CN115340232A - Organic wastewater treatment device and method - Google Patents
Organic wastewater treatment device and method Download PDFInfo
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- 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
- C02F1/722—Oxidation by peroxides
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- 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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- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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Abstract
The invention discloses an organic wastewater treatment device and method, and belongs to the technical field of wastewater treatment. The device comprises a static mixer, a main reaction zone, a side reaction zone and a coagulation sedimentation zone; the main reaction zone, the secondary reaction zone and the coagulation sedimentation zone are sequentially separated by a partition plate; the static mixer is provided with a water inlet pipe and a medicament adding port; a catalyst packed bed and an ultrasonic vibration rod are arranged in the main reaction zone; the bottom of the main reaction zone is provided with a microporous aeration head; the top of the device is provided with an air outlet. When the device disclosed by the invention is used for treating organic wastewater, the iron-carbon particle catalyst catalyzes and activates hydrogen peroxide to form a Fenton-like reaction; the iron-carbon micro-electrolysis effect exists in the iron-carbon; meanwhile, the ultrasonic wave can be used for enhancing the catalytic activation process of the reaction and relieving the surface passivation of the iron-carbon activating agent, thereby shortening the retention time and accelerating the degradation and mineralization of the wastewater; the device of the invention can remove COD in the organic wastewater by more than 90%.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to an organic wastewater treatment device and method.
Background
In the traditional treatment process of industrial wastewater (coal chemical wastewater, printing and dyeing wastewater, pharmaceutical wastewater and the like), effluent still contains a large amount of refractory organic pollutants, and the national relevant water quality requirements are difficult to meet. Fenton reaction (Fenton) is an early technique to achieve industrial applications in advanced oxidation technologies (AOPs). AOPs have been developed rapidly because they can generate active radicals (HO, etc.) with high reactivity and high redox ability to rapidly and thoroughly degrade organic substances and mineralize active pollutants. However, the conventional Fenton system can only operate effectively at a low pH value, a large amount of iron-containing sludge is generated, post-treatment is needed, the treatment cost is increased, and the mineralization degree of organic matters is not high. Thus, improved Fenton oxidation processes have been developed. The heterogeneous Fenton catalyst can be used for overcoming the defects and forming a Fenton-like reaction, for example, an iron-based catalyst comprises zero-valent iron, iron oxide, iron-carbon and the like. However, during the catalysis/activation reaction, the surface is passivated, e.g. by forming Fe 3+ The oxide layer is compact, and the Fenton-like catalysis/activation efficiency is reduced. The physical field assisted catalysis/activation, such as optical, electrical, acoustic, etc., has already formed an application trend, wherein the acoustic catalysis mainly utilizes the interaction of the ultrasonic wave and the medium in the transmission process to cause the medium to generate physical or chemical changes, and generates acoustic effects, which mainly include mechanical effects, thermal effects, cavitation effects and secondary effects caused by the mechanical effects. Wherein the ultrasonic action is convenient and clean without secondary pollution, and can effectively clean the heterogeneous activator surface oxidation layer, keep the activator effectively contacted with the liquid phase, and improve the generation amount and the speed of Reactive Oxidative Species (ROS), thereby improving the utilization rate of the oxidant, reducing the cost and shortening the retention timeIn the meantime, the degradation and mineralization of the wastewater are accelerated, and an acoustic catalysis Fenton reaction system needs to be designed on the basis of establishing a novel heterogeneous Fenton reaction system which can be used for treating the refractory organic wastewater so as to meet the requirement of treating the polluted wastewater in various complex and more practical scenes.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an organic wastewater treatment device and method.
In order to realize the purpose, the invention provides the following technical scheme:
the invention provides an organic wastewater treatment device, which comprises a static mixer, a main reaction zone, an auxiliary reaction zone and a coagulation sedimentation zone, wherein the main reaction zone is communicated with the main reaction zone; the outlet of the static mixer is connected with the inlet of the main reaction zone; the main reaction zone, the secondary reaction zone and the coagulation sedimentation zone are sequentially separated by a partition plate; the static mixer is provided with a water inlet pipe and a medicament adding port; a catalyst packed bed and an ultrasonic vibration rod are arranged in the main reaction zone; the bottom of the main reaction zone is provided with a microporous aeration head; the top of the device is provided with an air outlet;
one end of the ultrasonic vibration rod is connected with the ultrasonic generator, and the other end of the ultrasonic vibration rod is inserted into the catalyst packed bed;
the microporous aeration head is connected with a gas generator through an air inlet pipe.
Further, the number of the microporous aeration heads is more than or equal to 1; the number of the ultrasonic vibration rods is more than or equal to 1.
Furthermore, a baffle plate is arranged in the middle of the side reaction zone.
Furthermore, the side reaction zone is also provided with a secondary dosing port.
Further, a water outlet is formed in the bottom of the coagulation sedimentation area.
Further, the catalyst packed bed is filled with iron-carbon particle catalyst.
Further, copper is also doped into the iron-carbon particle catalyst.
The invention also provides a method for treating organic wastewater by adopting the organic wastewater treatment device, which comprises the following steps: organic wastewater to be treated enters a static mixer through a water inlet pipe, a reagent consisting of a hydrogen peroxide solution and a pH regulator is added into the static mixer through a reagent adding port, and after being mixed with the organic wastewater, the organic wastewater enters a main reaction zone through an inlet of the main reaction zone and gradually overflows into a catalyst packed bed, a gas generator and an ultrasonic generator are opened, aeration is carried out through a microporous aeration head, and an ultrasonic catalytic reaction is carried out in the area of the catalyst packed bed; the wastewater in the main reaction zone enters the auxiliary reaction zone through overflow to continue subsequent reaction, and then enters the coagulation sedimentation zone through overflow to perform coagulation sedimentation.
Further, the concentration of the hydrogen peroxide solution is 10-14 mL/L; the pH regulator regulates the pH of the system to 3-4; the frequency of the ultrasonic generator is 20-200 kHz; the gas flow rate of aeration is 0.2-0.8L/min; the gas comprises nitrogen, air or ozone.
Gas is introduced into a reaction system, so that a pneumatic stirring function can be provided, bubbles can synergistically promote ultrasonic cavitation, and meanwhile, an oxidizing agent can be coupled to enhance the catalytic oxidation effect of the system.
Further, the pH value is adjusted to 8-10 in the coagulation sedimentation process, and PAC and PAM are added.
Further, the PAC is 30% of PAC, and the adding amount is 15mol/L; the PAM is 1 percent of PAM, and the adding amount is 15mL/L.
When the device disclosed by the invention is used for treating organic wastewater, ultrasonic waves have cavitation effect, mechanical effect, thermal effect and the like, and can be beneficial to the degradation of organic matters in the wastewater, the ultrasonic drive iron-carbon activating agent and hydrogen peroxide form a Fenton-like system under a certain condition to generate an active intermediate, so that the polluted wastewater can be deeply treated, and meanwhile, the iron-carbon self has iron-carbon micro-electrolysis effect and can be further coupled to treat the polluted wastewater; the mechanical effect generated by the ultrasonic wave can remove an oxidation layer generated by the passivation of the oxidant in the treatment process of the iron-carbon particle filler, and fresh iron carbon is better contacted with a liquid phase.
Compared with the prior art, the invention has the following beneficial effects:
the invention uses iron-carbon particle catalyst to catalyze and activate hydrogen peroxide to form Fenton-like reaction; the iron and carbon self has an iron and carbon micro-electrolysis effect, so that the polluted wastewater can be further treated in a coupling way; meanwhile, under the ultrasonic assistance effect, the generated sound effect is applied to the process of enhancing the catalytic activation of the reaction, relieving the surface passivation of the iron-carbon activating agent and the like so as to improve the generation amount and the rate of active oxidation species, thereby improving the utilization rate of the oxidant, reducing the cost, shortening the retention time and accelerating the degradation and mineralization of the wastewater.
The method can realize effective treatment of high-concentration organic wastewater difficult to degrade, and the removal rate of COD in the organic wastewater can reach more than 90%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic structural diagram of an organic wastewater treatment device used in the invention, wherein the device comprises a water inlet pipe 1, a medicament adding port 2, a static mixer 3, a main reaction zone 4, a main reaction zone 5, a catalyst packed bed 6, a side reaction zone 7, an air outlet 8, a water outlet 9, an ultrasonic vibration rod 10, an ultrasonic generator 11, a microporous aeration head 12, an air inlet pipe 13, an air generator 14, a partition plate 15, a baffle plate 16, a secondary medicament adding port 17 and a coagulation sedimentation zone 18.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In addition, for numerical ranges in the present disclosure, it is understood that each intervening value, to the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the documents are cited. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. It is intended that the specification and examples be considered as exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
In the following examples, the iron-carbon particulate catalyst and the copper-doped iron-carbon particulate catalyst used were commercially available.
Example 1
The structure of the organic wastewater treatment device used in this example is schematically shown in FIG. 1, and the process of treating organic wastewater by using the device is as follows: organic wastewater to be treated (actual high-concentration toxic refractory organic wastewater with the COD content of 5000 mg/L) enters a static mixer 3 through a water inlet pipe 1, a reagent consisting of a hydrogen peroxide solution (10-14 ml/L) and a pH regulator (2.5 ml/L of sulfuric acid, the concentration of the sulfuric acid is 1;
sequentially opening a gas generator 14 and an ultrasonic generator 11 (the ultrasonic frequency is 28 kHz), and performing effective ultrasonic catalysis on the catalyst packed bed 6 through an ultrasonic vibration rod 10; the gas generator 14 introduces gas into the liquid phase reaction system through the gas inlet pipe 13 and the microporous aerator 12, the gas in this embodiment is nitrogen, the gas flow is 0.5L/min, and the tail gas is discharged from the gas outlet 8, wherein the gas outlet 8 is arranged at the upper parts of the main reaction zone 5 and the secondary reaction zone 7 and is positioned between the main reaction zone 5 and the secondary reaction zone 7;
after organic wastewater is treated for 3 hours in the main reaction zone 5, the organic wastewater overflows from the top of the partition plate 15 and enters the auxiliary reaction zone 7 to continue subsequent reaction, hydrogen peroxide (7.5 mL/L) is supplemented through a secondary dosing port 17 when necessary, the wastewater is baffled twice by a baffle plate 16 in the auxiliary reaction zone 7 to finish the treatment process, the treatment time in the auxiliary reaction zone is 3 hours, then the organic wastewater overflows from the top of the partition plate 15 and enters a coagulation sedimentation zone 18, and Ca (OH) is added into the coagulation sedimentation zone 18 2 (3.6 g/L) adjusting the pH of the system to 9, adding PAC with the concentration of 30% and PAM with the concentration of 1%, wherein the adding amount of the PAC and the PAM is 15mL/L, and discharging water from a water outlet 9 after coagulation and sedimentation for 1-2 h. The COD content of the discharged water is detected, and the removal rate of the COD in the organic wastewater is 85-90 percent according to the embodiment.
Example 2
The difference from example 1 is that the iron-carbon particulate catalyst packed in the catalyst packed bed 6 was replaced with a copper-doped iron-carbon particulate catalyst.
Through detection, the removal rate of COD in the organic wastewater is 90-95% in the embodiment.
As can be seen from the comparison of the COD removal rates of the embodiment 1 and the embodiment 2, after the iron-carbon particle catalyst is doped with copper, the removal rate of COD in the organic wastewater can be improved, because the metal copper is used as the catalyst (equivalent to a cathode), the copper is doped by utilizing the principle of catalyzing the internal electrolysis of iron, so that the potential difference of two poles is increased, the iron corrosion is accelerated, and the surface hardening of the iron-carbon material is slowed down, so that the iron is increasedThe generated iron ions can be helpful to catalyze H while the carbon micro-electrolysis effect is achieved 2 O 2 Generating active species for further processing of organic contaminants; and the ultrasonic effect is matched, so that the catalysis/activation performance of the material can be further improved.
Comparative example 1
The difference from example 1 is that the organic wastewater, the pH adjusting agent and the hydrogen peroxide are mixed in the static mixer 3 and then pass through the main reaction zone 5 only (i.e. the iron-carbon microelectrolysis coupling hydrogen peroxide, and the treatment process of the secondary reaction zone 7 and the coagulation sedimentation zone 18 is omitted).
The result shows that the removal rate of COD in the organic wastewater by the comparative example is only 50-60%.
Comparative example 2
The difference from example 1 is that the organic wastewater, the pH adjusting agent and the hydrogen peroxide solution are mixed in the static mixer 3 and then reacted only in the secondary reaction zone 7, and the iron-carbon particulate catalyst is added to the secondary reaction zone 7, that is, the wastewater is subjected to the operation of the secondary reaction zone 7 only, and the fenton reaction occurs in the secondary reaction zone 7, and the COD content of the water is detected and the COD removal rate is calculated.
The result shows that the removal rate of COD in the organic wastewater is only 10-25% in the comparative example.
Comparative example 3
The difference from example 1 is that the organic wastewater to be treated is subjected to coagulation sedimentation treatment only.
The results show that: the removal rate of COD in the organic wastewater by the comparative example is only 10-20%.
Comparative example 4
The difference from example 1 is that the main reaction zone 5 is directly connected to the coagulation sedimentation zone 18, and the organic wastewater passes through the main reaction zone 5 and is subjected to coagulation sedimentation operation (operation without the secondary reaction zone 7).
The results show that: the removal rate of COD in the organic wastewater by the comparative example is 65-75%.
Comparative example 5
The difference from example 1 is that the organic wastewater to be treated is directly passed through the secondary reaction zone 7, and the Fenton reaction is carried out by adding the iron-carbon particle catalyst in the secondary reaction zone 7, and is subjected to a coagulation sedimentation operation (not passed through the main reaction zone 5, that is, the wastewater is directly introduced into the secondary reaction zone 7).
The results show that: the removal rate of COD in the organic wastewater by the comparative example is 20-35%.
Comparative example 6
The difference from example 1 is that the COD removal rate was calculated by measuring the COD content of the organic wastewater after the treatment in the secondary reaction zone 7 was completed (i.e., the organic wastewater passed through the primary reaction zone 5 and the secondary reaction zone 7 without coagulation sedimentation treatment).
The results show that: the removal rate of COD in the organic wastewater by the comparative example is 60-80%.
The above description is only for the preferred embodiment of the present invention, and the protection scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical scope of the present invention, the technical solution and the inventive concept of the present invention equivalent or change within the technical scope of the present invention.
Claims (9)
1. An organic wastewater treatment device is characterized by comprising a static mixer, a main reaction zone, an auxiliary reaction zone and a coagulation sedimentation zone; the outlet of the static mixer is connected with the inlet of the main reaction zone; the main reaction zone, the secondary reaction zone and the coagulation sedimentation zone are sequentially separated by a partition plate; the static mixer is provided with a water inlet pipe and a medicament adding port; a catalyst packed bed and an ultrasonic vibration rod are arranged in the main reaction zone; the bottom of the main reaction zone is provided with a microporous aeration head; the top of the device is provided with an air outlet;
one end of the ultrasonic vibration rod is connected with an ultrasonic generator, and the other end of the ultrasonic vibration rod is inserted into the catalyst packed bed;
the microporous aeration head is connected with a gas generator through an air inlet pipe.
2. The organic wastewater treatment device according to claim 1, wherein the number of the microporous aeration heads is not less than 1; the number of the ultrasonic vibration rods is more than or equal to 1.
3. The organic wastewater treatment apparatus according to claim 1, wherein a baffle plate is provided in the middle of the secondary reaction zone.
4. The organic wastewater treatment device according to claim 4, wherein the secondary reaction zone is further provided with a secondary dosing port.
5. The organic wastewater treatment device according to claim 1, wherein the bottom of the coagulation sedimentation zone is provided with a water outlet.
6. The organic wastewater treatment apparatus according to claim 1, wherein the catalyst packed bed is packed with an iron-carbon particulate catalyst.
7. A method for treating organic wastewater using the organic wastewater treatment apparatus according to any one of claims 1 to 6, comprising the steps of: organic wastewater to be treated enters a static mixer through a water inlet pipe, a reagent consisting of a hydrogen peroxide solution and a pH regulator is added into the static mixer through a reagent adding port, mixed with the organic wastewater, enters a main reaction zone through an inlet of the main reaction zone, gradually overflows into a catalyst packed bed, a gas generator and an ultrasonic generator are opened, aeration is carried out through a microporous aeration head, and an ultrasonic catalytic reaction is carried out in the region of the catalyst packed bed; the wastewater in the main reaction zone enters the auxiliary reaction zone through overflow to continue subsequent reaction, and then enters the coagulation sedimentation zone through overflow to perform coagulation sedimentation.
8. The method of claim 7, wherein the concentration of the hydrogen peroxide solution is 10 to 14mL/L; the pH regulator regulates the pH of the system to 3-4; the frequency of the ultrasonic generator is 20-200 kHz; the gas flow rate of aeration is 0.2-0.8L/min; the gas comprises nitrogen, air or ozone.
9. The method of claim 7, wherein the pH is adjusted to 8-10 during the coagulation sedimentation process, and PAC and PAM are added.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115771930A (en) * | 2023-02-13 | 2023-03-10 | 天润(山东)生态环境科技有限公司 | Hydrogen peroxide enhanced iron-carbon micro-electrolysis system |
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