CN114524577B - Ultra-low emission advanced treatment method and system for industrial wastewater difficult to degrade - Google Patents
Ultra-low emission advanced treatment method and system for industrial wastewater difficult to degrade Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/22—O2
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1268—Membrane bioreactor systems
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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
- C02F7/00—Aeration of stretches of water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses an ultra-low emission advanced treatment method and system for industrial wastewater difficult to degrade. The system comprises ozone generators which are connected in sequence; a microbubble generator; an ozone catalytic oxidation reactor; an aeration deoxidizing tank; and aerobic biofilm reactors. The invention fully utilizes the strong oxidation capability and high reaction efficiency of micro-bubble (catalytic) ozonization and the low-cost operation of aerobic biochemical treatment, is applied to the advanced treatment of the refractory industrial wastewater, the ozone utilization rate reaches more than 90 percent, the mineralization removal rate of the refractory organic matters in single step treatment can reach 50-60 percent, the mineralization removal rate of the refractory organic matters in two-step circulation treatment or two-step treatment can reach 70-80 percent, the COD concentration of the treated effluent can be reduced to below 50mg/L, and the requirement of stricter emission standard is met.
Description
Technical Field
The invention relates to the field of advanced treatment of industrial wastewater, in particular to an ultra-low emission treatment method for high-efficiency low-cost refractory organic pollutants based on micro-bubble (catalytic) ozonization and biochemical step circulation or multi-stage treatment.
Background
There have been some studies on the treatment of a large amount of refractory organic pollutants in industrial wastewater. For example, CN106007256a discloses a microbubble ozone catalytic oxidation-aeration-free biochemical coupling process system and application thereof, adopts a microbubble technology to strengthen ozone mass transfer, improves ozone utilization rate, and utilizes a microbubble effect to strengthen oxidation capacity, thereby improving degradation-resistant pollutant removal efficiency, remarkably improving biodegradability, and having ozone tail gas concentration close to zero without treating ozone tail gas; meanwhile, dissolved oxygen generated after the ozone reaction and residual oxygen microbubbles can enter the biochemical treatment unit along with the liquid phase, so that sufficient dissolved oxygen is provided for biochemical treatment, the biochemical treatment unit does not need aeration, and the running cost is reduced.
However, the prior art is still unable to finally achieve the requirements and the aim of ultra-low emission for the removal of refractory organics.
Disclosure of Invention
The invention provides an ultra-low emission advanced treatment method and system for industrial wastewater difficult to degrade, which are based on micro-bubble (catalytic) ozonization and biochemical cascade circulation or multi-stage treatment to treat organic pollutants difficult to degrade with high efficiency and low cost and realize ultra-low emission.
An ultra-low emission advanced treatment system for industrial wastewater difficult to degrade comprises ozone generators which are connected in sequence; a microbubble generator; an ozone catalytic oxidation reactor; an aeration deoxidizing tank; an aerobic biomembrane reactor; the aeration deoxidizing tank removes excessive dissolved oxygen and residual dissolved ozone in the wastewater discharged from the ozone catalytic oxidation reactor through micro-bubble catalytic ozonation treatment.
Further, the ozone catalytic oxidation reactor also comprises a catalyst bed layer which is arranged at the middle upper part in the ozone catalytic oxidation reactor; the ozone catalytic oxidation reactor is divided into an upper catalytic ozonation reaction zone and a lower micro-bubble ozonation reaction zone by the catalyst bed layer.
Further, the catalyst in the transport catalyst bed is a particulate catalyst greater than or equal to 5mm, such as a coal particulate activated carbon catalyst or a particulate metal oxide catalyst.
Further, the ultra-low emission advanced treatment system for the industrial wastewater difficult to degrade further comprises a gas-water separation device which is arranged between the ozone catalytic oxidation reactor and the aeration deoxidizing tank; the gas-water separation device separates a gas-water mixture discharged from the ozone catalytic oxidation reactor through micro-bubble catalytic ozonation treatment; the separated wastewater enters an aeration deoxidizing tank.
Further, the aerobic biofilm reactor comprises a biological filler layer, wherein the biological filler is fiber woven suspension filler; preferably, the distance between the fiber braiding suspension fillers is 2-10 cm.
Further, the aerobic biomembrane reactor also comprises a subsurface flow stirring device which is arranged at the bottom of the aerobic biomembrane reactor.
Further, the ultra-low emission advanced treatment system for the industrial wastewater difficult to degrade comprises: an ozone generator connected in sequence; a microbubble generator; an ozone catalytic oxidation reactor; an aeration deoxidizing tank; and an aerobic biofilm reactor; the ozone catalytic oxidation reactor comprises a catalyst bed layer, and is arranged at the middle upper part in the ozone catalytic oxidation reactor; dividing an ozone catalytic oxidation reactor into an upper catalytic ozonation reaction zone and a lower micro-bubble ozonation reaction zone through a catalyst bed layer; the catalyst in the catalyst bed 301 is a particulate catalyst of greater than or equal to 5 mm; the aerobic biofilm reactor comprises a biological filler layer, wherein the biological filler is fiber woven suspension filler; the interval between the fiber woven suspension fillers is 2-10 cm;
ozone generated by the ozone generator is conveyed to the microbubble generator to generate ozone microbubbles; ozone microbubbles in the microbubble generator are mixed with the wastewater and then enter a microbubble ozonization reaction zone at the lower part of the ozone catalytic oxidation reactor; microbubble ozonization and heterogeneous catalytic ozonization reactions are generated in the ozone catalytic oxidation reactor by the microbubble ozone, the wastewater and the catalyst bed layer; the treated wastewater flows out from the top of the ozone catalytic oxidation reactor and enters an aeration deoxidizing tank from the bottom; the excessive dissolved oxygen and residual dissolved ozone are removed through air aeration, the deoxygenated effluent overflows from the upper part of the aeration deoxygenation tank, enters the aerobic biomembrane reactor from the bottom, contacts with biomembrane on the surface of the biological filler in the aerobic biomembrane reactor in the upstream process, and further removes easily degradable micromolecular organic matters by utilizing the aerobic degradation effect of the biomembrane, and then overflows from the top of the biochemical reactor and enters the water storage tank.
An ultra-low emission advanced treatment method for industrial wastewater difficult to degrade comprises the following steps:
1) Carrying out micro-bubble catalytic ozonation treatment on the wastewater to be treated;
2) Deoxidizing the wastewater treated in the step 1), and controlling the dissolved oxygen in the wastewater to be 2-8 mg/L, preferably 4-5 mg/L;
3) Carrying out aerobic biochemical treatment on the wastewater treated in the step 2); and discharging the wastewater reaching the treatment standard.
Further, the gas-water volume ratio in the micro-bubble catalytic ozonation treatment process in the step 1) is 1:5-1:10, and the pressure before the tube is more than or equal to 0.3MPa.
Further, the average diameter of the micro-bubbles in the micro-bubble catalytic ozonation treatment process in the step 1) is less than or equal to 30 mu m.
Further, in the step 1), the ratio of ozone addition amount to COD amount of wastewater inflow is controlled to be 0.2-1.0 mgO in the microbubble catalytic ozonation treatment process 3 The ratio of the ozone addition amount to the COD amount of the wastewater inlet water is 0.4 to 0.6. 0.6mgO 3 /mgCOD。
Further, the wastewater to be treated is high-salt degradation-resistant chemical synthesis wastewater or chemical cracking wastewater rich in nitrogen-containing heterocyclic ring organic matters or complex benzene ring organic matters.
The invention fully utilizes the strong oxidation capability and high reaction efficiency of micro-bubble (catalytic) ozonization and the low-cost operation of aerobic biochemical treatment, is applied to the advanced treatment of the refractory industrial wastewater, the ozone utilization rate reaches more than 90 percent, the mineralization removal rate of the refractory organic matters in single step treatment can reach 50-60 percent, the mineralization removal rate of the refractory organic matters in two-step circulation treatment or two-step treatment can reach 70-80 percent, the COD concentration of the treated effluent can be reduced to below 50mg/L, and the requirement of stricter emission standard is met.
Drawings
FIG. 1 is a schematic diagram of an ultra-low emission advanced treatment system for industrial wastewater difficult to degrade in an embodiment of the invention.
FIG. 2 is a schematic diagram of a wastewater treatment system of comparative example 1.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
The present inventors have found through intensive studies that the prior art has the following disadvantages: (1) When the particle size of the catalyst particles is not optimized, and a smaller particle catalyst is selected, the pore diameter of the catalyst bed layer is small, the porosity is low, so that micro bubbles are aggregated and combined in the pore channel when passing through the catalyst bed, large bubbles are formed, and the effect of enhancing the oxidation capability of the micro bubbles is reduced; (2) The concentration of dissolved oxygen in the effluent after the ozone catalytic oxidation treatment is extremely high, trace ozone remains, and the effluent directly enters the biochemical treatment to have a certain influence on the biological activity, so that the efficiency of the biochemical treatment is reduced; (3) The type of the filler is not optimized, and because the biochemical reactor runs without aeration, when a granular biological filler bed layer is adopted, the problem of short flow is easily caused, the contact between wastewater and a biological film is not facilitated, and the biochemical treatment effect is insufficient; (4) The biochemical treatment does not adopt auxiliary mixing measures, the biochemical reactor runs without aeration, a direct mixing means is lacked, the hydrodynamic condition is poor, the full contact between the wastewater and the biological membrane can be influenced, and the biochemical treatment effect is influenced. (5) Application countermeasures and corresponding researches coping with higher processing requirements and stricter processing standards are lacking.
The present invention aims to solve at least one of the above problems.
As shown in FIG. 1, the ultra-low emission advanced treatment system for the industrial wastewater difficult to degrade comprises an ozone generator 100 which is connected in sequence; a microbubble generator 200; an ozone catalytic oxidation reactor 300; an aeration deoxidizing tank 400; and an aerobic biofilm reactor 500.
In fig. 1, arrows indicate the flow direction of wastewater.
In some examples, the aerated deoxygenation tank removes excess dissolved oxygen and residual dissolved ozone from wastewater discharged from the ozone catalytic oxidation reactor via microbubble catalytic ozonation.
In some examples, the ultra-low emission advanced treatment system for nondegradable industrial wastewater further includes a water inlet pipe 800 for delivering wastewater to be treated.
In some examples, ozone microbubbles generated by microbubble generator 200 are mixed with wastewater in water intake conduit 800 before entering ozone catalytic oxidation reactor 300. In some examples, the mixed wastewater enters from the bottom of the ozone catalytic oxidation reactor 300.
In some examples, the water inlet pipe 800 and the microbubble generator 200 are each connected to the bottom of the ozone catalytic oxidation reactor 300. At the bottom of the ozone catalytic oxidation reactor 300, wastewater to be treated, which is conveyed by the water inlet pipe 800, is mixed with ozone generated by the microbubble generator 200.
In some examples, the system further comprises a water inlet pump 900 connected to the water inlet pipe 800 for delivering wastewater to be treated of the water inlet pipe 800.
In some examples, the ozone catalytic oxidation reactor 300 further includes a catalyst bed 301 disposed in a middle upper portion of the interior of the ozone catalytic oxidation reactor 300. The ozone catalytic oxidation reactor 300 is divided into a catalytic ozonation reaction zone 302 at the upper part by a catalyst bed layer 301, and the ozone catalytic oxidation reaction mainly generates hydroxyl radical oxidation reaction, and has a contribution rate of about 25% to the oxidative degradation of refractory organic matters; the ozone microbubble contraction and cracking of the lower microbubble ozonization reaction zone 303 mainly occurs to generate hydroxyl radical oxidation reaction, and the contribution rate to the oxidative degradation of refractory organic matters is about 75%.
Preferably, the catalyst in the transport catalyst bed 301 is a particulate catalyst greater than or equal to 5mm, such as a coal particulate activated carbon catalyst or a particulate metal oxide catalyst. The research shows that the catalyst with larger diameter particles is free to accumulate to form a bed layer, has larger bed layer pore channels, and reduces aggregation and merging effects when microbubbles pass through the bed layer. In some examples, the catalyst has a particle size of 5-8mm.
In some examples, the ozone catalytic oxidation reactor 300 also includes a pressure gauge 304 for measuring pressure.
In some examples, the ozone catalytic oxidation reactor 300 is a closed pressurized vessel operating at a pressure of less than or equal to 0.05-0.1MPa.
In some examples, the ultra-low emission advanced treatment system for industrial wastewater difficult to degrade further comprises a gas-water separation device 401 disposed between the ozone catalytic oxidation reactor 300 and the aeration deoxidizing tank 400, and separating the gas-water mixture discharged from the ozone catalytic oxidation reactor 300 through the micro-bubble catalytic ozonation treatment. The separated wastewater enters the aeration deoxidizing tank 400.
In some examples, the aeration deoxidizing tank 400 includes an air or nitrogen aeration device 402. Excess dissolved oxygen and residual dissolved ozone are removed by aeration deoxidizing tank 400. The aeration amount of the aeration device can be automatically or manually adjusted according to the control requirement of the dissolved oxygen.
In the existing wastewater treatment scheme, the micro-bubble catalytic ozonation treatment and the biochemical treatment are directly connected, and a buffer process is not arranged between the micro-bubble catalytic ozonation treatment and the biochemical treatment, so that the biochemical treatment effect is affected. In particular, the concentration of dissolved oxygen after the catalytic ozonation treatment of the microbubbles is not regulated, so that the concentration of the dissolved oxygen is too high (usually about 20-30 mg/L), which is unfavorable for the stable effect of subsequent biochemical treatment. The invention is characterized in that an aeration deoxidizing tank 400 is arranged between an ozone catalytic oxidation reactor 300 and an aerobic biomembrane reactor 500; the method has the multiple effects of buffering, regulating and controlling the concentration of dissolved oxygen, eliminating the influence of residual ozone and the like in the process link, thereby further improving the treatment efficiency of the refractory organic pollutants. In some preferred examples, the control range of dissolved oxygen in the wastewater treated by the aeration deoxidizing tank 400 is 2-8 mg/L, more preferably 4-5 mg/L. It was found that the treatment efficiency for hardly degradable organic contaminants is better under such conditions.
In some examples, the aerobic biofilm reactor 500 includes a layer of biofilm 501 that is a woven suspension of fibers.
In some examples, the fiber woven suspension filler is commercially available, for example, from Hebei Probiotics, inc.
In the existing wastewater treatment scheme, the biomembrane reactor adopts activated carbon or ceramsite filler in biochemical treatment, and a formed filler bed layer is easy to form short flow under the condition of no aeration; especially after the reactor is enlarged, the influence of the packed bed on the flow state of the biomembrane reactor is more obvious, the problem of uneven flow velocity distribution is more serious, and the treatment efficiency of the refractory organic pollutants is influenced. The invention adopts the fiber braiding suspension filler, can form good flow state and flow velocity distribution of the reactor under the condition of no aeration, improves the mass transfer and reaction conditions of the reactor, and improves the treatment effect. Another advantage of the hanging chain type fixed packing is that it can ensure the growth of biological film, and is beneficial to forming a good flow state in the reactor without aeration. In some examples, the fiber weave suspension filler is 2 to 10cm apart.
In some examples, the aerobic biofilm reactor 500 further includes a submerged stirring device 502 disposed at the bottom of the aerobic biofilm reactor 500. The undercurrent stirring device 502 is used as an auxiliary mixing measure, so that the hydrodynamic condition in the aerobic biomembrane reactor 500 can be enhanced, the mixing degree is increased, the contact of wastewater and biomembrane and the mass transfer of pollutants are promoted, and the biochemical treatment effect is improved.
In some examples, the aerobic biofilm reactor 500 does not include an aeration device.
In some examples, wastewater enters from the bottom of aerobic biofilm reactor 500 and overflows from the top, which can create up-flow treatment conditions that facilitate adequate contact of wastewater with the biofilm.
In some examples, the ultra-low emission advanced treatment system for industrial wastewater difficult to degrade further comprises a water storage tank 600 connected to the aerobic biofilm reactor 500 for collecting wastewater treated by the aerobic biofilm reactor 500.
In some examples, the ultra-low emission advanced treatment system for industrial wastewater with high degradation further comprises a reflux pump 700 connected to the water storage tank 600 for discharging wastewater in the water storage tank 600. In some examples, the wastewater in the water storage tank 600 is conveyed to a wastewater pool to be treated by a reflux pump 700 or directly conveyed to a water inlet pipeline, and is mixed with the water to be treated by a secondary step circulation treatment, or the water discharged from the water storage tank enters a next step treatment device to be treated, so that refractory organic matters are further removed, and different COD removal rates are controlled by adjusting the operation mode or the combination mode of multiple circulation or multistage treatment, so that the requirements of refractory organic matters removal and the aim of ultra-low emission are achieved. In some examples, the waste water in the water storage tank 600 can be discharged through the reflux pump 700 after reaching the discharge standard, so that the waste water can be safely discharged.
In some examples, the ozone generator 100 and the water inlet pipe 800 are respectively connected with the micro bubble generator 200, the micro bubble generator 200 is connected with the bottom of the ozone catalytic oxidation reactor 300, the upper part of the ozone catalytic oxidation reactor 300 is connected with the bottom of the aeration deoxidizing tank 400, and the upper part of the aeration deoxidizing tank 400 is connected with the bottom of the aerobic biofilm reactor 500.
In some examples, the ozone generator 100 generates ozone gas using pure oxygen as a gas source, and the ozone gas enters the microbubble generator 200 to generate ozone microbubbles, and the ozone microbubbles are mixed with the inlet water and then enter the ozone catalytic oxidation reactor 300 from the bottom. Microbubble ozone, wastewater and a catalyst bed layer generate microbubble ozonization and heterogeneous catalytic ozonization reactions in the ozone catalytic oxidation reactor 300, hydroxyl free radicals are generated through the shrinkage and cracking effect of the ozone microbubbles and the catalytic ozonolysis effect of the catalyst, nondegradable organic pollutants are removed, easily degradable micromolecular organic matters are generated, and the biodegradability of the wastewater is improved. The gas-water mixture after the ozone catalytic oxidation reaction flows out from the top of the ozone catalytic oxidation reactor 300 under the pressure effect without power transmission, enters the aeration deoxidizing tank 400 from the bottom, removes excessive dissolved oxygen and residual dissolved ozone through air aeration, overflows from the upper part of the aeration deoxidizing tank 400, enters the aerobic biomembrane reactor 500 from the bottom, contacts with a biomembrane on the surface of a biological filler in the aerobic biomembrane reactor 500 in the upward flow process, further removes easily degradable micromolecular organic matters by utilizing the aerobic degradation effect of the biomembrane, and overflows from the top of the biochemical reactor to enter the water storage tank 600.
The embodiment of the invention also provides application of the ultra-low emission advanced treatment system for the nondegradable industrial wastewater in wastewater treatment.
The embodiment of the invention also provides an ultra-low emission advanced treatment method for the industrial wastewater difficult to degrade, which comprises the following steps:
1) Carrying out micro-bubble catalytic ozonation treatment on the wastewater to be treated;
2) Deoxidizing the wastewater treated in the step 1), and controlling the dissolved oxygen in the wastewater to be 2-8 mg/L;
3) Carrying out aerobic biochemical treatment on the wastewater treated in the step 2); and discharging the wastewater reaching the treatment standard.
Preferably, in the deoxidation treatment of the step 2), the dissolved oxygen in the wastewater treated in the step 1) is controlled to be 4-5 mg/L.
In some examples, if the wastewater treated in the step 3) does not reach the discharge standard, returning to the step 1) for step circulation treatment; until the treatment reaches the standard.
In some examples, after one step treatment, refractory organic matters still remain in the effluent, a certain proportion of the effluent in the water storage tank is conveyed to a water inlet pipeline by a reflux pump and mixed with the inlet water for secondary treatment, or the effluent in the water storage tank enters a next step treatment device for treatment, so that refractory organic matters are further removed, different COD removal rates are controlled by adjusting the operation mode or the combination mode of multiple circulation or multistage treatment, and the requirements of refractory organic matters removal and the aim of ultra-low emission are achieved.
In some examples, the gas-to-water volume ratio in the microbubble generator 200 is controlled to be 1:5 to 1:10, and the pre-tube pressure is greater than or equal to 0.3MPa. In some examples, microbubbles having an average diameter of less than or equal to 30 μm are stably produced. The micro-bubble has the effects of generating hydroxyl radicals by stronger shrinkage and cracking and improving the oxidizing ability.
In some examples, the micro-bubble catalytic ozonation treatment in the step 1) controls the ratio of the ozone addition amount to the COD amount of the wastewater inflow to be 0.2-1.0 mgO 3 The ratio of the ozone addition amount to the COD amount of the wastewater inlet water is 0.4 to 0.6. 0.6mgO 3 /mgCOD. Therefore, the ozone adding rate and the ozone oxidation consumption rate are basically balanced, the rapid pollutant oxidation removal rate is ensured, the ozone is fully utilized, and the high ozone utilization efficiency is obtained.
In some examples, the wastewater to be treated is subjected to micro-bubble catalytic ozonation treatment, deoxidization treatment and aerobic biochemical treatment in sequence, the micro-bubble catalytic ozonation treatment oxidizes and degrades refractory organic matters by hydroxyl radicals, 30% -40% of refractory organic matters can be removed, meanwhile, partial refractory micromolecular organic matters are generated, excessive dissolved oxygen and residual dissolved ozone are generated after the deoxidization treatment is carried out to remove the micro-bubble (catalytic) ozonation treatment, the refractory micromolecular organic matters generated by the biochemical treatment are removed by aerobic biochemical treatment, and the organic matter removal efficiency can reach 30%.
In some examples, the step circulation or the multi-stage treatment is carried out, the effluent after the single step treatment enters the water storage tank, the effluent is returned to the water inlet pipeline by a reflux pump according to proportion aiming at the refractory organic matters which are not removed yet, and the effluent is mixed with the inlet water and then subjected to the step circulation treatment again, or enters a next-stage step treatment device for treatment, and the multi-stage step treatment is carried out, so that the refractory organic matters in the effluent are further reduced.
In some examples, the mineralization removal rate of the refractory organics in the step circulation treatment can reach 50-60% in a single step treatment, the mineralization removal rate of the refractory organics in the step circulation treatment or the two-stage step treatment can reach 70-80%, the reflux water proportion and the step treatment circulation times or the treatment stages are determined according to the refractory organics removal requirement, and different COD removal rates and effluent COD concentrations are controlled by adjusting the operation mode or the combination mode of multiple circulation or multistage treatment.
The embodiment of the invention also provides a wastewater treatment process based on the degradation-resistant industrial wastewater ultra-low emission advanced treatment system, which comprises the following steps of: ozone generated by the ozone generator 100 is delivered to the microbubble generator 200 to generate ozone microbubbles; ozone microbubbles are mixed with wastewater in the microbubble generator 200 and then enter a microbubble ozonization reaction zone 303 at the lower part of the ozone catalytic oxidation reactor 300; microbubble ozonation and heterogeneous catalytic ozonation reactions occur in the ozone catalytic oxidation reactor 300 with the microbubble ozone, wastewater and catalyst beds; the treated wastewater flows out from the top of the ozone catalytic oxidation reactor 300, enters the gas-water separation device 401, and separates a gas-water mixture discharged from the ozone catalytic oxidation reactor 300 through micro-bubble catalytic ozonation treatment; the separated wastewater enters an aeration deoxidizing tank 400; excess dissolved oxygen and residual dissolved ozone are removed through air aeration, the deoxygenated effluent overflows from the upper part of the aeration deoxygenation tank 400, enters the aerobic biofilm reactor 500 from the bottom, contacts with biofilm on the surface of biological filler in the aerobic biofilm reactor 500 in the upstream process, and further removes easily degradable micromolecular organic matters by utilizing the aerobic degradation effect of the biofilm, and then overflows from the top of the biochemical reactor and enters the water storage tank 600.
Waste water to be treated
Experiments prove that the treatment system and the treatment method are particularly suitable for treating high-salt degradation-resistant chemical synthesis type or chemical cracking type wastewater rich in nitrogen-containing heterocyclic ring type or complex benzene ring type organic matters. For example, the coal chemical wastewater of chemical cracking is rich in nitrogen-containing heterocyclic organic matters, the removal rate of the traditional catalytic ozonation and aerobic biochemical integrated COD is less than 30% under the same condition, and the removal rate of the COD in the microbubble catalytic ozonation can reach more than 40% and the removal rate of the integrated COD in one-step treatment can reach about 60% by adopting the treatment system and the treatment method. And then, like chemical synthesis of the production wastewater of p-phenyl benzonitrile products, the traditional catalytic ozonation and aerobic biochemical process has almost no removal effect on COD under the same conditions, and the COD removal rate can reach 40% -50% in the micro-bubble catalytic ozonation by adopting the treatment system and the treatment method of the invention, and the removal rate of the integral COD of one-step treatment can reach about 65%.
The embodiment of the invention is based on the high-efficiency low-cost degradation-resistant organic pollutant ultralow emission treatment method of microbubble (catalytic) ozonization and biochemical cascade circulation or multistage treatment, in the microbubble (catalytic) ozonization and biochemical cascade treatment, the microbubble technology is adopted to strengthen ozone mass transfer, improve ozone utilization rate, and the microbubble effect is utilized to strengthen oxidizing capacity, thereby improving degradation efficiency of degradation-resistant pollutants and production efficiency of degradation-resistant micromolecular organic matters, and remarkably improving biodegradability; meanwhile, the excessive dissolved oxygen and residual dissolved ozone generated after the ozone reaction are removed through deoxidation treatment, so that the influence on subsequent biochemical treatment can be avoided, meanwhile, proper dissolved oxygen is provided for the subsequent aerobic biochemical treatment, and the generated easily-degradable micromolecular organic matters are removed through the aerobic biochemical treatment, so that the running cost is reduced. On the basis, the degradation-resistant organic matters can be continuously reduced by controlling a certain reflux ratio to carry out step circulation treatment or by multistage treatment, and different COD removal rates and effluent COD concentrations are controlled by adjusting the operation mode or the combination mode of repeated circulation or multistage treatment, so that the degradation-resistant organic matters removal requirement and the aim of ultra-low emission are finally achieved.
Example 1
As shown in fig. 1, the embodiment provides an ultra-low emission advanced treatment system for industrial wastewater difficult to degrade, which comprises an ozone generator 100 connected in sequence; a microbubble generator 200; an ozone catalytic oxidation reactor 300; a gas-water separation device 401; an aeration deoxidizing tank 400; and aerobic biofilm reactor 500; the ozone catalytic oxidation reactor 300 includes a catalyst bed 301 disposed at a middle upper portion inside the ozone catalytic oxidation reactor 300; the ozone catalytic oxidation reactor 300 is divided into an upper catalytic ozonation reaction zone 302 and a lower microbubble ozonation reaction zone 303 by a catalyst bed 301; the catalyst in the catalyst bed 301 is a particulate catalyst (e.g., a coal particulate activated carbon catalyst or a particulate metal oxide catalyst) of greater than or equal to 5 mm; the aerobic biofilm reactor 500 comprises a biological filler layer 501, wherein the biological filler is a fiber woven suspension filler; the interval between the fiber woven suspension fillers is 2-10 cm;
ozone generated by the ozone generator 100 is delivered to the microbubble generator 200 to generate ozone microbubbles (average diameter less than or equal to 30 μm); ozone microbubbles are mixed with wastewater in the microbubble generator 200 and then enter a microbubble ozonization reaction zone 303 at the lower part of the ozone catalytic oxidation reactor 300; microbubble ozonation and heterogeneous catalytic ozonation reactions occur in the ozone catalytic oxidation reactor 300 with the microbubble ozone, wastewater and catalyst beds; the treated wastewater flows out from the top of the ozone catalytic oxidation reactor 300, enters the gas-water separation device 401, and separates a gas-water mixture discharged from the ozone catalytic oxidation reactor 300 through micro-bubble catalytic ozonation treatment; the separated wastewater enters an aeration deoxidizing tank 400; excess dissolved oxygen and residual dissolved ozone are removed through air aeration, the deoxygenated effluent overflows from the upper part of the aeration deoxygenation tank 400, enters the aerobic biofilm reactor 500 from the bottom, contacts with biofilm on the surface of biological filler in the aerobic biofilm reactor 500 in the upstream process, and further removes easily degradable micromolecular organic matters by utilizing the aerobic degradation effect of the biofilm, and then overflows from the top of the biochemical reactor and enters the water storage tank 600.
The COD concentration of the effluent water obtained by the traditional biochemical treatment of a certain pharmaceutical enterprise is about 400mg/L, the advanced treatment is carried out by adopting the ultra-low emission advanced treatment system and the ultra-low emission advanced treatment process of the industrial wastewater difficult to degrade in the embodiment 1, the catalytic oxidation of the micro-bubble ozone adopts a coal columnar particle activated carbon catalyst bed layer with the diameter of 5-8mm, the COD removal amount after the treatment reaches 130mg/L, and the removal rate reaches 32.4%; after the ozone catalytic oxidation effluent is subjected to air deoxidation treatment, the concentration of dissolved oxygen is controlled to be about 8mg/L, and then the effluent flows into an aerobic biochemical reactor which is a fiber woven suspended fixed filler biomembrane reactor, no aeration is carried out, the COD removal amount after the aerobic biochemical treatment reaches 120mg/L, the removal rate reaches 44.6%, the COD concentration of the final effluent is stabilized to be about 150mg/L, and the integral COD removal amount after the step treatment reaches 250mg/L.
Example 2
The effluent from the traditional biochemical treatment of a coal chemical industry enterprise has COD concentration of about 200mg/L, and the advanced treatment is carried out by adopting the ultra-low emission advanced treatment system of the industrial wastewater which is difficult to degrade in the embodiment 1: one-step treatment, micro-bubble ozone catalytic oxidation adopts a coal columnar particle active carbon catalyst bed layer with the diameter of 5-8mm, and the ozone adding amount and the wastewater inflow COD amount are controlledIn a ratio of 0.4 to 0.4mgO 3 The COD removal rate of the treated effluent reaches 35.0%, after the ozone catalytic oxidation effluent is subjected to air deoxidation treatment, the dissolved oxygen concentration is controlled to be 8mg/L, and then the effluent flows into an aerobic biochemical reactor which is a suspended chain fiber filler biomembrane reactor, no aeration is carried out, and the COD removal rate reaches 30.1% after the aerobic biochemical treatment; then carrying out secondary circulation step treatment, wherein the ratio of the reflux water to the raw water is 1:1, and the microbubble ozone catalytic oxidation treatment controls the ratio of the ozone addition amount to the COD amount of the wastewater inlet to be 0.3mgO 3 The COD removal rate of the treated effluent reaches 21.2%, after the ozone catalytic oxidation effluent is subjected to air deoxidation treatment, the concentration of dissolved oxygen is controlled at 5mg/L, and then the effluent flows into an aerobic biochemical reactor, and after the aerobic biochemical treatment, the COD removal rate reaches 18.6%. The COD concentration of the final effluent after the step secondary circulation treatment can be as low as 40mg/L, the overall COD removal rate is close to 80%, and the ultra-low emission requirement of the waste water COD is met.
Example 3
The COD concentration of effluent from the traditional biochemical treatment of a pharmaceutical intermediate production enterprise is about 1030mg/L, and the effluent contains a large amount of complex benzene ring organic matters.
The advanced treatment is carried out by adopting the ultra-low emission advanced treatment system of the industrial wastewater difficult to degrade in the embodiment 1, the catalytic oxidation of the micro-bubble ozone adopts a coal columnar granular activated carbon catalyst bed with the diameter of 5-8mm, the COD removal amount after the treatment reaches 460mg/L, and the removal rate reaches 44.7%; after the ozone catalytic oxidation effluent is subjected to air deoxidation treatment, the concentration of dissolved oxygen is controlled to be about 6-7 mg/L, and then the effluent flows into an aerobic biochemical reactor, wherein the aerobic biochemical reactor is a fiber woven suspension-fixed filler biomembrane reactor, no aeration is carried out, the COD removal amount reaches 220mg/L after the aerobic biochemical treatment, the removal rate reaches 38.6%, the COD concentration of the final effluent is stabilized to be about 350mg/L, and the integral COD removal rate of step treatment reaches 66.0%.
Comparative example 1
As shown in fig. 2, this comparative example provides a wastewater treatment system differing from that of embodiment 1 only in that an aeration deoxidizing tank 400 and a gas-water separator 401 are not included. The wastewater treatment process was the same as in example 1 except that the gas-water separator and the aeration deoxidizing tank were not used for deoxidizing treatment. In fig. 2, arrows indicate the flow direction of wastewater.
The COD concentration of the effluent is about 400mg/L in the traditional biochemical treatment effluent (same as that of the embodiment 1) of a certain pharmaceutical enterprise, the effluent is treated by adopting the wastewater treatment system of the comparative example 1, the micro-bubble ozone catalytic oxidation adopts a coal columnar granular activated carbon catalyst bed layer with the diameter of 5-8mm, the COD removal amount after treatment reaches 124mg/L, and the removal rate reaches 31.0%; after the ozone catalytic oxidation effluent is not subjected to deoxidization treatment, the dissolved oxygen concentration reaches about 28mg/L, the effluent directly flows into an aerobic biochemical reactor, the aerobic biochemical reactor is a fiber woven suspension-fixed filler biomembrane reactor, no aeration is carried out, the COD removal amount is gradually reduced to 93mg/L after the aerobic biochemical treatment, the removal rate is 33.7%, the COD concentration of the final effluent is stabilized at about 183mg/L, and the integral COD removal amount of step treatment reaches 217mg/L. Meanwhile, the biological film is obviously shed due to the peroxidation state in the aerobic biochemical reactor.
Comparative example 2
This comparative example provides a wastewater treatment system differing from example 1 only in that: the catalyst particle diameter in the transport catalyst bed 301 is 3 to 4mm.
The COD concentration of the effluent is about 400mg/L in the traditional biochemical treatment effluent (same as example 1) of a certain pharmaceutical enterprise, the effluent is treated by adopting the wastewater treatment system of comparative example 2, the catalytic oxidation of micro-bubble ozone adopts a coal particle activated carbon catalyst bed layer with the diameter of 3-4 mm, the COD removal amount after the treatment is about 110mg/L, and the removal rate is 27.5%; after the ozone catalytic oxidation effluent is subjected to air deoxidation treatment, the concentration of dissolved oxygen is controlled to be about 8mg/L, and then the effluent flows into an aerobic biochemical reactor which is a fiber woven suspended fixed filler biomembrane reactor, no aeration is carried out, the COD removal amount after the aerobic biochemical treatment reaches 105mg/L, the removal rate reaches 36.2%, the COD concentration of the final effluent is stabilized to be about 185mg/L, and the integral COD removal amount after the step treatment reaches 215mg/L. The efficiency of both ozone catalytic oxidation and aerobic biochemical is reduced compared to example 1.
Comparative example 3
This comparative example provides a wastewater treatment system differing from example 1 only in that: the aerobic biochemical reactor is not a fiber woven suspension filler biomembrane reactor, but a haydite bed biomembrane reactor. The effective biomass of the biofilm reactor of this comparative example 3 and example 1 was substantially equivalent, about 6-7 g/L (the amount of suspended solids SS in the wash solution was measured and calculated after washing the biofilm on a certain charge).
The COD concentration of the effluent is about 400mg/L in the traditional biochemical treatment effluent (same as example 1) of a certain pharmaceutical enterprise, the effluent is treated by adopting the wastewater treatment system of comparative example 3, the catalytic oxidation of micro-bubble ozone adopts a coal columnar granular activated carbon catalyst bed layer with the diameter of 5-8mm, the COD removal amount after the treatment is about 133mg/L, and the removal rate is 33.2%; after the ozone catalytic oxidation effluent is subjected to air deoxidation treatment, the concentration of dissolved oxygen is controlled to be about 8mg/L, and then the effluent flows into an aerobic biochemical reactor which is a ceramic particle bed biomembrane reactor, no aeration is carried out, the COD removal amount reaches 95mg/L after the aerobic biochemical treatment, the removal rate reaches 35.6%, the COD concentration of the final effluent is stabilized to be about 172mg/L, and the integral COD removal amount reaches 228mg/L after the step treatment. The biochemical treatment efficiency is obviously reduced.
Comparative example 4
As shown in fig. 2, the present comparative example provides a wastewater treatment system differing from that of example 1 only in that an aeration deoxidizing tank 400 and a gas-water separator 401 are not included; and the microbubble generator 200 is replaced with a normal bubble generator (the average diameter of the bubbles is greater than 1000 μm).
The effluent (same as example 3) of the traditional biochemical treatment of a pharmaceutical intermediate production enterprise has COD concentration of about 1030mg/L and contains a large amount of complex benzene ring organic matters. The wastewater treatment system and the wastewater treatment process of the comparative example 4 are adopted for treatment, and the COD removal efficiency is less than 10 percent.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (11)
1. An ultra-low emission advanced treatment system for industrial wastewater difficult to degrade comprises ozone generators which are connected in sequence; a microbubble generator; an ozone catalytic oxidation reactor; an aeration deoxidizing tank; an aerobic biomembrane reactor;
the microbubble generator generates ozone microbubbles having an average diameter of less than or equal to 30 μm;
the ozone catalytic oxidation reactor also comprises a catalyst bed layer which is arranged at the middle upper part in the ozone catalytic oxidation reactor; dividing the ozone catalytic oxidation reactor into an upper catalytic ozonation reaction zone and a lower micro-bubble ozonation reaction zone through the catalyst bed layer;
the catalyst in the catalyst conveying bed layer is a granular catalyst with the diameter of more than or equal to 5 mm;
the aeration deoxidizing tank is used for removing excessive dissolved oxygen and residual dissolved ozone from the wastewater discharged from the ozone catalytic oxidation reactor through micro-bubble catalytic ozonation treatment; the control range of the dissolved oxygen in the wastewater treated by the aeration deoxidizing tank is 2-8 mg/L;
the aerobic biofilm reactor comprises a biological filler layer, wherein the biological filler is fiber woven suspension filler.
2. The ultra-low emission advanced treatment system of refractory industrial wastewater according to claim 1, wherein the catalyst in the transported catalyst bed is a coal-based granular activated carbon catalyst or a granular metal oxide catalyst.
3. The ultra-low emission advanced treatment system for industrial wastewater difficult to degrade according to claim 1 or 2, further comprising a gas-water separation device arranged between the ozone catalytic oxidation reactor and the aeration deoxidizing tank; the gas-water separation device separates a gas-water mixture discharged from the ozone catalytic oxidation reactor through micro-bubble catalytic ozonation treatment; the separated wastewater enters an aeration deoxidizing tank.
4. The ultra-low emission advanced treatment system for nondegradable industrial wastewater according to claim 1, wherein the interval between the fiber woven suspension fillers is 2-10 cm.
5. The ultra-low emission advanced treatment system for industrial wastewater difficult to degrade according to claim 1 or 2, wherein the aerobic biofilm reactor further comprises a subsurface flow stirring device arranged at the bottom of the aerobic biofilm reactor.
6. The ultra-low emission advanced treatment system for refractory industrial wastewater according to claim 1, comprising: an ozone generator connected in sequence; a microbubble generator; an ozone catalytic oxidation reactor; an aeration deoxidizing tank; and an aerobic biofilm reactor; the ozone catalytic oxidation reactor comprises a catalyst bed layer, and is arranged at the middle upper part in the ozone catalytic oxidation reactor; dividing an ozone catalytic oxidation reactor into an upper catalytic ozonation reaction zone and a lower micro-bubble ozonation reaction zone through a catalyst bed layer; the catalyst in the catalyst bed 301 is a particulate catalyst of greater than or equal to 5 mm; the aerobic biofilm reactor comprises a biological filler layer, wherein the biological filler is fiber woven suspension filler; the interval between the fiber woven suspension fillers is 2-10 cm;
ozone generated by the ozone generator is conveyed to the microbubble generator to generate ozone microbubbles; ozone microbubbles in the microbubble generator are mixed with the wastewater and then enter a microbubble ozonization reaction zone at the lower part of the ozone catalytic oxidation reactor; microbubble ozonization and heterogeneous catalytic ozonization reactions are generated in the ozone catalytic oxidation reactor by the microbubble ozone, the wastewater and the catalyst bed layer; the treated wastewater flows out from the top of the ozone catalytic oxidation reactor, enters a gas-water separation device, and separates a gas-water mixture discharged from the ozone catalytic oxidation reactor through micro-bubble catalytic ozonation treatment; the separated wastewater enters an aeration deoxidizing tank; the excessive dissolved oxygen and residual dissolved ozone are removed through air aeration, the deoxygenated effluent overflows from the upper part of the aeration deoxygenation tank, enters the aerobic biomembrane reactor from the bottom, contacts with biomembrane on the surface of the biological filler in the aerobic biomembrane reactor in the upstream process, and further removes easily degradable micromolecular organic matters by utilizing the aerobic degradation effect of the biomembrane, and then overflows from the top of the biochemical reactor and enters the water storage tank.
7. Use of the ultra-low emission advanced treatment system for refractory industrial wastewater according to any one of claims 1-6 in wastewater treatment.
8. An ultra-low emission advanced treatment method for refractory industrial wastewater, using the ultra-low emission advanced treatment system for refractory industrial wastewater of any one of claims 1-6, the method comprising:
1) Carrying out micro-bubble catalytic ozonation treatment on the wastewater to be treated;
2) Deoxidizing the wastewater treated in the step 1), and controlling the dissolved oxygen in the wastewater to be 2-8 mg/L;
3) Carrying out aerobic biochemical treatment on the wastewater treated in the step 2); and discharging the wastewater reaching the treatment standard.
9. The ultra-low emission advanced treatment method of refractory industrial wastewater according to claim 8, wherein the step 2) controls the dissolved oxygen in the wastewater to be 4-5 mg/L.
10. The ultra-low emission advanced treatment method for refractory industrial wastewater according to claim 8 or 9, wherein,
step 1), the gas-water volume ratio in the microbubble catalytic ozonation treatment process is 1:5-1:10, and the pressure before the tube is more than or equal to 0.3MPa; and/or the number of the groups of groups,
step 1), the average diameter of the micro-bubbles in the micro-bubble catalytic ozonation treatment process is less than or equal to 30 mu m; and/or the number of the groups of groups,
the ratio of ozone addition amount to wastewater inflow COD amount is controlled to be 0.2-1.0 mgO in the step 1) of the microbubble catalytic ozonation treatment process 3 mgCOD; and/or the number of the groups of groups,
the wastewater to be treated is high-salt degradation-resistant chemical synthesis wastewater or chemical cracking wastewater rich in nitrogen-containing heterocyclic ring organic matters or complex benzene ring organic matters.
11. The refractory industrial wastewater superfluous of claim 10The low-emission advanced treatment method comprises the following steps of 1) controlling the ratio of ozone addition amount to wastewater inflow COD amount to be 0.4-0.6 mgO in the microbubble catalytic ozonation treatment process 3 /mgCOD。
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