel slag, coal gangue, fly ash, etc.

[0031] Preferably, the aggregate is a mixture of natural inorganic minerals and industrial inorganic solid wastes, wherein the industrial inorganic solid wastes account for 20-40wt% of the total amount of the aggregate.

[0032] As some examples of the present invention, the flux is selected from one or more of potassium oxide, magnesium oxide, calcium oxide, barium oxide, boron oxide, aluminum oxide, zinc oxide, calcium fluoride, magnesium fluoride, sodium borate, potassium borate, zinc borate, low-melting point glass powder, etc.

[0033] Preferably, the melting temperature of the flux is 300-1000°C.

[0034] More preferably, the melting temperature of the flux is 350-500°C.

[0035] Preferably, the pore former is an inorganic pore former.

[0036] As some examples of the present invention, the pore-forming agent is selected from one or more of calcium carbonate, ammonium carbonate, ammonium bicarbonate, ammonium chloride and the like.

[0037] Preferably, the binder is an inorganic sol.

[0038] More preferably, the solid content of the inorganic sol is 5-20wt%.

[0039] As some examples of the present invention, the binder is selected from one or more of silica sol, alumina sol, and zirconia sol.

[0040] By adding the binder on the basis of the reinforcing fibers, the mechanical strength and durability of the adsorbent material can be further improved.

[0041] Preferably, the average particle size of the plastic particles is 0.5-1 mm, that is, the particle size of the plastic particles should be comparable to the average particle size of the large-sized inorganic particles in the aggregate. If the particle size of the plastic particles is too small, the volume of the carbon material phase formed after carbonization is too small and it is easy to escape from the matrix.

[0042] Preferably, the plastic particles are particles of waste plastic.

[0043] Preferably, the melting temperature of the plastic particles is 100-300°C.

[0044] As some examples of the present invention, the plastic particles are selected from polyethylene (PE), polypropylene (PP), polystyrene (PS), etc. These types of plastics are relatively common, easy to collect, do not contain metal ions, have high carbon content, and deposit more residual carbon after calcination, which is more conducive to the formation of the carbide phase in the renewable adsorption material for sewage treatment of the present invention.

[0045] Waste plastics are scattered in the social environment, which can easily lead to fire hazards, soil pollution, water pollution such as oceans and rivers, and human health risks, seriously damaging the living environment. In the present invention, waste plastics are used to prepare renewable adsorbent materials for sewage treatment, which can not only achieve the recycling and utilization of waste plastics, provide a new way for the reuse of waste plastics, save environment, and comprehensively utilize resources, but also reduce the preparation cost of adsorbent materials, thereby reducing the cost of sewage treatment.

[0046] Further, such as Figure 1 As shown, the method for preparing the renewable adsorbent material for sewage treatment of the present invention comprises the steps of: S1, prepare aggregate: (1) First, the natural inorganic mineral particles and the industrial inorganic solid waste particles are screened to obtain natural inorganic mineral particles and industrial inorganic solid waste particles with an average particle size of 0.5-1 mm, natural inorganic mineral particles and industrial inorganic solid waste particles with an average particle size of 100-300 μm, and natural inorganic mineral particles and industrial inorganic solid waste particles with an average particle size of less than 100 μm; (2) Then, according to the weight ratio of large, medium and small inorganic particles in the aggregate, natural inorganic mineral particles or industrial inorganic solid waste particles of corresponding particle sizes are selected to prepare the aggregate, wherein the aggregate is a mixture of natural inorganic minerals and industrial inorganic solid waste, and the industrial inorganic solid waste accounts for 20-40wt% of the total amount of the aggregate; (3) Then, the selected industrial inorganic solid waste particles are dispersed in an alkaline solution, and after sufficient stirring, an alkaline suspension of the industrial inorganic solid waste particles is obtained, and the suspension is heated to 50-90° C., kept warm for 1-3 hours, filtered, and dried to obtain pretreated industrial inorganic solid waste particles; (4) mixing and stirring the pretreated industrial inorganic solid waste particles and natural inorganic mineral particles to obtain aggregate; S2, uniformly mixing the aggregate prepared in step S1 with a flux, a pore former and a binder in a prescribed amount to obtain a mixture I; S3, mixing the formulated amount of plastic particles with the mixture I uniformly to obtain a mixture II; S4, shaping the mixture II to obtain a profile III; S5, placing the profile III in a high-temperature carbonization furnace for calcination and carbonization, and then naturally cooling to room temperature to obtain the carbonized profile IV, which is the renewable adsorption material for sewage treatment.

[0047] As some examples of the present invention, when only natural inorganic mineral particles are selected as aggregates, the aggregates can be directly mixed with flux, pore former and binder in step S2 to obtain mixture I.

[0048] It should be noted that for general adsorption materials, in the preparation process of the aggregate, there is no specific limitation on the weight proportion of industrial inorganic solid waste in inorganic particles of large, medium and small particle sizes, and it can be configured according to needs, and it is only necessary to ensure that the proportion of industrial inorganic solid waste in the total amount of aggregate meets the requirements.

[0049] However, in a sewage treatment environment with a high sewage flow rate, severe scouring, and higher requirements for adsorption material strength, it is preferred that the weight proportion of industrial inorganic solid waste in inorganic particles of large, medium, and small particle sizes be set to increase in sequence, such as the weight proportion of industrial inorganic solid waste in inorganic particles of large particle size is 15wt%, the weight proportion of industrial inorganic solid waste in inorganic particles of medium particle size is 25wt%, and the weight proportion of industrial inorganic solid waste in inorganic particles of small particle size is 35wt%.

[0050] In the preparation process of the adsorption material described in the present invention, by placing the industrial inorganic solid waste in an alkaline solution for heating and soaking treatment, the surface structure of the industrial inorganic solid waste formed in the early high-temperature treatment process can be corroded and destroyed. On the one hand, the activity of soluble silica, alumina and other components inside the industrial inorganic solid waste can be released, and it is easy to combine with other components in the adsorption material, such as calcium oxide, in the subsequent high-temperature treatment process, thereby promoting the binding force between different aggregate particles, aggregate particles and flux, and aggregate particles and carbon material phases, greatly improving the strength of the final adsorption material.

[0051] Preferably, in step S1, the alkaline solution is one or more of strong alkaline solutions such as sodium hydroxide solution and potassium hydroxide solution.

[0052] Preferably, in step S1, the concentration of the alkaline solution is 5-15wt%.

[0053] Preferably, in step S1, the amount of the alkaline solution used is 1.5 to 3 times the weight of the industrial inorganic solid waste.

[0054] Preferably, in step S3, a screw extruder, a kneader, an internal mixer, etc. can be used to mix the plastic particles and the mixture I, the mixing time is 5 to 15 minutes, and the mixing temperature is determined according to the plasticizing temperature of the plastic particles, and the mixing temperature is preferably equal to or slightly higher than the plasticizing temperature of the plastic particles, such as 130-280° C. It should be noted that, generally, the mixing temperature should not exceed 300° C. to prevent the melt from decomposing.

[0055] As some examples of the present invention, in step S4, a plastic tool such as an injection molding machine or a flat-plate vulcanizing machine may be used to shape the mixture II to obtain the profile III.

[0056] Furthermore, in step S5, a staged carbonization process or a one-stage carbonization process may be used to perform high-temperature carbonization treatment on the profile III, specifically: The segmented carbonization process is: (1) Pre-oxidation treatment: First, place profile III in a high-temperature furnace at 300-500°C for pre-oxidation treatment in an air atmosphere for 20-60 minutes; (2) Carbonization treatment: The pre-oxidized profile III is placed in a high-temperature carbonization furnace, and calcined and carbonized at 600-1000° C. for 2-4 hours under the protection of an inert atmosphere, and then naturally cooled to room temperature to obtain the renewable adsorption material for sewage treatment.

[0057] One-stage carbonization process: placing profile III in a high-temperature carbonization furnace, calcining and carbonizing at 600-1000°C for 3-5 hours under the protection of an inert atmosphere, and then naturally cooling to room temperature to obtain the renewable adsorption material for sewage treatment.

[0058] As some examples of the present invention, the carbonization process can be performed under the protection of an inert atmosphere such as argon or helium.

[0059] In addition, in the present invention, after the adsorption material is obtained through the step S5, although the carbon material phase in the adsorption material has a simple pore structure, the pore size and specific surface area are not excellent enough. At this time, the adsorption material obtained in step S5 can be further post-processed by physical activation, plasma etching process, etc. after calcination and carbonization treatment.

[0060] As some examples of the present invention, physical activation can use water vapor as an activator to activate the carbonized profile IV at high temperature, and the specific process is as follows: First, the carbonized profile IV is placed in an argon atmosphere furnace, and then water vapor is loaded into the atmosphere furnace through argon as an activating agent, wherein the total flow rate of argon and water vapor is 50~80mL / min, and the volume ratio of argon to water vapor is 1:(1.2~1.8); and the furnace temperature in the atmosphere furnace is increased to 500~800℃ at a rate of 5~10℃ / min, and then kept warm for 0.5~1.5h. After natural cooling, the regenerable adsorption material for sewage treatment after post-treatment is obtained.

[0061] As some examples of the present invention, the plasma etching process is as follows: hydrogen fluoride is used as the etching gas, and the renewable adsorbent material for sewage treatment is subjected to plasma etching at an etching pressure of 40~60Pa, a gas flow rate of 40~80sccm, and a power of 50~60W. During the plasma etching process, it should be ensured that the surface of the adsorbent material is evenly exposed to the plasma, and the etching time is 20~60min. After the etching is completed, the adsorbent material is washed with water and dried at a low temperature of 40~80°C to obtain the renewable adsorbent material for sewage treatment after post-treatment.

[0062] The color of the renewable adsorption material for sewage treatment obtained by the invention is gray, black profile or granular matter.

[0063] As some examples of the present invention, the dosage of the renewable adsorption material for sewage treatment obtained by the present invention in the polluted water body is 1-10 g / L, which can be adjusted according to the content of pollutants in the sewage.

[0064] The preparation principle of the renewable adsorbent material for sewage treatment of the present invention is as follows: The natural ore powder and industrial inorganic solid waste powder in the material are bonded into a ceramic substrate at high temperature by using a flux, a binder and a reinforcing fiber. At the same time, since the raw material contains a pore-forming agent, a large number of pores will be formed in the material during the high-temperature melting, plasticizing and molding process. Furthermore, under the subsequent high-temperature calcination, the plastic particles are carbonized to form a carbon material phase in the adsorption material, which is dispersed in the ceramic substrate, and the pore size and specific surface area of ​​the carbon material phase are further optimized through the subsequent activation treatment, and finally a composite structure in which a porous ceramic substrate and a carbon material phase are staggered is formed. In this composite structure, the pores in the porous ceramic substrate can provide a low-resistance channel for the flow of the fluid, and the carbon material phase therein can provide favorable conditions for the adsorption of pollutants in the fluid, effectively combining the small-pore filtration and adsorption and impurity removal effects together to achieve efficient sewage treatment.

[0065] Compared with traditional methods of preparing adsorption materials by carbonizing sludge, combining biological organic matter with ceramic substrates, the carbon material obtained after plastic carbonization is harder, more wear-resistant, and resistant to fluid erosion, so it has better mechanical properties and stability, and is more stably combined with the ceramic substrate, and is not easy to escape from the pores of the adsorption material. The resulting adsorption material has higher strength and can be recycled more often.

[0066] In addition, the present invention also provides a method for regenerating the above-mentioned regenerable adsorbent material for sewage treatment, comprising the steps of: P1, placing the adsorbent material saturated with adsorption in a high-temperature furnace, calcining and carbonizing at 600-1000°C for 1-2h under the protection of argon atmosphere; P2, then water vapor is loaded into the atmosphere furnace as an activating agent through argon gas, wherein the total flow rate of argon gas and water vapor is 30~50mL / min, and the volume ratio of argon gas to water vapor is 1:(1.2~1.8); and the furnace temperature in the atmosphere furnace is increased to 500~800℃ at a rate of 10~15℃ / min, and then kept warm for 10~30min, and the regenerated adsorption material is obtained after natural cooling.

[0067] Preferably, after the regenerated adsorption material is obtained by calcination, the ash released from the adsorption material can be removed by shaking or the like.

[0068] On the basis of the adsorption material provided by the present invention, in order to improve the water treatment effect, those skilled in the art may also choose to load and set chemical agents such as photocatalysts on the adsorption material provided by the present invention to degrade pollutants in sewage through chemical reactions, so as to achieve the synergistic treatment effect of physical adsorption and chemical catalytic degradation.

[0069] The following is an example of the regenerable adsorbent material for sewage treatment and the preparation method thereof according to the present invention. Example 1 Preparation of renewable adsorbent materials for wastewater treatment: The raw materials used include: 70 parts by weight of aggregate, 20 parts by weight of flux, 10 parts by weight of pore-forming agent, 3 parts by weight of binder, and 30 parts of plastic particles, wherein the aggregate is a natural inorganic mineral with an average particle size of 250 um, the flux is a mixture of calcium oxide and low-melting-point glass powder, the pore-forming agent is ammonium carbonate, the binder is a silica sol with a solid content of 20wt%, and the plastic particles are a mixture of PE and PP; The preparation process of renewable adsorbent material for sewage treatment is as follows: The aggregate is directly mixed with the flux, pore former and binder in the formula amount to obtain mixture I; Then, the plastic particles in the formula amount are uniformly mixed with the mixture I to obtain a mixture II; The mixture II is molded to obtain a profile III; The profile III is placed in a high-temperature carbonization furnace, calcined and carbonized at 600° C. for 5 hours under the protection of an inert atmosphere, and then naturally cooled to room temperature to obtain the renewable adsorption material for sewage treatment.

[0070] Example 2 Preparation of renewable adsorbent materials for wastewater treatment: The raw materials used include: 70 parts by weight of aggregate, 20 parts by weight of flux, 10 parts by weight of pore-forming agent, 3 parts by weight of binder, and 30 parts of plastic particles, wherein the aggregate includes natural inorganic minerals with an average particle size of 1 mm, natural inorganic mineral particles with an average particle size of 200 um, and natural inorganic mineral particles with an average particle size of 40 um, the weight ratio of large-particle aggregate, medium-particle aggregate, and small-particle aggregate is 1:5:3, the flux is a mixture of calcium oxide and low-melting-point glass powder, the pore-forming agent is ammonium carbonate, the binder is a silica sol with a solid content of 20 wt%, and the plastic particles are a mixture of PE and PP; The preparation process of the regenerable adsorbent material for sewage treatment is the same as that in Example 1.

[0071] Example 3 Preparation of renewable adsorbent materials for wastewater treatment: The raw materials used include: 100 parts by weight of aggregate, 30 parts by weight of flux, 20 parts by weight of pore-forming agent, 8 parts by weight of binder, and 60 parts of plastic particles, wherein the aggregate includes natural inorganic minerals with an average particle size of 1 mm, natural inorganic mineral particles with an average particle size of 200 um, and natural inorganic mineral particles with an average particle size of 40 um, the weight ratio of large-particle aggregate, medium-particle aggregate, and small-particle aggregate is 2:5:2, the flux is a mixture of magnesium oxide, calcium oxide, potassium borate, and low-melting-point glass powder, the pore-forming agent is a mixture of ammonium carbonate and ammonium chloride, the binder is a silica sol with a solid content of 15 wt%, and the plastic particles are PE; The preparation process of renewable adsorbent material for sewage treatment is as follows: The aggregate is directly mixed with the flux, pore former and binder in the formula amount to obtain mixture I; Then, the plastic particles in the formula amount are uniformly mixed with the mixture I to obtain a mixture II; The mixture II is molded to obtain a profile III; The profile III is placed in a high-temperature carbonization furnace, calcined and carbonized at 800° C. for 4 hours under the protection of an inert atmosphere, and then naturally cooled to room temperature to obtain the renewable adsorption material for sewage treatment.

[0072] Example 4 Preparation of renewable adsorbent materials for wastewater treatment: The raw materials used include: 100 parts by weight of aggregate, 30 parts by weight of flux, 20 parts by weight of pore-forming agent, 8 parts by weight of binder, and 60 parts of plastic particles, wherein the aggregate includes a mixture of natural inorganic minerals with an average particle size of 1 mm and industrial inorganic solid waste, a mixture of natural inorganic mineral particles with an average particle size of 200 μm and industrial inorganic solid waste, and a mixture of natural inorganic mineral particles with an average particle size of 40 μm and industrial inorganic solid waste, the weight ratio of large-particle aggregate, medium-particle aggregate and small-particle aggregate is 2:5:2, and the industrial inorganic solid waste accounts for 30wt% of the total amount of aggregate; the flux is a mixture of magnesium oxide, calcium oxide, potassium borate and low-melting point glass powder, the pore-forming agent is a mixture of ammonium carbonate and ammonium chloride, the binder is a silica sol with a solid content of 15wt%, and the plastic particles are PE; The preparation process of renewable adsorbent material for sewage treatment is as follows: The selected industrial inorganic solid waste particles are dispersed in a 10wt% sodium hydroxide solution, wherein the amount of the sodium hydroxide solution added is twice the weight of the industrial inorganic solid waste particles, and after sufficient stirring, an alkaline suspension of the industrial inorganic solid waste particles is obtained, and the suspension is heated to 80°C, kept warm and soaked for 2 hours, filtered, and dried to obtain pretreated industrial inorganic solid waste particles; The pretreated industrial inorganic solid waste particles and natural inorganic mineral particles are mixed and stirred to obtain aggregate; The aggregate is uniformly mixed with the flux, pore former and binder in the formula amount to obtain mixture I; Then, the plastic particles in the formula amount are uniformly mixed with the mixture I to obtain a mixture II; The mixture II is molded to obtain a profile III; The profile III is placed in a high-temperature carbonization furnace, calcined and carbonized at 800° C. for 4 hours under the protection of an inert atmosphere, and then naturally cooled to room temperature to obtain the renewable adsorption material for sewage treatment.

[0073] Example 5 The only difference between this embodiment and the above-mentioned embodiment 4 is that the raw materials used for preparing the regenerable adsorbent material further include 5 parts by weight of mullite refractory fiber.

[0074] Example 6 Preparation of renewable adsorbent materials for wastewater treatment: The raw materials used include: 120 parts by weight of aggregate, 50 parts by weight of flux, 15 parts by weight of pore-forming agent, 10 parts by weight of binder, and 90 parts of plastic particles, wherein the aggregate includes a mixture of natural inorganic minerals with an average particle size of 0.8 mm and industrial inorganic solid waste, a mixture of natural inorganic mineral particles with an average particle size of 300 um and industrial inorganic solid waste, and a mixture of natural inorganic mineral particles with an average particle size of 30 um and industrial inorganic solid waste, the weight ratio of large-particle aggregate, medium-particle aggregate and small-particle aggregate is 3:6:3, and the industrial inorganic solid waste accounts for 40wt% of the total amount of aggregate; the flux is a mixture of magnesium oxide and low-melting point glass powder, the pore-forming agent is a mixture of ammonium carbonate and calcium carbonate, the binder is alumina sol with a solid content of 5wt%, and the plastic particles are a mixture of PE and PS; The preparation process of renewable adsorbent material for sewage treatment is as follows: The selected industrial inorganic solid waste particles are dispersed in a 15wt% sodium hydroxide solution, wherein the amount of the sodium hydroxide solution added is 1.5 times the weight of the industrial inorganic solid waste particles, and after sufficient stirring, an alkaline suspension of the industrial inorganic solid waste particles is obtained, and the suspension is heated to 90°C, kept warm and soaked for 3 hours, filtered, and dried to obtain pretreated industrial inorganic solid waste particles; The pretreated industrial inorganic solid waste particles and natural inorganic mineral particles are mixed and stirred to obtain aggregate; The aggregate is uniformly mixed with the flux, pore former and binder in the formula amount to obtain mixture I; Then, the plastic particles in the formula amount are uniformly mixed with the mixture I to obtain a mixture II; The mixture II is molded to obtain a profile III; Then, the profile III is first placed in a high-temperature furnace at 400°C for pre-oxidation treatment in an air atmosphere for 50 minutes; then the profile III after pre-oxidation treatment is placed in a high-temperature carbonization furnace, and calcined and carbonized at 800°C for 3 hours under the protection of an inert atmosphere, and then naturally cooled to room temperature to obtain the renewable adsorption material for sewage treatment. After the obtained adsorption material is cut, the cross-sectional morphology of its interior is as follows: Figure 2 shown.

[0075] Example 7 The only difference between it and the above-mentioned Example 6 is that the profile III is subjected to high-temperature carbonization treatment by adopting the one-stage carbonization process as shown below: the profile III is placed in a high-temperature carbonization furnace, calcined and carbonized at 800°C for 4 hours under the protection of an inert atmosphere, and then naturally cooled to room temperature to obtain the renewable adsorption material for sewage treatment.

[0076] Embodiment 8-9 Example 8 The renewable adsorbent material for sewage treatment prepared in Example 6 and Example 9 The renewable adsorbent material for sewage treatment prepared in Example 7 were post-treated. The post-treatment process is as follows: First, the regenerable adsorbent material for sewage treatment prepared in the above Examples 6 and 7 is placed in an argon atmosphere furnace, and then water vapor is loaded into the atmosphere furnace through argon as an activator, wherein the total flow rate of argon and water vapor is 60 mL / min, and the volume ratio of argon to water vapor is 1:1.5; and the furnace temperature in the atmosphere furnace is increased to 700°C at a rate of 8°C / min, and then kept warm for 1 hour. After natural cooling, the post-treated regenerable adsorbent material for sewage treatment is obtained.

[0077] Embodiment 10-11 Example 10 The renewable adsorbent material for sewage treatment prepared in Example 6 and Example 11 The renewable adsorbent material for sewage treatment prepared in Example 7 were post-treated. The post-treatment process is as follows: Hydrogen fluoride was used as the etching gas, and the renewable adsorbent material for sewage treatment prepared in the above Examples 6 and 7 was subjected to plasma etching at an etching pressure of 50 Pa, a gas flow rate of 60 sccm, and a power of 60 W. During the plasma etching process, it should be ensured that the surface of the adsorbent material was evenly exposed to the plasma. The etching time was 40 min. After the etching was completed, the adsorbent material was washed with water and dried at a low temperature of 50°C to obtain the renewable adsorbent material for sewage treatment after post-treatment.

[0078] Comparative Example 1 The only difference between it and the above-mentioned embodiment 1 is that no binder is added.

[0079] Comparative Example 2 The only difference between the above-mentioned embodiment 1 is that the regenerable adsorbent material for sewage treatment is prepared by using sludge of equal weight instead of plastic particles. The preparation process is as follows: The aggregate is directly mixed with the flux, pore former, binder and 40 parts by weight of water to obtain a mixture I; Then, the formulated amount of sludge particles is evenly mixed with mixture I to obtain mixture II; The mixture II is placed in a mold and pressed into shape to obtain a profile III; The profile III is placed in a high-temperature carbonization furnace, calcined and carbonized at 600° C. for 5 hours under the protection of an inert atmosphere, and then naturally cooled to room temperature to obtain the renewable adsorption material for sewage treatment.

[0080] Comparative Example 3 The only difference between it and the above-mentioned embodiment 1 is that no plastic particles are added.

[0081] Comparative Example 4 The only difference between it and the above-mentioned Example 4 is that no alkaline solution is used to perform alkaline soaking pretreatment on the industrial inorganic solid waste.

[0082] Test Example 1 The properties of the adsorbent materials prepared in the above Examples 1 to 11 and Comparative Examples 1 to 4 were tested, and the structures are shown in Table 1 below: Table 1 Performance test results of adsorption materials Test Example 2 The adsorption materials prepared in Examples 1 to 11 and Comparative Examples 1 to 4 were used to treat the same organic sewage, the initial COD of which was 265 mg / L, and the amount of adsorption material added was 5 g / L. The results are shown in Table 2 below: Table 2 Water treatment effect of adsorption materials Test Example 3 After the adsorbent prepared in Example 8 was saturated with adsorption, it was regenerated several times according to the adsorption material regeneration method of the present invention, and the COD removal rate (%) of the regenerated adsorbent was tested respectively. The results are shown in FIG. Figure 3 .

[0083] The embodiments of the present application are described above in conjunction with the accompanying drawings. In the absence of conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present application is not limited to the above-mentioned specific implementation methods. The above-mentioned specific implementation methods are merely illustrative and not restrictive. Under the guidance of the present application, ordinary technicians in this field can also make many forms without departing from the purpose of the present application and the scope of protection of the claims, all of which are within the protection of the present application.

Claims

1. A method for preparing a renewable adsorbent material for sewage treatment, characterized in that: The regenerable adsorption material for sewage treatment comprises the following raw materials in parts by weight: Aggregate 70~120 parts; 20~50 parts of flux; 10-20 parts of pore-forming agent; 3~10 parts of binder; 30~90 parts of plastic particles.

2. The method for preparing a renewable adsorbent material for sewage treatment according to claim 1, characterized in that: The renewable adsorbent material for sewage treatment further comprises 3 to 15 parts by weight of reinforcing fibers, and the fire-resistant temperature of the reinforcing fibers is ≥1100°C.

3. The method for preparing a renewable adsorbent material for sewage treatment according to claim 1, characterized in that: The aggregate includes inorganic particles of three sizes: large, medium and small, wherein the average particle size of the large-size inorganic particles is 0.5-1 mm, the average particle size of the medium-size inorganic particles is 100-300 um, and the average particle size of the small-size inorganic particles is less than 100 um. The aggregate is a mixture of natural inorganic minerals and industrial inorganic solid waste, wherein the industrial inorganic solid waste accounts for 20-40 wt% of the total amount of the aggregate.

4. The method for preparing a renewable adsorbent material for sewage treatment according to claim 1, characterized in that: The binder is an inorganic sol, and the solid content of the inorganic sol is 5-20wt%.

5. The method for preparing a renewable adsorbent material for sewage treatment according to claim 1, characterized in that: The particle size of the plastic particles is 0.5-1 mm, and the plastic particles are selected from one or more of polyethylene, polypropylene, and polystyrene.

6. The method for preparing a renewable adsorbent material for sewage treatment according to claim 1, characterized in that: The method for preparing the regenerable adsorbent material for sewage treatment comprises the steps of: S1, prepare aggregate: (1) First, the natural inorganic mineral particles and the industrial inorganic solid waste particles are screened to obtain natural inorganic mineral particles and industrial inorganic solid waste particles with an average particle size of 0.5-1 mm, natural inorganic mineral particles and industrial inorganic solid waste particles with an average particle size of 100-300 μm, and natural inorganic mineral particles and industrial inorganic solid waste particles with an average particle size of less than 100 μm; (2) Then, according to the weight ratio of large, medium and small inorganic particles in the aggregate, natural inorganic mineral particles or industrial inorganic solid waste particles of corresponding particle sizes are selected to prepare the aggregate, wherein the aggregate is a mixture of natural inorganic minerals and industrial inorganic solid waste, and the industrial inorganic solid waste accounts for 20-40wt% of the total amount of the aggregate; (3) Then, the selected industrial inorganic solid waste particles are dispersed in an alkaline solution, and after sufficient stirring, an alkaline suspension of the industrial inorganic solid waste particles is obtained, and the suspension is heated to 50-90° C., kept warm for 1-3 hours, filtered, and dried to obtain pretreated industrial inorganic solid waste particles; (4) mixing and stirring the pretreated industrial inorganic solid waste particles and natural inorganic mineral particles to obtain aggregate; S2, uniformly mixing the aggregate prepared in step S1 with a flux, a pore former and a binder in a prescribed amount to obtain a mixture I; S3, mixing the formulated amount of plastic particles with the mixture I uniformly to obtain a mixture II; S4, shaping the mixture II to obtain a profile III; S5, placing the profile III in a high-temperature carbonization furnace for calcination and carbonization, and then naturally cooling to room temperature to obtain the carbonized profile IV, which is the renewable adsorption material for sewage treatment.

7. The method for preparing a renewable adsorbent material for sewage treatment according to claim 6, characterized in that: In step S5, a staged carbonization process or a one-stage carbonization process is used to perform high-temperature carbonization treatment on the profile III: Among them, the segmented carbonization process is: (1) Pre-oxidation treatment: First, place profile III in a high-temperature furnace at 300-500°C for pre-oxidation treatment in an air atmosphere for 20-60 minutes; (2) Carbonization treatment: placing the pre-oxidized profile III in a high-temperature carbonization furnace, calcining and carbonizing it at 600-1000° C. for 2-4 hours under the protection of an inert atmosphere, and then naturally cooling it to room temperature to obtain the renewable adsorption material for sewage treatment; The one-stage carbonization process is as follows: placing the profile III in a high-temperature carbonization furnace, calcining and carbonizing it at 600-1000°C for 3-5 hours under the protection of an inert atmosphere, and then naturally cooling it to room temperature to obtain the renewable adsorption material for sewage treatment.

8. The method for preparing a renewable adsorbent material for sewage treatment according to claim 6, characterized in that: After the adsorption material is obtained through step S5, the adsorption material obtained in step S5 is post-processed by physical activation or plasma etching process, wherein: The physical activation process is as follows: firstly, the carbonized profile IV is placed in an argon atmosphere furnace, and then water vapor is loaded into the atmosphere furnace through argon gas as an activating agent, wherein the total flow rate of argon gas and water vapor is 50-80 mL / min, and the volume ratio of argon gas to water vapor is 1:(1.2-1.8); and the furnace temperature in the atmosphere furnace is raised to 500-800°C at a rate of 5-10°C / min, and then kept warm for 0.5-1.5h, and then naturally cooled to obtain the post-treated renewable adsorption material for sewage treatment; The plasma etching process is as follows: using hydrogen fluoride as etching gas, the renewable adsorbent material for sewage treatment is subjected to plasma etching at an etching pressure of 40-60 Pa, a gas flow rate of 40-80 sccm, and a power of 50-60 W. During the plasma etching process, it should be ensured that the surface of the adsorbent material is evenly exposed to the plasma. The etching time is 20-60 min. After the etching is completed, the adsorbent material is washed with water and dried at a low temperature of 40-80° C. to obtain the renewable adsorbent material for sewage treatment after post-treatment.

9. The method for preparing a renewable adsorbent material for sewage treatment according to claim 1, characterized in that: The regeneration process of the regenerable adsorbent material for sewage treatment comprises the steps of: P1, placing the adsorbent saturated material in a high-temperature carbonization furnace, calcining and carbonizing at 600-1000°C for 1-2 hours under the protection of argon atmosphere; P2, then water vapor is loaded into the atmosphere furnace as an activating agent through argon gas, wherein the total flow rate of argon gas and water vapor is 30~50mL / min, and the volume ratio of argon gas to water vapor is 1:(1.2~1.8); and the furnace temperature in the atmosphere furnace is increased to 500~800℃ at a rate of 10~15℃ / min, and then kept warm for 10~30min, and the regenerated adsorption material is obtained after natural cooling.

10. A renewable adsorption material for sewage treatment, characterized in that: The renewable adsorption material for sewage treatment is an adsorption material prepared by the preparation method described in any one of claims 1 to 9.

Images