CN112794400A - Sequencing batch energy-saving type device and method for treating organic wastewater by combining ultrasonic and ozone - Google Patents

Sequencing batch energy-saving type device and method for treating organic wastewater by combining ultrasonic and ozone Download PDF

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CN112794400A
CN112794400A CN202110364642.XA CN202110364642A CN112794400A CN 112794400 A CN112794400 A CN 112794400A CN 202110364642 A CN202110364642 A CN 202110364642A CN 112794400 A CN112794400 A CN 112794400A
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ozone
ultrasonic
wastewater
reactor
value
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陈阵
黄晓峰
杨佘维
林嘉润
郑刘进
刘红昌
白丹丹
曹喜凤
黄冬冬
蔡振霖
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Guangdong Yuelv Environmental Engineering Co ltd
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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
    • C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
    • C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
    • 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
    • C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/23—O3
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/38—Gas flow rate
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/42—Liquid level
    • 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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Physical Water Treatments (AREA)

Abstract

An organic wastewater treatment device and method by using sequencing batch energy-saving ultrasound and ozone in coordination comprises the following steps: introducing ozone into the wastewater for oxidation reaction, starting the ultrasonic and ozone for wastewater treatment when the pH value of the wastewater reaches an ultrasonic entry point, and discharging the wastewater when the COD value of the wastewater meets the discharge requirement; the wastewater treatment device comprises a reactor, an ozone preparation unit, an ozone valve, a porous diffuser, an ultrasonic generator, an ultrasonic vibration plate, a water inlet valve, a water outlet valve, a water inlet pipe, a water outlet pipe, a monitoring device and an automatic control device, wherein the ultrasonic vibration plate is arranged on the side wall of the reactor, and the reactor is also provided with a tail gas destructor. The invention introduces a sequencing batch process concept on the basis of the traditional ultrasonic-ozone synergistic process, more fully and reasonably utilizes the oxidation capacity of ozone and the continuous mineralization capacity of hydroxyl radicals, realizes energy-saving transformation of the traditional process, and realizes intelligent operation of the whole process based on research and judgment of conversion indexes of reaction stages.

Description

Sequencing batch energy-saving type device and method for treating organic wastewater by combining ultrasonic and ozone
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a sequencing batch energy-saving device and a sequencing batch energy-saving method for treating organic wastewater by combining ultrasonic and ozone.
Background
In order to continuously meet the increasing beautiful living needs of people, people put forward higher requirements on the water environment quality. How to efficiently treat high-concentration organic industrial wastewater, especially aromatic industrial wastewater which has high toxicity and is difficult to biodegrade, has been paid much attention to all the world. The technology for treating pollutants in wastewater by using ultrasonic waves, in particular to toxic organic pollutants difficult to biodegrade, is a novel environment treatment technology developed in recent years, is mild in operation condition and wide in application range, and has the problems of high energy consumption, long reaction time, low treatment efficiency on the difficult-to-volatilize and polar hydrophilic pollutants and the like. Ozone is a highly selective oxidant that can rapidly destroy organic pollutants in water, but its reaction intermediates are often not completely mineralized, which limits the widespread use of ozone.
The ultrasonic and ozone wastewater treatment technology is widely applied at home and abroad as a new means for industrial wastewater treatment, the ultrasonic and ozone oxidation technology is combined to fully disperse and dissolve ozone, the oxidation capacity of the ozone is improved while the addition of the ozone is reduced, and the decomposition of the ozone is enhanced through the ultrasonic cavitation effect and the physicochemical effect generated by the ultrasonic cavitation effect to generate more free radicals. However, the introduction of the ultrasonic energy field can greatly increase the energy consumption of wastewater treatment, and the current domestic ultrasonic-ozone wastewater treatment technology simultaneously acts ultrasonic and ozone, so that the total energy consumption of the ultrasonic generator and the ozone generator is too high, and the energy utilization efficiency is one of the key factors influencing the engineering application of the ultrasonic-ozone oxidation technology. Therefore, the method solves the energy consumption problem of the technology, seeks the synergistic application of the ultrasonic enhanced ozone technology, and has theoretical and practical significance.
Disclosure of Invention
The invention aims to overcome the defects of the ultrasonic-ozone oxidation technology and provide a sequencing batch energy-saving method for treating organic wastewater by combining ultrasonic and ozone and a device for realizing the method, wherein the method has low energy consumption and good treatment effect.
The invention adopts a sequencing batch reaction mode, namely ozone is independently used in the early stage, and the later-stage ozone and ultrasound have synergistic effect, so that the ultrasonic energy consumption in the early stage can be saved. In order to balance energy consumption and treatment effect and realize optimization of environmental and economic benefits of sequencing batch reaction, effective judgment on an ultrasonic introduction point is required. When ozone is introduced into the wastewater in the reactor, the ozone reacts with organic matters in the wastewater to continuously generate inorganic acid and micromolecular organic acid, meanwhile, part of micromolecular acid is further decomposed and mineralized, the pH value of the wastewater is continuously reduced along with the continuous accumulation and increase of the total amount of the micromolecular organic acid, but the pH reduction rate gradually tends to be gentle along with the reaction process, and when the decomposition rate of the micromolecular organic acid is greater than the generation rate of the micromolecular organic acid, the pH value in the solution is increased, which means that the wastewater oxidation capacity of the ozone at the stage is insufficient, and a more efficient oxidant (hydroxyl radical) needs to be introduced to achieve the purpose of further oxidative decomposition. Research shows that when the ultrasonic generator is started at the moment, the oxidation capacity of ozone in the front stage and the continuous mineralization capacity of hydroxyl radicals in the rear stage can be utilized to the maximum extent, meanwhile, the ultrasonic starting time is shortened, the energy consumption is saved, and the efficiency maximization is realized.
The invention is realized by the following technical scheme:
the method for treating organic wastewater by sequencing batch energy-saving ultrasonic and ozone comprises the following steps of constructing an integrated ultrasonic and ozone treatment device, monitoring the liquid level, pH value and COD value of wastewater in the wastewater treatment device, and comprehensively identifying and analyzing the reaction process to realize the automation and precision control of the treatment process:
s1, when the liquid level of the wastewater in the wastewater treatment device is lower than a low set value, closing the water outlet valve, opening the water inlet valve, injecting the wastewater into the reactor, and when the liquid level reaches a high set value, closing the water inlet valve;
s2, opening an ozone generator and an ozone valve, and introducing ozone into the wastewater for reaction;
s3, when the pH value of the wastewater reaches the ultrasonic introduction point, continuing introducing ozone, and simultaneously starting an ultrasonic generator to further treat the wastewater under the condition that ultrasonic waves cooperate with ozone;
and S4, when the COD value of the wastewater meets the discharge requirement, turning off the ultrasonic generator, turning off the ozone generator and the ozone valve, and turning on the water outlet valve to drain.
The processes all monitor the liquid level, the pH value and the COD value of the wastewater in real time, the automatic controller controls the opening, closing or flow regulation of the water inlet valve, the water outlet valve, the ozone generator, the ozone valve, the ultrasonic generator and other devices, and the steps from S1 to S4 are performed in a circulating manner, so that the automatic sequencing batch type energy-saving treatment of the wastewater is realized.
As an optimized technical scheme, the ultrasonic introduction point is a time point when the change rate of the pH value changes from a negative value to a positive value, namely, the ultrasonic is started when the pH value of the wastewater changes from a descending value to an ascending value, so that the ultrasonic and the ozone act synergistically. Thereby control system energy consumption through the opening time of supersound introduction point control, the pH value of waste water is constantly monitored to the processing procedure, opens the supersound when waste water pH value changes from descending into rising, makes supersound and ozone synergism play, and the opening of supersound is carried out automatic control through the procedure.
The change rate of the pH value of the wastewater containing different organic matter components is different in the ozone oxidation treatment process, but basically follows the same change rule (the change rate of the pH value is negative and then positive), and for most organic wastewater, the interval of the pH value rising after the pH value falling is 3-5, namely the ultrasonic introduction point is that the pH value reaches 3-5. Therefore, if no more effective means for monitoring the pH change rate exists, the ultrasonic entry point can be directly controlled according to the pH value, and the ultrasonic generating device is started when the pH value enters a range of 3-5, so that the control method is simplified. It is further preferred that the ultrasound is switched on when the pH value reaches between 3 and 4.
In some use situations, in order to further improve the wastewater treatment efficiency, as a further optimized technical scheme, a wastewater treatment device can be added or filled with a catalyst before ozone is introduced, so that the ozone oxidation reaction is carried out under the condition of the catalyst, wherein the catalyst is a metal oxide or a metal sulfide, or a mixture of several metal oxides or metal sulfides, or activated carbon loaded metal oxide or metal sulfide. The metal oxide and metal sulfide may be conventional ozone oxidation catalysts, such as MnO2、Mn3O4、TiO2、Al2O3、CuO、WS2、MoS2And the like. The catalyst is favorable for improving the speed of ozone oxidation degradation and improving the wastewater treatment efficiency, and can be directly added before ozone is introduced, or the catalyst is filled in a reactor before wastewater is injected, and a catalyst layer can be arranged in the reactor. Therefore, the technical scheme of the invention is suitable for any situation that the reactor is filled or not filled with the catalyst, and the addition or non-addition of the catalyst in the ozone oxidation process is within the protection scope of the invention.
Because the cavitation of ultrasonic waves is related to factors such as medium, pressure, pH value, temperature and frequency, the factors directly influence the degradation efficiency, and the oxidation capacity of ozone is closely related to factors such as the introduction amount of ozone, the pH value of the medium, the oxidation time and the temperature. As a further optimized technical scheme, the flow rate of the ozone is 0.1-1 L.min-1The concentration of ozone is 1-50 mg. L-1(ii) a The standard value of raw water COD value is 50-5000 mg. L-1The frequency of the ultrasonic wave generated by the ultrasonic generator is 20-1000 kHz. Preferably ultrasonic wavesHas a frequency of 200 kHz.
As a further optimized technical scheme, ozone is introduced from the bottom of the reactor, ultrasonic waves are generated on the side wall of the reactor, ultrasonic waves with different frequencies are generated on different surfaces of the side wall of the reactor, and the ultrasonic waves with different frequencies are opened simultaneously or are opened in a sequential combination mode after the pH value of the wastewater reaches an ultrasonic introduction point.
A sequencing batch energy-saving ultrasonic and ozone cooperative organic wastewater treatment device is used for realizing the method for treating organic wastewater by sequencing batch energy-saving ultrasonic and ozone cooperative, and comprises a reactor, a porous diffuser, an ozone preparation unit, an ozone valve, an ultrasonic vibration plate, an ultrasonic generator, a tail gas destructor, an automatic control device, a water inlet valve, a water outlet valve, a tail gas discharge pipe, a water inlet pipe, a water outlet pipe and monitoring equipment. The reactor can be designed into a polyhedron, the porous diffuser is arranged at the bottom of the reactor, the position of the center of the bottom is preferably selected, the ozone preparation unit and the ozone valve are connected with the porous diffuser through an air passage, ozone generated by the ozone generator enters wastewater after being cut into micro-bubbles through the porous diffuser, and the porous diffuser is arranged at the center of the bottom of the reactor, so that the full contact reaction of the ozone micro-bubbles and the wastewater is facilitated. The water inlet pipe is connected with the water inlet of the reactor through the water inlet valve, and the water outlet pipe is connected with the water outlet of the reactor through the water outlet valve; the water inlet of the reactor can be arranged above the reactor, and the water outlet is arranged below the reactor.
The monitoring equipment comprises an ozone flowmeter, an ozone concentration monitor, a liquid level meter, a pH real-time monitor and a COD real-time monitor. The ozone flowmeter, the ozone concentration monitor and the ozone valve are installed on an air passage between the ozone preparation unit and the porous diffuser, and the liquid level meter, the pH real-time monitor and the COD real-time monitor are respectively installed on the reactor.
The ultrasonic vibration plates are arranged on the side wall of the reactor, generally on the outer side wall, and are connected with the ultrasonic generator.
The tail gas destructor is connected with a tail gas discharge pipe arranged at the top of the reactor. Waste gas can be generated after the ozone reaction, a small amount of incompletely reacted ozone can be generated, and the gas can be discharged into the atmosphere only after being processed into gas reaching the standard, so that the environment pollution is avoided. The tail gas destructor decomposes ozone in the tail gas into oxygen in a catalytic heating decomposition mode and then discharges the oxygen into the atmosphere.
The automatic control device is respectively connected with the ozone flowmeter, the ozone concentration monitor, the liquid level meter, the pH real-time monitor, the COD real-time monitor, the ozone generator, the ozone valve, the ultrasonic generator, the water inlet valve and the water outlet valve. The automatic control device can realize remote control through the wireless communication module. The wireless communication module can comprise a terminal device such as a PC, a mobile phone or a tablet.
When the catalyst needs to be filled, a packing layer is arranged in the reactor, the packing layer is generally arranged at the middle section of the reactor and close to the ozone inlet, the surface of the packing layer is of a mesh structure and allows water flow to pass through, and the catalyst is filled in the middle of the packing layer and is replaced at regular time.
As a further improved technical scheme, a plurality of ultrasonic vibration plates can generate ultrasonic waves with different frequencies, and the ultrasonic vibration plates with different frequencies are arranged on different surfaces of the side wall of the reactor. As mentioned above, the ultrasonic vibration plates with different frequencies can be flexibly distributed on different surfaces of the side wall of the reactor, so that the ultrasonic waves with different frequencies are distributed at intervals, adjacently or oppositely, and the optimal effect is realized.
As a further improved technical scheme, the ozone preparation unit can select an air source ozone generation device, an oxygen-enriched source ozone generation device or an oxygen source ozone generation device, the air source ozone generation device, the oxygen-enriched source ozone generation device or the oxygen source ozone generation device comprises a dryer and an ozone generator, wherein the oxygen source ozone generation device also comprises an oxygen cylinder, oxygen in the oxygen cylinder enters the ozone generator after being dried by the dryer, and silent discharge is carried out through 5-25 KV alternating voltage to prepare ozone.
The invention can treat the refractory organic industrial wastewater containing one or more organic matters of chlorophenol, nitrophenol, solid alcohol acid, phthalate, bisphenol A and the like, and can also treat the municipal sewage or the advanced treatment process of a water works. Meanwhile, the wastewater treatment method can be combined with other wastewater treatment methods such as an activated sludge method, a biofilm method and the like, and is used for pretreatment or advanced treatment of wastewater with various complex components.
The invention fully combines the oxidative decomposition capacity of an ozone system on organic matters and the continuous mineralization capacity of an ultrasonic-synergetic ozone system on reaction intermediates, introduces the concept of a sequencing batch process, and forms a sequencing-sequence ultrasonic-synergetic ozone oxidation system, namely, ozone is used independently in the early stage, and the ozone and the ultrasonic have synergistic effect in the later stage, enhances the decomposition of the ozone through the ultrasonic cavitation effect and the generated physicochemical effect, and forms an ultrasonic-synergetic ozone oxidation system without selectivity and low pH dependence, thereby achieving the continuous mineralization effect, realizing better wastewater treatment effect, simultaneously saving the ultrasonic energy consumption in the early stage by controlling the timely delayed start of an ultrasonic generator, realizing the optimization of environmental and economic benefits, having the advantages of energy consumption saving, good reaction effect, good mixing effect and the like, being particularly suitable for the treatment of industrial wastewater difficult to degrade, and having the advantages of energy saving and synergism. Meanwhile, the automatic control and the remote control of the wastewater treatment process are realized by monitoring the wastewater parameters, so that the whole wastewater treatment process is fully automatic, the tail gas in the reaction device can be treated, and the environmental pollution is avoided; the efficiency of ozone oxidative degradation can be improved by adding the catalyst, and the application range of the ozone oxidation degradation device can be further expanded by setting ultrasonic waves with different frequencies and controlling the starting sequence of the ultrasonic waves with different frequencies.
Drawings
FIG. 1 is a flow chart of the steps of the process of the present invention
FIG. 2 is a schematic view showing the construction of an apparatus for treating waste water according to the present invention.
FIG. 3 is a schematic view of the connection control of the automatic control device according to the present invention.
Reference numerals: 1-a reactor; 2-a porous diffuser; 3-an ozone preparation unit; 4-an ozone flow meter; 5-ozone concentration monitor; 6-airway; 7-ozone valve; 8-ultrasonic vibration plate; 9-an ultrasonic generator; 10-a tail gas destroyer; 11-automatic control means; 12-a water inlet valve; 13-a water outlet valve; 14-a liquid level meter; 15-a real-time pH monitor; 16-COD real-time monitor; 17-a tail gas discharge pipe; 18-a water inlet pipe; 19-water outlet pipe; 80-low frequency ultrasonic vibration plate; 81-high frequency ultrasonic vibrating plate.
Detailed Description
A sequencing batch energy-saving ultrasonic and ozone cooperative organic wastewater treatment device is used for realizing the method for treating organic wastewater by sequencing batch energy-saving ultrasonic and ozone cooperative, and comprises a reactor 1, a porous diffuser 2, an ozone preparation unit 3, an ozone valve 7, an ultrasonic vibration plate 8, an ultrasonic generator 9, a tail gas destructor 10, an automatic control device 11, a water inlet valve 12, a water outlet valve 13, a water inlet pipe 18, a water outlet pipe 19 and monitoring equipment, wherein the ozone preparation unit 3 is used for preparing ozone. The reactor 1 is a polyhedron, the porous diffuser 2 is arranged at the bottom of the reactor 1, preferably at the center of the bottom, the ozone preparation unit 3 and the ozone valve 7 are connected with the porous diffuser 2 through the air passage 6, ozone generated by the ozone preparation unit 3 enters wastewater after being cut into micro-bubbles through the porous diffuser 2, and the porous diffuser 2 is arranged at the center of the bottom of the reactor 1, so that the ozone micro-bubbles and the wastewater are in full contact reaction. A plurality of ultrasonic vibration plates 8 are arranged on the outer side wall of the reactor 1, and the ultrasonic vibration plates 8 are connected with an ultrasonic generator 9.
The water inlet pipe 18 is connected with the water inlet of the reactor 1 through the water inlet valve 12, and the water outlet pipe 19 is connected with the water outlet of the reactor 1 through the water outlet valve 13; the water inlet of the reactor 1 is arranged above the reactor 1, and the water outlet is arranged below the reactor 1. The off-gas destructor 10 is connected to an off-gas discharge pipe 17 arranged at the top of the reactor 1. The exhaust gas destruction 10 may be selected from existing commercial products. The front end of the tail gas destructor 10 may also be provided with a means for removing water vapor to facilitate the decomposition of ozone at the rear end.
The monitoring facilities include ozone flowmeter 4, ozone concentration monitor 5, liquid level appearance 14, pH real time monitoring appearance 15 and COD real time monitoring appearance 16, ozone flowmeter 4, ozone concentration monitor 5, ozone valve 7 are installed on the air flue 6 between ozone preparation unit 3 and the porous diffuser 2, liquid level appearance 14, pH real time monitoring appearance 15 and COD real time monitoring appearance 16 are installed respectively on the reactor 1. As shown in fig. 3, the automatic control device 11 is respectively connected to the monitoring device, the ozone preparation unit 3, the ozone valve 7, the ultrasonic generator 9, the ultrasonic vibrating plate 8, the water inlet valve 12 and the water outlet valve 13, the automatic control device 11 obtains parameter values of each monitoring device, controls the opening and closing of the ozone preparation unit 3, the ozone valve 7, the ultrasonic generator 9, the water inlet valve 12 and the water outlet valve 13 according to monitoring data, and controls the flow rate of ozone according to the concentration of ozone. When the pH value reaches a set value, controlling and starting an ultrasonic generator 9, and generating ultrasonic waves through an ultrasonic vibrating plate 8; the COD real-time monitor 16 measures the COD concentration in the reactor 1, and when the COD value reaches the discharge requirement, the water outlet valve 13 is controlled to be opened; when the COD value does not reach the standard, controlling to close the water outlet valve 13; when the liquid level is lower, controlling to open the water inlet valve 12; when the liquid level reaches a prescribed value, the control closes the water inlet valve 12.
In one embodiment, a plurality of the ultrasonic vibration plates 8 can generate ultrasonic waves with different frequencies, in this embodiment, the ultrasonic vibration plates 8 include a low-frequency ultrasonic vibration plate 80 and a high-frequency ultrasonic vibration plate 81, and the ultrasonic vibration plates 8 with different frequencies are disposed on different surfaces of the sidewall of the reactor 1. As mentioned above, the ultrasonic vibration plates 8 with different frequencies can be flexibly distributed on a plurality of surfaces of the sidewall of the reactor 1, so that the ultrasonic waves with different frequencies are distributed in a staggered manner, thereby achieving the optimal effect. The coverage areas of the low-frequency ultrasonic vibration plate 80 and the high-frequency ultrasonic vibration plate 81 can be flexibly set according to the actual situation.
The ozone preparation unit 3 can be any existing structure or form of preparation equipment, such as an air source ozone generating device, an oxygen-rich source ozone generating device or an oxygen source ozone generating device. The embodiment is an oxygen source ozone generating device, which comprises an oxygen bottle, a dryer and an ozone generator which are connected in sequence, wherein oxygen in the oxygen bottle enters the ozone generator after being dried by the dryer, and silent discharge is carried out by 5-25 KV alternating voltage to prepare ozone.
The automatic control device 11 is connected with monitoring equipment, an ozone generator, an ozone valve 7, an ultrasonic vibration plate 8, an ultrasonic generator 9, a water inlet valve 12, a water outlet valve 13 and the like through a communication module, and controls the opening, closing or flow control of the equipment. The automatic control device 11 may remotely control the operation of the wastewater treatment apparatus through a wireless communication mode. The automatic control device 11 may include a terminal device such as a PC, a mobile phone, or a tablet.
In other embodiments, the reactor 1 may further comprise a packing layer, the packing layer is generally disposed at the middle section of the reactor and near the ozone inlet, the surface of the packing layer is a mesh structure to allow water flow, and the catalyst is filled in the middle of the packing layer and is replaced at regular time.
The method for treating organic wastewater by using sequencing batch energy-saving ultrasonic and ozone is carried out according to the following steps by combining the figures 1-3:
(1) after the main power supply is turned on, the oxygen cylinder, the ozone flowmeter 4, the ozone concentration monitor 5, the liquid level meter 14, the pH real-time monitor 15 and the COD real-time monitor 16 are simultaneously turned on;
(2) when the wastewater liquid level in the wastewater treatment device is lower than a low set value (10%), closing the water outlet valve 13, opening the water inlet valve 12, injecting wastewater into the reactor 1, and when the liquid level reaches a high set value (90%), closing the water inlet valve 12;
(3) switching on a power supply of an ozone generator, opening an ozone valve 7, drying oxygen by a dryer to remove residual moisture, then feeding the oxygen into the ozone generator, adjusting the flow of ozone required by reaction by ozone prepared by the ozone generator through an ozone flowmeter 4 and the ozone valve 7, measuring the concentration of the ozone by an ozone concentration monitor 5 after the flow is stable, and blowing the ozone into the reactor 1 through a porous diffuser 2 in the center of the reactor 1;
(4) the wastewater and ozone bubbles start to react, and when the pH value in the wastewater reaches an ultrasonic introduction point, the controller controls to turn on the ultrasonic generator 9 and indirectly controls the ultrasonic vibrating plate 8 to vibrate;
(5) when the COD real-time monitor 16 detects that the COD value reaches the discharge requirement value, the ultrasonic generator 9 is closed, the ozone generator and the ozone valve 7 are closed, the controller controls to open the water outlet valve 13, and the treated wastewater is discharged after reaching the standard;
and (5) repeating the steps (2) to (5) to continuously treat the wastewater, thereby realizing the continuous and automatic treatment process.
Through the real-time monitoring of the liquid level, the pH value and the COD value of the wastewater, the automatic control device is combined, the steps are circularly carried out, the inlet and outlet of the water to be treated and the treated water, the automatic opening and closing of the ozone, the flow control and the ultrasonic intervention time are automatically controlled, and the automatic sequencing batch type energy-saving treatment of the organic wastewater is realized. In the reaction process, a small part of ozone microbubbles are discharged to the tail gas destructor 10 through a tail gas discharge pipe 17, and are discharged into the atmosphere after being treated by the tail gas destructor 10.
In one preferred embodiment, the ultrasonic introduction point is a time point when the change rate of the pH value changes from a negative value to a positive value, namely the pH value of the wastewater is continuously monitored during the treatment process, the ultrasonic is started when the pH value of the wastewater changes from a falling value to a rising value, so that the ultrasonic and the ozone act in a synergistic manner, and the ultrasonic starting is automatically controlled by a program.
As one of the preferred embodiments, the ultrasound introduction point is a pH value of 3 to 5. If no more effective means for monitoring the pH change rate exists, the ultrasonic entry point can be directly controlled according to the pH value, and the ultrasonic generating device is started when the pH value enters a range of 3-5, so that the control method is simplified. It is further preferred that the ultrasound is switched on when the pH value reaches between 3 and 4.
As one embodiment, the wastewater treatment device may be added or filled with a catalyst before ozone is introduced, so that the ozone oxidation reaction is performed under the catalyst condition, and the catalyst is a metal oxide or a metal sulfide, or a mixture of several metal oxides or metal sulfides, or an activated carbon-supported metal oxide or metal sulfide. The metal oxide and metal sulfide may be conventional ozone oxidation catalysts, such as MnO2、Mn3O4、TiO2、Al2O3、CuO、WS2、MoS2And the like. The technical scheme of the invention is suitable for any situation that the reactor is filled or not filled with the catalyst, and the addition or non-addition of the catalyst in the ozone oxidation process is within the protection scope of the invention.
As one embodiment, the flow rate of the ozone is 0.1-1 L.min-1The concentration of ozone is 1-50 mg. L-1(ii) a The standard value of raw water COD value is 50-5000 mg. L-1Ultrasonic generator generationThe frequency of the ultrasonic waves of (a) is 20 to 1000 kHz, preferably 200 kHz.
As one embodiment, ozone is introduced from the bottom of the reactor, ultrasonic waves are generated on the side wall of the reactor, and ultrasonic waves of different frequencies are generated on different faces of the side wall of the reactor. The installation position of the ultrasonic wave generating device and the surface distribution of the ultrasonic waves with different frequencies can be flexibly set according to the volume size and the position of the reactor and the type of the treated wastewater, for example, the low-frequency ultrasonic waves and the high-frequency ultrasonic waves can be respectively arranged on the spacing surface of the side wall of the reactor; or the adjacent surfaces are respectively provided with low-frequency ultrasonic waves and high-frequency ultrasonic waves; or the opposite surfaces are respectively provided with low-frequency ultrasonic waves and high-frequency ultrasonic waves, or vice versa, and all the permutation and combination are in the protection scope of the application and are not listed here. The opening sequence of the ultrasonic waves with different frequencies can be set according to the type of wastewater, the difficulty of actual process operation and the like, and when the ultrasonic introduction point is reached, the ultrasonic waves with different frequencies can be simultaneously opened to simultaneously act; or after reaching the ultrasonic introduction point, the low-frequency ultrasonic wave is started for a period of time, and then the high-frequency ultrasonic wave is started to enable the high-frequency ultrasonic wave and the low-frequency ultrasonic wave to simultaneously act. The low frequency ultrasonic wave may be 20-100 kHz and the high frequency ultrasonic wave may be 100-1000 kHz. The low-frequency ultrasonic wave is favorable for shearing ozone into micro bubbles, changes the diffusion path of the micro bubbles, enhances the disordered diffusion of the micro bubbles in the wastewater, is more fully contacted with the wastewater, has more obvious cavitation effect of the high-frequency ultrasonic wave, generates higher heat, is favorable for the oxidative degradation of the ozone on organic matters, and further reduces the energy consumption due to the matching of the low frequency and the high frequency. To further improve the processing efficiency, the coverage of the high frequency ultrasound may be larger than the coverage of the low frequency ultrasound. Of course, the ultrasound on each side of the reactor can also be ultrasound of the same frequency.
The treatment effect of the invention is explained by taking the pharmaceutical wastewater from a certain pharmaceutical factory in south China as an example. The pharmaceutical wastewater is mainly characterized in that: COD is 2000 mg. L-1Around, the initial pH was 6.8. + -. 0.3. Ozone was prepared using a pure oxygen ozone generator at a flow rate of 0.35L. min-1Ozone concentration of 35 mg.L-1. For experimentsThe ultrasonic frequency was 200 kHz. The experiment was carried out as described above (the point of introduction of the ultrasound was when the rate of change of the pH value changed from negative to positive). Test results show that the COD removal limit value (about 50 percent) exists after the wastewater is decomposed for 2 hours by simply introducing an ozone (without ultrasonic synergy), the advanced treatment of the wastewater cannot be realized, the wastewater is difficult to be continuously decomposed even the reaction time is continuously prolonged, and no practical significance is realized (the COD removal energy consumption ratio is 14.20 g. kWh)-1The COD removal energy consumption ratio represents the removal amount of COD under unit electric energy consumption, and the larger the COD removal energy consumption ratio is, the higher the energy utilization efficiency is); the ozone is cooperated with the ultrasonic treatment system, COD can be removed by about 90% within 2 hours, the advanced treatment of the wastewater is realized, but the energy efficiency is low (the energy consumption ratio for removing the COD is 4.75 g. kWh)-1) (ii) a Sequencing batch ultrasonic synergistic ozone treatment system, ozone is simply introduced in earlier stage, the ultrasonic is started at the time point when the change rate of pH value is changed from negative value to positive value, COD can be removed by about 85% within 2 hours, the advanced treatment of wastewater is realized, and compared with the ozone synergistic ultrasonic treatment system, the energy efficiency is improved by about 50% (COD removal energy consumption ratio is 7.04 g. kWh)-1）。
Therefore, the sequencing batch ultrasonic synergistic ozone system is an energy-saving method for effectively removing COD (chemical oxygen demand) in organic industrial wastewater. In actual production, a plurality of oxidation towers (i.e. reactors) can be arranged to run in parallel for improving the processing capacity. Meanwhile, the wastewater treatment process can realize the full automation of the treatment process by monitoring the wastewater and the wastewater treatment device, particularly, the ultrasonic entry point can be automatically controlled according to the monitoring of the pH value of the wastewater in the wastewater treatment process, the randomness and the subjectivity of manual control are avoided, and the treatment efficiency and the treatment effect are improved.
The above detailed description is specific to possible embodiments of the present invention, and the embodiments are not intended to limit the scope of the present invention, and all equivalent implementations or modifications that do not depart from the scope of the present invention are intended to be included within the scope of the present invention.

Claims (8)

1. The method for treating organic wastewater by sequencing batch energy-saving ultrasonic and ozone is characterized in that the energy conservation, the accuracy and the automation control of the treatment process are realized by monitoring the liquid level, the pH value and the COD value of wastewater in a wastewater treatment device and comprehensively identifying and analyzing the reaction process, and comprises the following steps:
s1, when the liquid level of the wastewater in the wastewater treatment device is lower than a low set value, closing the water outlet valve, opening the water inlet valve, injecting the wastewater into the reactor, and when the liquid level reaches a high set value, closing the water inlet valve;
s2, opening an ozone generator and an ozone valve, and introducing ozone into the wastewater for reaction;
s3, when the pH value of the wastewater reaches the ultrasonic introduction point, continuing introducing ozone, and simultaneously starting an ultrasonic generator to further treat the wastewater under the condition that ultrasonic waves cooperate with ozone;
s4, when the COD value of the wastewater meets the discharge requirement, turning off the ultrasonic generator, turning off the ozone generator and the ozone valve, and turning on the water outlet valve to drain;
the steps S1-S4 are all real-time monitoring the liquid level, the pH value and the COD value of the wastewater, and the steps S1-S4 are controlled by an automatic controller to be circularly carried out;
the ultrasonic introduction point is a time point when the change rate of the pH value changes from a negative value to a positive value, namely the pH value of the wastewater is continuously monitored in the treatment process, and the ultrasonic is started when the pH value of the wastewater changes from descending to ascending; or the ultrasonic introduction point is when the pH value reaches 3-5.
2. The method for treating organic wastewater by using sequential energy-saving ultrasound and ozone in coordination according to claim 1, wherein a catalyst is added or filled in the wastewater treatment device before ozone is introduced, so that an ozone oxidation reaction is performed under the condition of the catalyst, and the catalyst is a metal oxide or a metal sulfide, or a mixture of several metal oxides or metal sulfides, or an activated carbon-supported metal oxide or metal sulfide.
3. The method for treating organic wastewater by using sequential energy-saving ultrasonic and ozone in coordination according to claim 1, wherein the ozone is generatedThe flow rate is 0.1-1 L.min-1The concentration of ozone is 1-50 mg.L-1(ii) a COD value of raw wastewater is 50-5000 mg. L-1The frequency of the ultrasonic wave generated by the ultrasonic generator is 20-1000 kHz.
4. The method for treating organic wastewater by using sequential energy-saving ultrasound and ozone as claimed in claim 1, wherein the frequency of the ultrasonic waves generated by the ultrasonic generator is 200 kHz.
5. The method for treating organic wastewater by using sequential energy-saving ultrasound and ozone as claimed in any one of claims 1 to 4, wherein the ozone is introduced from the bottom of the reactor, the ultrasonic waves are generated on the side wall of the reactor, and the ultrasonic waves with different frequencies are generated on different surfaces of the side wall of the reactor, and the ultrasonic waves with different frequencies are turned on simultaneously or in combination after the pH value of the wastewater reaches the ultrasonic introduction point.
6. A sequencing batch energy-saving ultrasonic and ozone collaborative organic wastewater treatment device for realizing the method for treating organic wastewater by sequencing batch energy-saving ultrasonic and ozone according to any one of claims 1 to 5, which is characterized by comprising a reactor, a porous diffuser, an ozone preparation unit, an ozone valve, an ultrasonic vibrating plate, an ultrasonic generator, a tail gas destructor, an automatic control device, a water inlet valve, a water outlet valve, a tail gas discharge pipe, a water inlet pipe, a water outlet pipe and monitoring equipment; the porous diffuser is arranged at the bottom of the reactor; the ozone preparation unit and the ozone valve are connected with the porous diffuser through the air passage; the ultrasonic vibration plates are arranged on the side wall of the reactor and connected with the ultrasonic generator; the tail gas destructor is connected with a tail gas discharge pipe arranged at the top of the reactor, the water inlet pipe is connected with a water inlet of the reactor through the water inlet valve, and the water outlet pipe is connected with a water outlet of the reactor through the water outlet valve; automatic control device respectively with monitoring facilities, ozone generator, ozone valve, ultrasonic generrator, water intaking valve and outlet valve link to each other, monitoring facilities includes ozone flowmeter, ozone concentration monitor, level appearance, pH real time monitoring appearance and COD real time monitoring appearance, ozone flowmeter, ozone concentration monitor, ozone valve are installed on the air flue between ozone preparation unit and the porous diffuser, be used for monitoring the flow of ozone, concentration and the volume of letting in of control ozone respectively, level appearance, pH real time monitoring appearance and COD real time monitoring appearance are installed respectively on the reactor for liquid level, pH value and the COD value of waste water in the monitoring reactor.
7. The apparatus for treating organic wastewater by using sequential batch energy-saving ultrasound and ozone as claimed in claim 6, wherein the plurality of ultrasonic vibration plates can generate ultrasonic waves with different frequencies, and the ultrasonic vibration plates with different frequencies are arranged on different surfaces of the side wall of the reactor.
8. The device for treating organic wastewater by using ultrasonic and ozone in coordination in a sequencing batch manner as claimed in claim 6, wherein the ozone preparation unit is an air source ozone generation device, an oxygen-rich source ozone generation device or an oxygen source ozone generation device, and each device comprises a dryer and an ozone generator, wherein the oxygen source ozone generation device further comprises an oxygen cylinder, oxygen in the oxygen cylinder is dried by the dryer and then enters the ozone generator, and silent discharge is performed by using an alternating voltage of 5-25 KV to prepare ozone.
CN202110364642.XA 2021-04-06 2021-04-06 Sequencing batch energy-saving type device and method for treating organic wastewater by combining ultrasonic and ozone Pending CN112794400A (en)

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Application publication date: 20210514