CN110818064A - Fluidized bed type ozone catalytic oxidation three-phase separation reaction device and system - Google Patents
Fluidized bed type ozone catalytic oxidation three-phase separation reaction device and system Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 101
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 49
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 49
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- 238000005191 phase separation Methods 0.000 title claims abstract description 26
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000000926 separation method Methods 0.000 claims abstract description 57
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- 238000006385 ozonation reaction Methods 0.000 claims description 10
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- 229920011532 unplasticized polyvinyl chloride Polymers 0.000 description 4
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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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
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 a system thereof.
Background
With the rapid development of modern industry, the amount of industrial wastewater generated by industries such as printing and dyeing, leather, chemical industry and the like is larger and larger, and the industrial wastewater not only has complex and variable components and complex structure, but also has certain toxicity and is difficult to biochemically treat. At present, the common industrial wastewater treatment process at home and abroad is mostly treated by a biochemical method, but with the stricter discharge standards of all places, the industrial wastewater which is high in salt content, low in B/C ratio, complex in component and difficult to degrade and is treated by the biochemical process only can hardly reach the discharge standard.
The treatment of wastewater with high salinity, low B/C ratio, complex components and difficult degradation is a hot point and a key point of research of scholars at home and abroad in recent years. To meet higher treatment requirements, physical adsorption and chemical oxidation processes are often used to treat such wastewater. Physical adsorption mainly comprises activated carbon adsorption and resin adsorption, but the method has the defects that the adsorption material needs to be regenerated after being adsorbed and saturated, the regeneration process has high energy consumption, and the regeneration liquid generally contains high-concentration organic matters and can cause secondary pollution; the common chemical oxidation is mainly an advanced oxidation process, but the oxidation process has short exploration time, incomplete basic theory and complicated and various actual pollution systems, so that the technology has many problems to be researched and solved in theoretical research and industrial application.
Compared with biological and physical methods, the advanced oxidation technology has the advantages of high efficiency, short retention time, deep treatment degree and the like in the aspect of treating wastewater. The ozone catalytic oxidation technology is one of a plurality of advanced oxidation technologies, and the ozone catalytic oxidation improves the oxidation efficiency through a catalyst, reduces the activation energy of the reaction, and ensures that the oxidation reaction can obtain good oxidation effect at normal temperature and normal pressure. However, because the industrial wastewater has complex components and more pollutants, the phenomena of low ozone utilization rate, incomplete pollutant treatment and the like still exist by adopting a single catalyst and a conventional catalytic oxidation process. According to the characteristic that the components of industrial wastewater are complex, more efficient catalyst combination is adopted and the wastewater is treated by combining an efficient ozone utilization device and an advanced reaction device, so that the catalytic oxidation treatment efficiency is improved, and the reduction of construction and operation costs becomes more and more important.
Disclosure of Invention
The method aims to overcome the defects that the conventional catalytic oxidation catalyst adopts a fixed bed placing mode, has narrow application range on suspended matters, low system catalytic efficiency, low ozone utilization rate, small absolute load of COD removal, long reaction residence time and high operation and investment cost. The invention provides a fluidized bed type ozone catalytic oxidation three-phase separation reaction device and a system thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
a fluidized bed type three-phase separation reaction device for catalytic ozonation 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 of the outer side of the gas-liquid separation guide device, an overflow weir is further arranged on the reaction chamber at the upper part of the outer side of the solid-liquid separation partition plate, a clarification area is arranged between the lower part of the overflow weir and the outer side of the gas-liquid separation guide device and between the solid-liquid separation partition plate, 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-, 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.
Furthermore, the gas-liquid separation guiding 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 guiding cylinder, and the pipeline separation part is communicated with the top gas circulation outlet.
Furthermore, 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.
Furthermore, the outer side of the bottom of the reaction cavity is also provided with a guided wave level meter, the drain outlet is positioned at the bottom of the space between the guide cylinder and the reaction cavity, the guided wave level meter detects the height of the sediment, and the drain outlet can be automatically opened when the sediment reaches a certain height.
Furthermore, the suspension catalyst comprises a spherical support frame, and a columnar floater and an active component attaching base material which are arranged in the spherical support frame. The active component is attached to the base material, and the density of the suspension catalyst is 0.5-0.7.
Furthermore, 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.
The invention relates to a fluidized bed type multiple-effect ozone catalytic oxidation three-phase separation reaction system, which comprises at least one reaction device, wherein a liquid circulation port of a first-stage reaction device 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 reaction device 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 reaction device is connected with a high-efficiency gas dissolving device corresponding to a next-stage reaction device, a water inlet pump is connected with the high-efficiency gas dissolving device corresponding to the first-stage reaction device, a water outlet of a last-stage reaction device is connected with a gas-liquid separator, and a tail gas port of each-stage reaction.
Further, the efficient gas dissolving device comprises a gas-liquid mixing pump and an ejector connected with the gas-liquid mixing pump, the ozone generator is connected with the gas-liquid mixing pump and an air extraction opening of the ejector, a gas circulation outlet of each stage of reaction device is connected with the air extraction opening of the corresponding ejector, a liquid circulation outlet of each stage of reaction device is connected with the gas-liquid mixing pump, a water outlet of the first stage of reaction device is connected with a liquid circulation outlet pipe corresponding to the 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.
Further, 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 greater than 0.2 MPa.
Furthermore, the adding amount of the suspension catalyst is 1-7%, and the working pressure of the reaction device is less than 0.05 MPa.
The invention can be matched with a flowmeter, a regulating valve, a concentration meter and a level meter for automatic control to realize the aim. The efficient air dissolving device is formed by connecting a gas-liquid mixing pump and an ejector in series, and the dissolving efficiency of ozone after air dissolving through the efficient air dissolving device can reach more than 98%. The gas recycling device is composed of a gas-liquid separation clapboard and a suction pipe matched with the ejector, and the device can form closed circulation recycling by the suction effect of the ejector on undissolved ozone. The air-lift internal circulating fluidized bed device is composed of a small-resistance air distributor and a guide cylinder. The suspension catalyst consists of a gamma-alumina spherical carrier with the diameter of 2-16mm and the density of more than 1, a plastic frame with the diameter of 40-80mm and a floater with the density of less than 1, the suspension catalyst is formed into a suspension shape after being reasonably proportioned by alumina pellets and the floater, the bulk density of the catalyst is 0.5-0.7, and a closed internal circulation turbulent flow motion state with the center facing upwards and the edge facing downwards is formed in the rising process of a gas-water mixture at the bottom of the reactor.
The ozone generator comprises an oxygen generator, an ozone generator and an air compressor, the ozone generator can determine the ozone adding concentration and output according to the wastewater amount and the water quality to be treated, the ozone generator can be automatically controlled to be turned off through a PLC, the flow of the air compressor is increased, and the online circular cleaning of the air of the reactor can be realized.
The high-efficiency gas dissolving device adopts a gas-liquid mixing pump and jet device gas dissolving mode, the gas-liquid mixing pump gas-water ratio can be controlled at 0-1/9, the jet flow device gas-water ratio is controlled at 0-1.8, the outlet pressure of the gas-liquid mixing pump is greater than 0.2MPa, the ozone dissolving efficiency can reach more than 98%, and the ozone adding amount can be flexibly adjusted according to COD load in engineering application.
The ozone catalytic oxidation reactor is a closed container with pressure, the working pressure is less than 0.05 MPa, and the inside of the ozone catalytic oxidation reactor is subjected to anticorrosion treatment or directly selects an anticorrosion material.
The high-efficiency gas dissolving device can flexibly increase the serial quantity or the circulating flow according to the COD load of the incoming water and the circulating water quantity.
The suspension catalyst carrier adopts gamma-alumina pellets as an attached base material of a plurality of noble metal active components, UPVC or ABS material as a supporting frame and plastic foam as a floating object, the suspension requirements of different water qualities are met by adjusting the proportional relation of the gamma-alumina pellets, the UPVC or the ABS material, and the bulk density of the integral catalyst is 0.5-0.7.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention increases the contact area of ozone, sewage and ozone catalyst, reduces the mass transfer power consumption and greatly improves the treatment efficiency by using the high-efficiency gas dissolving device, the ozone catalytic oxidation three-phase separation reaction device and the catalyst, the reaction device and the system have small head loss, low power consumption, high COD removal load, small catalyst dosage, high catalytic efficiency, strong impact load resistance, short retention time and low operation cost, really realizes gas-liquid-solid three-phase circulating fluidization, online cleaning and online pollution discharge, effectively solves the influence of fluctuation of water suspended matters, and simultaneously ensures the stability of the water suspended matters.
(2) Particularly in the aspect of advanced treatment of industrial wastewater difficult to degrade, based on the improvement of the utilization rate of ozone and the combination of a suspension catalyst carrier of multiple precious metals, the invention realizes the gas-liquid-solid three-phase circulating fluidized reaction state, enhances the conversion of hydroxyl radicals while improving the utilization rate of ozone, further improves the removal efficiency of pollutants difficult to degrade, obviously improves the biodegradability, improves the COD treatment load, ensures that the concentration of ozone tail gas is close to zero, and can meet the engineering application by properly adding a tail gas destructor.
Drawings
FIG. 1 is a schematic view of a fluidized bed type catalytic ozonation three-phase separation reaction apparatus according to the present invention;
FIG. 2 is a schematic view of a suspended catalyst support of the present invention;
FIG. 3 is a schematic flow diagram of a reaction system of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention. In the examples, the description of COD shall be defined as the soluble non-biodegradable COD.
EXAMPLE 1
As shown in fig. 1, the fluidized bed type catalytic ozonation three-phase separation reaction device of the present embodiment includes a reaction chamber, a draft tube 3.1 is disposed in the reaction chamber, a suspension catalyst 4 is disposed in the draft tube 3.1, a water distributor 3.3 is disposed at the bottom of the draft tube 3.1, a partition plate 3.2 with holes is disposed at the top of the draft tube 3.1, the bottom of the draft tube 3.1 is communicated with a gas-water inlet 3.13, a gas-liquid separation flow guide device 3.4 is disposed above the draft tube 3.1, a solid-liquid separation partition plate 3.5 is disposed outside the gas-liquid separation flow guide device 3.4, an overflow weir plug is further disposed outside the gas-liquid separation flow guide device 3.4, and a clarification zone 3.6 is formed between the lower portion of the overflow weir and the.
The outer side of the bottom of the reaction cavity is also provided with a guided wave level meter 3.7, and a sewage outlet 3.12 is positioned at the bottom of a space between the guide cylinder 3.1 and the cavity wall. The guided wave level meter 3.7 and the sewage draining exit can be connected with the PLC control system, the guided wave level meter 3.7 detects the height of the sediment, and the sewage draining exit is opened when the sediment reaches a certain height.
The gas-liquid separation guiding device 3.4 of this embodiment is the funnel form that falls, including conical surface separator part and the pipeline separator part of locating conical surface separator part top, conical surface separator part is located draft tube 3.1, and pipeline separator part and top gas circulation export 3.8 intercommunication. The solid-liquid separation baffle 3.5 is conical and is arranged on the conical separation part, and one end of the baffle is connected with the wall of the reaction chamber. Based on the structure, an ozone gas-water mixture enters the guide shell 3.1 from a gas-water inlet 3.13 at the bottom and is fully mixed with the suspended catalyst 4 to form gas-liquid rising type internal circulation flow and generate heterogeneous catalytic oxidation reaction, the gas-water mixture after reaction passes through the partition plate 3.2 with holes, the undissolved majority of the mixture enters the gas circulation outlet 3.8, the dissolved minority of the mixture enters the tail gas port 3.9 through the upper part of the gas-liquid separation guide flow device 3.4, the other minority of the mixture after the mixture passes through the clarification zone and intercepts suspended matters flows out from the water outlet 3.10 of the overflow part, and the solid-liquid mixture enters the space between the guide shell 3.1 and the cavity wall after the mixture intercepts the suspended matters through the clarification zone and flows out from the liquid circulation port 3..
As shown in fig. 2, the suspension catalyst 4 comprises a spherical support frame 15, a columnar float 16 disposed in the spherical support frame 15, and an active component attaching base material. The active component is attached to the substrate and the density of the suspended catalyst mass is 0.5-0.7. In the embodiment, UPVC or ABS material is used as a supporting frame 15, plastic foam is used as a floating object, the proportion relation among the UPVC or ABS material, the plastic foam and the floating object is controlled according to the experience of technicians in the field to adapt to the suspension requirements of different water qualities, the active component attaching base material is gamma-alumina pellets, the active component is an existing product and is composed of Ru, Pt, Cu, Mo and other metals and Ce and other rare earths, the active component attaching base material is attached to the inside and the surface of a gamma-alumina pellet micro-gap structure according to the existing modes of dipping and the like, the diameter of the pellets is 2-16mm, and the diameter of a spherical.
As shown in fig. 3, the three-phase fluidized bed type multi-effect ozone catalytic oxidation three-phase separation reaction system of the present embodiment includes two or more reaction devices 3, such as the device 3 constitutes a first-stage reaction, and the device 11 constitutes a second-stage reaction.
The liquid circulation port 3.11 and the gas circulation outlet 3.8 of the first-stage reaction device 3 are connected with a high-efficiency gas dissolving device, the high-efficiency gas dissolving device is connected with an even water distributor at the bottom of the reaction device 3 and enters a gas water inlet, an ozone generator is connected with each stage of high-efficiency gas dissolving device, the water outlet 3.10 of the first-stage reaction device 3 is connected with the high-efficiency gas dissolving device corresponding to the next-stage reaction device, the water inlet pump 2 is connected with the high-efficiency gas dissolving device corresponding to the first-stage reaction device 3, the water outlet 3.10 of the second-stage reaction device 11 is connected with a gas-liquid separator 7, and the gas-liquid separator 7 and the tail gas port 3.9 of each stage of reaction device are connected with a.
The high-efficiency gas dissolving device comprises a gas-liquid mixing pump 5 and an ejector 6 connected with the gas-liquid mixing pump 5, an ozone generator 1 is connected with gas pumping ports of the gas- liquid mixing pumps 5 and 9 and the ejectors 6 and 10, gas circulation outlets of the reaction devices are connected with the air pumping ports of the ejectors, liquid circulation outlets of the reaction devices are connected with the gas-liquid mixing pump, a water outlet 3.10 of a first-stage reaction device 3 is connected with the gas-liquid mixing pump 9 corresponding to a second-stage reaction device 11, and a water inlet pump 2 is connected with the gas-liquid mixing pump 5 corresponding to the first-stage reaction device 3.
In the embodiment of the invention, the ozone generator 1 is the existing commercially available equipment, comprises an oxygen generator, an air compressor and an ozone generator, is an integrated device, has flexible and adjustable ozone concentration and flow, can determine the ozone adding concentration and output according to the quality and the quantity of the treated wastewater, and realizes the on-line cleaning of a large amount of air flow of the reactor by switching the generation of the ozone.
In the system of the embodiment, the wastewater is fully mixed and efficiently dissolved in the gas-liquid mixing pump 5, the ejector 6 and the ozone generator 1 through the high-concentration ozone provided by the gas-liquid mixing pump 5 and the ejector 6, and then enters the first-stage reaction device 3 through the low-resistance gas distributor 3.3 in the form of a micro-bubble gas-water mixture, the micro-bubble gas-water mixture forms a circular flow state with a central ascending edge descending due to the upward bubble floating and the upward sewage flowing action in the guide cylinder 3.1 of the first-stage reaction device 3, the suspension catalyst 4 promotes a large amount of ozone to be converted into OH under the action to generate ozone self-oxidation and OH oxidation reactions, and the unreacted small amount of dissolved ozone continues to react in the clarification area 3.6 of the reaction device 3 or enters the next-stage reaction device 11 and even the gas-liquid separator 7 to be consumed or decomposed completely under the, The unused ozone is collected by the gas-liquid separation flow guide device 3.10 and continuously recycled by the suction effect of the air suction opening of the ejector, and the tail gas destructor 8 is respectively connected with the top exhaust opening of each stage of reaction device and the gas-liquid separator 7 to treat the possibly existing unreacted ozone tail gas so as to achieve the safety standard. The gas-liquid separation guiding device in the catalytic oxidation reactor is additionally provided with a sampling port, and the sampling port can detect whether ozone is contained or not through a portable ozone concentration detector, so that whether gas internal circulation and circulation volume are started or not is judged.
The gas-liquid mixing pump 5 and the ejector 6 are commercially available products, the minimum lift of the mixing pump is 22m, the gas-liquid ratio is 1/9, the gas dissolving efficiency reaches more than 95%, micro bubbles below 50um can be stably generated, the gas-liquid mixing pump has stable performance and is widely applied to the ship industry, the gas dissolving ratio is limited, the gas-liquid mixing pump is often combined with the ejector for use, the ejector has high gas dissolving ratio, stable performance, no maintenance and suitability for large-scale engineering application, and the total gas-liquid ratio of the combined gas-liquid mixing pump still has more than 95% of dissolving efficiency within 1.
The ozone catalytic oxidation three-phase separation reaction device is a closed pressure container, the working pressure is less than 0.05 MPa, the inside and the contact part of the ozone catalytic oxidation three-phase separation reaction device and the water vapor are subjected to antiseptic treatment, the treatment time is determined according to the quality of wastewater, generally not more than 1 hour, and the adding amount of a catalyst in a reactor is in the range of 1-7%.
The gas-liquid separator 7 and the tail gas destructor 8 are commercially available products, and can be correspondingly selected according to gas-liquid separation amount, tail gas treatment amount and operation pressure.
In the system of the embodiment, an internal circulation outlet of the ozone catalytic oxidation three-phase separation reaction device is respectively connected with an inlet of a gas-liquid mixing pump 5, an outlet of the gas-liquid mixing pump 5 is directly connected with an ejector 6, an outlet of the ejector 6 is connected with a uniform water distributor at the bottom of the catalytic oxidation reactor, and an ozone generator 1 is respectively connected with the gas-liquid mixing pump 5 and the ejector 6 to form a two-stage efficient gas dissolving device; the ozone generator 1 generates ozone gas by taking air as a gas source,
ozone gas is guided by a gas-liquid mixing pump and an ejector to form micro bubbles, is dissolved in water in a large amount, and then enters an ozone catalytic oxidation three-phase separation reaction device through the bottom of a uniform water-gas distributor in the form of a gas-water mixture. The suspension catalyst 4 is fully mixed with the ozone gas-water mixture in the ozone catalytic oxidation three-phase separation reaction device 3 to form gas-liquid lifting type internal circulation flow and generate heterogeneous catalytic oxidation reaction, through the self-oxidation of ozone and the non-selective oxidation of hydroxyl free radicals generated in the presence of a catalyst, organic pollutants which are difficult to degrade are removed, the biochemical property of wastewater is improved, a gas-water mixture after the catalytic oxidation reaction of ozone effectively intercepts SS through a clarification zone and a three-phase separator and then flows to a next-stage reactor from a top overflow weir, finally flows to a gas-liquid separator 7 after the catalytic oxidation reaction of a multi-stage reactor, the gas-liquid separation is discharged after reaching standards, solid pollutants such as SS (suspended solids) and the like naturally settle in a settling zone of an outer cylinder of a guide cylinder, a blow-down valve realizes the online discharge of sludge through the online sludge level monitoring of a guide wave level meter, and gas is treated through a tail gas destructor 8 to reach the discharge standard.
The ozone catalytic oxidation three-phase separation reaction device is sequentially provided with a water filling port, a sewage draining port, a small-resistance water and gas distributor, a guided wave level meter, a side wall internal circulation outlet, a guide cylinder, a gas-liquid separation baffle, a solid-liquid separation baffle, an overflow weir, a water draining port and an air exhausting port from bottom to top, and is functionally divided into a three-phase fluidized catalytic reaction zone, a natural settling zone, a three-phase separation zone, a clarification zone and the like from the region; the device comprises a solid phase circulation formed by a suspended catalyst in a reaction zone and descending along the central rising edge, a gas phase circulation formed by an ejector gas-liquid mixing pump sucking ozone tail gas formed by a gas-liquid separation partition pipeline for recycling, and a liquid phase circulation formed by a gas-liquid mixing pump and water inlet at the center of the water outlet bottom of the side wall of the reactor.
In this embodiment, according to the COD degradation load of the incoming water, the number of the three-phase separation reaction devices for catalytic ozonation in series can be increased, and the number of the high-efficiency gas dissolving devices can be increased in parallel, so as to increase the application range of the three-phase fluidized bed type multi-effect catalytic ozonation reaction technology and the device.
Due to the negative pressure suction of the ejector and the multi-stage structural action of the ozone generator, the reactor can realize the online cleaning of air water without changing any pipeline valve under the conditions that the air-liquid mixing pump is started, the air compressor is started, and the oxygen generator and the ozone generator are stopped.
The guide wave level meter additionally arranged in the ozone catalytic oxidation three-phase separation reaction device can realize automatic online sludge discharge through interlocking with the discharge valve.
The suspension catalyst carrier adapts to suspension requirements of different water qualities by adjusting the proportional relation among the small alumina balls, the floating objects and the supporting frames, and shows a closed circulating flow state that the center position of the reaction zone ascends and the edge descends under the action of ascending water flow and air flow due to the pushing action of the water flow and the air flow in the reaction zone, and simultaneously shows a rotating state under the action of the shearing force of the water flow and the air flow on the supporting frames with the rotating fan blades.
The inlet of the gas-liquid mixing pump is connected with the internal circulation outlet of the reactor and the water inlet pump or the water outlet of the previous stage reactor, the outlet is connected with the ejector, the outlet of the ejector is connected with the water distributor, the gas-liquid mixing pump and the air exhaust opening of the ejector are connected in parallel with the ozone generator pipeline, the parallel pipeline is respectively provided with a check valve, a flowmeter and a control valve, the gas-liquid ratio and the gas supply quantity can be flexibly adjusted according to different water quality conditions, the gas-liquid mixing pump and the ejector form a high-efficiency gas dissolving device, and the three-phase fluidized bed type multiple-effect ozone catalytic oxidation reaction technology and device can control the ozone adding quantity and COD degradation absolute load in a large range according to the parallel quantity of the high.
The system of this embodiment can also be equipped with current block terminal and PLC system, has still installed check valve, flowmeter, governing valve, online instrument etc. additional in the pipeline, and the PLC system is through interlocking with online instrument, can accurate automatic control ozone input volume and circulation water yield and convenient the maintenance.
The effluent after biochemical treatment of a sewage treatment plant in an industrial park is treated by adopting the system of the embodiment, the COD concentration of the small test influent is about 74mg/L, the BOD/COD is about 0.03, the biochemical polarization is poor, the effluent is stably treated by the multi-effect catalytic oxidation reaction system in a fluidized bed form to reach 20-28mg/L, the maximum removal load reaches 1.3 kg/(m 3. d), the ozone utilization rate reaches more than 95%, the ozone addition/COD removal amount of the water fluctuates within the range of 1.5-3 according to the removal COD concentration of 50mg/L under the requirement of surface IV water, the treatment cost is 0.6-1.2 yuan (RMB)/m, the electricity price is 0.8 yuan/meter, and the treatment cost is obviously lower than that of the conventional advanced oxidation treatment process.
EXAMPLE 2
The system of this example is the same as example 1.
The system of the embodiment is adopted to treat tail water after printing and dyeing and chemical biochemical treatment in a certain park, and the front end of the tail water adopts hydrolysis acidification + A2Performing biochemical treatment on O + MBR and the like, wherein the biochemical retention time exceeds 40h, the B/C of tail water is almost zero, the COD is maintained at 70-100mg/L fluctuation, the wastewater mainly contains azo and heterocyclic groups through GC/MS analysis, the molecular weight of the wastewater is more than 10k and more than 50%, the wastewater can be basically considered as a biochemical degradation-resistant part, the pilot scale treatment scale is 1m till/h, the retention time is 0.5h, a single-stage catalytic oxidation system is continuously operated, the catalyst addition amount is 3%, the water inflow COD concentration is 80-100mg/L, the effluent stability is 35mg/L, the absolute COD removal amount is 40-60mg/L, the COD removal rate is stably more than 60%, the ozone addition amount is 60-90mg/L, the ozone addition amount/COD removal amount is 1.2-1.5, the treatment cost is 0.84-1 yuan/m for dry-by-mass spectrometry, electricity prices are in 0.8 yuan/meter.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments 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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