CN111807599A - System for treating refractory organic matters through microwave catalysis combined advanced oxidation - Google Patents
System for treating refractory organic matters through microwave catalysis combined advanced oxidation Download PDFInfo
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Abstract
The invention discloses a system for treating refractory organic matters by combining microwave catalysis and advanced oxidation, wherein refractory organic matters to be treated sequentially enter a feeding unit, a microwave catalysis unit, an advanced oxidation unit and a water outlet unit for treatment until the refractory organic matters reach the standard and can be discharged; the system for treating the refractory organic matters by protecting the microwave catalysis and the advanced oxidation comprises a first oxidation degradation treatment unit integrating microwave radiation, catalysis and oxidation, and a second oxidation degradation treatment unit adopting ozone oxidation for advanced oxidation. The degradation treatment efficiency of the refractory organic matters in the industrial pollutants is improved, and the problems of low treatment efficiency, slow reaction rate, strict reaction conditions and the like in the prior art are solved. And the pollution of the discharge of the catalyst to the environment is avoided by recycling and reusing the catalyst. The treatment method has the advantages of simple operation, strong engineering applicability, thorough oxidative degradation of the organic pollutants difficult to degrade, and no secondary pollution.
Description
Technical Field
The invention relates to the technical field of organic wastewater treatment, in particular to a system for treating refractory organic matters by combining microwave catalysis and advanced oxidation.
Background
The total discharge amount of industrial wastewater in China is continuously reduced for four years, but the water quantity base number of the wastewater in China is still very large, the wastewater treatment efficiency is low, and the improvement of the treatment efficiency of the industrial wastewater becomes a key problem to be urgently solved in the field of industrial wastewater.
The main pollutant in the industrial wastewater is refractory organic matter which is mainly produced by chemical production of petrochemical industry, papermaking, dyes and the like, and the industrial wastewater has the advantages of complex structure and components, strong biotoxicity, difficult degradation, long-term residue and biological accumulation, and can seriously harm human health and influence ecological environment. Therefore, the problem of degradation treatment of organic matters difficult to degrade is directly related to the sustainable development of the economic health of China and also related to the quality and health level of the public. The prior art generally adopts physical methods such as a gravity precipitation method, an air floatation method, a filtration method and the like, and adopts a plurality of methods for combined treatment and sectional treatment when chemically and biologically treating the waste water containing the refractory organic matters. But the physical method mainly purifies materials containing large suspended particles or oils, sand and the like; chemical methods such as coagulation and redox methods mainly select chemical agents and addition amount, and have obvious risk of secondary pollution; biological methods such as aerobic biological methods and anaerobic biological methods, which utilize microorganisms for wastewater treatment, maintain the continuous activity of the microorganisms, but are not suitable for oily wastewater. The treatment method in the prior art has the defects of low degradation efficiency, slow reaction rate, high requirement on reaction conditions, easy generation of secondary pollution and the like.
Therefore, with the development of the treatment work of the wastewater containing refractory organic matters and the improvement of strict wastewater standard and supervision of China, how to form an industrial wastewater treatment method which has high degradation efficiency, high reaction rate, mild reaction conditions and no secondary pollution is a problem to be solved urgently in the field of industrial wastewater treatment at present.
Disclosure of Invention
The invention provides a system for treating refractory organic matters by combining microwave catalysis and advanced oxidation, which comprises an oxidation degradation treatment mode integrating microwave radiation, catalysis and oxidation, and a further oxidation degradation treatment mode of advanced oxidation by adopting ozone oxidation. The degradation treatment efficiency of the refractory organic matters in the industrial pollutants is improved, and the problems of low treatment efficiency, slow reaction rate, strict reaction conditions and the like in the prior art are solved. And the pollution of the discharge of the catalyst to the environment is avoided by recycling and reusing the catalyst. The treatment method has the advantages of simple operation, strong engineering applicability, thorough oxidative degradation of the organic pollutants difficult to degrade, and no secondary pollution.
In order to achieve the purpose, the invention adopts the following technical scheme:
a system for treating refractory organic matters by microwave catalysis combined advanced oxidation comprises a feeding unit, a microwave catalysis unit, an advanced oxidation unit and a water outlet unit from upstream to downstream in sequence;
the feeding unit comprises a water inlet device; the microwave catalysis unit comprises a microwave radiation device, a catalyst bearing device, a magnetic filtering device, an oxidant adding device and a catalyst adding device; the advanced oxidation unit comprises an advanced oxidation reaction device and an ozone generator; the water outlet unit is used for discharging the organic wastewater which is difficult to degrade and has the pollutant content value reaching a set target value after being treated;
the water inlet device, the catalyst bearing device, the advanced oxidation reaction device and the water outlet unit are sequentially communicated through pipelines, and the water outlet unit is communicated with the water inlet device through a return pipeline; the water inlet device is provided with a wastewater inlet for adding the refractory organic wastewater to be treated;
the microwave radiation device is arranged on the catalyst bearing device, and the oxidant adding device and the catalyst adding device are respectively communicated with the catalyst bearing device; the magnetic filtering device is arranged in a pipeline which is communicated with the catalyst bearing device and the advanced oxidation reaction device and is communicated with the catalyst adding device, and the magnetic filtering device is used for recovering the catalyst contained in the wastewater discharged by the catalyst bearing device;
the ozone generator is communicated with the advanced oxidation reaction device.
Furthermore, the water distribution structure of the water inlet device is in one of a circular ring shape, a square shape and a circular net shape.
Furthermore, the wavelength of the electromagnetic wave generated by the microwave radiation device is 8-2800mm, and the frequency is 600-10000 MHz.
Further, the oxidant added by the oxidant adding device is one or more of oxygen, ozone, air, hydrogen peroxide, persulfate, perchlorate, ferrate, chlorine dioxide and sodium hypochlorite.
Furthermore, the catalyst adding device adds catalytically active components and carriers, wherein the catalytically active components are CoO and Ti2O and Al2O3The carrier is Fe-containing3O4And one or two of FeO, the catalyst bearing device is of a multilayer bearing structure, and the residence time of the wastewater in the catalyst bearing device is 1-600 min.
Further, the magnetic filter device comprises a magnetic gathering medium and an electromagnetic generator, and the working magnetic field intensity of the electromagnetic generator 212 is 0.1-15T.
Further, the magnetism-gathering medium is one of woven mesh magnetic stainless steel, sponge magnetic stainless steel, vertical grid magnetic stainless steel, sponge ferromagnetic amorphous alloy, plated layer of sponge ferromagnetic amorphous alloy, fibrous ferromagnetic metal, rod-like magnetic stainless steel, spherical ferrite magnetic stainless steel and triangular toothed plate iron-cobalt alloy, the filling rate of the magnetism-gathering medium is 1% -30%, and the surface of the magnetism-gathering medium is plated or passivated.
Further, the ozone generator is a high-voltage discharge type ozone generator, the frequency of the used high voltage is 400-1000Hz, the speed of ozone generation is 1-2000kg/h, and the retention time of the refractory organic wastewater to be treated in the advanced oxidation device 301 is 1-600 min.
Further, the water outlet unit comprises a water outlet device, a reflux device and a monitoring device; the monitoring device is arranged on the water outlet device and used for detecting the content of pollutants in the wastewater in the water outlet device and sending information on whether the content meets a set target value, and the water outlet device is communicated with the water inlet device through the reflux device.
Furthermore, the water outlet device is provided with a drain valve opening and closing control device, and when the monitoring system detects that the pollutant content value of water in the water outlet device is less than or equal to a set target value, the drain valve of the water outlet device is opened; otherwise, when the monitoring system detects that the pollutant content value of the water in the water outlet device is larger than the set target value, the drain valve of the water outlet device is kept closed.
The invention has the beneficial effects that:
the invention discloses a system for treating refractory organic matters by combining microwave catalysis and advanced oxidation, which has multiple functions of microwave, catalysis, oxidation and ozone advanced oxidation.
Electromagnetic waves generated by the microwave catalytic system can trigger the strong oscillation of molecules of the refractory organic matter, the catalyst and the oxidant, the oxidant is excited to generate free radicals with strong oxidizing property, and the refractory organic matter is oxidized and degraded into micromolecular organic matter under the multiple synergistic effects of microwave radiation, catalysis and oxidation; when the micromolecular organic matter degraded by the refractory organic matter wastewater to be treated passes through the advanced oxidation system device, the micromolecular organic matter is decomposed into CO by ozone oxidation reaction2And H2O; the monitoring device is used for treating the refractory organic waste to be treated in the water outlet unitThe water is subjected to online monitoring of the content of pollutants or COD, if the detection result of the pollutants or COD of the refractory organic wastewater to be treated in the water outlet system does not reach the standard, the wastewater is continuously subjected to circular treatment, so that the discharged water treated by the treatment method provided by the invention is ensured to reach the standard.
The microwave catalytic system is protected to integrate microwave radiation, catalysis and oxidation into a treatment system, so that the reaction activity and speed of an oxidant and refractory organic matters in the catalyst bearing device are improved, the degradation treatment efficiency of the refractory organic matters in industrial pollutants is improved, and the problems of low treatment efficiency, low reaction rate, strict reaction conditions and the like in the prior art are solved. The magnetic filter device realizes the recovery and the recycling of the catalyst, and avoids the pollution of the discharge of the catalyst to the environment. The treatment method has the advantages of simple operation, strong engineering applicability, thorough oxidative degradation of the organic pollutants difficult to degrade, and no secondary pollution.
The high-voltage discharge type ozone generator adopted by the invention has the advantages of high ozone generation speed, low power consumption, small volume, no secondary pollution in the oxidation process and capability of effectively reducing the application environment risk. The treatment method combining microwave radiation catalysis and advanced oxidation is adopted to carry out oxidation degradation treatment twice on the refractory organics contained in the refractory organic wastewater to be treated, the reaction conditions are mild at normal temperature and normal pressure, and the treatment efficiency is high.
Drawings
FIG. 1 is a flow chart of a process for treating refractory organic wastewater by combining microwave pendulous sewage and advanced oxidation according to an embodiment of the invention;
wherein: a feed unit 1; a microwave catalytic unit 2; an advanced oxidation unit 3; a water outlet unit 4; a water inlet device 101; a power plant 102; a microwave radiation device 201; a catalyst support 202; an oxidizing agent addition device 203; a catalyst adding device 204; a magnetic filter device 21; a magnetic flux collecting medium 211; an electromagnetic generator 212; an advanced oxidation reaction apparatus 301; an ozone generator 302; a water outlet device 401; a reflow apparatus 402; a monitoring device 403.
Detailed Description
The technical solution of the present invention is further described with reference to fig. 1 and the detailed description.
A system for treating refractory organic matters by microwave catalysis combined advanced oxidation comprises a feeding unit 1, a microwave catalysis unit 2, an advanced oxidation unit 3 and a water outlet unit 4 from upstream to downstream in sequence;
the feed unit 1 comprises a water inlet means 101; the microwave catalytic unit 2 comprises a microwave radiation device 201, a catalyst carrying device 202, a magnetic filtering device 21, an oxidant adding device 203 and a catalyst adding device 204; the advanced oxidation unit 3 comprises an advanced oxidation reaction device 301 and an ozone generator 302; the water outlet unit 4 is used for discharging the wastewater containing the refractory organic matters with the pollutant content value reaching a set target value after treatment;
the water inlet device 101, the catalyst bearing device 202, the advanced oxidation reaction device 301 and the water outlet unit 4 are sequentially communicated through pipelines, and the water outlet unit 4 is communicated with the water inlet device 101 through a return pipeline; the water inlet device 101 is provided with a wastewater inlet for adding refractory organic wastewater to be treated;
the microwave radiation device 201 is installed on the catalyst carrying device 202, and the oxidant feeding device 203 and the catalyst feeding device 204 are respectively communicated with the catalyst carrying device 202; the magnetic filtering device 21 is installed in a pipeline where the catalyst carrying device 202 is communicated with the advanced oxidation reaction device 301, and is communicated with the catalyst adding device 204, and the magnetic filtering device 21 is used for recovering a catalyst contained in wastewater discharged by the catalyst carrying device 202;
the ozone generator 302 is communicated with the advanced oxidation reaction device 301.
The feeding unit 1 comprises a water inlet device 101 and a power device 102; the power plant 102 is arranged on a pipeline between the water inlet device 101 and the catalyst carrying device 202 and is used for inputting the refractory organic wastewater to be treated from the water inlet device 101 to the catalyst carrying device 202;
the invention discloses a system for treating refractory organic matters through microwave catalysis and advanced oxidation, wherein wastewater of refractory organic matters to be treated is subjected to circulating treatment sequentially through a water inlet unit 1, a microwave catalysis unit 2, an advanced oxidation unit 3 and a water outlet unit 4.
When the wastewater containing the refractory organic matters to be treated passes through the microwave catalytic unit 2, the electromagnetic waves generated by the microwave radiation device cause the molecules of the refractory organic matters, the catalyst and the oxidant to strongly vibrate, the oxidant is excited to generate free radicals with strong oxidizing property, and the activity of the polar structure of the refractory organic matters and the oxidation reaction of the free radicals are further excited and improved under the synergistic action of the catalyst, namely, the refractory organic matters are rapidly oxidized and degraded into micromolecular organic matters under the multiple synergistic action of microwave radiation, catalysis and oxidation; after entering the high-level oxidation unit 3, the micromolecular organic matter and the ozone are subjected to oxidation reaction and decomposed into CO2And H2O。
According to the invention, microwave radiation, catalysis and oxidation are combined into a chemical reaction treatment system in the microwave catalysis unit, so that the reaction activity and speed of an oxidant and refractory organic matters in the catalyst bearing device are improved, the degradation treatment efficiency of the system for treating the refractory organic matters by combining microwave catalysis and advanced oxidation on the industrial pollutants is improved, and the problems of low treatment efficiency, low reaction rate, strict reaction conditions and the like in the prior art are solved. And the catalyst is recovered and recycled by the magnetic filter device, so that the pollution of the catalyst to the environment is avoided. The treatment method has the advantages of simple operation, strong engineering applicability, thorough oxidative degradation of the organic pollutants difficult to degrade, and no secondary pollution.
Further, the water distribution structure of the water inlet device 101 is one of a circular ring shape, a square shape and a circular net shape.
Different water distribution structures, the treatment effect that obtains is different, and inhomogeneous water distribution structure can cause rivers to produce short stream, block up or dead zone phenomenon, and even water distribution structure can promote the effect of handling. The circular net-shaped water distribution effect is best, not only can prevent suspended matters in the water body, but also can uniformly distribute water, and is favorable for improving the treatment quality of the wastewater for treating refractory organic matters.
Further, the wavelength of the electromagnetic wave generated by the microwave radiation device 201 is 8-2800mm, and the frequency is 600-10000 MHz.
Because the molecular chains of different catalysts have different structures and molecular weights, and the activation efficiency of electromagnetic waves with different wavelengths on the refractory organic matters is different, the wavelength and the frequency of the electromagnetic waves generated by the microwave radiation device 201 can be adjusted according to needs and treatment effects, so as to obtain a relatively ideal activation effect. Therefore, the microwave radiation device 201 of the present invention has a wider adjustable range of wavelength and frequency, and a wide application range.
Further, the oxidant added by the oxidant adding device 203 is one or more of oxygen, ozone, air, hydrogen peroxide, persulfate, perchlorate, ferrate, chlorine dioxide and sodium hypochlorite.
The components of the refractory organic matters generated by industrial pollution are complex, different oxidants are adopted to obtain organic matters with different oxidation effects, and the organic matters contained in the refractory organic matters are chemically analyzed, so that one or more proper oxidants can be selected to achieve the better oxidation effect. The oxidant feeding device 203 is suitable for adding and using various oxidants, and has a good application range.
Further, the catalyst adding device 204 adds catalytically active components and carriers, wherein the catalytically active components are CoO and Ti2O and Al2O3The carrier is Fe-containing3O4And FeO, the catalyst bearing device 202 is of a multilayer bearing structure, and the residence time of the wastewater in the catalyst bearing device 202 is 1-600 min.
The catalyst bearing device 202 is a multilayer bearing structure, and compared with a common bearing device, the multilayer bearing structure increases the contact area between the refractory organic wastewater to be treated and the catalyst, thereby being beneficial to improving the continuity and continuity of catalytic reaction and improving the reaction efficiency of the catalyst in the catalyst bearing device 202.
The retention time of the refractory organic wastewater to be treated in the catalyst carrier 202 is 1-600min, and the retention time can be adjusted according to the concentration of the pollutant content of the refractory organic wastewater to be treated so as to obtain a better treatment effect; if the residence time of the refractory organic wastewater to be treated in each treatment system is synchronously set to be 1-5min, the refractory organic wastewater to be treated can keep uninterrupted circulating flow in each treatment system; on the contrary, the persistent organic wastewater to be treated can be intensively treated in each treatment system by setting longer retention time, so as to ensure the treatment effect of the persistent organic wastewater to be treated containing high-concentration persistent organic matters. The treatment method of the invention has the advantages of environment-friendly and energy-saving design and good operation convenience, and the retention time can be adjusted under the condition of keeping the treatment effect.
Further, the magnetic filter device 21 comprises a magnetic collecting medium 211 and an electromagnetic generator 212, and the working magnetic field intensity of the electromagnetic generator 212 is 0.1-15T.
The magnetic field strength influences the working efficiency of the magnetic medium for adsorbing the metal compound, the working magnetic field strength of the electromagnetic generator 212 needs to be adjusted according to the content of the metal catalytic substance in the refractory organic wastewater to be treated discharged by the catalyst bearing device 202 so as to obtain a better recovery effect, and the phenomenon of energy waste exists due to the overhigh working magnetic field strength, so that the working magnetic field strength has a proper adjustable range for 0.1-15T, and the environment-friendly and energy-saving effects are facilitated.
Further, the magnetism-gathering medium 211 is one of woven mesh magnetic stainless steel, sponge magnetic stainless steel, vertical grid magnetic stainless steel, sponge ferromagnetic amorphous alloy, plated layer of sponge ferromagnetic amorphous alloy, fibrous ferromagnetic metal, rod-like magnetic stainless steel, spherical ferrite magnetic stainless steel and triangular toothed plate iron cobalt alloy, the filling rate of the magnetism-gathering medium 211 is 1% -30%, and the surface of the magnetism-gathering medium 211 is plated or passivated.
The magnetic recording medium 211 has various shapes and materials.
The shape of the magnetic medium has great influence on the distribution of the magnetic field around the magnetic medium, and when the magnetization of the magnetic medium is not in a saturated state, the more obvious the surface edge angle is, the smaller the relative size is, and the higher the generated magnetic field gradient is. The magnetic field gradients of the magnetic gathering media with different shapes are ordered from large to small into fiber, sponge, woven mesh, rod and toothed plate.
After the catalyst carriers containing different metal compounds are adsorbed by the magnetism-gathering medium 211, the catalyst carriers need to be cleaned to separate from the magnetism-gathering medium 211, and then the catalyst carriers are put into the catalyst carrier 202 through the catalyst adding device 204 to participate in catalytic reaction, the catalyst carriers with different shapes are adsorbed by the magnetism-gathering medium 211 and then have different recycling efficiencies, and the catalyst carriers are arranged into toothed plates, fibers, rods, sponges and woven nets from large to small.
Amorphous alloys have better corrosion resistance than stainless steel, iron-cobalt alloys or ferrite. The vertical grid type magnetic gathering medium has better fluid passing performance and is not easy to block.
Because the influence of factors such as the flow resistance of the magnetism gathering medium, the collecting area in unit volume, the recycling and cleaning effect and the like needs to be comprehensively considered, the magnetism gathering medium with proper shape and material is selected aiming at the catalyst material containing different metal compounds and the communication pipelines with different cross sections. Therefore, the invention provides a plurality of shapes of the magnetic gathering media which can be selected according to requirements.
The higher the filling rate of the magnetism collecting medium 211 is, the higher the adsorption recovery capacity of the catalyst containing the metal compound is, but the too high filling rate can cause the adsorbed catalyst to be adhered to the magnetism collecting medium 211 and not smoothly separated from the magnetism collecting medium to enter the catalyst adding device 204, and the actual recovery utilization rate is reduced. Therefore, the catalyst can smoothly pass through the magnetic filter device 21 to enter the catalyst adding device 204 only by keeping a moderate filling rate range, so that the magnetism collecting medium 211 has better adsorption capacity and higher recovery rate for the catalyst, the recycling treatment of the refractory organic wastewater to be treated can further improve the recycling of the catalyst containing metal compounds, and the pollution of the catalyst containing metal compounds to the environment is reduced. Therefore, the magnetic recording medium 211 preferably has a filling rate of 5% to 30%.
The surface of the magnetic medium 211 is plated or passivated, so that the corrosion resistance of the magnetic medium 211 is improved, and the service life of the magnetic medium 211 can be effectively prolonged.
Further, the ozone generator 302 is a high-voltage discharge type ozone generator, the frequency of the used high voltage is 400-1000Hz, the speed of the ozone generation is 1-2000kg/h, and the retention time of the refractory organic wastewater to be treated in the advanced oxidation device 301 is 1-600 min.
The high-voltage discharge type ozone generator adopted by the ozone generator 302 has the advantages of high ozone generation speed, low power consumption and small volume, and secondary pollution is not generated in the ozone oxidation process, so that the application environment risk of the ozone generator can be effectively reduced.
Further, the water outlet unit 4 comprises a water outlet device 401, a backflow device 402 and a monitoring device 403; the monitoring device 403 is installed in the water outlet device 401, and is configured to detect the pollutant content of the wastewater in the water outlet device 401 and send information on whether a set target value is met, and the water outlet device 401 is communicated with the water inlet device 101 through the backflow device 402.
Through monitoring devices 403 carries out on-line monitoring of COD content on the refractory organic wastewater to be treated in water outlet unit 4, if the COD detection result of the refractory organic wastewater to be treated in water outlet unit 4 does not reach the standard, the refractory organic wastewater to be treated flows back to water inlet unit 1, and then the wastewater is circulated again to each unit for degradation and oxidation treatment, and continuous cyclic treatment is adopted to ensure that the treated refractory organic wastewater to be treated reaches the standard.
Further, the water outlet device 401 is provided with a drain valve opening and closing control device, and when the monitoring system 403 detects that the pollutant content value of the water in the water outlet device 401 is less than or equal to a set target value, the drain valve of the water outlet device 401 is opened; conversely, when the monitoring system 403 detects that the pollutant content value of the water in the water outlet device 401 is greater than the set target value, the drain valve of the water outlet device 401 remains closed.
The water outlet device 401 is provided with a drain valve opening and closing control device, whether set discharge standards are met or not is confirmed according to the pollutant content or COD value of water in the water outlet device 401 detected by the monitoring system 403, the control device controls the opening or closing of the drain valve of the water outlet device 401, and unqualified refractory organic wastewater to be treated continues to be subjected to circular treatment. The invention can ensure that the treated discharged water reaches the standard, ensures the treatment quality, simultaneously keeps the continuity of the circular treatment of the refractory organic waste water to be treated, and has good treatment efficiency.
The target value may be set to different detectable item values, such as COD, CODcr, BOD5, or TOC.
Example one
The method for treating the refractory organics is adopted to carry out degradation treatment on the papermaking wastewater, the COD of the refractory organics wastewater to be treated is 780mg/L, and the target value of dischargeable COD is set to be 50 mg/L. The specific treatment method comprises the following steps:
1) the waste water of refractory organics to be treated enters the water inlet system 1, is input through the annular water inlet device 101, and is conveyed to the microwave catalytic unit 2 through the power device 102.
2) In the microwave catalytic unit 2, the wavelength of the electromagnetic wave generated by the microwave radiation device 201 is 10mm, and the frequency is 800 MHz; the catalyst carrier added is Fe3O4Nano particles, the active component of the added catalyst is TiO2The magnetic medium 211 is woven mesh magnetic stainless steel, the filling rate of the magnetic medium 211 is 6%, the magnetic medium 211 is passivated and antiseptic by adopting a tetrafluoroethylene coating, and the refractory organic wastewater to be treated is in the catalystThe residence time in the bearing device 202 is 25min, and the refractory organic wastewater to be treated by the microwave catalytic unit 2 flows into the advanced oxidation unit 3.
3) In the advanced oxidation unit 3, the high-voltage frequency of the ozone generator 302 is 450Hz, the ozone generation rate is 15kg/h, the retention time of the refractory organic wastewater to be treated in the advanced oxidation reaction device 301 is 20min, and the refractory organic wastewater to be treated by the advanced oxidation unit 3 flows into the water outlet unit 4.
4) The monitoring device 403 detects the COD index of the refractory organic wastewater to be treated flowing into the water outlet unit 4, and if the COD index of the refractory organic wastewater to be treated exceeds the set dischargeable target value of 50mg/L, the drain valve of the water outlet device 401 is kept closed, and the refractory organic wastewater to be treated flows back to the water inlet device 101 for recycling degradation treatment; and when the monitoring device 403 detects that the COD value of the water in the water outlet device 401 is less than or equal to the set dischargeable target value COD value of 50mg/L, the drain valve of the water outlet device 401 is opened, and the treated water is discharged out of the water outlet device 401.
The system for treating refractory organic matters by combining microwave catalysis and advanced oxidation in the embodiment comprises the following steps:
1) conveying the refractory organic wastewater to be treated to the microwave catalytic unit 2 through the water inlet system 1;
2) adding the catalyst into the microwave catalytic unit 2;
3) the microwave radiation device 201 generates electromagnetic waves;
4) the refractory organic wastewater to be treated, the electromagnetic waves and the catalyst resonate in the microwave catalytic unit 2, fully contact and react chemically, and refractory organic matters in the refractory organic wastewater to be treated are oxidized and degraded into micromolecular organic matters;
5) the to-be-treated refractory organic wastewater treated by the microwave catalytic unit 2 flows into the advanced oxidation unit 3, and the ozone generator generates ozone O3;
6) the wastewater of the refractory organic matters to be treated and the ozone O3 are fully contacted and subjected to chemical reaction in the advanced oxidation unit 3, and the organic matters in the wastewater of the refractory organic matters to be treated are decomposed into CO2And H2O；
7) The organic wastewater which is treated by the advanced oxidation unit 3 and is difficult to degrade flows into the water outlet unit 4;
8) monitoring the COD index of the refractory organic wastewater to be treated by the monitoring device 403 of the water outlet unit 4, and if the index does not reach the standard, the refractory organic wastewater to be treated flows back to the water inlet device 101 again for cyclic treatment until the target value is reached and the refractory organic wastewater can be discharged.
After the treatment by the method for treating the refractory organic matters, the COD value of the water discharged by the drain valve of the water outlet device 401 is 40mg/L, the COD removal rate is 94.87%, and the treated water is clear and transparent and has no peculiar smell. The reaction treatment time of the refractory organic wastewater to be treated in the system for treating the refractory organic matters by combining microwave catalysis and advanced oxidation is 60min, and the reaction rate is high.
Example two
The method for treating the refractory organics is adopted to carry out degradation treatment on the printing and dyeing wastewater, the COD of the refractory organics wastewater to be treated is 1400mg/L, and the target value of the dischargeable COD is set to be 40 mg/L. The specific treatment method comprises the following steps:
1) the waste water of refractory organics to be treated enters the water inlet system 1, is input through the square water inlet device 101, and is conveyed to the microwave catalytic unit 2 through the power device 102.
2) In the microwave catalytic unit 2, the wavelength of the electromagnetic wave generated by the microwave radiation device 201 is 20 mm, the frequency is 2450MHz, and the added catalyst carrier is Fe3O4Nanoparticles, catalyst active components are CoO and TiO2The magnetic medium 211 is vertical grid type magnetic conductive stainless steel, the filling rate of the magnetic medium 211 is 10 percent, and the likeThe magnetism gathering medium 211 is passivated and antisepticized by a tetrafluoroethylene coating, the retention time of the organic wastewater difficult to degrade to be treated in the catalyst bearing device 202 is 30min, and the organic wastewater difficult to degrade to be treated by the microwave catalytic unit 2 flows into the advanced oxidation unit 3.
3) In the advanced oxidation unit 3, the high-voltage frequency of the ozone generator 302 is 700Hz, the ozone generation rate is 18kg/h, the retention time of the refractory organic wastewater to be treated in the advanced oxidation reaction device 301 is 25min, and the refractory organic wastewater to be treated by the advanced oxidation unit 3 flows into the water outlet unit 4.
4) The monitoring device 403 detects the COD index of the refractory organic wastewater to be treated flowing into the water outlet unit 4, and if the COD index of the refractory organic wastewater to be treated exceeds the set dischargeable target value of 40mg/L, the drain valve of the water outlet device 401 is kept closed, and the refractory organic wastewater to be treated flows back to the water inlet device 101 to be recycled for degradation treatment.
The system for treating refractory organics by microwave catalysis combined with advanced oxidation in the embodiment comprises the steps substantially identical to those in the first embodiment, and will not be described again here.
After the treatment by the method for treating the refractory organic matters, the COD value of the water discharged by the drain valve of the water outlet device 401 is 38mg/L, the COD removal rate is 97.29 percent, and the treated water is clear and transparent and has no peculiar smell. The reaction treatment time of the refractory organic wastewater to be treated in the system for treating the refractory organic by combining microwave catalysis and advanced oxidation is 80min, and the reaction rate is high.
EXAMPLE III
The method for treating the refractory organics is adopted to carry out degradation treatment on the coating wastewater, the COD of the refractory organics wastewater to be treated is 15000mg/L, and the target value of dischargeable COD is set to be 55 mg/L. The specific treatment method comprises the following steps:
1) the waste water of refractory organics to be treated enters the water inlet system 1, is input through the water inlet device 101 in a circular net shape, and is conveyed to the microwave catalytic unit 2 through the power device 102.
2) In the microwave catalytic unit 2, the wavelength of the electromagnetic wave generated by the microwave radiation device 201 is 30mm, and the frequency is 4700 MHz; the catalyst carrier added is Fe3O4And FeO nanoparticles, the active components of the catalyst added are CoO and Al2O3The magnetic medium 211 is a triangular toothed plate iron-cobalt alloy, the filling rate of the magnetic medium 211 is 14%, the magnetic medium 211 is passivated and anticorrosive by a tetrafluoroethylene coating, the retention time of the to-be-treated refractory organic wastewater in the catalyst bearing device 202 is 35min, and the to-be-treated refractory organic wastewater treated by the microwave catalytic unit 2 flows into the advanced oxidation unit 3.
3) In the advanced oxidation unit 3, the high-voltage frequency of the ozone generator 302 is 850Hz, the ozone generation rate is 27kg/h, the retention time of the refractory organic wastewater to be treated in the advanced oxidation reaction device 301 is 36min, and the refractory organic wastewater to be treated by the advanced oxidation unit 3 flows into the water outlet unit 4.
4) The monitoring device 403 detects the COD index of the refractory organic wastewater to be treated flowing into the water outlet unit 4, and if the COD index of the refractory organic wastewater to be treated exceeds the set dischargeable target value of 55mg/L, the drain valve of the water outlet device 401 is kept closed, and the refractory organic wastewater to be treated flows back to the water inlet device 101 to be recycled for degradation treatment.
The system for treating refractory organics by microwave catalysis combined with advanced oxidation in the embodiment comprises the steps substantially identical to those in the first embodiment, and will not be described again here.
After the treatment by the method for treating the refractory organic matters, the COD value of the water discharged by the drain valve of the water outlet device 401 is 52mg/L, the COD removal rate is 99.62%, and the treated water is clear and transparent and has no peculiar smell. The reaction treatment time of the refractory organic wastewater to be treated in the system for treating refractory organic matters by combining microwave catalysis and advanced oxidation is 100min, and the reaction rate is high.
In conclusion, the method for treating the refractory organic matters improves the degradation capability of the refractory organic matters by adopting the microwave radiation combined advanced oxidation process and adopting the microwave catalysis and advanced oxidation method, and the COD removal rate of the refractory organic matter wastewater exceeds 94 percent. The multi-metal catalyst is used, and the microwave catalysis effect is combined, so that the energy consumption is reduced, and the speed and the treatment efficiency of the degradation oxidation reaction are improved. The catalyst bearing device is a multilayer bearing device, and compared with a common bearing device, the catalyst bearing device increases the contact area between the refractory organic wastewater to be treated and the catalyst, is more beneficial to the catalytic reaction and further improves the reaction rate. The catalyst is recycled by a magnetic filtration technology, the advanced oxidation device adopts a high-pressure discharge type ozone generator, the ozone generation rate is high, the power consumption is low, the size is small, no secondary pollution is generated in the oxidation process, and the application environment risk of the invention is reduced. The method for treating the refractory organic matters performs two times of oxidative degradation treatment on the refractory organic matter wastewater to be treated, is suitable for treating the refractory organic matter wastewater with high concentration and complex components, can use mild reaction conditions at normal temperature and normal pressure, and has high treatment efficiency. The reaction treatment time of the refractory organic wastewater to be treated in the system for treating refractory organic matters by combining microwave catalysis and advanced oxidation is not more than 120min, and the reaction rate is high.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive other specific embodiments of the present invention without inventive efforts, which shall fall within the scope of the present invention.
Claims (10)
1. A system for treating refractory organic matters by combining microwave catalysis and advanced oxidation is characterized by sequentially comprising a feeding unit, a microwave catalysis unit, an advanced oxidation unit and a water outlet unit from upstream to downstream;
the feeding unit comprises a water inlet device; the microwave catalysis unit comprises a microwave radiation device, a catalyst bearing device, a magnetic filtering device, an oxidant adding device and a catalyst adding device; the advanced oxidation unit comprises an advanced oxidation reaction device and an ozone generator; the water outlet unit is used for discharging the organic wastewater which is difficult to degrade and has the pollutant content value reaching a set target value after being treated;
the water inlet device, the catalyst bearing device, the advanced oxidation reaction device and the water outlet unit are sequentially communicated through pipelines, and the water outlet unit is communicated with the water inlet device through a return pipeline; the water inlet device is provided with a wastewater inlet and is used for adding refractory organic wastewater to be treated;
the microwave radiation device is arranged on the catalyst bearing device, and the oxidant adding device and the catalyst adding device are respectively communicated with the catalyst bearing device; the magnetic filtering device is arranged in a pipeline which is communicated with the catalyst bearing device and the advanced oxidation reaction device and is communicated with the catalyst adding device, and the magnetic filtering device is used for recovering the catalyst contained in the wastewater discharged by the catalyst bearing device;
the ozone generator is communicated with the advanced oxidation reaction device.
2. The system for treating refractory organics by microwave catalytic combined advanced oxidation as claimed in claim 1, wherein the water distribution structure of the water inlet device is in the shape of one of a circular ring, a square and a circular net.
3. The system for treating refractory organics by microwave catalytic combined advanced oxidation as claimed in claim 1, wherein the wavelength of the electromagnetic wave generated by the microwave radiation device is 8-2800mm, and the frequency is 600-10000 MHz.
4. The system for treating refractory organic matters through microwave catalysis and advanced oxidation in combination with claim 1, wherein the oxidant added by the oxidant adding device is one or more of oxygen, ozone, air, hydrogen peroxide, persulfate, perchlorate, ferrate, chlorine dioxide and sodium hypochlorite.
5. The system for treating refractory organics by microwave catalytic combined advanced oxidation as claimed in claim 1, wherein the catalyst adding device adds catalytically active components and carriers, and the catalytically active components are CoO and Ti2O and Al2O3The carrier is Fe-containing3O4And one or two of FeO, the catalyst bearing device is of a multilayer bearing structure, and the residence time of the wastewater in the catalyst bearing device is 1-600 min.
6. The system for treating refractory organics through combination of microwave catalysis and advanced oxidation according to claim 1, wherein the magnetic filtration device comprises a magnetic medium and an electromagnetic generator, and the operating magnetic field strength of the electromagnetic generator 212 is 0.1-15T.
7. The system for treating refractory organics through combination of microwave catalysis and advanced oxidation according to claim 6, wherein the magnetism-gathering medium is one of woven mesh magnetic stainless steel, sponge magnetic stainless steel, vertical grid magnetic stainless steel, sponge ferromagnetic amorphous alloy, plated layer of sponge ferromagnetic amorphous alloy, fibrous ferromagnetic metal, rod-shaped magnetic stainless steel, spherical ferrite magnetic stainless steel and triangular toothed plate iron-cobalt alloy, the filling rate of the magnetism-gathering medium is 1% -30%, and the surface of the magnetism-gathering medium is plated or passivated.
8. The system for treating refractory organic matters by microwave catalysis and advanced oxidation in combination as claimed in claim 1, wherein the ozone generator is a high-voltage discharge type ozone generator, the frequency of the used high voltage is 400-1000Hz, the ozone generation speed is 1-2000kg/h, and the retention time of the refractory organic matter wastewater to be treated in the advanced oxidation device 301 is 1-600 min.
9. The system for treating refractory organics through microwave catalytic combined advanced oxidation according to claim 1, wherein the effluent unit comprises an effluent device, a reflux device and a monitoring device; the monitoring device is arranged on the water outlet device and used for detecting the content of pollutants in the wastewater in the water outlet device and sending information whether the content meets a set target value, and the water outlet device is communicated with the water inlet device through the reflux device.
10. The system for treating refractory organics by microwave catalytic combined advanced oxidation according to claim 9, wherein the effluent device is provided with a drain valve on-off control device, and when the monitoring system detects that the pollutant content value of water in the effluent device is less than or equal to a set target value, the drain valve of the effluent device is opened; otherwise, when the monitoring system detects that the pollutant content value of the water in the water outlet device is larger than the set target value, the drain valve of the water outlet device is kept closed.
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Application publication date: 20201023 |