CN112723517A - Integrated system for inducing advanced oxidative degradation of unsymmetrical dimethylhydrazine wastewater through hydrodynamic cavitation - Google Patents
Integrated system for inducing advanced oxidative degradation of unsymmetrical dimethylhydrazine wastewater through hydrodynamic cavitation Download PDFInfo
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- CN112723517A CN112723517A CN202011439437.7A CN202011439437A CN112723517A CN 112723517 A CN112723517 A CN 112723517A CN 202011439437 A CN202011439437 A CN 202011439437A CN 112723517 A CN112723517 A CN 112723517A
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- hydrodynamic cavitation
- unsymmetrical dimethylhydrazine
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
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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
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
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Abstract
The utility model provides an integrated system of induced advanced oxidative degradation unsymmetrical dimethylhydrazine waste water of hydrodynamic cavitation, includes storage water tank, water pump and hydrodynamic cavitation reactor, and the storage water tank bottom is connected with the inlet of water pump, and the liquid outlet of water pump passes through bypass pipeline on the one hand and connects storage water tank upper portion, and on the other hand passes through the entry of main line connection hydrodynamic cavitation reactor, and the exit linkage storage water tank upper portion of hydrodynamic cavitation reactor is provided with the catalyst room in the hydrodynamic cavitation reactor. The system operates in a closed-loop recirculation mode, waste water containing the unsymmetrical dimethylhydrazine is injected into a water storage tank, a water pump is started, the waste water is pressed into a hydraulic cavitation reactor on a main pipeline by using pressure to generate cavitation, and the aim of degrading the unsymmetrical dimethylhydrazine waste water is fulfilled by using energy released from generation to collapse of cavitation bubbles. The method utilizes the advanced oxidation method induced by hydrodynamic cavitation to degrade the unsymmetrical dimethylhydrazine wastewater, and the combined treatment process generates a synergistic effect, thereby greatly improving the degradation efficiency.
Description
Technical Field
The invention relates to a method for degrading unsymmetrical dimethylhydrazine wastewater, belonging to the technical field of wastewater treatment.
Background
Unsym-dimethyl hydrazine is an important hydrazine propellant, has the characteristics of high stability, high combustion heat value and high specific impulse, is an energetic material with excellent performance, and is also used for manufacturing plant growth regulators, photosensitive chemicals, stabilizers used as fuel additives, absorbents used as acid gases and the like. But unsymmetrical dimethylhydrazine has high toxicity, teratogenicity, carcinogenicity and mutagenicity, can cause damage to the central nervous system, liver, kidney and the like of a human body to different degrees, can generate a large amount of waste water in the processes of transportation, storage, transfer injection and the like of the unsymmetrical dimethylhydrazine, seriously pollutes the ecological environment and harms the health of people, and particularly has increased space launching activities in recent years, and the pollution caused by the unsymmetrical dimethylhydrazine becomes a problem which is paid more and more attention to by people. The unsymmetrical dimethylhydrazine wastewater can be discharged after being treated, otherwise, the unsymmetrical dimethylhydrazine wastewater can cause great harm to the environment and related workers.
At present, unsymmetrical dimethylhydrazine wastewater treatment methods mainly comprise an adsorption method, an oxidation method, biodegradation and a combined treatment process. Physical adsorption method, catalytic oxidation method and natural degradation method have the defects of incomplete treatment, more intermediate products and the like. The photocatalytic oxidation method has the defects of complex process, high energy consumption and the like. The Fenton oxidation method and the ozone oxidation method belong to advanced oxidation treatment methods, can oxidize and decompose a plurality of refractory organic matters, but when unsymmetrical dimethylhydrazine wastewater is treated, a large amount of diazo compounds are generated in the early oxidation stage by single ozone oxidation treatment, the reaction system is complex, and a plurality of refractory intermediate products exist. The unsymmetrical dimethylhydrazine wastewater is treated by utilizing the synergistic action of ultraviolet rays and ozone, the treatment speed can be improved by more than one hundred times, but a small amount of intermediate products still exist and are difficult to degrade. The pure ozone oxidation method or the ozone-ultraviolet combined oxidation method can not meet the actual requirement of unsymmetrical dimethylhydrazine wastewater treatment.
Hydrodynamic cavitation is a form of advanced oxidation process, and shows great prospects in wastewater treatment applications due to its simple operation and its ability to generate a strong oxidizer hydroxyl radical in situ. The existing combined treatment process is highly valued due to the inevitable defect of single mode treatment. Therefore, the technology of combining hydrodynamic cavitation and other advanced oxidation processes needs to be studied deeply to generate expected synergistic effect, and a safe and efficient unsymmetrical dimethylhydrazine wastewater treatment method is sought.
Disclosure of Invention
Aiming at the problems and the defects in the existing unsymmetrical dimethylhydrazine wastewater degradation technology, the invention provides an integrated system for inducing advanced oxidative degradation of unsymmetrical dimethylhydrazine wastewater by hydrodynamic cavitation, which has high treatment efficiency and good effect.
The invention discloses an integrated system for inducing advanced oxidative degradation of unsymmetrical dimethylhydrazine wastewater by hydrodynamic cavitation, which adopts the following technical scheme:
the system comprises a water storage tank, a water pump and a hydrodynamic cavitation reactor, wherein the bottom of the water storage tank is connected with a liquid inlet of the water pump, a liquid outlet of the water pump is connected with the upper part of the water storage tank through a bypass pipeline on the one hand, and is connected with an inlet of the hydrodynamic cavitation reactor through a main pipeline on the other hand, an outlet of the hydrodynamic cavitation reactor is connected with the upper part of the water storage tank, and a catalyst chamber is arranged in the hydrodynamic cavitation reactor.
A flow control valve V is arranged on a connecting pipeline between the bottom of the water storage tank and the liquid inlet of the water pump1。
A flow control valve V is arranged on the bypass pipeline2。
One end of an inlet and one end of an outlet of the hydrodynamic cavitation reactor are respectively provided with a flow control valve V3And a flow control valve V4。
And a flow meter is arranged on a connecting pipeline between the outlet of the hydraulic cavitation reactor and the water storage tank.
And pressure sensors are arranged at the liquid outlet of the water pump and the inlet and the outlet of the hydraulic cavitation reactor.
The water storage tank is provided with a temperature adjusting and controlling device which is used for controlling and adjusting the temperature in the water storage tank to be 25 +/-1 ℃. The temperature regulation control device adopts a heating or refrigerating system in the prior art.
The hydrodynamic cavitation reactor comprises a stator, a rotating shaft and a catalyst chamber, wherein the stator is a closed cavity, a wastewater inlet and a wastewater outlet are respectively arranged at two ends of the stator, cavitation holes are distributed on the inner wall of the stator and are blind holes, the rotating shaft is installed in the stator, and the catalyst chamber is installed on the rotating shaft. The ratio of the diameter to the depth of the cavitation holes is 2:5, the diameter of the cavitation holes is 20mm, and the depth of the cavitation holes is 50 mm. The distance between the outer edge of the catalyst chamber and the outer end of the cavitation hole is 4-8 mm. The flow rate of the wastewater at the wastewater inlet is 1.5-4.5m 3/h。
The catalyst chamber is a cylinder body with two open ends, and iron blades are distributed in the cylinder body. Through holes are distributed on the iron blades, and the inner diameter of each through hole is 1-3 mm.
The system operates in a closed-loop recirculation mode, the water pump provides pressure, waste water containing the unsymmetrical dimethylhydrazine is injected into the water storage tank, the water pump is started, the waste water is pressed into the hydraulic cavitation reactor on the main pipeline by using the pressure to generate cavitation bubbles, and the aim of degrading the unsymmetrical dimethylhydrazine waste water is fulfilled by using energy released from the generation to the collapse of the cavitation bubbles.
Cavitation means that when the liquid pressure is reduced to the saturated vapor pressure of the liquid or even below, a large amount of cavitation bubbles are generated due to the violent vaporization of the liquid, the cavitation bubbles expand along with the flow of the liquid, and when the liquid pressure is recovered, the cavitation bubbles are instantaneously collapsed to form micro jet and shock waves, so that instantaneous local high temperature and instantaneous high pressure are generated. The released energy is utilized, and the effect of sterilizing and disinfecting the liquid raw material can be realized.
The catalyst chamber is arranged in the hydrodynamic cavitation reactor to form an integrated system, the unsymmetrical dimethylhydrazine wastewater is degraded by utilizing a hydrodynamic cavitation induced advanced oxidation method, a synergistic effect is generated by a combined treatment process, and the degradation efficiency is greatly improved.
The invention has the following characteristics:
1. the hydraulic cavitation technology is adopted to induce an advanced oxidation method to degrade the unsymmetrical dimethylhydrazine wastewater, and the two methods are combined to generate a synergistic effect and have high efficiency.
2. The catalyst chamber is arranged in the hydrodynamic cavitation reactor, and the integrated equipment simplifies the whole process flow of unsymmetrical dimethylhydrazine wastewater degradation.
3. The blades of the catalyst chamber are distributed with through holes, so that the degradation efficiency can be improved.
4. The wastewater can be circularly degraded for multiple times to finally reach the discharge standard for closed-loop operation.
5. The water pump is adopted to output pressure, the output quantity can be adjusted by the valve at will, and the liquid discharge is uniform and has no pulse phenomenon.
6. The bypass pipeline is arranged to control the liquid flow in the main pipeline.
7. The iron metal blade is used as a heterogeneous catalyst, so that the generation of hydroxyl free radicals can be enhanced, and the oxidative decomposition process is promoted.
8. The invention has simple structure, strong adaptability, safety and reliability, and is easy to realize industrialization.
9. The method is not limited to unsymmetrical dimethylhydrazine wastewater treatment, and is expected to have good treatment effect on other types of wastewater treatment.
Drawings
FIG. 1 is a schematic diagram of the structure of the integrated system of the present invention.
FIG. 2 is a schematic diagram of the configuration of the hydrodynamic cavitation reactor of the present invention.
Fig. 3 is a schematic diagram of the catalyst chamber arrangement in the present invention.
In the figure: 1. the device comprises a water storage tank, 2, a temperature regulation control device, 3, a centrifugal pump, 4, a cavitation reactor, 5, a flow meter and 6, a data acquisition unit; v1、V2、V3、V4: flow control valve, P1、P3、P3: a pressure sensor; t is1: a thermometer;
7. the device comprises a waste water inlet, 8. a rotating shaft, 9. a stator end cover, 10. a cavitation hole (blind hole), 11. a stator, 12. a catalyst chamber and 13. a water outlet;
14. iron blade, 15 through holes.
Detailed Description
The invention discloses an integrated system for inducing advanced oxidative degradation of unsymmetrical dimethylhydrazine wastewater by hydrodynamic cavitation, which comprises a water storage tank as shown in figure 11. A temperature regulation control device 2, a centrifugal pump 3 and a hydrodynamic cavitation reactor 4. The bottom of the water storage tank 1 is connected with a liquid inlet of the centrifugal pump 3, and a flow control valve V is arranged on the connecting pipeline1. The liquid outlet of the centrifugal pump 3 is connected with the upper part of the water storage tank 1 through a bypass pipeline on one hand, and is connected with the inlet (see a wastewater inlet 7 in fig. 2) of the hydrodynamic cavitation reactor 4 through a main pipeline on the other hand, and the outlet (see a water outlet 14 in fig. 2) of the hydrodynamic cavitation reactor 4 is connected with the upper part of the water storage tank 1. A flow control valve V is arranged on the bypass pipeline2The inlet end and the outlet end of the hydrodynamic cavitation reactor 4 are respectively provided with a flow control valve V 3And a flow control valve V4And a vortex flowmeter 5 is arranged on a connecting pipeline between the outlet of the hydraulic cavitation reactor 4 and the water storage tank 1. A piezoelectric pressure sensor P is arranged at the liquid outlet of the centrifugal pump 31The inlet and outlet of the hydrodynamic cavitation reactor 4 are respectively provided with a piezoelectric pressure sensor P2And P3. The periphery of the water storage tank 1 is provided with a temperature adjusting and controlling device 2, the temperature adjusting and controlling device 2 adopts a refrigerating system in the prior art, and the outer side of the water storage tank 1 is provided with a thermometer T1The temperature is controlled not to be too high and is kept at 25 +/-1 ℃. Flowmeter 5, thermometer T1And each pressure sensor is connected with the data acquisition unit 6. A catalyst chamber 12 is arranged in the hydrodynamic cavitation reactor 4.
The device operates in a closed-loop recirculation mode, the centrifugal pump 3 provides pressure for the device, the hydrodynamic cavitation reactor 4 is used for generating cavitation reaction, the bypass pipeline and the control valve V1For controlling the liquid flow of the main line, a control valve V2Remains open until the centrifugal pump 3 reaches its maximum speed, and then the control valve V is actuated2Fully or partially closed to achieve the desired pressure at the inlet of hydrodynamic cavitation reactor 4. The ends of the main and bypass lines are inserted below the level of the internal liquid of the tank 1 to prevent the introduction of gas (air) into the liquid due to the sudden drop of the liquid jet. The pressure sensors are respectively used for measuring the outlet pressure of the centrifugal pump 3, the inlet pressure of the hydrodynamic cavitation reactor 4 and the outlet pressure of the hydrodynamic cavitation reactor 4. The water storage tank 1 has a capacity of 200L and the inner diameter of the pipe used is 3 8mm and an outer diameter of 40 mm.
The structure of the hydrodynamic cavitation reactor 4 is shown in fig. 2, and comprises a stator 11, a rotating shaft 8 and a catalyst chamber 12, wherein the stator 11 is a closed hollow chamber with end covers 9 at two ends, the end covers 9 at two ends are provided, a wastewater inlet 7 and a wastewater outlet 13 are respectively arranged on the end covers 9, cavitation holes 4 are distributed on the inner wall of the stator 11, and the cavitation holes 4 are blind holes. The ratio of the diameter to the depth of the cavitation holes is 2:5, the optimal diameter is 20mm, and the depth is 50 mm. A rotating shaft 8 is installed in the stator 11, a catalyst chamber 6 is arranged on the rotating shaft 8, and the distance between the outer edge of the catalyst chamber 6 and the outer end of the cavitation hole 4 is 4-8 mm.
Fig. 3 shows the internal structure of the catalyst chamber 12, which is a cylinder with openings at two ends, radial iron blades 14 are distributed in the cylinder, 16 iron blades 14 are arranged, the length of the iron blades is consistent with the length of the cylinder, the width of the iron blades is 15mm, and the thickness of the iron blades is 1 mm. The iron blades are distributed with through holes 15, the inner diameter of each through hole 15 is 1-3mm, and the through holes are distributed on the blades in 3 rows and 10 rows, so that cavitation effect is generated, and further wastewater is degraded.
The process of degrading unsymmetrical dimethylhydrazine wastewater by the system is as follows.
First, some experiments were conducted to investigate the effect of the hydrodynamic cavitation reactor on the degradation of unsymmetrical dimethylhydrazine. 150L of fresh deionized water was filled into the storage tank and the pH was adjusted to 3 by the appropriate amount of dilute hydrochloric acid solution. And (3) opening the centrifugal pump 3, collecting a first sample, properly diluting the collected sample, analyzing the content of iron generated in the hydrodynamic cavitation reactor 4, obtaining that the total dissolved iron content is increased all the time, and then carrying out an experiment by using 150L of unsymmetrical dimethylhydrazine-containing solution, wherein the content of the unsymmetrical dimethylhydrazine is 5 mL/L. The pH was chosen to be 3, the cycle time 120 minutes, and the inlet pressure (P) of the cavitation reactor 2) 5.5bar, outlet pressure (P)3) 1bar was used as a suitable condition for investigating the effect of degradation. According to experiments, the oxidation rate is relatively high and the degradation efficiency of unsymmetrical dimethylhydrazine is also high under the condition.
Then, injecting the waste water containing unsymmetrical dimethylhydrazine into a water storage tank 1, opening a centrifugal pump 3, pressing the waste water into a hydraulic cavitation reactor 4 on a main pipeline by using pressure, and entering hydraulic powerThe waste water flow of the cavitation reactor 4 is 1.5-4.5m3H is used as the reference value. The waste water generates cavitation reaction in the hydrodynamic cavitation reactor 4 to generate cavitation bubbles, the aim of degrading the unsymmetrical dimethylhydrazine waste water is achieved by utilizing the energy released from the cavitation bubbles in the process from generation to collapse, an iron blade 14 is used as a heterogeneous catalyst in a catalyst chamber 12 to enhance the generation of hydroxyl free radicals, and the unsymmetrical dimethylhydrazine is removed from the waste water. And degrading the unsymmetrical dimethylhydrazine wastewater for multiple times in a closed loop circulation mode to finally enable the wastewater to reach the discharge standard for discharge.
Claims (9)
1. An integrated system for inducing advanced oxidative degradation of unsymmetrical dimethylhydrazine wastewater by hydrodynamic cavitation is characterized in that: the device comprises a water storage tank, a water pump and a hydrodynamic cavitation reactor, wherein the bottom of the water storage tank is connected with a liquid inlet of the water pump, a liquid outlet of the water pump is connected with the upper part of the water storage tank through a bypass pipeline on the one hand, and is connected with an inlet of the hydrodynamic cavitation reactor through a main pipeline on the other hand, an outlet of the hydrodynamic cavitation reactor is connected with the upper part of the water storage tank, and a catalyst chamber is arranged in the.
2. The integrated system for inducing high-grade oxidative degradation of unsymmetrical dimethylhydrazine wastewater by hydrodynamic cavitation as claimed in claim 1, wherein a flow control valve V is arranged on a connecting pipeline between the bottom of the water storage tank and the liquid inlet of the water pump1(ii) a A flow control valve V is arranged on the bypass pipeline2(ii) a One end of an inlet and one end of an outlet of the hydrodynamic cavitation reactor are respectively provided with a flow control valve V3And a flow control valve V4。
3. The integrated system for inducing advanced oxidative degradation of unsymmetrical dimethylhydrazine wastewater by hydrodynamic cavitation as claimed in claim 1, wherein pressure sensors are disposed at the outlet of the water pump and the inlet and outlet of the hydrodynamic cavitation reactor.
4. The integrated system for the hydrodynamic cavitation induced advanced oxidative degradation of unsymmetrical dimethylhydrazine wastewater as claimed in claim 1, wherein a temperature adjusting and controlling device is arranged on the water storage tank to control and adjust the temperature in the water storage tank to 25 ± 1 ℃.
5. The integrated system for inducing advanced oxidative degradation of unsymmetrical dimethylhydrazine wastewater according to the hydrodynamic cavitation of the claim 1, wherein the hydrodynamic cavitation reactor comprises a stator, a rotating shaft and a catalyst chamber, the stator is a closed cavity, both ends of the stator are respectively provided with a wastewater inlet and a wastewater outlet, cavitation holes are distributed on the inner wall of the stator, the cavitation holes are blind holes, the rotating shaft is installed in the stator, and the catalyst chamber is installed on the rotating shaft.
6. The integrated system for the hydrodynamic cavitation induced advanced oxidative degradation of unsymmetrical dimethylhydrazine wastewater as claimed in claim 5, wherein the ratio of the diameter to the depth of the cavitation holes is 2: 5.
7. The integrated system for inducing advanced oxidative degradation of unsymmetrical dimethylhydrazine wastewater by hydrodynamic cavitation as claimed in claim 5, wherein the cavitation holes have a diameter of 20mm and a depth of 50mm, and the distance from the outer edge of the catalyst chamber to the outer end of the cavitation holes is 4-8 mm.
8. The integrated system for inducing advanced oxidative degradation of unsymmetrical dimethylhydrazine wastewater by hydrodynamic cavitation as claimed in claim 5, wherein the catalyst chamber is a cylinder with two open ends, and iron blades are distributed in the cylinder.
9. The integrated system for inducing advanced oxidative degradation of unsymmetrical dimethylhydrazine wastewater by hydrodynamic cavitation as claimed in claim 9, wherein the iron blades are distributed with through holes, the inner diameter of which is 1-3 mm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008132681A2 (en) * | 2007-04-26 | 2008-11-06 | Resource Ballast Technologies (Proprietary) Limited | Water treatment system |
| US20120124894A1 (en) * | 2004-09-13 | 2012-05-24 | Donnelly Joseph L | Enclosed rotor-based cavitational and catalytic flow-through reaction chamber |
| CN107244709A (en) * | 2017-07-31 | 2017-10-13 | 核工业理化工程研究院 | A kind of single impeller rotary vane Hydrodynamic cavitation generating means and Hydrodynamic cavitation process |
| CN111807497A (en) * | 2020-07-31 | 2020-10-23 | 山东大学 | Antibiotic waste water degree of depth degradation device based on hydrodynamic cavitation |
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2020
- 2020-12-11 CN CN202011439437.7A patent/CN112723517A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120124894A1 (en) * | 2004-09-13 | 2012-05-24 | Donnelly Joseph L | Enclosed rotor-based cavitational and catalytic flow-through reaction chamber |
| WO2008132681A2 (en) * | 2007-04-26 | 2008-11-06 | Resource Ballast Technologies (Proprietary) Limited | Water treatment system |
| CN107244709A (en) * | 2017-07-31 | 2017-10-13 | 核工业理化工程研究院 | A kind of single impeller rotary vane Hydrodynamic cavitation generating means and Hydrodynamic cavitation process |
| CN111807497A (en) * | 2020-07-31 | 2020-10-23 | 山东大学 | Antibiotic waste water degree of depth degradation device based on hydrodynamic cavitation |
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