CN112456706A - Treatment device and method for catalytically oxidizing organic wastewater based on secondary cavitation and persulfate - Google Patents
Treatment device and method for catalytically oxidizing organic wastewater based on secondary cavitation and persulfate Download PDFInfo
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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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
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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Abstract
本发明涉及一种基于二级空化协同过硫酸盐催化氧化有机废水的处理装置，包括：两台吸附氧化催化设备、空压机、进出水系统和气水反冲洗系统；进出水系统包括原水箱和两台产水箱；两台吸附氧化催化设备并联或串联连接；每台吸附氧化催化设备均包括吸附氧化催化床反应器；吸附氧化催化床反应器中部设置催化氧化区，催化氧化区内部填充金属催化剂。本发明的有益效果是：本发明在吸附氧化催化床反应器内设有空化活化区和催化氧化区，避免了单一活化方式的不足；根据进水水质情况实时调控两台吸附氧化催化设备并联或串联连接，降低系统运行成本；可以灵活选取空化活化区的空化预处理方式，提高了空化预处理的效率。
The invention relates to a treatment device based on two-stage cavitation synergistic persulfate catalytic oxidation of organic wastewater, comprising: two adsorption and oxidation catalytic equipment, an air compressor, an inlet and outlet water system and a gas-water backwash system; the inlet and outlet water system includes a raw water tank and two water production tanks; two adsorption and oxidation catalytic devices are connected in parallel or in series; each adsorption and oxidation catalytic device includes an adsorption and oxidation catalytic bed reactor; a catalytic oxidation zone is set in the middle of the adsorption and oxidation catalytic bed reactor, and the interior of the catalytic oxidation zone is filled with metal catalyst. The beneficial effects of the present invention are as follows: the present invention is provided with a cavitation activation zone and a catalytic oxidation zone in the adsorption oxidation catalytic bed reactor, so as to avoid the deficiency of a single activation mode; according to the water quality of the influent water, the parallel connection of two adsorption and oxidation catalytic devices is regulated in real time Or connected in series to reduce the operating cost of the system; the cavitation pretreatment method in the cavitation activation zone can be flexibly selected, which improves the efficiency of cavitation pretreatment.
Description
Technical Field
The invention belongs to the technical field of organic wastewater treatment, and particularly relates to a treatment device and method for catalytically oxidizing organic wastewater based on secondary cavitation and persulfate.
Background
The continuous development of the industry causes the discharge amount of industrial wastewater to be greatly increased, wherein the organic wastewater generated in the industries of chemical engineering, electroplating, printing and dyeing, medicine and the like has the characteristics of high organic matter concentration, difficult degradation, poor biodegradability and the like, and is one of the difficult problems of wastewater treatment. The conventional physical method, biological method and the like are difficult to technically and economically meet the treatment requirements of the organic wastewater, and advanced oxidation technologies (AOPs) become hot spot technologies for treating the organic wastewater due to strong oxidation capability and high treatment efficiency.
At present, the mature advanced oxidation technology mainly takes Fenton oxidation, electrochemical oxidation, ozone oxidation and the like as main materials, and is an oxidation system based on OH free radicals, but has more defects; if the requirement on pH is high, the oxidation performance of some pollutants is poor, and in addition, a large amount of iron mud precipitate is generated, so that the treatment difficulty is increased.
The persulfate is activated to generate sulfate radicals to degrade organic wastewater, the method has the advantages of strong oxidizability, good stability, no toxicity, no harm and the like, can oxidize and decompose organic matters within a wider pH range, has the half-life period of the sulfate radicals as long as about 4 seconds, has longer reaction time with the organic matters, is more favorable for degrading the organic matters, and is a novel advanced oxidation technology with good development prospect. The core of the application of persulfate advanced oxidation technology is how to efficiently activate to generate sulfate radicals. However, the effect of the single activation mode of heat, alkali, transition metal ions and the like is insufficient at present, and a more efficient technology for treating organic wastewater by persulfate oxidation is urgently needed.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a treatment device and a treatment method for organic wastewater based on secondary cavitation and persulfate catalytic oxidation.
The treatment device for catalytically oxidizing organic wastewater based on the two-stage cavitation and persulfate catalysis comprises two adsorption oxidation catalysis devices, an air compressor, a water inlet and outlet system and an air-water backwashing system; the water inlet and outlet system comprises a raw water tank and two water production tanks; the two adsorption oxidation catalytic devices are connected in parallel or in series; each adsorption oxidation catalytic device comprises an adsorption oxidation catalytic bed reactor; a catalytic oxidation area is arranged in the middle of the adsorption oxidation catalytic bed reactor, and a metal catalyst is filled in the catalytic oxidation area; the lower part of the adsorption oxidation catalytic bed reactor is provided with a cavitation activation zone; an ultrasonic source is arranged outside the cavitation activation area, and a plurality of ultrasonic transducers are arranged inside the cavitation activation area; the cavitation activation zone is connected with the input end of the ejector, and the output end of the ejector is connected with the cavitation activation zone at the lower part of the adsorption oxidation catalytic bed reactor through a booster pump to form a circulation loop; an outlet of a catalytic oxidation zone of the adsorption oxidation catalytic bed reactor is connected to an inlet of a water production tank, and an outlet of the water production tank is provided with a manual valve; the dosing boxes are respectively connected with the medicament metering boxes in each adsorption oxidation catalysis device; the adsorption oxidation catalytic bed reactor comprises an adsorption oxidation catalytic bed reactor A and an adsorption oxidation catalytic bed reactor B; one end of the gas-water back flushing system is divided into two paths and is respectively connected with the water outlets of the water production tanks in the two adsorption oxidation catalytic devices, and the other end of the gas-water back flushing system is divided into two paths and is respectively connected with the cavitation activation area at the lower part of the adsorption oxidation catalytic bed reactor in the two adsorption oxidation catalytic devices; the air-water backwashing system comprises a water inlet pump C, an electromagnetic flowmeter C and a pneumatic regulating valve C.
Preferably, when two adsorption oxidation catalytic devices are connected in parallel: the raw water tank outlet pipeline is provided with a three-way valve, and the raw water tank outlet pipeline is divided into two paths after passing through the three-way valve: one path is connected with a water inlet pump A, an electromagnetic flowmeter A and a pneumatic regulating valve A in sequence and then is connected with a cavitation activation area A at the lower part of an adsorption oxidation catalytic bed reactor A; the other path is connected with a water inlet pump B, an electromagnetic flow meter B and a pneumatic regulating valve B in sequence and then is connected with a cavitation activation area B at the lower part of an adsorption oxidation catalytic bed reactor B; the cavitation activation area A is connected into the ejector A through a pressure pump A, and the cavitation activation area B is connected into the ejector B through a pressure pump B; the dispensing box is respectively connected with the agent metering box A and the agent metering box B in two ways; the agent metering box A is connected with the ejector A, and a one-way check valve A is arranged on a connecting pipeline of the agent metering box A; the reagent metering box B is connected with the ejector B, and a one-way check valve B is arranged on a connecting pipeline of the reagent metering box B.
Preferably, when two adsorption oxidation catalytic devices are connected in series: the raw water tank outlet pipeline is provided with a three-way valve, is only connected to one side of a water inlet pump A after passing through the three-way valve, is sequentially connected with an electromagnetic flowmeter A and a pneumatic regulating valve A, and is connected to a cavitation activation area A at the lower part of an adsorption oxidation catalytic bed reactor A, and is connected to a jet device A through a pressure pump A; the dispensing box is connected with the agent metering box A and then is connected with the ejector A; an outlet of a catalytic oxidation area A of the adsorption oxidation catalytic bed reactor A is connected to an inlet of a water production tank A; the outlet of the water production tank A is connected with a manual valve A and then is connected with the inlet of a water inlet pump B, a pipeline behind the water inlet pump B is sequentially provided with an electromagnetic flowmeter B and a pneumatic regulating valve B, and the pipeline behind the pneumatic regulating valve B is connected with a cavitation activation area B at the lower part of an adsorption oxidation catalytic bed reactor B; the cavitation activation zone B is connected into the ejector B by a pressure pump B; the dosing box is connected with the agent metering box B and then is connected with the ejector B; an outlet of a catalytic oxidation zone B of the adsorption oxidation catalytic bed reactor B is connected to an inlet of a water production tank B, and an outlet of the water production tank B is provided with a manual valve B.
Preferably, the adsorption oxidation catalytic bed reactor A and the adsorption oxidation catalytic bed reactor B are both adsorption oxidation catalytic bed reactors with lower water inlet and upper water outlet.
Preferably, a stirrer is arranged in the dosing tank.
The working method of the treatment device for catalytically oxidizing organic wastewater based on secondary cavitation and persulfate comprises the following steps:
step 1, adding persulfate into a dispensing box, and dissolving the persulfate through stirring and heating;
step 2, switching the operation modes of the two adsorption oxidation catalytic devices through the control of a three-way valve, and if the two adsorption oxidation catalytic devices operate in parallel, simultaneously introducing the wastewater into an adsorption oxidation catalytic bed reactor A and an adsorption oxidation catalytic bed reactor B from a raw water tank, and simultaneously executing the step 3 and the step 4; if the two adsorption oxidation catalysis devices operate in series, the effluent of the water production tank of the first adsorption oxidation catalysis device is connected to the inlet of the water inlet pump of the second adsorption oxidation catalysis device, and the step 3 and the step 4 are executed in sequence;
and 4, carrying out catalytic oxidation on the waste water containing persulfate.
Preferably, step 3 specifically comprises the following steps:
3.1, enabling the wastewater to enter a cavitation activation area at the lower part of an adsorption oxidation catalytic bed reactor from a raw water tank through a water inlet pump, an electromagnetic flowmeter and a pneumatic regulating valve, and then introducing the wastewater into a jet device through a pressure pump;
3.2, introducing the persulfate solution into the ejector from the dosing box through the agent metering box, and mixing the persulfate solution with the wastewater; under the flow limiting effect of the ejector, the local static pressure of the mixed solution is sharply reduced and is lower than the saturated vapor pressure or generates negative pressure, and the solution generates hydrodynamic cavitation; the peroxygen bond O-O of persulfate is broken to generate sulfate radical:
step 3.3, carrying out oxidative degradation reaction on sulfate radicals generated in the formula (1) and organic matters in the wastewater:
the sulfate radical generated in the formula (1) and alcohols, alkanes, ethers and esters compounds generate hydrogen abstraction reaction:
the sulfate radical generated in the formula (1) and the aromatic compound have electron transfer reaction:
addition reaction of sulfate radical generated in formula (1) with unsaturated olefin compound:
step 3.4, returning the solution after reaction in the ejector to the cavitation activation area;
3.5, starting an ultrasonic source connected to the outside of the cavitation activation area, and performing hydraulic and ultrasonic two-stage cavitation pretreatment on the wastewater; an ultrasonic source generates an ultrasonic external field, and peroxide bonds O-O of persulfate are broken under the activation of ultrasonic cavitation energy generated by an ultrasonic transducer to generate sulfate radicals:
further enhancing the extent of electron transfer, hydrogen abstraction, or addition oxidative degradation reactions.
Preferably, the step 4 specifically comprises the following steps:
step 4.1, enabling the waste water containing persulfate to enter a catalytic oxidation area in the middle of an adsorption oxidation catalytic bed reactor, filling a transition metal catalyst in the catalytic oxidation area, and activating and breaking peroxide bonds O-O of persulfate to generate sulfate radicals under the action of the catalyst:
and 4.2, continuously oxidizing and degrading organic matters in the wastewater by sulfate radical through electron transfer, hydrogen abstraction or addition reaction, and enabling the reacted solution to enter a water production tank.
Preferably, the ultrasound source is selectively switched in step 3.5.
Preferably, the air compressor is a pneumatic source of the pneumatic regulating valve A, the pneumatic regulating valve B and the pneumatic regulating valve C, the air compressor is a back flushing air source of an air-water back flushing system, the air compressor is an aeration air source of the water production tank, and corresponding safety devices such as a safety valve, a pressure gauge and the like are matched with the air compressor.
The invention has the beneficial effects that: the invention provides a device and a method for efficiently activating persulfate to generate sulfate radicals. Firstly, the persulfate is activated by adopting a mode of combining cavitation pretreatment and catalytic oxidation, so that the defect of a single activation mode is avoided; secondly, single hydrodynamic cavitation or hydrodynamic and ultrasonic two-stage cavitation pretreatment can be flexibly selected, so that the efficiency of the cavitation pretreatment is improved; thirdly, the parallel/serial connection mode of the two adsorption oxidation catalytic devices can be regulated and controlled in real time according to the water quality condition of the inlet water, and the system operation cost is reduced.
Drawings
FIG. 1 is a schematic structural diagram of a treatment device for catalytic oxidation of organic wastewater by two-stage cavitation in cooperation with persulfate.
Description of reference numerals: an adsorption oxidation catalytic bed reactor A1, a catalytic oxidation zone A2, a cavitation activation zone A3, an ultrasonic source A4, an ultrasonic transducer A5, a booster pump A6, a jet device A7, a medicament metering tank A7, a dosing tank 9, a stirrer 10, a one-way check valve A7, a raw water tank 12, a three-way valve 13, a water inlet pump A7, an electromagnetic flowmeter A7, a pneumatic regulating valve A7, a water production tank A7, a manual valve A7, an adsorption oxidation catalytic bed reactor B7, a catalytic oxidation zone B7, a cavitation activation zone B7, an ultrasonic source B7, an ultrasonic transducer B7, a booster pump B7, a jet device B7, a medicament metering tank B7, a one-way check valve B7, a water inlet pump B7, an electromagnetic flowmeter B7, a pneumatic regulating valve B7, a water production tank B7, a manual water inlet valve B7, a water inlet pump C7, an electromagnetic air compressor C3636 and an air compressor.
Detailed Description
The present invention will be further described with reference to the following examples. The following examples are set forth merely to aid in the understanding of the invention. It should be noted that, for a person skilled in the art, several modifications can be made to the invention without departing from the principle of the invention, and these modifications and modifications also fall within the protection scope of the claims of the present invention.
The principle of the invention is mainly that three persulfate activation modes of hydrodynamic cavitation, ultrasonic cavitation and transition metal catalytic oxidation are cooperatively utilized to form sulfate radicals with strong oxidizing property, so that the degradation efficiency of organic matters is improved.
As shown in fig. 1, a reaction apparatus for catalytic oxidation of organic wastewater by two-stage cavitation in cooperation with persulfate comprises two catalytic adsorption and oxidation apparatuses and a water inlet and outlet system, wherein a catalytic oxidation area a2 is arranged in the middle of an catalytic adsorption and oxidation bed reactor a1, and a cavitation activation area A3 is arranged in the lower part; an ultrasonic source A4 is arranged outside the cavitation activation area A3, and a plurality of ultrasonic transducers A5 are arranged inside the cavitation activation area A3; the cavitation activation region A3 is connected with the input end of an ejector A7, and the output end of an ejector A7 is connected with a cavitation activation region A3 at the lower part of an adsorption oxidation catalytic bed reactor A1 through a booster pump A6 to form a circulation loop; a catalytic oxidation zone B20 is arranged in the middle of the adsorption oxidation catalytic bed reactor B19, a cavitation activation zone B21 is arranged at the lower part of the adsorption oxidation catalytic bed reactor B3578, an ultrasonic source B22 is arranged outside the cavitation activation zone B21, a plurality of ultrasonic transducers B23 are arranged inside the cavitation activation zone B21, the cavitation activation zone B21 is connected with the input end of a jet device B25, and the output end of the jet device B25 is connected with the cavitation activation zone B21 at the lower part of the adsorption oxidation catalytic bed reactor B19 through a booster pump B24 to form a circulation loop; the interiors of both catalytic oxidation zone a2 and catalytic oxidation zone B20 are filled with a metal catalyst.
Example 1
As shown in figure 1, the reaction device for the catalytic oxidation of organic wastewater by the two-stage cavitation in cooperation with persulfate comprises two adsorption oxidation catalytic devices and a water inlet and outlet system, wherein the water inlets of the two adsorption oxidation catalytic devices are connected in parallel.
The organic wastewater is divided into two paths by a raw water tank 12 through a three-way valve 13, and simultaneously enters an adsorption oxidation catalytic bed reactor A1 and a cavitation activation region A3 and a cavitation activation region B21 at the lower part of the adsorption oxidation catalytic bed reactor B19 after passing through a water inlet pump A14, a water inlet pump B28, an electromagnetic flow meter A15, an electromagnetic flow meter B29, a pneumatic regulating valve A16 and a pneumatic regulating valve B30, and then is respectively introduced into a jet device A7 and a jet device B25 by a pressure pump A6 and a pressure pump B24; the persulfate solution is introduced into an ejector A7 and an ejector B25 from a dosing box 9 through a reagent metering box A8 and a reagent metering box B26, is mixed with the wastewater, generates sulfate radicals through hydrodynamic cavitation, performs oxidative degradation reaction and returns to a cavitation activation area A3 and a cavitation activation area B21.
And (3) starting an ultrasonic source A4 and an ultrasonic source B22, and carrying out ultrasonic cavitation on persulfate in the wastewater in the cavitation activation zone A3 and the cavitation activation zone B21 through an ultrasonic transducer A5 and an ultrasonic transducer B23 to further strengthen the oxidative degradation reaction.
After the reaction, the wastewater enters a middle catalytic oxidation area A2 and a catalytic oxidation area B20 from a cavitation activation area A3 and a cavitation activation area B21, metal catalysts (such as transition metal oxides loaded by aluminum base or carbon base and the like) are filled in the catalytic oxidation area A2 and the catalytic oxidation area B20, under the action of the catalysts, persulfate is activated to generate sulfate radicals, and organic matters in the wastewater are continuously oxidized and degraded through electron transfer, hydrogen abstraction or addition reaction.
After reaction, the solution enters the water production tank 17 and the water production tank B31 and flows out of the system through a manual valve A18 and a manual valve B32.
Example 2
As shown in figure 1, the reaction device for the catalytic oxidation of organic wastewater by the two-stage cavitation in cooperation with persulfate comprises two adsorption oxidation catalytic devices and a water inlet and outlet system, wherein the water inlets of the two adsorption oxidation catalytic devices are connected in series.
The organic wastewater passes through a three-way valve 13 from a raw water tank 12 and then is only connected to one side of a water inlet pump A14, passes through an electromagnetic flowmeter A15 and a pneumatic regulating valve A16 and then enters a cavitation activation area A3 at the lower part of an adsorption oxidation catalytic bed reactor A1, and then is introduced into an ejector A7 by a pressurizing pump A6; the persulfate solution is introduced into the ejector A7 from the dosing box 9 through the agent metering box A8, is mixed with the wastewater, generates sulfate radicals through hydrodynamic cavitation, performs oxidative degradation reaction and returns to the cavitation activation area A3.
And an ultrasonic source A4 is started, and ultrasonic cavitation is carried out on persulfate in the wastewater in the cavitation activation zone A3 through an ultrasonic transducer A5, so that the oxidative degradation reaction is further enhanced.
After the reaction, the wastewater enters a middle catalytic oxidation zone A2 from a cavitation activation zone A3, a metal catalyst (such as transition metal oxide loaded by aluminum base or carbon base) is filled in the catalytic oxidation zone, persulfate is activated to generate sulfate radical free radicals under the action of the catalyst, and organic matters in the wastewater are continuously oxidized and degraded through electron transfer, hydrogen abstraction or addition reaction.
The solution after reaction enters a water production tank A17, is accessed to the inlet of a water inlet pump B28 after passing through a manual valve A18, enters a cavitation activation zone B21 at the lower part of an adsorption oxidation catalytic bed reactor B19 after passing through an electromagnetic flowmeter B29 and a pneumatic regulating valve B30, and is then introduced into an ejector B25 through a booster pump B24; the persulfate solution is introduced into a jet device B25 from a dosing box 9 through a reagent metering box B26, is mixed with the wastewater, generates sulfate radicals through hydrodynamic cavitation, performs oxidative degradation reaction and returns to a cavitation activation area B21.
And an ultrasonic source B22 is started, and the ultrasonic transducer B23 is used for carrying out ultrasonic activation on persulfate in the wastewater in the cavitation activation zone B21, so that the oxidative degradation reaction is further enhanced.
After the reaction, the wastewater enters a middle catalytic oxidation zone B20 from a cavitation activation zone B21, a metal catalyst (such as transition metal oxide loaded by aluminum base or carbon base) is filled in the catalytic oxidation zone, persulfate is activated to generate sulfate radicals under the action of the catalyst, and organic matters in the wastewater are continuously oxidized and degraded through electron transfer, hydrogen abstraction or addition reaction.
After reaction, the solution enters a water production tank B31 and flows out of the system through a manual valve B32.
Example 3
As shown in figure 1, the reaction device for the catalytic oxidation of organic wastewater by the two-stage cavitation in cooperation with persulfate comprises two adsorption oxidation catalytic devices and a water inlet and outlet system, wherein the water inlets of the two adsorption oxidation catalytic devices are connected in parallel.
The organic wastewater is divided into two paths by a raw water tank 12 through a three-way valve 13, and simultaneously enters an adsorption oxidation catalytic bed reactor A1 and a cavitation activation region A3 and a cavitation activation region B21 at the lower part of the adsorption oxidation catalytic bed reactor B19 after passing through a water inlet pump A14, a water inlet pump B28, an electromagnetic flow meter A15, an electromagnetic flow meter B29, a pneumatic regulating valve A16 and a pneumatic regulating valve B30, and then is respectively introduced into a jet device A7 and a jet device B25 by a pressure pump A6 and a pressure pump B24; the persulfate solution is introduced into an ejector A7 and an ejector B25 from a dosing box 9 through a reagent metering box A8 and a reagent metering box B26, is mixed with the wastewater, generates sulfate radicals through hydrodynamic cavitation, performs oxidative degradation reaction and returns to a cavitation activation area A3 and a cavitation activation area B21.
The ultrasonic source A4 and the ultrasonic source B22 are not opened, and the wastewater is not subjected to ultrasonic cavitation.
The waste water enters a middle catalytic oxidation area A2 and a catalytic oxidation area B20 from a cavitation activation area A3 and a cavitation activation area B21, metal catalysts (such as transition metal oxides loaded by aluminum base or carbon base and the like) are filled in the catalytic oxidation area, persulfate is activated to generate sulfate radicals under the action of the catalysts, and organic matters in the waste water are continuously oxidized and degraded through electron transfer, hydrogen abstraction or addition reaction.
After reaction, the solution enters a water production tank A17 and a water production tank B31 and flows out of the system through a manual valve A18 and a manual valve B32.
Claims (9)
1. The utility model provides a processing apparatus based on organic waste water of two grade cavitations cooperation persulfate catalytic oxidation which characterized in that: comprises two adsorption oxidation catalytic devices, an air compressor (36), a water inlet and outlet system and an air-water backwashing system; the water inlet and outlet system comprises a raw water tank (12) and two water production tanks; the two adsorption oxidation catalytic devices are connected in parallel or in series;
each adsorption oxidation catalytic device comprises an adsorption oxidation catalytic bed reactor; a catalytic oxidation area is arranged in the middle of the adsorption oxidation catalytic bed reactor, and a metal catalyst is filled in the catalytic oxidation area; the lower part of the adsorption oxidation catalytic bed reactor is provided with a cavitation activation zone; an ultrasonic source is arranged outside the cavitation activation area, and a plurality of ultrasonic transducers are arranged inside the cavitation activation area; the cavitation activation zone is connected with the input end of the ejector, and the output end of the ejector is connected with the cavitation activation zone at the lower part of the adsorption oxidation catalytic bed reactor through a booster pump to form a circulation loop; an outlet of a catalytic oxidation zone of the adsorption oxidation catalytic bed reactor is connected to an inlet of a water production tank, and an outlet of the water production tank is provided with a manual valve; the dosing boxes (9) are respectively connected with the medicament metering boxes in each adsorption oxidation catalysis device; the adsorption oxidation catalytic bed reactor comprises an adsorption oxidation catalytic bed reactor A (1) and an adsorption oxidation catalytic bed reactor B (19);
one end of the gas-water back flushing system is divided into two paths and is respectively connected with the water outlets of the water tanks in the two adsorption oxidation catalytic devices, and the other end of the gas-water back flushing system is divided into two paths and is respectively connected with the cavitation activation area at the lower part of the adsorption oxidation catalytic bed reactor in the two adsorption oxidation catalytic devices.
2. The apparatus for treating organic wastewater based on secondary cavitation and persulfate catalytic oxidation as claimed in claim 1, wherein when two adsorption oxidation catalytic devices are connected in parallel: set up three-way valve (13) on former water tank (12) outlet conduit, former water tank (12) outlet conduit divide into two the tunnel behind three-way valve (13): one path is connected with a water inlet pump A (14), an electromagnetic flowmeter A (15) and a pneumatic regulating valve A (16) in sequence and then is connected with a cavitation activation area A (3) at the lower part of an adsorption oxidation catalytic bed reactor A (1); the other path is connected with a water inlet pump B (28), an electromagnetic flowmeter B (29) and a pneumatic regulating valve B (30) in sequence and then is connected to a cavitation activation area B (21) at the lower part of an adsorption oxidation catalytic bed reactor B (19); the cavitation activation area A (3) is connected to the ejector A (7) through a pressure pump A (6), and the cavitation activation area B (21) is connected to the ejector B (25) through a pressure pump B (24); the dispensing box (9) is respectively connected with a medicament metering box A (8) and a medicament metering box B (26) in two ways; the agent metering box A (8) is connected with the ejector A (7), and a one-way check valve A (11) is arranged on a connecting pipeline of the agent metering box A; the medicament metering box B (26) is connected with the ejector B (25), and a one-way check valve B (27) is arranged on a connecting pipeline of the medicament metering box B.
3. The device for treating organic wastewater based on secondary cavitation and persulfate catalytic oxidation as claimed in claim 1, wherein when two adsorption oxidation catalytic devices are connected in series:
the outlet pipeline of the raw water tank (12) is provided with a three-way valve (13), the outlet pipeline of the raw water tank (12) is only connected to one side of a water inlet pump A (14) after passing through the three-way valve (13), and is connected to a cavitation activation area A (3) at the lower part of the adsorption oxidation catalytic bed reactor A (1) after being sequentially connected with an electromagnetic flow meter A (15) and a pneumatic regulating valve A (16), and the cavitation activation area A (3) is connected to a jet device A (7) through a pressure pump A (6); the medicine dispensing box (9) is connected with the medicine metering box A (8) and then is connected with the ejector A (7); an outlet of a catalytic oxidation area A (2) of the adsorption oxidation catalytic bed reactor A (1) is connected to an inlet of a water production tank A (17);
an outlet of the water production tank A (17) is connected with a manual valve A (18) and then is connected to an inlet of a water inlet pump B (28), a pipeline behind the water inlet pump B (28) is sequentially provided with an electromagnetic flowmeter B (29) and a pneumatic regulating valve B (30), and a pipeline behind the pneumatic regulating valve B (30) is connected to a cavitation activation region B (21) at the lower part of an adsorption oxidation catalytic bed reactor B (19); the cavitation activation area B (21) is connected to a jet device B (25) by a booster pump B (24); the medicine dispensing box (9) is connected with a medicine metering box B (26) and then is connected with a jet device B (25); the outlet of the catalytic oxidation zone B (20) of the adsorption oxidation catalytic bed reactor B (19) is connected to the inlet of the water production tank B (31), and the outlet of the water production tank B (31) is provided with a manual valve B (32).
4. The device for treating organic wastewater based on secondary cavitation in cooperation with persulfate catalytic oxidation as claimed in claim 1, is characterized in that: the adsorption oxidation catalytic bed reactor A (1) and the adsorption oxidation catalytic bed reactor B (19) are both adsorption oxidation catalytic bed reactors with lower water inlet and upper water outlet.
5. The device for treating organic wastewater based on secondary cavitation in cooperation with persulfate catalytic oxidation as claimed in claim 1, is characterized in that: a stirrer (10) is arranged in the medicine dispensing box (9).
6. The working method of the treatment device for the catalytic oxidation of the organic wastewater based on the secondary cavitation in cooperation with the persulfate as set forth in claim 1 is characterized by comprising the following steps:
step 1, adding persulfate into a dosing tank (9), and dissolving the persulfate through stirring and heating;
step 2, controlling and switching the operation modes of the two adsorption oxidation catalytic devices through a three-way valve (13), if the two adsorption oxidation catalytic devices operate in parallel, enabling the wastewater to simultaneously enter an adsorption oxidation catalytic bed reactor A (1) and an adsorption oxidation catalytic bed reactor B (19) from a raw water tank (12), and simultaneously executing the step 3 and the step 4; if the two adsorption oxidation catalysis devices operate in series, the effluent of the water production tank of the first adsorption oxidation catalysis device is connected to the inlet of the water inlet pump of the second adsorption oxidation catalysis device, and the step 3 and the step 4 are executed in sequence;
step 3, carrying out cavitation activation pretreatment on the waste water containing persulfate:
and 4, carrying out catalytic oxidation on the waste water containing persulfate.
7. The working method of the treatment device for catalytically oxidizing organic wastewater based on secondary cavitation in cooperation with persulfate according to claim 6, wherein the step 3 specifically comprises the following steps:
3.1, the wastewater enters a cavitation activation area at the lower part of the adsorption oxidation catalytic bed reactor from a raw water tank (12) through a water inlet pump, an electromagnetic flowmeter and a pneumatic regulating valve, and then is introduced into a jet device through a pressure pump;
3.2, introducing the persulfate solution into the ejector from the dosing tank (9) through the agent metering tank, and mixing the persulfate solution with the wastewater; under the flow limiting effect of the ejector, the local static pressure of the mixed solution is sharply reduced and is lower than the saturated vapor pressure or generates negative pressure, and the solution generates hydrodynamic cavitation; the peroxygen bond O-O of persulfate is broken to generate sulfate radical:
step 3.3, carrying out oxidative degradation reaction on sulfate radicals generated in the formula (1) and organic matters in the wastewater:
the sulfate radical generated in the formula (1) and alcohols, alkanes, ethers and esters compounds generate hydrogen abstraction reaction:
the sulfate radical generated in the formula (1) and the aromatic compound have electron transfer reaction:
addition reaction of sulfate radical generated in formula (1) with unsaturated olefin compound:
step 3.4, returning the solution after reaction in the ejector to the cavitation activation area;
3.5, starting an ultrasonic source connected to the outside of the cavitation activation area, and performing hydraulic and ultrasonic two-stage cavitation pretreatment on the wastewater; an ultrasonic source generates an ultrasonic external field, and peroxide bonds O-O of persulfate are broken under the activation of ultrasonic cavitation energy generated by an ultrasonic transducer to generate sulfate radicals:
8. the working method of the treatment device for catalytically oxidizing organic wastewater based on secondary cavitation in cooperation with persulfate according to claim 6, wherein the step 4 specifically comprises the following steps:
step 4.1, enabling the waste water containing persulfate to enter a catalytic oxidation area in the middle of an adsorption oxidation catalytic bed reactor, filling a transition metal catalyst in the catalytic oxidation area, and activating and breaking peroxide bonds O-O of persulfate to generate sulfate radicals under the action of the catalyst:
and 4.2, continuously oxidizing and degrading organic matters in the wastewater by sulfate radical through electron transfer, hydrogen abstraction or addition reaction, and enabling the reacted solution to enter a water production tank.
9. The working method of the treatment device for the catalytic oxidation of the organic wastewater based on the secondary cavitation in cooperation with the persulfate according to the claim 7 is characterized in that: the opening and closing of the ultrasonic source in step 3.5 is optional.
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