Water treatment device and method for treating waste liquid

Abstract

This invention discloses a water treatment device and a wastewater treatment method. The water treatment device includes: a slurry bed membrane reactor with a reaction chamber inside and a drain outlet; a first inlet pipe connected to the slurry bed membrane reactor and connected in series with a first drive pump for transporting wastewater to the reaction chamber; an ozone generator for generating ozone; a gas membrane distributor arranged inside the reaction chamber and connected to the ozone generator for generating ozone micro-nano bubbles; a storage tank for storing a catalytic adsorbent configured to adsorb impurities in the wastewater and catalyze ozone decomposition; and a connecting pipe connecting the storage tank and the slurry bed membrane reactor for supplying the catalytic adsorbent into the reaction chamber. According to the water treatment device of this invention, deep treatment of wastewater can be achieved, reducing residue problems caused by chemical dosing at the source and avoiding secondary pollution caused by chemical agents, making the entire water treatment process more green and environmentally friendly.

Description

Technical Field

[0001] This invention relates to the field of water treatment technology, and in particular to a water treatment device and a waste liquid treatment method. Background Technology

[0002] Thermal power generation is a major consumer of industrial water, and its circulating cooling water systems discharge wastewater characterized by large volume, high hardness, and the presence of organic corrosion and scale inhibitors and microorganisms. Current traditional treatment methods require the addition of large quantities of chemicals, resulting in high wastewater treatment costs, easy scaling, the growth of biological sludge, and potential secondary pollution. Summary of the Invention

[0003] This invention aims to at least solve one of the technical problems existing in the prior art. To this end, this invention proposes a water treatment device that can achieve deep treatment of waste liquid, reducing the residue problems caused by chemical dosing at the source, avoiding secondary pollution caused by chemical agents, and making the entire water treatment process greener and more environmentally friendly with lower operating costs.

[0004] The present invention also proposes a waste liquid treatment method.

[0005] According to a first aspect of the present invention, a water treatment apparatus is used to treat wastewater generated during the circulating cooling process of a power plant. The water treatment apparatus comprises: a slurry bed membrane reactor having a reaction chamber inside, the slurry bed membrane reactor having a drain outlet; a first inlet pipe connected to the slurry bed membrane reactor and connected in series with a first drive pump for conveying the wastewater to the reaction chamber; an ozone generator for generating ozone; a gas membrane distributor arranged in the reaction chamber and connected to the ozone generator for generating ozone micro-nano bubbles; a storage tank for storing a catalytic adsorbent configured to adsorb impurities in the wastewater and catalyze the decomposition of ozone; a connecting pipe connecting the storage tank and the slurry bed membrane reactor for conveying the catalytic adsorbent into the reaction chamber; and a drain pipe connected to the drain outlet for discharging the treated liquid obtained after treatment in the slurry bed membrane reactor.

[0006] According to the water treatment device of the present invention, wastewater is purified by synergistic treatment using a catalytic adsorbent and an ozone micro-nano bubble system. This allows for deep treatment of wastewater without the need for traditional chemical agents, reducing residue problems caused by chemical additions at the source and avoiding secondary pollution caused by chemical agents. This makes the entire water treatment process greener and more environmentally friendly, with lower operating costs. Simultaneously, due to the synergistic effect of the catalytic adsorbent and the ozone micro-nano bubble system, ozone can be used to deeply oxidize and degrade adsorbed pollutants while simultaneously regenerating the adsorption sites of the catalytic adsorbent. This overcomes the bottleneck of easy saturation of traditional adsorbents, achieving deep and simultaneous removal of organic matter, ammonia nitrogen, turbidity, and microorganisms. Furthermore, based on the high specific surface area and high gas-liquid mass transfer efficiency of nanobubbles, the ozone dosage can be significantly reduced while ensuring the same treatment effect, thereby further improving the process economy and treatment stability.

[0007] According to some embodiments of the present invention, the water treatment apparatus further includes: a filtration device arranged in the reaction chamber, the filtration device including a filter membrane, at least a portion of the filter membrane being arranged at the drain outlet for achieving solid-liquid separation; and a rinsing device for rinsing the filter membrane.

[0008] According to some embodiments of the present invention, the water treatment device further includes: a storage tank, which is connected to the slurry bed membrane reactor via the drain pipe for storing the treated liquid; a filtration device, which is arranged between the slurry bed membrane reactor and the storage tank for solid-liquid separation, and the filtration device is provided with a filter membrane; and a rinsing device for rinsing the filter membrane.

[0009] According to some embodiments of the present invention, the rinsing device includes: a rinsing tank, a second drive pump, and a rinsing pipe. The rinsing tank is connected to the filter device through the rinsing pipe, and the second drive pump is connected in series with the rinsing pipe to drive the rinsing medium in the rinsing tank into the filter device.

[0010] According to some embodiments of the present invention, the filtration device is a ceramic material microfiltration module or a ceramic material ultrafiltration module.

[0011] According to some embodiments of the present invention, the gas membrane distributor is a ceramic membrane aerator, and the average pore size of the ceramic membrane is 50nm-300nm.

[0012] According to a wastewater treatment method of a second aspect of the present invention, based on the water treatment apparatus of the first aspect of the present invention, the method includes: step S1, injecting wastewater into a slurry bed membrane reactor; step S2, adding a catalytic adsorbent into the slurry bed membrane reactor; step S3, forming ozone micro-nano bubbles at the bottom of the slurry bed membrane reactor to achieve uniform mixing of the liquid phase; step S4, confirming that the residence time of the catalytic adsorbent in the slurry bed membrane reactor reaches a preset time; and step S5, pumping out the treated liquid formed after the reaction in the slurry bed membrane reactor is completed.

[0013] According to the wastewater treatment method of the present invention, the catalytic adsorbent and the ozone micro-nano bubble system are used to synergistically treat the wastewater to achieve purification. This allows for deep treatment of the wastewater without the need to add traditional chemical agents during the treatment process, reducing the residue problems caused by the addition of agents from the source, avoiding secondary pollution caused by chemical agents, and making the entire water treatment process greener and more environmentally friendly with lower operating costs.

[0014] According to some embodiments of the present invention, the concentration of the catalytic adsorbent is 0.5 kg / m3-3 kg / m3, and the concentration of the catalytic adsorbent is positively correlated with the concentration of pollutants in the waste liquid.

[0015] According to some embodiments of the present invention, the ozone concentration in the ozone micro-nano bubbles is 5 mg / L-50 mg / L, and the ozone concentration is positively correlated with the pollutant concentration in the waste liquid.

[0016] According to some embodiments of the present invention, before step S1, the method further includes: S0, preparing a catalytic adsorbent. The preparation of the catalytic adsorbent includes: step S01, treating fly ash raw material to obtain pretreated material; step S02, preparing an alkaline solution and adding the pretreated material to the alkaline solution and stirring to obtain a mixture; step S03, placing the mixture in a hydrothermal reactor for hydrothermal reaction to obtain reactants; and step S04, filtering and drying the reactants to obtain the catalytic adsorbent. And / or, the preparation of the catalytic adsorbent further includes: step S01, treating fly ash raw material to obtain pretreated material; step S02, preparing an alkaline solution and adding the pretreated material to the alkaline solution and stirring to obtain a mixture; step S03, placing the mixture in a hydrothermal reactor for hydrothermal reaction to obtain reactants; step S04, filtering and drying the reactants to obtain secondary treated material; step S05, adding the secondary treated material to an aqueous solution to obtain a suspension; step S06, sequentially adding a precursor solution and a precipitant to the suspension and adjusting the pH to obtain a precipitated mixed slurry; step S07, washing, filtering, drying, and calcining the precipitated mixed slurry at high temperature to obtain the catalytic adsorbent.

[0017] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of a water treatment apparatus according to an embodiment of the present invention; Figure 2 This is a schematic diagram of a water treatment apparatus according to another embodiment of the present invention; Figure 3 This is a flowchart of a waste liquid treatment method according to an embodiment of the present invention; Figure 4 This is a graph showing the change in the removal rate of target pollutants in waste liquid over time under the same conditions for catalytic adsorbent and fly ash raw materials.

[0019] Figure label: 100. Water treatment equipment; 10. Slurry bed membrane reactor; 101. Reaction chamber; 11. First inlet pipe; 12. Connecting pipe; 13. First drive pump; 14. Drain pipe; 21. Ozone generator; 22. Gas membrane distributor; 23. Ozone concentration detector; 24. Gas-liquid separator; 25. Ozone decomposer; 30. Storage tanks; 40. Liquid storage tank; 50. Filtration device; 60. Flushing device; 61. Flushing tank; 62. Second drive pump; 63. Flushing pipe; 70. Control system. Detailed Implementation

[0020] Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0021] The following is for reference. Figures 1-2 A water treatment apparatus 100 according to an embodiment of the first aspect of the present invention is described.

[0022] like Figures 1-2 As shown, a water treatment apparatus 100 according to a first aspect embodiment of the present invention is used to treat waste liquid generated during the circulating cooling process of a power plant. The water treatment apparatus 100 includes: a slurry bed membrane reactor 10, a first inlet pipe 11, an ozone generator 21, a gas membrane distributor 22, a storage tank 30, a connecting pipe 12, and a drain pipe 14.

[0023] The slurry bed membrane reactor 10 includes a reaction chamber 101 and a drain outlet. A first inlet pipe 11 is connected to the slurry bed membrane reactor 10 and a first drive pump 13 is connected in series to transport waste liquid to the reaction chamber 101. An ozone generator 21 is used to generate ozone. A gas membrane distributor 22 is arranged inside the reaction chamber 101 and connected to the ozone generator 21 to generate ozone micro-nano bubbles. A storage tank 30 is used to store a catalytic adsorbent, which is configured to adsorb impurities in the waste liquid and catalyze ozone decomposition. A connecting pipe 12 connects the storage tank 30 and the slurry bed membrane reactor 10 to transport the catalytic adsorbent into the reaction chamber 101. A drain pipe 14 is connected to the drain outlet to discharge the treated liquid obtained after treatment in the slurry bed membrane reactor 10.

[0024] The slurry bed membrane reactor 10 mainly provides reaction space for the physical and chemical reactions of the waste liquid; the first inlet pipe 11 is mainly used to transport the waste liquid into the reaction chamber 101; the first drive pump 13 mainly provides driving force for the flow of the waste liquid; the ozone generator 21 is mainly used to provide ozone for the generation of ozone micro-nano bubbles; the gas membrane distributor 22 is mainly used to generate nanobubbles; the storage tank 30 is mainly used to store the catalytic adsorbent; the connecting pipe 12 is mainly used to transport the catalytic adsorbent into the reaction chamber 101; and the drain pipe 14 is mainly used to discharge the treated liquid obtained after treatment in the slurry bed membrane reactor 10 so that the slurry bed membrane reactor 10 can carry out the next water treatment.

[0025] When waste liquid needs to be treated, the first drive pump 13 is used to transport the waste liquid into the reaction chamber 101. Then, a catalytic adsorbent is added into the reaction chamber 101 to form a uniformly suspended slurry bed in the reactor. Then, the ozone generator 21 and the gas membrane distributor 22 are started to continuously supply ozone micro-nano bubbles into the reactor to form a gas-liquid-solid three-phase reaction with the catalytic adsorbent and the waste liquid, thereby achieving deep treatment of the waste liquid.

[0026] Specifically, within the slurry bed, the catalytic adsorbent rapidly enriches organic matter, colloids, some hardness ions, and microorganisms in the water through physical and chemical adsorption. On the other hand, it catalyzes the decomposition of ozone to generate hydroxyl radicals (·OH) with stronger oxidizing power, enabling them to deeply oxidize and degrade the adsorbed pollutants, thereby achieving deep treatment of wastewater. In addition, since the hydroxyl radicals can also oxidize and regenerate the adsorption sites of the catalytic adsorbent, the catalytic adsorbent can regain its adsorption capacity, realizing a dynamic cycle of "adsorption-catalytic oxidation-in-situ regeneration".

[0027] It should be noted that the catalytic adsorbent is particulate matter.

[0028] According to the water treatment device 100 of the present invention, wastewater is purified by synergistic treatment using a catalytic adsorbent and an ozone micro-nano bubble system. This allows for deep treatment of wastewater without the need for traditional chemical agents, reducing residue problems caused by chemical additions at the source and avoiding secondary pollution caused by chemical agents. This makes the entire water treatment process greener and more environmentally friendly, with lower operating costs. Simultaneously, due to the synergistic effect of the catalytic adsorbent and the ozone micro-nano bubble system, ozone can be used to deeply oxidize and degrade adsorbed pollutants while simultaneously regenerating the adsorption sites of the catalytic adsorbent. This overcomes the bottleneck of easy saturation of traditional adsorbents, achieving deep and simultaneous removal of organic matter, ammonia nitrogen, turbidity, and microorganisms. Furthermore, based on the high specific surface area and high gas-liquid mass transfer efficiency of nanobubbles, the ozone dosage can be significantly reduced while ensuring the same treatment effect, thereby further improving the process economy and treatment stability.

[0029] According to some embodiments of the present invention, such as Figure 1As shown, the water treatment device 100 further includes a filtration device 50 and a rinsing device 60. The filtration device 50 is arranged inside the reaction chamber 101 and includes a filter membrane, at least a portion of which is located at the drain outlet for solid-liquid separation. The rinsing device 60 is used to rinse the filter membrane. Specifically, the filtration device 50 is mainly used to separate the catalytic adsorbent and the treated liquid, allowing the treated liquid to be discharged while the catalytic adsorbent is retained in the reaction chamber 101 to continue participating in the reaction. This allows the catalytic adsorbent to be recycled, thereby reducing the cost of the entire water treatment process.

[0030] In addition, the filter device 50 is arranged inside the reaction chamber 101, which can save space occupied by the entire water treatment device 100; at the same time, the advanced oxidation effect of ozone micro-nano bubbles on the filter membrane surface and the shear force formed on the filter membrane surface by the flow of aqueous solution can be used to achieve online control and mitigation of filter membrane fouling.

[0031] The flushing device 60 is mainly used to flush the filter membrane to prevent it from clogging, thereby ensuring the normal operation of the water treatment device 100.

[0032] According to some embodiments of the present invention, such as Figure 2 As shown, the water treatment device 100 also includes: a storage tank 40, a filtration device 50, and a flushing device 60. The storage tank 40 is connected to the slurry bed membrane reactor 10 via a drain pipe 14 and is used to store the treated liquid. The filtration device 50 is arranged between the slurry bed membrane reactor 10 and the storage tank 40 to achieve solid-liquid separation, and a filter membrane is provided inside the filtration device 50. The flushing device 60 is used to flush the filter membrane. Specifically, the storage tank 40 is mainly used to store the treated liquid; the filtration device 50 is mainly used to separate the catalytic adsorbent and the treated liquid; the flushing device 60 is mainly used to flush the filter membrane and backflush the catalytic adsorbent in the filtration device 50 back into the slurry bed membrane reactor 10 to achieve the recycling of the catalytic adsorbent.

[0033] In addition, the filter device 50 is located between the slurry bed membrane reactor 10 and the storage tank 40, which facilitates the maintenance of the filter device 50.

[0034] According to some embodiments of the present invention, such as Figures 1-2 As shown, the rinsing device 60 includes a rinsing tank 61, a second drive pump 62, and a rinsing pipe 63. The rinsing tank 61 is connected to the filter device 50 via the rinsing pipe 63. The second drive pump 62 is connected in series with the rinsing pipe 63 and is used to drive the rinsing medium in the rinsing tank 61 into the filter device 50. The rinsing tank 61 is mainly used to store the rinsing medium, and the second drive pump 62 is mainly used to transport the rinsing medium to the filter device 50 to achieve rinsing of the filter membrane.

[0035] It should be noted that the rinsing medium can be either gas or liquid; there are no restrictions here.

[0036] According to some embodiments of the present invention, the filtration device 50 is a ceramic material microfiltration module or a ceramic material ultrafiltration module. It is understood that in some specific embodiments, the filtration device 50 is a ceramic microfiltration module, while in other specific embodiments, the boiler device is a ceramic ultrafiltration module. It should be noted that ultrafiltration modules can intercept impurities with smaller particle sizes, while microfiltration modules have a relatively higher throughput than ultrafiltration modules. Therefore, the filtration device 50 can be selected according to actual conditions.

[0037] Among them, ceramic materials have the characteristics of being resistant to acid and alkali corrosion, resistant to high temperature aging, high mechanical strength and good stability. Therefore, the filter device 50 is a ceramic material microfiltration component or a ceramic material ultrafiltration component, which can improve the service life of the filter device 50.

[0038] According to some embodiments of the present invention, the gas membrane distributor 22 is a ceramic membrane aerator, and the ceramic membrane has an average pore size of 50nm-300nm. The ceramic material is characterized by its resistance to acid and alkali corrosion, resistance to high-temperature aging, high mechanical strength, and good stability. Therefore, by setting the gas membrane distributor 22 as a ceramic membrane aerator, the reliability and service life of the water treatment device 100 can be further improved. At the same time, the ceramic material also has the characteristics of being anti-fouling, not easily clogged, and easy to clean and regenerate, thereby improving the ease of maintenance of the gas membrane distributor 22.

[0039] For example, the average pore size of the ceramic membrane can be 50nm, 100nm, 150nm, 200nm, 250nm or 300nm.

[0040] By setting the average pore size of the ceramic membrane to 50nm-300nm, the diameter of the generated ozone micro-nano bubbles can typically be between 250nm-750nm. This ensures the mass transfer efficiency and residence time of the micro-nano bubbles, thereby improving the utilization efficiency of ozone.

[0041] Optionally, the average pore size of the ceramic membrane can be 100 nm.

[0042] Optionally, the water treatment device 100 also includes a control system 70, which is used to regulate operating parameters such as ozone dosage, air intake flow rate, membrane filtration flux, and reactor internal circulation status.

[0043] According to the wastewater treatment method of the second aspect of the present invention, based on the water treatment apparatus 100 of the first aspect of the present invention, such as Figure 3 As shown, the method includes: Step S1: Inject waste liquid into the slurry bed membrane reactor 10; Step S2: Add catalytic adsorbent into the slurry bed membrane reactor 10; Step S3: Ozone micro-nano bubbles are formed at the bottom of the slurry bed membrane reactor 10, so that the liquid phase is uniformly mixed. Step S4: Confirm that the residence time of the catalytic adsorbent in the slurry bed membrane reactor 10 has reached the preset time; Step S5: Pump out the treatment liquid formed after the reaction in the slurry bed membrane reactor 10.

[0044] For example, the water treatment apparatus 100 also includes a buffer tank for storing waste liquid to be treated, and a first inlet pipe 11 is connected between the buffer tank and the slurry bed membrane reactor 10 for transferring the waste liquid in the buffer tank into the reaction chamber 101.

[0045] Specifically, when waste liquid needs to be treated, the first drive pump 13 is used to transport the waste liquid in the buffer tank to the reaction chamber 101, and then a sufficient amount of catalytic adsorbent is added to the slurry bed membrane reactor 10 to form a uniform suspended slurry bed in the reaction chamber 101.

[0046] Subsequently, ozone generator 21 is activated to generate ozone. Simultaneously, the ozone is pumped into gas membrane distributor 22 via a gas pump, and then passes through gas membrane distributor 22 to form ozone micro-nano bubbles, which enter the slurry bed membrane reactor 10 to form a gas-liquid-solid three-phase reaction with the catalytic adsorbent and waste liquid. It should be noted that due to the high mass transfer efficiency and long residence time of micro-nano bubbles, ozone can be utilized efficiently.

[0047] Then, it was confirmed that the residence time of the catalytic adsorbent in the slurry bed membrane reactor 10 reached the preset time. During its residence in the slurry bed membrane reactor 10, the catalytic adsorbent mainly plays two roles: first, it rapidly enriches organic matter, colloids, some hardness ions, and microorganisms in the water through physical and chemical adsorption; second, it catalyzes ozone decomposition through its surface active sites (especially supported metal oxides or modified active groups), generating hydroxyl radicals (·OH) with stronger oxidizing power, which deeply oxidize and degrade the adsorbed pollutants, while simultaneously oxidizing and regenerating the adsorption sites of the catalytic adsorbent, restoring its adsorption capacity, and achieving a dynamic cycle of "adsorption-catalytic oxidation-in-situ regeneration".

[0048] Finally, after the residence time reaches the preset time, the processed liquid formed after the reaction in the slurry bed membrane reactor 10 is pumped out of the slurry bed membrane reactor 10 and transported to the storage tank 40 for storage. It should be noted that since a filter device 50 is provided at the outlet, the filter device 50 can intercept solid particles. That is, when the processed liquid is pumped out of the slurry bed membrane reactor 10, the filter device 50 can intercept the catalytic adsorbent in the reactor, allowing it to be recycled, thereby reducing the use of catalytic adsorbent.

[0049] Optionally, the water treatment device 100 also includes: an ozone concentration detector 23, a gas-liquid separator 24, and an ozone decomposer 25. The ozone concentration detector 23 is mainly used to monitor the ozone concentration in order to control the ozone flow rate; the gas-liquid separator 24 is mainly used for gas and liquid; and the ozone decomposer 25 is mainly used for the decomposer of unused ozone.

[0050] According to the wastewater treatment method of the present invention, the catalytic adsorbent and the ozone micro-nano bubble system are used to synergistically treat the wastewater to achieve purification. This allows for deep treatment of the wastewater without the need to add traditional chemical agents during the treatment process, reducing the residue problems caused by the addition of agents from the source, avoiding secondary pollution caused by chemical agents, and making the entire water treatment process greener and more environmentally friendly with lower operating costs.

[0051] According to some embodiments of the present invention, the concentration of the catalytic adsorbent is 0.5 kg / m³ to 3 kg / m³, and the concentration of the catalytic adsorbent is positively correlated with the concentration of pollutants in the waste liquid. Specifically, 0.5 kg to 3 kg of catalytic adsorbent needs to be added per cubic meter of waste liquid. This ensures that the concentration of the catalytic adsorbent is not too low, thereby ensuring the treatment effect of the catalytic adsorbent on the waste liquid, while also preventing excessive dosage, which could lead to problems such as water turbidity and difficulties in solid-liquid separation.

[0052] For example, the concentration of the catalytic adsorbent can be 0.5 kg / m3, 1 kg / m3, 1.5 kg / m3, 2 kg / m3, 2.5 kg / m3, or 3 kg / m3.

[0053] According to some embodiments of the present invention, the ozone concentration in the ozone micro-nano bubbles is 5 mg / L-50 mg / L, and the ozone concentration is positively correlated with the pollutant concentration in the waste liquid. It is understood that the ozone concentration is related to the pollutant concentration in the waste liquid, and the higher the pollutant concentration in the waste liquid, the greater the amount of ozone added. This ensures that the ozone content meets the requirements for waste liquid treatment, thereby guaranteeing the effective oxidation and degradation of pollutants in the waste liquid.

[0054] For example, the ozone concentration added to ozone micro-nano bubbles can be 5 mg / L, 10 mg / L, 15 mg / L, 20 mg / L, 25 mg / L, 30 mg / L, 35 mg / L, 40 mg / L, 45 mg / L, or 50 mg / L.

[0055] According to some embodiments of the present invention, before step S1, the method further includes: S0, preparing a catalytic adsorbent. The preparation of catalytic adsorbents includes: Step S01: Process the fly ash raw material to obtain pretreated material; it should be noted that processing the fly ash raw material mainly aims to make the particle size of the fly ash meet the preset requirements.

[0056] Step S02: Prepare an alkaline solution and add the pretreated material to the alkaline solution and stir to mix, thereby obtaining a mixture; wherein, the alkaline solution can be a sodium hydroxide solution, etc.

[0057] Step S03: The mixture is placed in a hydrothermal reactor to carry out a hydrothermal reaction to obtain the reactants; In step S04, the reactants are filtered and dried to obtain the catalytic adsorbent. This catalytic adsorbent not only possesses catalytic properties but also adsorption energy absorption capabilities. It should be noted that the catalytic adsorbent can be a zeolite-like structure or a material with high adsorption activity.

[0058] It should be further explained that the fly ash raw material is solid waste from coal-fired power plants. That is, this embodiment utilizes the solid waste fly ash from power plants to transform it into high-value-added water treatment functional materials. In this way, the resource utilization and high-value utilization of solid waste are realized, the cost of raw materials is reduced, and it is in line with the concept of circular economy.

[0059] Furthermore, compared with fly ash raw materials, the modified catalytic adsorbent has a relatively high removal rate and a shorter treatment time, for example... Figure 4 As shown, using 20 ppm methylene blue as a typical target pollutant in water, and with the experimental conditions of 2 g / L for both the catalytic adsorbent and fly ash raw material, the experiment showed that the removal rate of the original fly ash was 10.63%, and the removal rate of the modified catalytic adsorbent was 82%, both reaching adsorption equilibrium in about 10 minutes.

[0060] According to some embodiments of the present invention, the preparation of the catalytic adsorbent further includes: Step S01: Process fly ash raw material to obtain pretreated material; Step S02: Prepare an alkaline solution, and add the pretreated material to the alkaline solution and stir to mix, thereby obtaining a mixture; Step S03: The mixture is placed in a hydrothermal reactor to carry out a hydrothermal reaction to obtain the reactants; Step S04: The reactants are filtered and dried to obtain the secondary processed material; Step S05: Add the secondary processed material to the aqueous solution to obtain a suspension; Step S06: Add the precursor solution and precipitant to the suspension in sequence, and adjust the pH to obtain a precipitated mixed slurry; Step S07 involves washing, filtering, drying, and calcining the precipitated mixture to obtain the catalytic adsorbent.

[0061] It is understood that in this embodiment, the catalytic adsorbent is first prepared by converting fly ash raw material into a zeolite-like structural material through an alkaline fusion-hydrothermal method, and then by loading transition metal oxide active components through a precipitation method. In this way, the catalytic adsorbent can have a high specific surface area, abundant pore structure and active sites for catalytic ozone decomposition, thereby improving the adsorption capacity, stability, low-temperature activity and oxidation performance of the catalytic adsorbent.

[0062] It should be noted that the precursor solution is a metal salt solution obtained by adding a metal oxide carrier to an alkaline solution and stirring and mixing, wherein the metal oxide is at least one of manganese oxide and iron oxide.

[0063] The following will refer to Figures 1-4 A water treatment apparatus 100 according to two specific embodiments of the present invention is described.

[0064] Example 1, Reference Figure 1 The water treatment device 100 includes: a slurry bed membrane reactor 10, a first inlet pipe 11, a first drive pump 13, an ozone generator 21, a gas membrane distributor 22, a storage tank 30, a connecting pipe 12, and a drain pipe 14.

[0065] The slurry bed membrane reactor 10 includes a reaction chamber 101 and a drain outlet. A first inlet pipe 11 is connected to the slurry bed membrane reactor 10 and a first drive pump 13 is connected in series to transport waste liquid to the reaction chamber 101. An ozone generator 21 is used to generate ozone. A gas membrane distributor 22 is arranged inside the reaction chamber 101 and connected to the ozone generator 21 to generate ozone micro-nano bubbles. A storage tank 30 is used to store a catalytic adsorbent, which is configured to adsorb impurities in the waste liquid and catalyze ozone decomposition. A connecting pipe 12 connects the storage tank 30 and the slurry bed membrane reactor 10 to transport the catalytic adsorbent into the reaction chamber 101. A drain pipe 14 is connected to the drain outlet to discharge the treated liquid obtained after treatment in the slurry bed membrane reactor 10.

[0066] The water treatment device 100 also includes a storage tank 40, which is connected to the slurry bed membrane reactor 10 via a drain pipe 14 and is used to store the treated liquid.

[0067] The water treatment device 100 further includes a filtration device 50 and a flushing device 60. The filtration device 50 is arranged in the reaction chamber 101 and includes a filter membrane. At least a portion of the filter membrane is arranged at the drain outlet for solid-liquid separation. The flushing device 60 is used to flush the filter membrane and includes a flushing tank 61, a second drive pump 62, and a flushing pipe 63. The flushing tank 61 is used to store the flushing medium. The flushing tank 61 is connected to the filtration device 50 through the flushing pipe 63. The second drive pump 62 is connected in series with the flushing pipe 63 for driving the flushing medium in the flushing tank 61 into the filtration device 50.

[0068] The water treatment device 100 also includes a control system 70, which is used to regulate operating parameters such as ozone dosage, air intake flow rate, membrane filtration flux, and reactor internal circulation status.

[0069] Based on the above-described water treatment apparatus 100, a waste liquid treatment method is described: First, a catalytic adsorbent with dual functions of catalysis and adsorption is prepared by hydrothermal method or precipitation method, and the catalyst is stored in storage tank 30. Then, the waste liquid in the buffer tank is transported to the reaction chamber 101 by the first drive pump 13. Then, a sufficient amount of catalytic adsorbent is added to the slurry bed membrane reactor 10 to form a uniform suspended slurry bed in the reaction chamber 101.

[0070] Subsequently, the ozone generator 21 is started to generate ozone. At the same time, the ozone is pumped into the gas membrane distributor 22 by the gas pump, and enters the slurry bed membrane reactor 10 as ozone micro-nano bubbles through the gas membrane distributor 22, forming a gas-liquid-solid three-phase reaction with the catalytic adsorbent and waste liquid.

[0071] Then, it was confirmed that the residence time of the catalytic adsorbent in the slurry bed membrane reactor 10 reached the preset time in order to achieve deep purification of the waste liquid.

[0072] Finally, after the residence time reaches the preset time, the processed liquid formed after the reaction in the slurry bed membrane reactor 10 is pumped out of the slurry bed membrane reactor 10 and transported to the storage tank 40 for storage.

[0073] According to the water treatment device 100 of the present invention, wastewater is purified by synergistic treatment using a catalytic adsorbent and an ozone micro-nano bubble system. This allows for deep treatment of wastewater without the need for traditional chemical agents, reducing residue problems caused by chemical additions at the source and avoiding secondary pollution caused by chemical agents. This makes the entire water treatment process greener and more environmentally friendly, with lower operating costs. Simultaneously, due to the synergistic effect of the catalytic adsorbent and the ozone micro-nano bubble system, ozone can be used to deeply oxidize and degrade adsorbed pollutants while simultaneously regenerating the adsorption sites of the catalytic adsorbent. This overcomes the bottleneck of easy saturation of traditional adsorbents, achieving deep and simultaneous removal of organic matter, ammonia nitrogen, turbidity, and microorganisms. Furthermore, based on the high specific surface area and high gas-liquid mass transfer efficiency of nanobubbles, the ozone dosage can be significantly reduced while ensuring the same treatment effect, thereby further improving the process economy and treatment stability.

[0074] Example 2, This embodiment has a structure that is largely the same as that of Embodiment 1, with the same components using the same reference numerals. The only difference is that the filter device 50 described in Embodiment 1 is arranged inside the reaction chamber 101, while the filter device 50 described in this Embodiment 2 is arranged outside the slurry bed membrane reactor 10.

[0075] A filtration device 50 is arranged between the slurry bed membrane reactor 10 and the storage tank 40 to achieve solid-liquid separation. The filtration device 50 is equipped with a filter membrane. A rinsing device 60 is used to rinse the filter membrane and to flush the catalytic adsorbent on the filter membrane back into the slurry bed membrane reactor 10.

[0076] The following tests were conducted on the TOC removal rate, TN removal rate, and suspended solids removal rate in the waste liquid under various experimental conditions in Example 2.

[0077] Experimental condition one: only the catalytic adsorbent was added to the waste liquid; Experimental condition two: Add catalytic adsorbent to the waste liquid and turn on the filter device at 50°C; Test condition three: Add catalytic adsorbent and ozone micro-nano bubbles to the waste liquid and turn on the filter device 50.

[0078] It should be noted that the catalytic adsorbent mentioned above was prepared using a hydrothermal method with 4 mol / L NaOH solution. BET testing showed that the original fly ash had a surface area of ​​2.4 m² / g and a pore size of 3.3 nm, while the catalytic adsorbent had a specific surface area of ​​54.5 m² / g and a pore size of 13.4 nm. The catalytic adsorbent dosage was 3 g / L of treated water. Ozone micro-nano bubbles were generated by a ceramic membrane aerator (100 nm pore size), and the ozone dosage was 15 mg / L of treated water. The filter device 50 was an external tubular membrane module (50 nm pore size). The wastewater was actual circulating cooling water from a power plant. The reactor was made of stainless steel, and the treatment time was 15 min. The treatment results are shown in Table 1 below. Table 1

[0079] Experimental results show that the catalytic adsorbent alone has a certain effect, but the effect is limited. After the catalytic adsorbent and ozone react together in the slurry reactor system, the removal of TOC, TN and suspended solids is good. For TOC removal, the synergistic effect of fly ash and ozone, combined with the filtration device 50 in the slurry reactor system, clearly achieves a removal rate of 95.2%, and the removal of suspended solids reaches 99.9%, with good interception effect. As for total nitrogen in water, the catalytic adsorbent cannot be effectively removed without separation from the water system, and the value may even increase slightly. However, after adding the filtration device 50, the removal of total nitrogen increases significantly.

[0080] In the description of this invention, it should be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," and "circumferential" indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0081] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this invention, "a plurality of" means two or more, unless otherwise explicitly specified.

[0082] In this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection, an electrical connection, or a communication connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0083] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0084] Although embodiments of the invention have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.

Claims

1. A water treatment device (100) for treating wastewater generated during the circulating cooling process of a power plant, characterized in that, include: A slurry bed membrane reactor (10) has a reaction chamber (101) inside, and the slurry bed membrane reactor (10) has a drain outlet; The first inlet pipe (11) is connected to the slurry bed membrane reactor (10) and is connected in series with a first drive pump (13) for transporting the waste liquid to the reaction chamber (101); Ozone generator (21) for generating ozone; A gas membrane distributor (22) is arranged in the reaction chamber (101) and connected to the ozone generator (21) to generate ozone micro-nano bubbles; Storage tank (30) for storing catalytic adsorbent, the catalytic adsorbent being configured to adsorb impurities in the waste liquid and catalyze the decomposition of ozone; A connecting pipe (12) is connected between the storage tank (30) and the slurry bed membrane reactor (10) for conveying the catalytic adsorbent into the reaction chamber (101); The drain pipe (14) is connected to the drain outlet and is used to discharge the treated liquid obtained after treatment in the slurry bed membrane reactor (10).

2. The water treatment device (100) according to claim 1, characterized in that, Also includes: A filtration device (50) is arranged in the reaction chamber (101), the filtration device (50) includes a filter membrane, at least a portion of which is arranged at the drain outlet for solid-liquid separation. A rinsing device (60) is used to rinse the filter membrane.

3. The water treatment device (100) according to claim 1, characterized in that, Also includes: A storage tank (40) is connected to the slurry bed membrane reactor (10) via the drain pipe (14) and is used to store the treatment liquid; A filtration device (50) is arranged between the slurry bed membrane reactor (10) and the storage tank (40) to achieve solid-liquid separation. The filtration device (50) is equipped with a filter membrane inside. A rinsing device (60) is used to rinse the filter membrane.

4. The water treatment apparatus (100) according to any one of claims 2-3, characterized in that, The rinsing device (60) includes: a rinsing tank (61), a second drive pump (62) and a rinsing pipe (63). The rinsing tank (61) is connected to the filter device (50) through the rinsing pipe (63). The second drive pump (62) is connected in series with the rinsing pipe (63) to drive the rinsing medium in the rinsing tank (61) into the filter device (50).

5. The water treatment apparatus (100) according to any one of claims 2-3, characterized in that, The filtration device (50) is a ceramic material microfiltration module or a ceramic material ultrafiltration module.

6. The water treatment apparatus (100) according to claim 1, characterized in that, The gas membrane distributor (22) is a ceramic membrane aerator with an average pore size of 50nm-300nm.

7. A waste liquid treatment method, characterized in that, Based on the water treatment apparatus (100) according to any one of claims 1-6, the method comprises: Step S1: Inject waste liquid into the slurry bed membrane reactor (10); Step S2: Add catalytic adsorbent into the slurry bed membrane reactor (10); Step S3: Ozone micro-nano bubbles are formed at the bottom of the slurry bed membrane reactor (10) to ensure uniform mixing of the liquid phase; Step S4: Confirm that the residence time of the catalytic adsorbent in the slurry bed membrane reactor (10) reaches the preset time; Step S5: Pump out the treatment liquid formed after the reaction in the slurry bed membrane reactor (10).

8. The waste liquid treatment method according to claim 7, characterized in that, The concentration of the catalytic adsorbent is 0.5 kg / m³ to 3 kg / m³, and the concentration of the catalytic adsorbent is positively correlated with the concentration of pollutants in the waste liquid.

9. The waste liquid treatment method according to claim 7, characterized in that, The ozone concentration in the ozone micro-nano bubbles is 5 mg / L-50 mg / L, and the ozone concentration is positively correlated with the pollutant concentration in the waste liquid.

10. The waste liquid treatment method according to claim 7, characterized in that, Before step S1, the method further includes: S0, preparing a catalytic adsorbent. The preparation of the catalytic adsorbent includes: Step S01: Process fly ash raw material to obtain pretreated material; Step S02: Prepare an alkaline solution, and add the pretreated material to the alkaline solution and stir to mix, thereby obtaining a mixture; Step S03: The mixture is placed in a hydrothermal reactor to carry out a hydrothermal reaction to obtain reactants; Step S04: The reactants are filtered and dried to obtain the catalytic adsorbent; And / or, the preparation of the catalytic adsorbent further includes: Step S01: Process fly ash raw material to obtain pretreated material; Step S02: Prepare an alkaline solution, and add the pretreated material to the alkaline solution and stir to mix, thereby obtaining a mixture; Step S03: The mixture is placed in a hydrothermal reactor to carry out a hydrothermal reaction to obtain reactants; Step S04: The reactants are filtered and dried to obtain the secondary processed material; Step S05: Add the secondary processed material to an aqueous solution to obtain a suspension; Step S06: Add the precursor solution and precipitant to the suspension in sequence, and adjust the pH to obtain a precipitated mixed slurry; Step S07: The precipitated mixture is washed, filtered, dried, and calcined at high temperature to obtain a catalytic adsorbent.

Images