CN112028216A - Continuous wastewater treatment method and device based on microwave-assisted catalytic oxidation - Google Patents
Continuous wastewater treatment method and device based on microwave-assisted catalytic oxidation Download PDFInfo
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- 239000002351 wastewater Substances 0.000 claims abstract description 60
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- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/302—Treatment of water, waste water, or sewage by irradiation with microwaves
-
- 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
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- 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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
- C02F2201/007—Modular design
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a continuous wastewater treatment method based on microwave-assisted catalytic oxidation and a device thereof, wherein a rotatable roller is used for bearing a plurality of support plates with catalyst carriers, part of the roller is soaked in wastewater, and part of the roller is continuously irradiated under the action of microwaves, so that the catalyst carriers on each support plate are continuously switched between the functions of soaking the wastewater, adsorbing organic matters and performing microwave-assisted catalytic oxidation, thereby realizing the catalytic oxidation treatment of the wastewater. The invention can carry out continuous microwave-assisted catalytic oxidation treatment on the pharmaceutical and chemical wastewater, effectively improve the wastewater treatment efficiency and greatly reduce the COD content in the wastewater.
Description
Technical Field
The invention relates to a continuous wastewater treatment method and device based on microwave-assisted catalytic oxidation, and belongs to the technical field of wastewater treatment.
Background
With the development of the pharmaceutical chemical industry in China, the pharmaceutical chemical industry is also a typical heavy pollution industry in China. According to investigation, most production processes in the pharmaceutical and chemical industry relate to a plurality of links such as synthesis, extraction, distillation and the like, and a large amount of organic matters such as solvents, auxiliaries, catalysts and the like are introduced in the production process, so that the production wastewater has the characteristics of complex pollutant components, high content of toxic and harmful substances, high salt content of partial wastewater, high content of ammonia nitrogen and organic nitrogen and the like, and great difficulty is brought to the treatment of the wastewater.
Chemical synthetic pharmaceuticals are processes for preparing drugs or intermediates from organic or inorganic raw materials by chemical reactions, and include pure chemical synthetic pharmaceuticals and semi-synthetic pharmaceuticals. The amount of waste water generated in the production process is small, but the concentrations of residual reactants, products, solvents, catalysts and the like are high, and the COD concentration value can reach hundreds of thousands of mg/L; wherein, some residual raw materials or products such as phenolic compounds, aniline compounds, heavy metals, benzene series, halogenated hydrocarbon solvents and the like have obvious biological toxicity.
Generally, for the treatment of COD, the method of air floatation combined with catalytic oxidation is adopted to degrade organic matters in wastewater, thereby reducing the content of COD in wastewater.
The microwave refers to ultrahigh frequency electromagnetic wave with the frequency of 300MHz to 300GHz and the wavelength of 1mm to 1 m. In recent years, microwave technology has attracted more and more attention in the field of environmental protection, especially in the research of treating refractory substances therein, because of the advantages of selective heating, rapidness, high efficiency, small equipment volume, no secondary pollution, energy conservation, cleanness, simple operation conditions and the like. At present, the microwave technology is mainly applied to three modes of wastewater treatment: the first method is that absorbing the pollutant in the waste water by the absorbing material, then taking out the absorbing material and placing it in the microwave field for radiation, so as to degrade the absorbed pollutant; the second is directly using microwave radiation to carry out degradation treatment on the polluted solution containing (or not containing) wave-absorbing materials; the third is the use in combination with other techniques (e.g., photocatalysis, homogeneous oxidation, etc.). The third method needs to be matched with a photocatalytic technology, so that the current technology is not mature, generally stays in a laboratory stage in the aspect of wastewater treatment, and is rarely used for industrial treatment. The first and second methods are also commonly used.
The first method is to put wave-absorbing material into the reaction vessel containing waste water for pre-adsorption, then radiate the waste water with microwave to make the organic matter adsorbed on the wave-absorbing material undergo the process of strong catalytic oxidation, then load the waste water again after the completion, stop the microwave to wait for adsorption, and then restart the microwave for treatment, i.e. the whole process is discontinuous and the efficiency is relatively low. And because the existing wave-absorbing materials are all filled in a heap mode, and the radiation penetration capacity of microwaves is limited, the catalytic oxidation process is not particularly efficient in the deep liquid level. For example, chinese invention CN201810806093.5 discloses a device and a method for microwave catalytic oxidation treatment of refractory organic wastewater, which is a typical adsorption-treatment-regeneration process, and the method improves the structure of the reaction vessel to increase the treatment efficiency, thereby further enabling the reaction vessel to withstand higher temperature, and further improving the treatment efficiency by increasing the microwave power. However, this method still needs to adopt intermittent microwave treatment, and the utilization rate of microwave equipment is not high, and the relative treatment efficiency is low.
The second method has the biggest problem that the wave-absorbing material needs to be uniformly mixed with the wastewater, and the wave-absorbing material needs to be made into powder to achieve the required effect. In order to recover the wave-absorbing material, a certain solid-liquid separation technology is required to support, and the requirement on separation equipment is high. The Chinese patent application with the application number of 201711375971.4 discloses a method for treating wastewater by self-circulation microwave catalytic oxidation, which adopts a trapped pulse separator to separate catalysts, and achieves the aim of continuous treatment, but the treatment efficiency is limited by the separation efficiency of the trapped pulse separator.
Disclosure of Invention
The invention aims to provide a continuous wastewater treatment method and a continuous wastewater treatment device based on microwave-assisted catalytic oxidation. The invention can carry out continuous microwave-assisted catalytic oxidation treatment on the pharmaceutical and chemical wastewater, effectively improve the wastewater treatment efficiency and greatly reduce the COD content in the wastewater.
The technical scheme of the invention is as follows: a continuous wastewater treatment method based on microwave-assisted catalytic oxidation is characterized by comprising the following steps: the rotatable roller is used for bearing a plurality of supporting plates with catalyst carriers, one part of the roller is soaked in the wastewater, the other part of the roller continuously irradiates under the action of microwaves, and the roller is rotated to continuously switch the catalyst carriers on each supporting plate between the functions of soaking the wastewater, adsorbing organic matters and assisting the catalytic oxidation by microwaves, so that the catalytic oxidation treatment of the wastewater is realized.
In the continuous wastewater treatment method based on microwave-assisted catalytic oxidation, one end of the roller continuously irradiating microwaves is positioned above the wastewater liquid level, so that the catalyst carrier is only carried with a small amount of moisture when irradiating microwaves, the power of the microwaves can be fully utilized, and the temperature of the catalyst carrier can be rapidly increased under the action of the microwaves, thereby improving the catalytic oxidation efficiency. Compared with the method of directly irradiating the microwaves in the wastewater, the method can ignore the microwave penetrability, ensure the effectiveness of the microwave action and fully utilize the microwave power.
In the continuous wastewater treatment method based on microwave-assisted catalytic oxidation, in order to improve the treatment capacity, the wastewater reaction container is divided into a plurality of areas, and the rollers and the microwave generating devices are respectively arranged to perform multistage catalytic oxidation treatment, so that the wastewater inlet flow can be increased, and the final treatment effect is achieved by means of multistage catalytic oxidation.
In the continuous wastewater treatment method based on microwave-assisted catalytic oxidation, in order to fully utilize energy, wastewater subjected to catalytic oxidation treatment is transferred to a wastewater inlet end for heat exchange, on one hand, the wastewater entering the treatment is preheated, so that the power requirement of the catalytic oxidation on microwaves is reduced, on the other hand, the temperature of the discharged wastewater is reduced, and the next biochemical treatment is facilitated.
The continuous wastewater treatment device for realizing the method is characterized in that: the device comprises an oxidation pond, wherein a roller is arranged in the oxidation pond, supporting plates with catalyst carriers are uniformly distributed on the roller, a microwave generator is arranged above the roller, and an oxidant releasing pipe is arranged below the roller; the front side of the oxidation pond is provided with a preheating pond, the rear side of the oxidation pond is provided with an overflow trough, and the overflow trough is connected with a water outlet pipe; a waste water inlet pipe is arranged on the front side of the preheating tank; the bottom of the preheating tank is provided with an overflowing hole communicated to the oxidation tank; the preheating tank is internally provided with a heat exchange tube, the lower end of the heat exchange tube is provided with a diversion cavity communicated to the water outlet pipe, and the upper end of the heat exchange tube is provided with a converging cavity communicated to the liquid discharge pipe.
In the continuous wastewater treatment device, the number of the rollers is two or more, a baffle groove is arranged in front of each roller, the baffle groove consists of a short baffle plate at the front side and a high baffle plate at the rear side, and an overflowing hole is formed in the lower side of the high baffle plate; a microwave generator and an oxidant releasing pipe are respectively arranged above and below each roller.
In the continuous wastewater treatment apparatus, the oxidant release pipe is connected to the ozone pipe and the second manifold pipe through the first manifold pipe, and the second manifold pipe is connected to the air pipe and the water pipe.
In the continuous wastewater treatment apparatus, the catalyst carrier on the support plate is activated carbon; the support plate is composed of two clamping plates with meshes, and the catalyst carrier is arranged between the two clamping plates.
In the continuous wastewater treatment apparatus, the catalyst on the catalyst support is a metal salt. The metal salt may be a hydrochloride, nitrate or sulfate of a transition metal such as iron, cobalt, nickel, manganese, cadmium, vanadium, copper or zinc, and among them, iron, copper or manganese is more preferable.
In the continuous wastewater treatment device, the oxidation tank and the preheating tank are both composed of a tank body and a cover body, and the tank body and the cover body are both coated with heat-insulating material layers.
Compared with the prior art, the invention utilizes the rotary roller to bear the catalyst carrier, so that the catalyst carrier can be alternately in waste water and under microwave, the adsorption and catalytic oxidation desorption time of the catalyst carrier can be fully given, and the microwave generator can continuously work the catalyst carrier continuously overturned to the irradiation position, thereby improving the utilization rate of the microwave generator and further improving the catalytic oxidation efficiency of the waste water. Moreover, the microwave catalytic oxidation object of the invention is an organic matter adsorbed on a catalyst carrier, the surface of the organic matter only has a part of carried water film, the microwave barrier effect can be ignored, the effectiveness of the microwave effect can be guaranteed, and the microwave power can be fully utilized, therefore, the microwave power consumption of the invention can be lower on the premise of the same wastewater treatment capacity. Therefore, the invention can greatly reduce the COD content in the wastewater under lower power consumption.
Drawings
FIG. 1 is a schematic diagram of a top view of the present invention;
fig. 2 is a schematic view of the internal structure of the present invention.
Detailed Description
The invention is further illustrated by the following figures and examples, which are not to be construed as limiting the invention.
Examples are given. A continuous type wastewater treatment device is structurally shown in figures 1 and 2: the device comprises an oxidation pond 1, wherein a roller 2 is arranged in the oxidation pond 1, supporting plates 3 with catalyst carriers are uniformly distributed on the roller 2, a microwave generator 4 is arranged above the roller 2, and an oxidant release pipe 5 is arranged below the roller 2; a preheating tank 6 is arranged on the front side of the oxidation tank 1, an overflow tank 7 is arranged on the rear side of the oxidation tank, and a water outlet pipe 8 is connected to the overflow tank 7; a waste water inlet pipe 9 is arranged on the front side of the preheating tank 6; the bottom of the preheating pool 6 is provided with an overflowing hole communicated to the oxidation pool 1; a heat exchange tube 10 is arranged in the preheating pool 6, a shunting cavity 11 communicated to the water outlet tube 8 is arranged at the lower end of the heat exchange tube 10, and a converging cavity 12 communicated to the liquid discharge tube 13 is arranged at the upper end of the heat exchange tube 10. The number of the rollers 2 is two or more (2 are taken as an example in the embodiment), a diversion groove 14 is arranged in front of each roller 2, the diversion groove 14 consists of a short baffle on the front side and a high baffle on the rear side, and an overflowing hole is formed in the lower side of the high baffle; a microwave generator 4 and an oxidant discharge pipe 5 are provided above and below each drum 2, respectively. The oxidant discharge pipe 5 is connected to an ozone pipe 16 and a second manifold 17 through a first manifold 15, and the second manifold 17 is connected to an air pipe 18 and a water pipe 19. The catalyst carrier on the support plate 3 is activated carbon; the support plate 3 is composed of two clamp plates with meshes, and the catalyst carrier is arranged between the two clamp plates. The catalyst on the catalyst support is a metal salt. The oxidation tank 1 and the preheating tank 6 are both composed of a tank body and a cover body, and the tank body and the cover body are both coated with heat-insulating material layers.
The working principle of the embodiment is as follows: wastewater enters the oxidation pond 1 from the bottom through the preheating pond 6 from the wastewater inlet pipe 9, and is heated by the heat exchange pipe 10 in the process that the wastewater passes through the preheating pond 6; air and ozone are mixed with water in advance, then enter the oxidation tank 1 through the oxidant releasing pipe 5, and are fully mixed with the wastewater in a floating and roller-matched stirring manner; the part of the roller below the wastewater level adsorbs organic matters of the catalyst carrier, and the part carries the organic matters, the catalyst carrier and moisture rich in oxidant, and is rapidly heated, catalytically oxidized and desorbed by the microwave irradiation; the wastewater after the primary treatment can pass through the diversion trench 14 for secondary microwave treatment; the waste water after two-stage treatment has relatively high temperature and is sent to the heat exchange tube 10 of the preheating tank 6 to be used as a heat source, and after passing through the preheating tank 6, the temperature of the waste water is sharply reduced and can be sent to a biochemical tank for further treatment.
Examples of the experiments.
Experimental apparatus:
an oxidation pond: processing capacity 300L/h, model size: 800X 400X 800 mm.
Preheating a pool: processing capacity 300L/h, model size: 200X 400X 800 mm.
Roller: the number is 2, the diameter is 350mm, the width is 360mm, and the rotating speed is 1.5 r/min.
A support plate: number 10 × 2, model size: 360mm by 90mm by 50 mm;
catalyst carrier: activated carbon, 35mm in thickness;
catalyst: copper sulfate, in the form of 0.6mol/L solution, soaked in activated carbon and dried to be fixed on the activated carbon.
A microwave generator: number 2 × 2, power 1500 watts.
Oxidizing agent: the mol ratio of the ozone to the wastewater is 0.15: 10; the molar ratio of air to wastewater was 0.5: 10.
A source of wastewater: is taken from wastewater after desolventizing and desalting of pharmaceutical and chemical enterprises in Zhejiang.
The experiments are shown in the following table.
As can be seen from the table above, the device of the invention can basically complete about 80% of COD removal rate of the wastewater with high concentration COD, and has remarkable effect. The main reason for slight decrease of the subsequent COD removal rate is that factors such as porosity decrease of activated carbon, catalyst falling and the like are caused, and the catalyst carrier is replaced. In addition, the temperature of the wastewater treated by the device is not obviously increased, and the discharged water can enter a biochemical pool for treatment without further temperature reduction, which shows that the microwave is discharged from the system in a heat energy mode with less power consumption, and the energy utilization rate of the system is higher.
Claims (10)
1. A continuous wastewater treatment method based on microwave-assisted catalytic oxidation is characterized by comprising the following steps: the rotatable roller is used for bearing a plurality of supporting plates with catalyst carriers, one part of the roller is soaked in the wastewater, the other part of the roller continuously irradiates under the action of microwaves, and the roller is rotated to continuously switch the catalyst carriers on each supporting plate between the functions of soaking the wastewater, adsorbing organic matters and assisting the catalytic oxidation by microwaves, so that the catalytic oxidation treatment of the wastewater is realized.
2. A continuous wastewater treatment method based on microwave-assisted catalytic oxidation according to claim 1, characterized in that: the end of the roller continuously irradiating the microwave action is positioned above the liquid level of the wastewater, so that the catalyst carrier only carries a small amount of moisture when irradiating the microwave action, the power of the microwave can be fully utilized, and the catalyst carrier can be rapidly heated under the microwave action, thereby improving the catalytic oxidation efficiency.
3. A continuous wastewater treatment method based on microwave-assisted catalytic oxidation according to claim 1, characterized in that: the wastewater reaction container is divided into a plurality of areas, and a roller and a microwave generating device are respectively arranged to carry out multi-stage catalytic oxidation treatment.
4. A continuous wastewater treatment method based on microwave-assisted catalytic oxidation according to claim 1, characterized in that: the wastewater after catalytic oxidation treatment is transferred to a wastewater inlet end for heat exchange, so that the wastewater entering the treatment is preheated on one hand, the power requirement of the catalytic oxidation on microwaves is reduced, and the temperature of the discharged wastewater is reduced on the other hand, thereby facilitating the next biochemical treatment.
5. A continuous wastewater treatment system for carrying out the method according to any one of claims 1 to 4, characterized in that: the device comprises an oxidation pond (1), wherein a roller (2) is arranged in the oxidation pond (1), supporting plates (3) with catalyst carriers are uniformly distributed on the roller (2), a microwave generator (4) is arranged above the roller (2), and an oxidant release pipe (5) is arranged below the roller (2); a preheating tank (6) is arranged on the front side of the oxidation tank (1), an overflow tank (7) is arranged on the rear side of the oxidation tank, and a water outlet pipe (8) is connected to the overflow tank (7); a waste water inlet pipe (9) is arranged on the front side of the preheating tank (6); the bottom of the preheating tank (6) is provided with an overflowing hole communicated to the oxidation tank (1); a heat exchange tube (10) is arranged in the preheating pool (6), a shunting cavity (11) communicated to the water outlet tube (8) is formed in the lower end of the heat exchange tube (10), and a converging cavity (12) communicated to the liquid discharge tube (13) is formed in the upper end of the heat exchange tube (10).
6. A continuous wastewater treatment apparatus according to claim 5, characterized in that: the number of the rollers (2) is two or more, a diversion groove (14) is arranged in front of each roller (2), the diversion groove (14) consists of a short baffle plate on the front side and a high baffle plate on the rear side, and an overflowing hole is formed in the lower side of the high baffle plate; a microwave generator (4) and an oxidant releasing pipe (5) are respectively arranged above and below each roller (2).
7. A continuous wastewater treatment apparatus according to claim 6, characterized in that: the oxidant releasing pipe (5) is connected with an ozone pipe (16) and a second collecting pipe (17) through a first collecting pipe (15), and the second collecting pipe (17) is connected with an air pipe (18) and a water pipe (19).
8. A continuous wastewater treatment apparatus according to claim 5, characterized in that: the catalyst carrier on the support plate (3) is activated carbon; the support plate (3) is composed of two clamp plates with meshes, and the catalyst carrier is arranged between the two clamp plates.
9. A continuous wastewater treatment apparatus according to claim 8, characterized in that: the catalyst on the catalyst support is a metal salt.
10. A continuous wastewater treatment apparatus according to claim 5, characterized in that: the oxidation pond (1) and the preheating pond (6) are both composed of a pond body and a cover body, and the outside of the pond body and the cover body are both coated with heat-insulating material layers.
Priority Applications (1)
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| CN114031168A (en) * | 2021-11-22 | 2022-02-11 | 山东省科学院能源研究所 | Method and device for continuously treating high-concentration organic wastewater by using multistage rotating wheel |
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