CN109748353B - Device and method for water treatment based on fluid control microbubble-ozone coupling - Google Patents
Device and method for water treatment based on fluid control microbubble-ozone coupling Download PDFInfo
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Abstract
The invention discloses a device and a method for water treatment based on flow control microbubble-ozone coupling, wherein the device comprises an oxygen gas supply source (1), an ozone generator (2), a pressure regulating and filtering assembly (4), a flow control assembly (6) and a water pool (7) to be treated, which are sequentially connected with one another through a drainage tube (9), the device also comprises an ultrasonic assembly (11), and an ultraviolet radiation assembly (10) is arranged in the water pool (7) to be treated. In the invention, the micro-bubble technology is utilized to rapidly improve the mass transfer efficiency of ozone and the solubility of ozone, and meanwhile, ultrasonic-induced micro-bubbles are utilized to break and generate free radicals, and synchronous ultrasonic cavitation pyrolysis and ultraviolet radiation are utilized to promote the ozone to generate the free radicals so as to improve the yield of the ozone.
Description
Technical Field
The invention relates to the field of water treatment, in particular to water treatment by using an ozone oxidation technology, and specifically relates to a device and a method for water treatment based on flow control microbubble-ozone coupling.
Background
The regeneration treatment and the recycling of water resources are important ways for solving the current water supply crisis and restraining the water environment deterioration, and the research and the development of the water treatment technology are the key points in the current field. A large amount of refractory soluble organic matters are remained in various water bodies such as surface water bodies, underground water, sewage, secondary effluent of sewage treatment plants, reclaimed water and the like, and the traditional physicochemical method or the addition of retention chemicals is easy to cause secondary pollution or is subject to various limitations due to complex process and high cost.
Ozone oxidation is of great interest for reasons such as its high oxidation efficiency, no persistent residue in the environment, and simple process flow. However, the practical engineering application of ozone oxidation is limited by two bottlenecks, namely, low ozone solubility in water and limited radical yield.
Disclosure of Invention
In order to solve the above problems, the present inventors have made intensive studies, and have proposed that water treatment is performed based on a combination of a flow control microbubble technology and an ozone oxidation technology, and at the same time, ultraviolet radiation and ultrasonic treatment are added, the flow control microbubble technology is used to rapidly improve the mass transfer efficiency of ozone and improve the solubility of ozone, ultrasonic-induced microbubble is used to destroy generated radicals, and synchronous ultrasonic cavitation pyrolysis and ultraviolet radiation are used to promote the generation of the radicals by ozone, thereby improving the yield, and the present invention is applied to advanced treatment of secondary effluent of an urban sewage plant, reducing the organic matter content, changing the organic matter structure, and improving the biodegradability thereof, thereby completing the present invention.
The invention provides a water treatment device based on fluid control microbubble-ozone coupling, which is embodied in the following aspects:
(1) the utility model provides a device based on fluid control microbubble-ozone coupling carries out water treatment, a serial communication port, the device includes oxygen air supply source 1, ozone generator 2, pressure regulating filter assembly 4, fluid control subassembly 6 and the pond 7 of treating through drainage tube 9 interconnect in proper order, wherein, the device still includes ultrasonic component 11, just is in be provided with ultraviolet radiation subassembly 10 in the pond 7 of treating.
(2) The apparatus according to the above (1), wherein,
an air diffusing component 8 is arranged at the bottom of the pool 7 to be treated and communicated with the flow control component 6, and preferably, the air diffusing component is a microporous plate; and/or
The ultraviolet radiation assembly 10 includes a plurality of ultraviolet lamps.
(3) The apparatus according to the above (1), wherein,
the ultrasonic assembly 11 comprises an ultrasonic generator 111 and one or more side ultrasonic vibration plates 112 connected with the ultrasonic generator, and preferably, the side ultrasonic vibration plates 112 are arranged in the water tank 7 to be treated.
(4) The apparatus according to the above (1), wherein,
a control valve 3 is arranged between the ozone generator 2 and the pressure-regulating filtering component 4; and/or
A flow meter 5 is arranged between the pressure-regulating filtering component 4 and the flow control component 6.
(5) The apparatus according to one of the above (1) to (4), wherein the flow control assembly 6 has a hollow inner cavity for ozone gas flow;
along the flowing direction of the ozone airflow, the hollow inner cavity sequentially comprises an air inlet section 61, a steady flow section 62, a speed-increasing introduction section 63, a primary self-excitation pulse section 64, a primary self-excitation pulse leading-out section 65 and a buffer transition section 66; and/or
In the flow direction of the ozone gas flow, after the buffer transition section 66, the hollow inner cavity further comprises a jet flow section 67, a final self-excitation pulse section 68 and a pulse diversion section 69 in sequence.
(6) The apparatus according to the above (5), wherein,
the air inlet section 61, the speed-increasing leading-in section 63, the primary self-excitation pulse section 64, the primary self-excitation pulse leading-out section 65, the buffering transition section 66 and the jet flow section 67 are all cylindrical inner cavities; and/or
The steady flow section 62 is a fusiform inner cavity; and/or
The final self-excited pulse section 68 is an inner cavity with a trapezoidal cross section.
(7) The apparatus according to the above (6), wherein,
from the air inlet section 61 to the flow stabilizing section 62, the inner diameter of the hollow inner cavity is gradually increased; and/or
From the flow stabilizing section 62 to the speed-increasing introduction section 63, the inner diameter of the hollow inner cavity is gradually reduced; and/or
From the speed-increasing introduction section 63 to the preliminary self-excitation pulse section 64, the inner diameter of the hollow inner cavity is suddenly increased; and/or
The jet section 67 comprises two or more jet pipes 671, preferably, the ratio of the inner diameter of the jet pipe to the inner diameter of the buffer transition section 66 is (0.03-0.05): 1.
in another aspect, the present invention provides a method for water treatment using the apparatus of the first aspect of the present invention, which is embodied in the following aspects:
(8) a method for water treatment using the apparatus of any one of (1) to (7) above, wherein the method comprises the steps of:
step 2, generating ozone in an ozone generator, outputting ozone airflow, and performing stable pressure filtration treatment on the output ozone airflow;
3, introducing the ozone airflow into a flow control assembly for flow control, and enhancing the fluctuation of the ozone airflow;
and 4, shunting and leading out the ozone airflow in the flow control assembly, and introducing the ozone airflow into a pool to be treated after air dissipation treatment to form ozone microbubbles.
(9) The method according to the above (8), wherein step 5 is performed after step 4, and the ultraviolet irradiation treatment and the ultrasonic treatment are performed simultaneously on the ozone microbubbles in the pool to be treated.
In a third aspect, the invention provides the use of the device of the first aspect of the invention for water treatment to degrade organic contaminants in water, and in particular to degrade soluble organic contaminants in secondary water.
Drawings
FIG. 1 shows a schematic view of a water treatment device according to the present invention, wherein the arrows indicate the flow direction of the ozone gas stream;
FIG. 2 shows an axial cross-sectional view of the flow control assembly of FIG. 1, wherein the arrows indicate the direction of ozone gas flow;
FIG. 3 shows the results of the effect of the flow control member on the solubility of ozone in Experimental example 1;
FIG. 4 shows the COD, TOC and UV of the target water body treated by the apparatus of the present invention in Experimental example 2254The duration is changed;
fig. 5 shows structural changes of organic substances with different molecular weights in a target water body before and after the water body is treated by the device in experimental example 2.
Description of the reference numerals
1-oxygen supply source; 2-an ozone generator; 3-a control valve; 4-a pressure-regulating filter assembly; 5-a flow meter; 6-a fluidic component; 61-an inlet section; 62-steady flow section; 63-a speed-increasing introduction section; 64-preliminary self-excitation pulse section; 65-preliminary self-excited pulse leading-out section; 66-a buffer transition section; 67-jet section; 671-jet pipe; 68-final self-excitation pulse section; 69-pulse shunt section; 691-an outlet pipe; 6' -a fixing frame; 7-a pool to be treated; 8-an air diffusing component; 9-a drainage tube; 10-an ultraviolet radiation assembly; 11-an ultrasound assembly; 111-an ultrasonic generator; 112-side ultrasonic vibration plate.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
In one aspect, the present invention provides a device for water treatment based on flow control microbubble-ozone coupling, as shown in fig. 1, the device comprises an oxygen gas supply source 1, an ozone generator 2, a pressure regulating filter assembly 4, a flow control assembly 6 and a pool 7 to be treated, which are sequentially connected with each other through a drainage tube 9.
Wherein the oxygen supply source 1 is used for providing oxygen supply for the ozone generator 2; the ozone generator 2 is used for generating ozone airflow by using oxygen; the pressure regulating filter assembly 3 is used for filtering the ozone airflow generated by the ozone generator 2 to remove moisture and particle dust in the airflow; the flow control assembly 6 is used for controlling the flow rate of the ozone airflow and performing fluctuation treatment, so that mass transfer and reaction of ozone in the water tank to be treated are promoted, and hydroxyl radicals are generated.
According to a preferred embodiment of the invention, a control valve 3 is provided between the ozone generator 2 and the pressure-regulated filter assembly 4 for controlling the magnitude of the supply air flow (ozone air flow).
Wherein the air supply source is required to be capable of providing an air inlet pressure of not less than 1bar, and the start and the stop are controlled by an anti-leakage safety control valve.
According to a preferred embodiment of the present invention, a flow meter 5 is disposed between the pressure-regulating filter assembly 4 and the flow control assembly 6.
Wherein, the flowmeter 5 is used for regulating and controlling the flow rate of the gas (ozone gas) according to the actual aeration quantity.
According to a preferred embodiment of the invention, an air diffusing assembly 8 is arranged at the bottom of the pool 7 to be treated and is communicated with the flow control assembly 6.
The gas dispersing component 8 is used for performing ozone microbubble aeration at the bottom of the water tank 7 to be treated to generate microbubbles, the microbubbles can rapidly improve the mass transfer efficiency of ozone in a liquid phase and improve the ozone solubility, and the ozone microbubbles can generate free radicals when being destroyed in water and can be used for degrading organic matters in the water.
In a further preferred embodiment, the gas diffusion component is a microporous plate, and the pore diameter of the gas diffusion component is preferably 15-60 μm.
In the invention, the air diffusing component can also be an aeration disc, an air diffusing pipe, a thinning device, a microporous sheet and the like which are commonly found in the market, and the pressure of the front end air inlet pressure regulating valve is required to be not more than the tolerance pressure of the air diffusing component.
In the invention, the flow control assembly is arranged to enable the ozone airflow to generate fluctuation, so that the led-out airflow is unstable, further the pressure is in a non-horizontal state and fluctuates, and the fluctuated airflow is divided and then is introduced into the pool to be treated, so that intermittent air inlet is formed among a plurality of airflows introduced into the pool to be treated in a liquid phase, the period of forming the bubbles at the orifice is shortened, the inflow volume of the bubbles is reduced, the size of generated bubbles is reduced, the bubbles can be driven to oscillate and break by intermittent fluctuation action, the miniaturization of the generated ozone bubbles is further intensified, and the mass transfer efficiency and the solubility of the more tiny bubbles in the liquid phase are higher.
According to a preferred embodiment of the invention, an ultraviolet radiation assembly 10 is also arranged in the basin 7 to be treated.
In a further preferred embodiment, the uv radiation module 10 is arranged above the air dispersion module 8.
In a still further preferred embodiment, the ultraviolet radiation assembly 10 comprises a plurality of ultraviolet lamps.
Wherein, the ultraviolet lamp can be a submersible ultraviolet lamp and radiates ultraviolet outwards. In the invention, the yield of hydroxyl radicals in the ozone decomposition process is improved by ultraviolet radiation, and the micro-bubble collapse can also generate radicals to jointly promote the efficiency of oxidizing pollutants. The mechanism is shown in figure 1.
In the invention, the flow control microbubble technology is utilized to rapidly improve the mass transfer efficiency of ozone and the solubility of ozone, and simultaneously, the ultraviolet radiation is utilized to promote the ozone to generate free radicals to improve the yield.
In accordance with a preferred embodiment of the present invention, as shown in fig. 2, the fluidic module 6 has a hollow interior for airflow.
Wherein the size of the inner diameter of the hollow inner cavity is changed, and the hollow inner cavity is used for controlling the air flow passing through.
In a further preferred embodiment, as shown in fig. 2, the hollow inner cavity comprises an air inlet section 61, a flow stabilizing section 62, a speed-increasing introduction section 63, a preliminary self-excited pulse section 64, a preliminary self-excited pulse leading-out section 65 and a buffer transition section 66 in sequence along the airflow flowing direction.
Wherein the air inlet section 61 is used for introducing air flow; the steady flow section 62 is used for stabilizing the airflow; the speed-increasing introduction section 63 is used for increasing the speed of the airflow; the preliminary self-excited pulse section 64 is a cavity space where preliminary self-excited pulses occur; wherein, the speed-increasing leading-in section 63, the preliminary self-excited pulse section 64 and the preliminary self-excited pulse leading-out section 65 act together to form a preliminary pulse turbulent condition; the buffer transition section 66 has the function of transmitting the pressure fluctuation at the outlet of the primary self-excitation pulse section to the jet pipe of the final pulse section to form the boundary condition of pressure pulse, which is favorable for strengthening the turbulent fluctuation of the cavity airflow of the final pulse section.
In a further preferred embodiment, as shown in fig. 2, the hollow interior also includes a jet section 67, a final self-excited pulse section 68, and a pulse splitter section 69 in that order, following the buffer transition section 66, in the direction of gas flow.
The jet section 67 accelerates the airflow with initial pulsation to form a high-speed jet flow, the high-speed jet flow enters the cavity of the final self-excited pulse section 68, vortex and airflow deflection are formed in the cavity through the processes of entrainment, wall attachment, collision feedback and the like, and the periodically pulsating deflection airflow flows out through the outlet of the flow dividing section 69 and is connected with the air dispersing component.
According to a preferred embodiment of the present invention, as shown in fig. 2, the air inlet section 61, the speed-increasing inlet section 63, the preliminary self-excited pulse section 64, the preliminary self-excited pulse outlet section 65, the buffer transition section 66 and the jet section 67 are all cylindrical cavities.
In a further preferred embodiment, as shown in fig. 2, the flow stabilizer 62 is a fusiform lumen.
In a further preferred embodiment, as shown in fig. 2, the final self-excited pulse section 68 is a trapezoidal shaped lumen in cross-section.
The cavity of the final self-excitation pulse section 68 is trapezoidal, so that stable turbulent pulse jet flow is formed, the depth of the cavity is not too deep, the depth is limited, and the ratio of the cavity depth (the cavity depth of the cavity of the final self-excitation pulse section 68) to the inlet width ratio of the jet pipe is (0.5-3): 1.
in the present invention, it is preferable that the flow control member is composed of a stainless material, and other materials are considered when the gas supply is a special gas.
According to a preferred embodiment of the present invention, the inner diameter of the hollow inner cavity gradually increases from the air intake section 61 to the flow stabilizing section 62.
In a further preferred embodiment, the ratio of the inner diameter of the air intake section 61 to the maximum inner diameter of the flow stabilizing section 62 is (0.4 to 0.6): 1.
in a further preferred embodiment, the ratio of the inner diameter of the air intake section 61 to the maximum inner diameter of the flow stabilizing section 62 is 0.5: 1.
the airflow enters the steady flow section from the air inlet section and enters the large space from the small space, and the airflow is gradually stabilized to carry out steady flow control. Wherein, if the ratio is too large, the pressure loss of the sudden expansion pipe increases, and if the ratio is too small, the stable and uniform flow distribution is not performed.
According to a preferred embodiment of the present invention, the inner diameter of the hollow inner cavity is gradually reduced from the flow stabilizing section 62 to the speed increasing introduction section 63.
In a further preferred embodiment, the ratio of the inner diameter of the speed-increasing introduction section 63 to the maximum inner diameter of the flow stabilizing section 62 is (0.2 to 0.3): 1.
the inner diameter of the speed-increasing leading-in section 63 is mainly matched with a primary self-excitation pulse cavity 64 and a leading-out section 65 thereof, the cavity inner diameter of the primary self-excitation pulse section 64 is the same as the inner diameter of the flow stabilizing section 62, and according to the characteristics of the primary self-excitation pulse section, the ratio of the inner diameter of the speed-increasing leading-in section 63 to the maximum inner diameter of the flow stabilizing section 62 is set to be (0.2-0.3): the pressure amplitude difference is high and the oscillation characteristic is good under the condition of 1.
And from the flow stabilizing section to the speed increasing introduction section, the inner diameter is reduced, particularly the inner diameter of the speed increasing introduction section is very small, so that the airflow enters a tiny space from a large space, and the speed is increased to realize the acceleration of the airflow.
According to a preferred embodiment of the present invention, the length ratio of the steady flow section 62 to the speed-increasing introduction section 63 is (2-3): 1.
the gradual change sections on the two sides of the steady flow section and the middle fixed inner diameter section are slightly longer, and the sudden expansion angle is reduced, so that the entering gas can form gradual change flow to transition to constant flow, and the steady flow of the gas is facilitated.
In a further preferred embodiment, the length ratio of the flow stabilizing section 62 to the speed-increasing introduction section 63 is (2.4-2.8): 1.
if the speed-increasing leading-in section is too short and the local sudden shrinkage deformation is large, the gradual change flow cannot be changed into the constant flow, and the airflow distribution and the speed-increasing effect are influenced.
According to a preferred embodiment of the invention, the inner diameter of the hollow cavity becomes suddenly larger from the speed-increasing introduction section 63 to the preliminary self-excitation pulse section 64.
In a further preferred embodiment, the ratio of the inner diameter of the speed-increasing introduction section 63 to the inner diameter of the preliminary self-excitation pulse section 64 is 1 (3.5-5).
The inner diameter of the cavity is suddenly increased from the acceleration introduction section to the primary self-excitation pulse section, the accelerated airflow is injected into the self-excitation cavity and is subjected to momentum exchange with fluid in the cavity to form an unstable shear layer with a certain thickness, and the shear layer is entrained by the jet flow to generate vortex to be spread downstream. When the jet flow with initial oscillation and the continuously produced vortex reach a downstream collision wall, a pressure disturbance wave with a certain frequency is induced in a collision area, the disturbance wave is reflected upwards to the inlet of the chamber at a high speed, the process is repeated continuously, and finally an oscillation jet flow acceleration introduction section with overlapped amplification is formed at the outlet of the primary self-excitation pulse section.
In a further preferred embodiment, the ratio of the inner diameter of the speed-increasing introduction section 63 to the inner diameter of the preliminary self-excited pulse section 64 is 1 (4-4.5).
According to the characteristics of the primary self-excitation pulse section and a large number of experiments of the inventor, the pressure amplitude difference is high and the oscillation characteristic is good under the condition.
According to a preferred embodiment of the present invention, the ratio of the length of the preliminary self-excitation pulse section 64 to the length of the speed-increasing introduction section 63 is (0.3-0.8): 1.
in a further preferred embodiment, the ratio of the length of the preliminary self-excitation pulse section 64 to the length of the speed-increasing introduction section 63 is (0.5-0.6): 1.
wherein, the length of the speed-increasing leading-in section 63 is generally more than 3-4 times of the inner diameter so as to ensure that the sudden-shrinkage gradual-change flow is transited into a constant flow; the length of the primary self-excitation pulse section is preferably 3-5 times of the diameter of the speed-increasing leading-in section so as to form a better self-excitation oscillation effect.
According to a preferred embodiment of the present invention, the ratio (1.1-1.8) of the inner diameters of the preliminary self-excited pulse leading-out section 65 and the speed-increasing leading-in section 63 is 1.
In a further preferred embodiment, the ratio (1.2-1.5) of the inner diameters of the preliminary self-excited pulse leading-out section 65 and the speed-increasing leading-in section 63 is 1.
According to a preferred embodiment of the present invention, the ratio of the inner diameters of the primary self-excitation pulse section 64 and the buffer transition section 66 is (0.8-1.2): 1.
in a further preferred embodiment, the ratio of the inner diameters of the preliminary self-excited pulse section 64 and the buffer transition section 66 is 1: 1.
according to a preferred embodiment of the invention, the inner diameter ratio of the primary self-excitation pulse section 64, the primary self-excitation pulse leading-out section 65 and the buffer transition section 66 is 1 (0.2-0.5): 1.
In a further preferred embodiment, the inner diameter ratio of the primary self-excitation pulse section 64, the primary self-excitation pulse leading-out section 65 and the buffer transition section 66 is 1 (0.2-0.3): 1.
In the invention, a speed-increasing leading-in section 63, a primary self-excitation pulse section 64 and a primary self-excitation pulse leading-out section 65 jointly form a self-excitation pulse assembly, the speed-increasing leading-in section 63 is arranged to form a high-speed entering jet flow, the primary self-excitation pulse leading-out section 65 leads out a primary pulsating jet flow, and a buffer transition section 66 is used for transmitting pressure fluctuation at the outlet of the primary self-excitation pulse section to a jet pipe of an ultimate pulse section to form a boundary condition of pressure pulse, thereby being beneficial to strengthening turbulent fluctuation of cavity airflow of the ultimate pulse section. The ratio of the inner diameter of the primary self-excitation pulse leading-out section 65 to the inner diameter of the speed-increasing leading-in section 63 is preferably about 1.2: 1.
According to a preferred embodiment of the present invention, the jet section 67 comprises two or more jet pipes 671.
Wherein the gas flow is divided into two or more jets by means of a jet pipe.
In a further preferred embodiment, the ratio of the inner diameter of the jet pipe to the inner diameter of the buffer transition section 66 is (0.03-0.05): 1.
wherein, the jet pipe with small inner diameter is used for guiding out the preliminary turbulent airflow and further increasing the jet speed, so that the jet pipe is convenient for reaching higher Reynolds number (10 to 10)5)。
According to a preferred embodiment of the present invention, the inner diameter of the hollow inner cavity increases from the jet pipe 671 to the final self-excitation pulse section 68.
The ratio of the inner diameter of the jet pipe 671 to the inner diameter of the final self-excitation pulse section 68 is (0.03-0.06): 1.
in a further preferred embodiment, the ratio of the inner diameter of the jet pipe to the upper bottom width of the trapezoidal section of the final-stage self-excited pulse section 68 and the lower bottom width of the trapezoidal section of the final-stage self-excited pulse section 68 is 1 (12-22): 28-35.
In a further preferred embodiment, the ratio of the lower base width of the trapezoidal cross section of the final-stage self-excited pulse segment 68 to the height of the trapezoidal cross section is (1-1.3): 1, for example 1.125: 1.
The final self-excited pulse section 68 is trapezoidal, so that stable turbulent pulse jet flow is formed, the depth of a cavity is not too deep, the depth is limited, and the ratio of the cavity depth to the inlet width of a jet flow pipe is generally (0.5-3): 1.
wherein, the jet flow with certain pressure intensity is ejected into the cavity with enlarged volume (final self-excited pulse section 68), the original static fluid medium in the cavity at both sides of the jet flow is driven by the high-speed jet flow to form entrainment phenomenon, because two or more jet flow pipes are interfered by the initial self-excited pulse and the flow characteristics are different inevitably, and because of the strictness and uniformity of the cavity size on the microscopic scale, the external fluid entrained at the same time between the jet flow at both sides of the main jet flow and different nozzle jets of the same nozzle is not equal, the wall attachment effect generated based on maintaining the jet flow balance is different, and further the pressure difference at both sides of each jet flow inevitably deflects the jet flow, in the process, the air flow also collides with the inner wall of the cavity and then returns and vibrates continuously, vortex turbulence between the wall attachment at both sides and the jet flow of each nozzle is comprehensively formed, and the continuous periodic deflection fluctuation of the outlet, therefore, the pressure flow of the jet pipe at the outlet of the final self-excitation pulse cavity has the fully turbulent pulse characteristic.
According to a preferred embodiment of the invention, the pulse diverging section 69 comprises two or more outlet pipes 691.
In a further preferred embodiment, the pulse diverging section 69 comprises two outlet pipes 691.
In a further preferred embodiment, the outlet tube 691 communicates with the air dispersion assembly 8 through a draft tube 9.
Therefore, the airflow is divided into two parts at the outlet, and the fluid has wave property due to the flow control in the step 2, so that when the two parts are led out into a cavity (a water pool to be treated), the airflow of the two air outlets is intermittently and turbulently discharged, the inflow volume of the bubbles is favorably reduced, the size of the generated bubbles is reduced, and meanwhile, the intermittent fluctuation action can also drive the bubbles to oscillate and break, so that the miniaturization of the generated bubbles is further intensified.
According to a preferred embodiment of the invention, the device further comprises an ultrasound assembly 11.
In a further preferred embodiment, the ultrasonic assembly 11 comprises an ultrasonic generator 111 and a plurality of side ultrasonic vibration plates 112 connected thereto.
Thus, the side ultrasonic vibration plate 112 can generate ultrasonic waves under the action of the ultrasonic generator 111. In the present invention, the side type ultrasonic vibration plate is preferably formed by adhering an ultrasonic transducer in a fully sealed stainless steel vibration box.
In a further preferred embodiment, the plurality of side ultrasonic vibration plates 112 are disposed in the pool 7 to be treated.
The side type ultrasonic vibration plate 112 is arranged in the pool 7 to be treated to provide ultrasonic waves for the pool 7 to be treated, and ozone micro bubbles in the pool can be further promoted to vibrate and collapse under the action of the ultrasonic waves, so that the invention utilizes the ultrasonic induction of ozone micro bubble collapse and the synchronous ultrasonic cavitation pyrolysis to generate hydroxyl radicals.
According to a preferred embodiment of the present invention, the power of the ultrasonic generator is 150-2000W, and the frequency is 20-100 kHz.
In a further preferred embodiment, the frequency of the ultrasonic generator is 30-50 kHz.
Among them, the inventor has found through a lot of experiments that the ozone microbubble destroys and generates the best effect of free radicals when the frequency is 30-50 kHz.
In the invention, the flow control microbubble technology can be used for rapidly improving the mass transfer efficiency of ozone and the ozone solubility, and the ultrasonic-induced microbubble collapse, the synchronous ultrasonic cavitation pyrolysis and the ultraviolet radiation can also promote the ozone to generate free radicals, improve the yield of the ozone and promote the efficiency of oxidizing pollutants.
In a second aspect, the present invention provides a method of water treatment using the apparatus of the first aspect of the invention, the method comprising the steps of:
step 2, generating ozone in an ozone generator, outputting ozone airflow, and optionally performing stable pressure filtration treatment on the output ozone airflow;
wherein, the introduced oxygen is reacted into ozone in the ozone generator, and the ozone is output to form ozone airflow.
in step 3, the ozone gas flow fluctuates through the flow control assembly gas flow, so that the led-out gas flow is unstable, the pressure is enabled to be in a non-horizontal state and fluctuates, the fluctuant gas flow is divided and then introduced into the water pool to be treated, therefore, intermittent air intake is performed among a plurality of gas flows introduced into the liquid-phase water pool to be treated, the period of forming orifice bubbles is shortened, the inflow volume in the bubbles is reduced, the size of generated bubbles is reduced, the bubbles can be driven to oscillate and break through intermittent fluctuation action, the miniaturization of generated ozone bubbles is further intensified, and the mass transfer efficiency and the solubility of the more tiny bubbles in the liquid phase are higher.
and 5, simultaneously carrying out ultraviolet irradiation treatment and ultrasonic treatment on the ozone microbubbles in the pool to be treated.
Wherein, ultraviolet radiation is utilized to improve the yield of hydroxyl radicals in the ozone decomposition process, and meanwhile, the micro-bubble collapse can also generate radicals to jointly promote the efficiency of oxidizing pollutants. The mechanism is shown in fig. 3. The ozone microbubble in the pool can be further promoted to vibrate and collapse by utilizing ultrasonic treatment, and the further generation of hydroxyl radicals is promoted.
In a third aspect, the invention provides the use of a device according to the first aspect of the invention for the treatment of water to degrade organic contaminants in the water. Especially for degrading soluble organic pollutants in secondary water.
The method can be particularly applied to treating various water bodies such as surface water bodies, underground water, sewage, secondary effluent of sewage treatment plants, reclaimed water and the like with residual soluble organic matters, and is used for removing the soluble organic matters in the water bodies.
The invention has the following beneficial effects:
(1) when the method is used for water treatment, no chemical substance is required to be added, and secondary pollution to a water body is avoided;
(2) the device and the method adopt the coupling of a micro-bubble (MB) technology and an ozone oxidation technology, improve the ozone solubility, utilize the self-destruction of the micro-bubbles and ultrasonic enhancement thereof to generate free radicals and synchronously radiate the ozone with ultraviolet to improve the yield of the free radicals, are applied to the advanced treatment of secondary effluent of the urban sewage plant, reduce the content of organic matters, change the structure of the organic matters and improve the biodegradability of the urban sewage plant;
(3) the device and the method also carry out ultraviolet radiation and ultrasonic treatment on the ozone microbubbles, so as to further promote the generation of hydroxyl radicals;
(4) compared with the traditional air-dispersing type technology, the method or the device adopts the flow control component to control the fluctuation of the ozone airflow, can reduce the size of the formed ozone bubbles, and increase the residence time of the ozone bubbles in water and the gas-liquid contact area, thereby improving the dissolution of the ozone bubbles in water and further promoting the direct contact oxidation of ozone and the generation and removal efficiency of hydroxyl radicals.
(5) After the device and the method are adopted to treat the water body, the variation of pH, salinity and conductivity is small, and the performance of the water body is not obviously influenced;
(6) after the water body is treated by adopting the device and the method, the COD removal rate reaches 39.5 percent, and the UV removal rate is up to 39.5 percent254The removal rate reaches 93.0 percent.
Examples of the experiments
Experimental example 1 Effect of fluidic Components on ozone solubility
(1) The device which is formed by removing the ultraviolet radiation component and the ultrasonic component in the pool to be treated on the basis of the device is taken as an experimental object 1, and (2) the device which is formed by removing the flow control component in the experimental object on the basis of the position 1 of the experimental object is taken as an experimental object 2, wherein the experimental object 1 is different from the experimental object 2 in that: the experimental object 1 is provided with a flow control component for aerating flow control microbubbles; the experimental subject 2 was not provided with a flow control assembly and was subjected to ordinary aeration.
The ozone concentration in the subject 1 and subject 2 pools was measured to illustrate the effect of the fluidic components on the mass transfer efficiency of ozone. The results are shown in FIG. 3.
As can be seen from fig. 3:
(1) under the condition of flow-controlled microbubble aeration (an experimental object 1), the concentration of ozone in water is obviously higher than that of common aeration (an experimental object 2);
(2) the maximum concentration of ozone in water under the action of internal flow control micro-bubble aeration within 30min can reach 5.32mg/L, while the maximum concentration of ozone in common aerated water is 4.17mg/L, and the maximum concentration of ozone in micro-bubble aerated water is about 1.3 times of that of common aeration, which is improved by 27.6%;
(3) it can also be seen from the calculation of the mass transfer coefficients of the two aeration modes that the mass transfer coefficient of the flow-controlled microbubble aeration (ozone) is 0.0726s-1Is larger than common aeration (ozone) (mass transfer coefficient is 0.0314 s)-1) The time (16.5min) for the fluid control microbubble aeration to enter the relatively stable stage is about 7min earlier than the time for the ordinary aeration (23.5min), and the speed of the rapid lifting stage is increased by 29.8%.
Thus, the flow control component can obviously promote the mass transfer efficiency of the ozone.
Experimental example 2 removal Effect of soluble organic substances
The experimental raw water is taken from a discharge point of secondary effluent of a certain sewage treatment plant to a river, about 20L of water sample passing through a 0.45-micron filter membrane is taken (mainly judging the removal effect of the soluble organic matters), and the water sample enters the device for treatment.
Wherein the percentage of the ozone generator is adjusted to 50 percent, the ozone generator generates ozone at the flow rate of 1L/min, the gas outlet is shunted, and the air input of the follow-up connected flow control micro-bubble generating device is controlled to be 0.5-0.6L/min and the pressure is controlled to be 2 Bar.
The ozone gas concentration was measured by iodometry to determine an average concentration of 44.64 mg/L. The total treatment time of the experiment is 30min, the change conditions of the ozone concentration and the water temperature in the water are monitored in real time, and the conductivity, the pH and the salinity of the water body, as well as COD, TOC and UV in the experiment process are monitored254And the like (as shown in fig. 4), and the purification effect of the device and the method of the invention on the target water quality is evaluated.
Wherein, the variation of pH, salinity and conductivity is small in the experimental process, which shows that the performance of the water body is not greatly influenced.
Moreover, as can be seen from fig. 4, the apparatus and method of the present invention actively improve various water quality indexes, and the removal effect of the pollution factor is obvious, specifically as follows:
(1) in a short time (30min), the COD removal rate reaches 39.5 percent;
(2) the TOC is slightly reduced (organic substances are changed from macromolecules to micromolecules, but are not completely oxidized);
(3)UV254the removal rate reaches 93.0 percent.
Meanwhile, the molecular weight test results before and after treatment show that a large amount of macromolecular organic matters are removed and converted into small molecular substances (<500Da), the proportion of the small molecular substances is changed from 27.5% to 64.3%, the small molecular substances are increased by 36.8%, and the biodegradability of a water body is greatly improved after treatment.
The analysis reason is as follows: the invention utilizes the flow control micro-bubbles to rapidly improve the mass transfer efficiency of ozone and the solubility of ozone, utilizes ultrasonic to induce micro-bubble collapse, and utilizes synchronous ultrasonic cavitation pyrolysis and ultraviolet radiation to promote the ozone to generate free radicals, thereby promoting the efficiency of oxidizing pollutants.
Wherein, Chemical Oxygen Demand (COD) and total organic carbon (TOTAL organic carbon) are used as comprehensive indicators for evaluating the organic pollution degree. UV (ultraviolet) light254The absorbance at 254nm is measured by an ultraviolet spectrophotometer, and reflects the content of humus macromolecular organic matters and aromatic compounds containing C ═ C double bonds and C ═ O double bonds naturally existing in water.
Experimental example 3 detection of hydroxyl radical content in Water to be treated
In the experimental process, an APF (3' -p- (aminophenyl)) fluorescent reagent is used as a hydroxyl radical trapping agent, APF has no fluorescence intensity, and can generate strong fluorescence after being combined with hydroxyl radicals. Collecting a water sample (10mL) at a specific moment in the reaction tank, quickly adding an APF (ammonium fluoride) capture reagent (2uL), and detecting fluorescence by using a fluorescence spectrophotometer. Specifically, the following are mentioned: for the experimental situation related to the micro-bubbles, considering that the free collapse of the bubbles is slow, and the measurement of APF response is relatively time-consuming, a sample added with APF is processed by short-time ultrasound (5s, 40kHz) to accelerate the collapse of the bubbles (whole-course light-shielding operation), and then the fluorescence intensity is measured (other bubble-free situations adopt the same steps to ensure comparability). The APF is calibrated by using hydrogen peroxide, and the fluorescence intensity y and the millimole number of the oxidizing substance are foundThere is a good linear relationship between x y 134.61x (R)2＝0.9954)。
Based on this, the hydroxyl radical content in the treatment process was measured:
(1) by adopting the method (ozone-microbubble-ultraviolet-ultrasonic combination), the highest fluorescence intensity can reach 37 a.u.;
(2) treating by adopting a single ozone process, wherein the highest fluorescence intensity is 4 a.u.;
(3) treating by adopting a single ultrasonic process, wherein the highest fluorescence intensity is 3 a.u.;
(4) the single microbubble process is adopted for treatment, and the highest fluorescence intensity is 12 a.u.;
(5) treating by adopting an ozone-ultraviolet combined process, wherein the highest fluorescence intensity is 6 a.u.;
(6) the highest fluorescence intensity is 22a.u. after the treatment by adopting an ozone-microbubble-ultraviolet combined process.
Wherein, the hydroxyl radical has very high oxidation-reduction potential (2.8eV), can oxidize organic matters through various ways such as electron transfer reaction, hydrogen extraction reaction, addition reaction and the like, and the reaction rate of the hydroxyl radical to the organic matters is basically 108～1010M-1·s-1The reaction on organic matters has almost no selectivity, and the technology has good water treatment efficiency only through the synergistic generation of hydroxyl radicals.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (12)
1. A device for water treatment based on flow control microbubble-ozone coupling is characterized by comprising an oxygen gas supply source (1), an ozone generator (2), a pressure regulating and filtering assembly (4), a flow control assembly (6) and a water pool (7) to be treated, which are sequentially connected with one another through a drainage tube (9), wherein the device further comprises an ultrasonic assembly (11), and an ultraviolet radiation assembly (10) is arranged in the water pool (7) to be treated;
the flow control assembly (6) is provided with a hollow inner cavity for flowing ozone airflow;
along the flowing direction of the ozone airflow, the hollow inner cavity sequentially comprises an air inlet section (61), a flow stabilizing section (62), a speed-increasing introduction section (63), a primary self-excitation pulse section (64), a primary self-excitation pulse leading-out section (65) and a buffer transition section (66); and
the hollow inner cavity also sequentially comprises a jet flow section (67), a final self-excitation pulse section (68) and a pulse shunt section (69) after the buffer transition section (66) along the flowing direction of the ozone airflow.
2. The apparatus of claim 1,
an air diffusing component (8) is arranged at the bottom of the pool (7) to be treated and communicated with the flow control component (6), and the air diffusing component is a microporous plate; and/or
The ultraviolet radiation assembly (10) comprises a plurality of ultraviolet lamps.
3. The apparatus of claim 1,
the ultrasonic assembly (11) comprises an ultrasonic generator (111) and a single or a plurality of side ultrasonic vibration plates (112) connected with the ultrasonic generator.
4. The apparatus according to claim 3, wherein the single or multiple side ultrasonic seismic plates (112) are disposed within the basin (7) to be treated.
5. The apparatus of claim 1,
a control valve (3) is arranged between the ozone generator (2) and the pressure-regulating filtering component (4); and/or
And a flowmeter (5) is arranged between the pressure-regulating filtering component (4) and the flow control component (6).
6. The apparatus of claim 1,
the air inlet section (61), the speed-increasing leading-in section (63), the primary self-excitation pulse section (64), the primary self-excitation pulse leading-out section (65), the buffering transition section (66) and the jet flow section (67) are all cylindrical inner cavities; and/or
The steady flow section (62) is a fusiform inner cavity; and/or
The final self-excitation pulse section (68) is an inner cavity with a trapezoidal section.
7. The apparatus of claim 6,
from the air inlet section (61) to the flow stabilizing section (62), the inner diameter of the hollow inner cavity is gradually increased; and/or
From the flow stabilizing section (62) to the speed-increasing introduction section (63), the inner diameter of the hollow inner cavity is gradually reduced; and/or
From a speed-increasing introduction section (63) to a preliminary self-excitation pulse section (64), the inner diameter of the hollow inner cavity is suddenly increased; and/or
The jet section (67) comprises two or more jet pipes (671).
8. The apparatus according to claim 7, wherein the ratio of the inner diameter of the jet pipe to the inner diameter of the buffer transition section (66) is (0.03-0.05): 1.
9. a method of water treatment using the apparatus of any one of claims 1 to 8, the method comprising the steps of:
step 1, providing oxygen to an ozone generator by using an oxygen supply source;
step 2, generating ozone in an ozone generator, outputting ozone airflow, and performing stable pressure filtration treatment on the output ozone airflow;
step 3, introducing the ozone airflow into a flow control assembly for flow control, and enhancing the volatility of the ozone airflow;
and 4, shunting and leading out the ozone airflow in the flow control assembly, and introducing the ozone airflow into a pool to be treated after air dissipation treatment to form ozone microbubbles.
10. The method of claim 9, wherein step 4 is followed by step 5 of simultaneously performing ultraviolet irradiation treatment and ultrasonic treatment on the microbubbles of ozone in the pool to be treated.
11. Use of the device according to any one of claims 1 to 8 for water treatment, for degrading organic contaminants in water.
12. Use according to claim 11, wherein the device is used for degrading soluble organic contaminants in secondary water.
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| CN111533344B (en) * | 2020-05-12 | 2021-01-01 | 上海市政工程设计研究总院（集团）有限公司 | Disinfection and sterilization system for long-distance pipeline and application method thereof |
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