CN110818064A - A fluidized bed type ozone catalytic oxidation three-phase separation reaction device and system - Google Patents

Abstract

The invention relates to a fluidized bed type ozone catalytic oxidation three-phase separation reaction device and a system, wherein the reaction device comprises a reaction cavity, a guide cylinder is arranged in the reaction cavity, a suspended catalyst is arranged in the guide cylinder, a water distributor is arranged at the bottom of the guide cylinder, a partition plate with holes is arranged at the top of the guide cylinder, the bottom of the guide cylinder is communicated with a gas-water inlet, a gas-liquid separation guide device is arranged above the guide cylinder, a solid-liquid separation partition plate is arranged outside the gas-liquid separation guide device, an overflow weir is also arranged outside the gas-liquid separation guide device, and a clarification zone is formed between the lower part of the overflow weir, the outer side. The invention improves the utilization rate of ozone to the maximum extent, enhances the gas-liquid-solid three-phase mass transfer efficiency of the reactor, shortens the retention time and improves the treatment effect; the influence of fluctuation of the water suspended matters is solved, and the stability of the water suspended matters is ensured; the device and the system have the advantages of less head loss, high catalytic efficiency, large impact load resistance, low investment and operation cost and wide application range.

Description

A fluidized bed type ozone catalytic oxidation three-phase separation reaction device and system

technical field

The invention relates to a reaction device in the field of wastewater treatment, in particular to a fluidized bed type ozone catalytic oxidation three-phase separation reaction device and the system.

Background technique

With the rapid development of modern industry, the amount of industrial wastewater from printing and dyeing, leather, chemical and other industries is increasing. This kind of industrial wastewater is not only complex and changeable in composition and structure, but also has certain toxicity and is difficult to biochemically treat. At present, most of the common industrial wastewater treatment processes at home and abroad are treated by biochemical methods. However, with the increasingly strict discharge standards in various places, biochemical process treatment alone is especially suitable for high salinity, low B/C ratio, complex components, and refractory degradation. It is difficult for industrial wastewater to meet discharge standards.

The treatment of wastewater with high salinity, low B/C ratio, complex composition and refractory degradation has been a hotspot and focus of domestic and foreign scholars in recent years. In order to achieve higher treatment requirements, physical adsorption and chemical oxidation processes are often used to treat such wastewater. Physical adsorption mainly includes activated carbon adsorption and resin adsorption, but the disadvantage of this type of method is that the adsorption material needs to be regenerated after the adsorption is saturated, and the regeneration process not only consumes high energy, and the regeneration liquid generally contains high concentration of organic matter, which will cause secondary pollution. The commonly used chemical oxidation is mainly advanced oxidation process, but due to the short exploration time of this oxidation process, the basic theory is not very perfect, and the actual pollution system is complex and diverse, so that this technology has many theoretical research and industrial applications. issues to be resolved.

Compared with biological methods and physical methods, advanced oxidation technology has the advantages of high efficiency, short residence time and deep treatment degree in wastewater treatment. Ozone catalytic oxidation technology is one of many advanced oxidation technologies. Ozone catalytic oxidation uses a catalyst to improve the oxidation efficiency and reduce the activation energy of the reaction, so that the oxidation reaction can achieve a good oxidation effect at normal temperature and pressure. However, due to the complex composition of industrial wastewater and many pollutants, the use of a single catalyst and conventional catalytic oxidation processes still have low ozone utilization and incomplete treatment of pollutants. According to the complex characteristics of industrial wastewater, it is becoming more and more important to use a more efficient catalyst combination combined with the use of high-efficiency ozone utilization devices and advanced reaction devices to treat such wastewater to improve the efficiency of catalytic oxidation treatment and reduce construction and operating costs.

SUMMARY OF THE INVENTION

In order to solve the shortcomings of conventional catalytic oxidation catalysts in fixed bed placement, the application range of suspended solids is narrow, the catalytic efficiency of the system is low, the utilization rate of ozone is low, the absolute load of COD removal is small, the reaction residence time is long, and the operation and investment costs are high. The invention provides a fluidized bed type ozone catalytic oxidation three-phase separation reaction device and the system.

To achieve the above object, the present invention provides the following technical solutions:

A fluidized bed type ozone catalytic oxidation three-phase separation reaction device, the reaction device is provided with a reaction chamber and an inner central guide tube, a suspended catalyst is arranged in the guide tube, a water distributor is arranged at the bottom of the guide tube, and a top is provided with The baffle with holes, the bottom of the guide cylinder is connected with the gas-water inlet pipe, the upper part of the guide cylinder is provided with a gas-liquid separation guide device, the upper part of the outer side of the gas-liquid separation guide device is provided with a solid-liquid separation baffle, and a solid-liquid separation baffle The upper part of the outer side is also provided with an overflow weir on the reaction chamber, the lower part of the overflow weir and the outer side of the gas-liquid separation guide device and the solid-liquid separation baffle are provided with a clarification zone, and the top of the reaction device is provided with a gas circulation outlet and a tail gas discharge outlet , the gas circulation outlet is directly connected with the gas-liquid separation guide device, and the lower part of the reaction chamber is provided with a liquid circulation outlet. The ozone gas-water mixture in the reaction device enters the guide tube and is fully mixed with the suspended catalyst to form a gas-liquid lift-type internal circulation flow Heterogeneous catalytic oxidation reaction occurs, the reacted gas-water mixture passes through the perforated partition, most of the undissolved gas enters the gas circulation outlet, and a small part of the dissolved gas passes through the gas-liquid separation guide device and the solid-liquid with the water flow. The separation baffle enters the exhaust port, and the gas-liquid mixture with a very small part of the gas dissolved will pass through the clarification zone to intercept the suspended solids and flow out from the overflow weir outlet. The clarification space between the reaction chamber and the reaction chamber is used for natural sedimentation solid-liquid separation, the separated suspended matter is discharged from the sewage outlet, and the water enters the liquid circulation outlet for recycling.

Further, the gas-liquid separation diversion device is in the shape of an inverted funnel, and includes a cone surface separation part and a pipe separation part arranged on the top of the cone surface separation part, the cone surface separation part is located on the diversion cylinder, and the pipe separation part circulates with the top gas. Exit connection.

Further, the solid-liquid separation baffle has a conical shape, is arranged on the conical surface separation component, and one end is connected with the reaction chamber wall.

Further, there is a guided wave level gauge on the outside of the bottom of the reaction chamber. The sewage outlet is located at the bottom of the space between the diversion cylinder and the reaction chamber. The guided wave level gauge detects the height of the sediment. When the sediment reaches a certain height, the sewage outlet can be opened automatically.

Further, the suspension type catalyst includes a spherical support frame, and the columnar floats and the active component attached to the base material are arranged in the spherical support frame. The active component is attached to the substrate, and the active component is attached to the substrate, and the density of the suspended catalyst stack is 0.5-0.7.

Further, the active component attachment substrate is γ-alumina spheres, the active components are attached to the inside and surface of the microporous structure of the γ-alumina spheres, the diameter of the spheres is 2-16mm, and the spherical support frame is 40-80mm.

The present invention relates to a fluidized bed type multi-effect ozone catalytic oxidation three-phase separation reaction system, comprising at least one of the above-mentioned reaction devices, the liquid circulation port of the first-stage reaction device is connected with the high-efficiency dissolved gas device, and the high-efficiency dissolved gas device is connected with The gas-water inlet at the bottom of the reaction device is connected and connected to the uniform water distributor, the ozone generator is connected to the high-efficiency dissolved gas device port, and the water outlet of the first-stage reaction device is connected to the high-efficiency dissolved-gas device corresponding to the next-stage reaction device, The inlet water pump is connected to the high-efficiency gas dissolving device corresponding to the first-stage reaction device, the water outlet of the last-stage reaction device is connected to the gas-liquid separator, and the gas-liquid separator and the tail gas outlet of the reaction device of each stage are connected to the tail gas destroyer.

Further, the high-efficiency gas-dissolving device includes a gas-liquid mixing pump and a jet connected to the gas-liquid mixing pump, the ozone generator is connected to the gas-liquid mixing pump and the air suction port of the jet, and the gas circulation outlet of the reaction device at each level is connected to the corresponding jet. The air outlet of the first-stage reaction device is connected to the gas-liquid mixing pump, the water outlet of the first-stage reaction device is connected to the liquid circulation outlet pipe corresponding to the next-stage reaction device, and the inlet water pump is connected to the first-stage reaction device. Corresponding liquid circulation outlet pipe connection.

Further, the gas-water ratio of the gas-liquid mixing pump is controlled at 0-1/9, the gas-water ratio of the ejector is controlled at 0-1.8, and the outlet pressure of the gas-liquid mixing pump is greater than 0.2MPa.

Further, the dosage of the suspended catalyst is 1%-7%, and the working pressure of the reaction device is less than 0.05 MPa.

The present invention can be matched with flowmeter, regulating valve, concentration meter and material level meter for automatic control to achieve the above purpose. The high-efficiency gas-dissolving device is composed of a gas-liquid mixing pump and an ejector in series, and the dissolution efficiency of ozone can reach more than 98% after being dissolved by the high-efficiency gas-dissolving device. The gas recycling device is composed of a gas-liquid separation baffle and a suction pipe matched with the ejector, and the device can form a closed cycle for reuse of the undissolved ozone through the suction action of the ejector. The air-lift internal circulating fluidized bed device is composed of a small resistance water distributor and a guide tube. The suspended catalyst is composed of a γ-alumina spherical carrier with a diameter of 2-16mm and a density of >1, a plastic frame with a diameter of 40-80mm and a float with a density of <1. The suspended catalyst passes through the alumina balls and the float. After a reasonable ratio, it forms a suspended state, and the bulk density of the catalyst is 0.5-0.7. With the rise of the gas-water mixture at the bottom of the reactor, a closed-type internal circulation turbulent motion state with the center upward and the edge downward is formed.

The ozone generator includes an oxygen generator, an ozone generator and an air compressor. The generator can determine the concentration and output of ozone according to the amount and water quality of the wastewater to be treated. It can also automatically control the closing of the ozone generator and the height of the air compressor through PLC. The flow rate can also realize the online circulation cleaning of the reactor air.

The high-efficiency gas-dissolving device adopts the method of gas-liquid mixing pump and jet device. When the pressure is greater than 0.2MPa, the ozone dissolution efficiency can reach more than 98%, and the ozone dosage can be flexibly adjusted according to the COD load in engineering applications.

The ozone catalytic oxidation reactor is a closed pressure vessel, and the working pressure is less than 0.05 MPa. The interior of the ozone catalytic oxidation reactor is treated with anti-corrosion treatment or directly selected from anti-corrosion materials.

The high-efficiency dissolved air device can flexibly increase the number of series or the circulating flow according to the COD load of the incoming water and the amount of circulating water.

The suspended catalyst carrier of the present invention adopts γ-alumina pellets as the attachment base material of the multi-precious metal active components, UPVC or ABS material as the supporting frame, and plastic foam as the floating material. For the suspension requirements, the bulk density of the monolithic catalyst is 0.5-0.7.

Compared with the prior art, the beneficial effects of the present invention are:

(1) The present invention increases the contact area of ozone, sewage and ozone catalyst through the use of a high-efficiency dissolved gas device, an ozone catalytic oxidation three-phase separation reaction device and a catalyst, reduces the consumption of mass transfer power, and greatly improves the treatment efficiency. And the system has small head loss, low power consumption, high COD removal load, small catalyst dosage, high catalytic efficiency, strong impact load resistance, short residence time, and low operating cost. , On-line cleaning, on-line sewage discharge, effectively solve the impact of the fluctuation of the suspended solids in the incoming water, and also ensure the stability of the suspended solids in the effluent.

(2) The present invention, especially in the advanced treatment of refractory industrial wastewater, is based on improving the utilization rate of ozone and combining with the use of multi-precious metal suspended catalyst carriers to achieve a gas-liquid-solid three-phase circulating fluidized reaction state, improving the utilization rate of ozone and enhancing the The conversion of hydroxyl radicals is improved, the removal efficiency of refractory pollutants is improved, the biodegradability is significantly improved, the COD treatment load is increased, and the concentration of ozone tail gas is close to zero. Appropriate addition of tail gas destroyers can meet the engineering application.

Description of drawings

Fig. 1 is the schematic diagram of the fluidized bed type ozone catalytic oxidation three-phase separation reaction device of the present invention;

Fig. 2 is the schematic diagram of the suspension type catalyst carrier of the present invention;

Figure 3 is a schematic flow diagram of the reaction system of the present invention.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention. In the examples, the description of COD shall be defined as soluble non-biodegradable COD.

Implement column 1

As shown in FIG. 1 , the fluidized bed type ozone catalytic oxidation three-phase separation reaction device in this embodiment includes a reaction chamber, a flow guide tube 3.1 is arranged in the reaction chamber, and a suspension catalyst 4 is arranged in the flow guide tube 3.1. The bottom of the flow cylinder 3.1 is provided with a water distributor 3.3, the top is provided with a perforated partition 3.2, the bottom of the guide cylinder 3.1 is connected with the gas-water inlet 3.13, and the upper part of the guide cylinder 3.1 is provided with a gas-liquid separation guide device 3.4, gas-liquid separation The outer side of the diversion device 3.4 is provided with a solid-liquid separation baffle 3.5, and the outer side of the gas-liquid separation diversion device 3.4 is also provided with an overflow weir. A clearing zone 3.6 is formed therebetween.

There is also a guided wave level gauge 3.7 on the outside of the bottom of the reaction chamber, and the sewage outlet 3.12 is located at the bottom of the space between the guide tube 3.1 and the chamber wall. The guided wave level meter 3.7 and the sewage outlet can be connected with the PLC control system. The guided wave level meter 3.7 detects the height of the sediment. When the sediment reaches a certain height, the sewage outlet is opened.

The gas-liquid separation and diversion device 3.4 in this embodiment is in the shape of an inverted funnel, and includes a conical surface separation part and a pipe separation part arranged on the top of the conical surface separation part. The gas circulation outlet 3.8 is communicated. The solid-liquid separation baffle 3.5 has a conical shape, is arranged on the conical surface separation part, and one end is connected with the wall of the reaction chamber. Based on the above structure, the ozone gas-water mixture enters the guide tube 3.1 from the bottom gas-water inlet 3.13, and is fully mixed with the suspended catalyst 4 to form a gas-liquid lift-type internal circulation flow and a heterogeneous catalytic oxidation reaction occurs. The gas-water mixture after the reaction After passing through the perforated partition 3.2, most of the undissolved part enters the gas circulation outlet 3.8, and a small part of the dissolved part enters the tail gas port 3.9 through the upper part of the gas-liquid separation diversion device 3.4, and the other small part after intercepting the suspended matter through the clarification zone Then it flows out from the water outlet 3.10 of the overflow part, and the solid-liquid mixture passes through the clarification zone to intercept the suspended matter and enters the space between the guide tube 3.1 and the cavity wall, and flows out from the liquid circulation port 3.11 in the middle of the reaction chamber.

As shown in FIG. 2 , the suspended catalyst 4 includes a spherical support frame 15 , a columnar float 16 disposed in the spherical support frame 15 and a base material for attaching active components. The active components are attached to the substrate, and the density of the suspended catalyst stack is 0.5-0.7. In this embodiment, UPVC or ABS material is used as the support frame 15, and plastic foam is used as the floating object. According to the experience of those skilled in the art, by controlling the proportional relationship between the three, it can adapt to the suspension requirements of different water quality. Alumina spheres, the active components are existing products, which are composed of metals such as Ru, Pt, Cu, Mo and rare earths such as Ce, and are attached to the interior and surface of the microvoid structure of γ-alumina spheres according to existing methods such as dipping. , the diameter of the ball is 2-16mm, and the spherical support frame is 40-80mm.

As shown in FIG. 3 , the three-phase fluidized bed type multi-effect ozone catalytic oxidation three-phase separation reaction system of this embodiment includes two or more of the above-mentioned reaction devices 3. If the device 3 constitutes a first-stage reaction, the device 11 constitutes a second-order reaction.

The liquid circulation port 3.11 and the gas circulation outlet 3.8 of the first-stage reaction device 3 are connected to the high-efficiency dissolved gas device, and the high-efficiency dissolved gas device is connected to the uniform water and gas distributor at the bottom of the reaction device 3, and enters the gas-water inlet. The high-efficiency dissolved gas devices at all levels are connected, the water outlet 3.10 of the first-stage reaction device 3 is connected with the high-efficiency dissolved-gas device corresponding to the next-stage reaction device, and the inlet pump 2 is connected with the high-efficiency dissolved gas device corresponding to the first-stage reaction device 3, The water outlet 3.10 of the second-stage reaction device 11 is connected to the gas-liquid separator 7 , and the gas-liquid separator 7 and the tail gas outlet 3.9 of the reaction devices of each stage are connected to the tail gas destroyer 8 .

The high-efficiency gas-dissolving device includes a gas-liquid mixing pump 5 and an ejector 6 connected to the gas-liquid mixing pump 5. The ozone generator 1 is connected to the gas-liquid mixing pumps 5 and 9 of all levels and the air extraction ports of the ejectors 6 and 10. The gas circulation outlet of the device is connected to the air extraction port of the ejector, the liquid circulation outlet of the reaction devices of each level is connected to the gas-liquid mixing pump, and the water outlet 3.10 of the first-stage reaction device 3 is mixed with the corresponding gas-liquid mixing of the second-stage reaction device 11. The pump 9 is connected, and the inlet pump 2 is connected with the gas-liquid mixing pump 5 corresponding to the first-stage reaction device 3 .

In the implementation of the present invention, the ozone generator 1 is an existing commercially available equipment, including an oxygen generator, an air compressor and an ozone generator. The amount of water determines the concentration and output of ozone, and by switching whether ozone is generated or not, the reactor can be cleaned online with a large flow of air.

In the system of this embodiment, the waste water is fully mixed and efficiently dissolved in the gas-liquid mixing pump 5 and the ejector 6 through the high-concentration ozone provided by the inlet pump 2, the gas-liquid mixing pump 5 and the ejector 6 and the ozone generator 1, and then the microbubbles are dissolved in the gas-liquid mixing pump 5 and the ejector 6. The gas-water mixture enters the first-stage reaction device 3 through the small-resistance water distributor 3.3, and the micro-bubble gas-water mixture is in the guide tube 3.1 of the first-stage reaction device 3. Due to the upward flow of the bubbles and the upward flow of the sewage, a central rising edge is formed. The descending circulating flow state, under the action of the suspended catalyst 4, a large amount of ozone is converted into OH, and the ozone self-oxidation and OH oxidation reaction occur, and a small amount of unreacted dissolved ozone acts on the clarification area of the reaction device 3 along with the water flow. Continue to react in 3.6 or enter the next-stage reaction device 11 and even the gas-liquid separator 7 to be consumed or decomposed completely, while the undissolved and unused ozone is collected by the gas-liquid separation guide device 3.10 and pumped through the jet. The suction effect of the gas port continues to be recycled, and the tail gas destroyer 8 is connected to the exhaust port at the top of each stage of the reaction device and the gas-liquid separator 7, respectively, to process the unreacted part of the ozone tail gas that may exist to meet the safety standard. The gas-liquid separation diversion device in the catalytic oxidation reactor is equipped with a sampling port, and the sampling port can detect whether it contains ozone through a portable ozone concentration detector, and then judge whether to open the gas circulation and the size of the circulation.

The gas-liquid mixing pump 5 and the ejector 6 are all commercially available products. The minimum head of the mixing pump is 22m, the gas-liquid ratio is 1/9, the dissolved gas efficiency is over 95%, and it can stably generate micro-bubbles below 50um. This gas-liquid mixing pump It has stable performance and has been widely used in the shipbuilding industry. Due to the limited dissolved gas ratio, it is often used in combination with a jet device. The jet device has a high dissolved gas ratio, stable performance, maintenance-free, and is suitable for large-scale engineering applications. The total gas-liquid ratio of the gas-liquid mixing pump still has a dissolution efficiency of more than 95% within 1.

The ozone catalytic oxidation three-phase separation reaction device is a closed pressure vessel, the working pressure is less than 0.05 MPa, and the interior and the parts in contact with water and gas are treated with anti-corrosion treatment. The treatment time is determined according to the quality of the wastewater, generally not more than 1 hour. The dosage is in the range of 1%-7%.

The gas-liquid separator 7 and the exhaust gas destroyer 8 are commercially available products, and can be selected according to the gas-liquid separation volume, the exhaust gas treatment volume and the operating pressure.

In the system of the present embodiment, the circulation outlet in the ozone catalytic oxidation three-phase separation reaction device is respectively connected with the inlet of the gas-liquid mixing pump 5, the outlet of the gas-liquid mixing pump 5 is directly connected with the ejector 6, and the outlet of the ejector 6 is connected with the catalytic oxidation reactor The uniform water and gas distributor at the bottom is connected, and the ozone generator 1 is connected with the gas-liquid mixing pump 5 and the jet 6 respectively to form a two-stage high-efficiency gas-dissolving device; the ozone generator 1 uses air as the gas source to generate ozone gas,

The ozone gas flows through the gas-liquid mixing pump and the ejector to form microbubbles and dissolves in water in large quantities, and then enters the ozone catalytic oxidation three-phase separation reaction device in the form of a gas-water mixture through the bottom of the evenly distributed water vaporizer. The suspended catalyst 4 is fully mixed with the ozone gas-water mixture in the ozone catalytic oxidation three-phase separation reaction device 3 to form a gas-liquid lift-type internal circulation flow and a heterogeneous catalytic oxidation reaction occurs. The hydroxyl group generated by the self-oxidation of ozone and the presence of the catalyst Free radicals have no selective oxidation, remove refractory organic pollutants, and improve the biochemical properties of wastewater. The gas-water mixture after the ozone catalytic oxidation reaction passes through the clarification zone and the three-phase separator to effectively intercept the SS, and then flows from the top overflow weir to the bottom. The first-stage reactor finally flows to the gas-liquid separator 7 after the catalytic oxidation reaction of the multi-stage reactor. After the gas-liquid separation, it is discharged up to the standard. The sludge can be discharged online through the on-line monitoring of the mud level with the guided wave level meter, and the gas is processed by the exhaust gas destroyer 8 to meet the discharge standard.

The ozone catalytic oxidation three-phase separation reaction device is provided with a water injection port, a sewage outlet, a small resistance water distributor, a guided wave level meter, a circulation outlet in the side wall, a guide tube, a gas-liquid separation baffle, The solid-liquid separation baffle, overflow weir, water outlet and exhaust outlet are functionally divided into three-phase fluidized catalytic reaction zone, natural sedimentation zone, three-phase separation zone and clarification zone, etc. The suspended catalyst is in the reaction zone. The solid-phase circulation formed in the center of the rising edge and the falling edge, the gas-liquid mixing pump of the gas-liquid mixing pump pumping the gas-liquid separation baffle pipe and the gas-phase circulation of the ozone tail gas reuse, the gas-liquid mixing pump and the center of the effluent bottom of the side wall of the reactor. The liquid phase cycle formed by water.

In this embodiment, according to the size of the COD degradation load of the incoming water, the three-phase fluidized bed type multi-effect ozone catalytic oxidation can be improved by increasing the number of the ozone catalytic oxidation three-phase separation reaction devices in series and the number of high-efficiency dissolved gas devices in parallel. Scope of application of reaction technologies and devices.

Due to the negative pressure suction of the ejector and the multi-stage structure of the ozone generator, the reactor does not change any pipeline valves when the gas-liquid mixing pump is turned on, the air compressor is turned on, and the oxygen generator and ozone generator are stopped. Gas-water online cleaning can be achieved under the condition of

The guided wave level meter installed in the ozone catalytic oxidation three-phase separation reaction device can also realize automatic online sewage discharge of sludge by interlocking with the sewage valve.

The suspended catalyst carrier adapts to the suspension requirements of different water quality by adjusting the proportional relationship between the alumina balls, floats, and support frames. Due to the promotion of the water flow and airflow in the reaction zone, the suspended catalyst carrier plays a role in the rising water flow and airflow. The bottom shows a closed-loop flow state in which the rising edge at the center of the reaction zone falls, and the support frame with rotating fan blades is affected by the shear force of the water flow and the airflow. The suspended catalyst carrier also presents a rotating state at the same time.

The inlet of the gas-liquid mixing pump is connected with the circulation outlet in the reactor and the inlet water pump or the drainage port of the upper stage reactor, the outlet is connected with the ejector, the outlet of the ejector is connected with the water distributor, and the gas-liquid mixing pump and the air outlet of the ejector are connected with the ejector. The ozone generator pipelines are connected in parallel, and check valves, flow meters and control valves are installed in the parallel pipelines, which can flexibly adjust the air-water ratio and air supply volume according to different water quality conditions. The three-phase fluidized bed type multi-effect ozone catalytic oxidation reaction technology and device can control the ozone dosage and the absolute load of COD degradation in a wide range according to the parallel number of high-efficiency dissolved gas devices.

The system of this embodiment can also be provided with an existing distribution box and a PLC system, and a check valve, a flow meter, a regulating valve, an online instrument, etc. are also installed in the pipeline. The PLC system is interlocked with the online instrument to accurately Automatically control the dosage of ozone and the amount of circulating water and facilitate maintenance.

The system of this embodiment is used to treat the effluent after biochemical treatment of a sewage treatment plant in an industrial park. The COD concentration of the influent in the small test is about 74 mg/L, the BOD/COD is about 0.03, and the biochemical property is extremely poor. After treatment by the efficient catalytic oxidation reaction system, the effluent is stable at 20-28 mg/L, the maximum removal load is 1.3 kg/(m3·d), and the ozone utilization rate is over 95%. According to the removal of COD concentration of 50mg/L, the dosage of ozone/COD removal fluctuates in the range of 1.5-3, the treatment cost is 0.6-1.2 yuan (RMB)/m³, and the electricity price is calculated at 0.8 yuan/kWh, the treatment cost is significantly lower in the current conventional advanced oxidation treatment process.

Implement column 2

The system of this embodiment is the same as that of Embodiment 1.

The system of this embodiment is used to treat the tail water after printing and dyeing and chemical biochemical treatment in a certain park. The front end of the tail water adopts biochemical treatment such as hydrolysis and acidification + A ₂ O + MBR, the biochemical residence time exceeds 40h, and the B/C of the tail water is almost zero. , the COD fluctuates at 70-100mg/l. The wastewater is analyzed by GC/MS. The water mainly contains azo and heterocyclic groups, and the molecular weight is greater than 10k and more than 50%. Basically, all of them can be considered as biochemical refractory parts. , the pilot-scale treatment scale is 1m³/h, the residence time is 0.5h, the single-stage catalytic oxidation system runs continuously, the catalyst dosage is 3%, the COD concentration of the influent is 80-100mg/L, the effluent is stable up to 35mg/L, and the absolute amount of COD removal is It is 40-60mg/l, the COD removal rate is stable above 60%, the ozone dosage is 60-90mg/L, the ozone dosage/COD removal amount is 1.2-1.5, the treatment cost is 0.84-1 yuan/m³, electricity price According to 0.8 yuan / degree.

It will be apparent to those skilled in the art that the present invention is not limited to the details of the above-described exemplary embodiments, but that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments are to be regarded in all respects as illustrative and not restrictive, and the scope of the invention is to be defined by the appended claims rather than the foregoing description, which are therefore intended to fall within the scope of the claims. All changes within the meaning and scope of the equivalents of , are included in the present invention. Any reference signs in the claims shall not be construed as limiting the involved claim.

In addition, it should be understood that although this specification is described in terms of embodiments, not each embodiment only includes an independent technical solution, and this description in the specification is only for the sake of clarity, and those skilled in the art should take the specification as a whole , the technical solutions in each embodiment can also be appropriately combined to form other implementations that can be understood by those skilled in the art.

Claims (10)

1. A fluidized bed type ozone catalytic oxidation three-phase separation reaction device is characterized in that: the reaction device is provided with a reaction chamber and an internal central guide cylinder, a suspended catalyst is arranged in the guide cylinder, a water distributor is arranged at the bottom of the guide cylinder, a partition plate with holes is arranged at the top of the guide cylinder, the bottom of the guide cylinder is communicated with a gas-water inlet pipe, a gas-liquid separation guide device is arranged above the guide cylinder, a solid-liquid separation partition plate is arranged at the upper part outside the gas-liquid separation guide device, an overflow weir is also arranged on the reaction chamber at the upper part outside the solid-liquid separation partition plate, a clarification zone is arranged between the lower part of the overflow weir and the outside of the gas-liquid separation guide device and between the solid-liquid separation plates, a gas circulation outlet and a tail gas discharge outlet are arranged at the top of the reaction device, the gas circulation outlet is directly connected with the gas-liquid separation guide device, a liquid circulation, the gas-water mixture after reaction passes through a clapboard with holes, most undissolved gas enters a gas circulation outlet, a small part of dissolved gas enters an exhaust port along with water flow through a gas-liquid separation flow guide device and a solid-liquid separation clapboard, the gas-liquid mixture with a small part of dissolved gas flows out from a water outlet of an overflow weir after a clarification zone intercepts suspended matters, part of solid-liquid mixture after the clarification zone intercepts the suspended matters enters a clarification space between a flow guide cylinder and a reaction chamber for natural sedimentation solid-liquid separation, the separated suspended matters are discharged from a sewage discharge outlet, and water enters a liquid circulation outlet for recycling.

2. The catalytic ozonation three-phase separation reaction unit as set forth in claim 1, wherein: the gas-liquid separation flow guide device is in an inverted funnel shape and comprises a conical surface separation part and a pipeline separation part arranged at the top of the conical surface separation part, the conical surface separation part is positioned on the flow guide cylinder, and the pipeline separation part is communicated with a top gas circulation outlet.

3. The catalytic ozonation three-phase separation reaction unit as set forth in claim 2, wherein: the solid-liquid separation baffle is conical and is arranged on the conical separation part, and one end of the solid-liquid separation baffle is connected with the wall of the reaction cavity.

4. The catalytic ozonation three-phase separation reaction unit as set forth in claim 1, wherein: the guide wave level meter is arranged on the outer side of the bottom of the reaction cavity, the drain outlet is located at the bottom of a space between the guide cylinder and the reaction cavity, the guide wave level meter automatically detects the height of the sediment, and the drain outlet can be automatically opened when the sediment reaches a certain height.

5. The catalytic ozonation three-phase separation reaction unit as set forth in claim 1, wherein: the suspension catalyst comprises a spherical support frame, a columnar floater arranged in the spherical support frame and an active component attaching base material. The active component is attached to the base material, and the density of the suspension catalyst is 0.5-0.7.

6. The catalytic ozonation three-phase separation reaction unit as set forth in claim 5, wherein: the active component attaching base material is a gamma-alumina pellet, the active component is attached to the inside and the surface of a micro-pore structure of the gamma-alumina pellet, the diameter of the pellet is 2-16mm, and the spherical support frame is 40-80 mm.

7. A fluidized bed type multi-effect ozone catalytic oxidation reaction system is characterized in that: the reactor comprises at least one reactor as claimed in any one of claims 1 to 6, wherein a liquid circulation port of a first stage reactor is connected with a high-efficiency gas dissolving device, the high-efficiency gas dissolving device is connected with a gas-water inlet at the bottom of the reactor and is connected with a uniform water distributor, an ozone generator is connected with a port of the high-efficiency gas dissolving device, a water outlet of the first stage reactor is connected with a high-efficiency gas dissolving device corresponding to a next stage reactor, a water inlet pump is connected with the high-efficiency gas dissolving device corresponding to the first stage reactor, a water outlet of a last stage reactor is connected with a gas-liquid separator, and a tail gas port of each stage reactor is connected with a tail gas destructor.

8. The multi-effect ozone catalytic oxidation reaction system of the fluidized bed type according to claim 7, characterized in that: the efficient gas dissolving device comprises a gas-liquid mixing pump and an ejector connected with the gas-liquid mixing pump, an ozone generator is connected with the gas-liquid mixing pump and an ejector extraction opening, a gas circulation outlet of each stage of reaction device is connected with the corresponding ejector extraction opening, a liquid circulation outlet of each stage of reaction device is connected with the gas-liquid mixing pump, a water outlet of a first stage of reaction device is connected with a liquid circulation outlet pipe corresponding to a next stage of reaction device, and a water inlet pump is connected with the liquid circulation outlet pipe corresponding to the first stage of reaction device.

9. The multi-effect ozone catalytic oxidation reaction system of the three-phase fluidized bed type according to claim 8, characterized in that: the gas-water ratio of the gas-liquid mixing pump is controlled to be 0-1/9, the gas-water ratio of the jet device is controlled to be 0-1.8, and the outlet pressure of the gas-liquid mixing pump is more than 0.2 MPa.

10. The multi-effect ozone catalytic oxidation reaction system of the three-phase fluidized bed type according to any one of claims 7 to 9, wherein: the adding amount of the suspension catalyst is 1 to 7 percent, and the working pressure of the reaction device is less than 0.05 MPa.

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