CN111747600A - Ozone oxidation-biochemical coupling water treatment method - Google Patents
Ozone oxidation-biochemical coupling water treatment method Download PDFInfo
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- C02F3/00—Biological treatment of water, waste water, or sewage
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
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Abstract
The invention discloses an ozone oxidation-biochemical coupling water treatment method, wherein water to be treated is sequentially subjected to front-end ozone oxidation treatment and rear-end biochemical treatment, back-flowing biochemical effluent to front-end ozone oxidation influent, and performing multiple circulating treatment on the water to be treated in an ozone oxidation-biochemical system through back-flowing; the biodegradability of the ozone oxidation is improved and the synergistic coupling effect of biochemical low-cost mineralization is enhanced by controlling the reflux ratio of biochemical effluent. The method can improve the treatment efficiency under the condition of the determined total ozone adding amount, reduce the ozone consumption under the condition of the determined removal rate, and reduce the investment cost, the operation cost and the engineering occupation area of water treatment.
Description
Technical Field
The invention belongs to the technical field of water treatment and sewage treatment, and also belongs to the technical field of ozone oxidation application, in particular to an ozone oxidation-biochemical coupling water treatment method.
Background
The oxidation of organic matter by ozone includes direct oxidation and indirect oxidation. Direct oxidation of ozone refers to molecular ozone O3The reaction mechanism of the compound directly reacts with organic matters mainly comprises electrophilic reaction, nucleophilic reaction and nucleophilic reaction. The indirect oxidation of ozone refers to the oxidation reaction of the secondary oxidant hydroxyl radical OH formed by self-decomposition of the ozone after induction and organic matters, and the oxidation mechanism mainly comprises electrophilic addition reaction, dehydrogenation reaction and electron transfer reaction. Generally, the reaction rate of OH and organic matters is high, the selectivity is low, and therefore the organic matters which are difficult to degrade in the environment can be effectively degraded. In general, the organic species with high ozone oxidation rate include unsaturated aromatic compounds, unsaturated aliphatic compounds and some special functional groups. Ozone oxidation is used for sewage treatment, and direct oxidation is dominant in an acidic environment with pH less than 4; indirect oxidation is dominant in an alkaline environment with pH > 10; in a neutral environment at pH 7, both reaction pathways are important.
Ozone oxidation is a technology which is commonly applied in water treatment at present. Ozone is mainly used for deep purification treatment of water in feedwater treatment, and degradation is carried out on trace pollutants such as NOM, POPs and the like in water. The application of ozone in sewage treatment comprises sewage pretreatment and sewage advanced treatment, mainly aiming at toxic and difficult biodegradation in sewageThe pollutants of (2) create conditions for subsequent biochemical treatment. At present ozone oxidation has developed O3Contact oxidation, O3Catalytic oxidation, O3/H2O2And the like.
The ozone oxidation speed is high, the efficiency is high, but the ozone oxidation cost is high, and the ozone oxidation is rarely used independently. Biochemical methods are the cheapest and most effective method for removing contaminants. In the feed water treatment, the water treated by ozone is treated by an activated carbon filter, and toxic and harmful pollutants are degraded by microorganisms on filter materials of the activated carbon filter. In the field of sewage pretreatment, high-concentration toxic sewage generated in the industries of pesticides, chemical pharmacy, electroplating, printing and dyeing, fine chemical engineering and the like can be subjected to Fenton oxidation, ozone oxidation, electrocatalytic oxidation and other processes to reduce the toxicity of the wastewater and improve the biodegradability to enter a subsequent biochemical treatment unit. In the deep treatment, the secondary effluent of the sewage station after biochemical pretreatment has low biodegradability and is difficult to continue biodegradation. The products of the organic matters which are difficult to biodegrade after being oxidized by ozone are usually biodegradable, and the ozone oxidation process and the biodegradation process are combined, so that the ozone adding amount can be reduced, and the operation cost is reduced. Nevertheless, the overall investment and operation cost of ozone oxidation-biochemistry are high in the ratio of the tap water treatment cost and the sewage treatment cost, and how to reduce the operation cost of ozone oxidation is still an important technical problem to be solved for the application of the ozone oxidation-biochemistry technology in the water treatment field.
According to the ozone oxidation principle and the chemical reaction kinetics, the two-section or multi-section ozone oxidation-biochemical process can reduce the ozone adding amount under the condition of achieving the same treatment effect, but the occupied area and the investment cost of the two-section or multi-section ozone oxidation-biochemical system are greatly increased, the power consumption increase caused by the multi-stage hydraulic lifting can offset the reduction of the operation cost caused by the reduction of the ozone adding amount, and the whole operation cost of the ozone oxidation is not necessarily reduced. Therefore, the improvement of the water treatment technology based on ozone oxidation is still mainly based on a one-stage ozone oxidation-biochemical process. Generally, the main methods adopted to reduce the cost of ozone oxidation include:
(1) lifting deviceHigh ozone utilization efficiency, for example, ① using a pressure ozone oxidation reactor to increase the efficiency of the ozone solute and the reaction rate, ② using an ozone oxidation catalyst to increase the selectivity and COD removal rate of the ozone oxidation reaction, ③ using advanced oxidation technology such as O3/H2O2Technique, O3the/UV technology increases the yield of hydroxyl radicals in the ozone oxidation process.
(2) The synergistic treatment effect of ozone oxidation and biochemical treatment is improved, for example: the tail gas oxidized by ozone is used for biochemical treatment, so that the aeration cost of the biochemical treatment is reduced; secondly, an integrated ozone oxidation-biochemical treatment device is adopted, so that the system investment and the occupied area are saved; reasonably controlling the ozone adding amount and the COD removing rate of the front-section ozone oxidation, and utilizing the biodegradation effect of the biochemical treatment of the rear section more, so that the whole operation cost is reduced.
Chinese patent application No. 201511020280.3 discloses a water treatment method of post-ozone reflux secondary oxidation. The method is characterized in that a rear ozone oxidation tank is added on the basis of the traditional ozone and biological filter combined process, and the effluent of the rear ozone oxidation tank flows back to the biological filter to be biochemically treated together with the effluent of the front ozone oxidation tank. The method effectively utilizes the selectivity of ozone oxidation, and can realize high COD removal rate; however, the invention needs to control the COD removal rate of the front ozone oxidation tank to be 35%, the ozone adding amount is higher, the operation cost is not reduced, and the investment and the occupied area are increased due to the added rear ozone oxidation tank and the clean water tank.
Chinese patent application No. 201210011851.7 discloses a method and apparatus for advanced treatment processes to deal with sudden organic contamination of drinking water. Adding a water purifying agent adding procedure before ozone activated carbon or ozone-biological activated carbon in the traditional drinking water advanced treatment process, and adding a reducing agent adding procedure after the water purifying agent adding procedure. The method improves the effect of ozone-biochemistry on deep purification of drinking water by a medicine adding method, and has high cost.
Chinese patent application No. 201510010373.1 discloses a method for treating acrylic fiber wastewater, wherein ozone oxidation is adopted for pretreatment, and the biochemical process after ozone pretreatment is ABR anaerobic-contact oxidation process. The method can ensure that the acrylic fiber wastewater treatment reaches the connection standard of a garden, but the ozone consumption is higher.
Chinese patent application No. 201410850428.5 provides a pressure type ozone reaction and microbubble biological aerated filter sewage advanced treatment device, which comprises an oxygen source ozone generating device, a sewage inlet pipe, an air dissolving device, a pressure type ozone reactor and a biological aerated filter; the method realizes the ozone reaction in a high-pressure state by arranging the dissolved air device, the pressure type ozone reactor and the dissolved air release head for releasing pressure, improves the reaction rate of ozone oxidation, greatly shortens the retention time of the ozone reactor and greatly reduces the equipment investment; through the release of dissolved gas water under a high pressure state, the mass transfer rate of oxygen in the form of micro bubbles is high, the utilization rate of oxygen is improved, residual oxygen generated by ozone is effectively utilized, and the operating cost of the biological aerated filter is reduced. Although the method of the invention has the advantages that the effluent of the biological aerated filter flows back to the ozone oxidation water inlet end, the backflow water is mainly used for adjusting the backflow amount of the air dissolving device and the pressure of the air dissolving device so as to adjust the adding amount of ozone and oxygen; and the air dissolving device is only suitable for small-scale sewage advanced treatment devices, and the application range is limited.
Chinese patent application No. 201511020280.3 discloses a sewage advanced treatment method of post-ozone reflux secondary oxidation. The method adds a rear ozone oxidation tank on the basis of the traditional ozone and biological filter combined process, and the water discharged from the rear ozone oxidation tank flows back to the biological filter and is treated by the aeration biological filter together with the water discharged from the front ozone oxidation tank. The method of the invention controls the adding amount of ozone to lead the removal rate of the front ozone COD to be 35 percent, and the COD removal rate of the back ozone is improved by leading the back ozone effluent to flow back to the biological aerated filter, thereby improving the overall COD removal rate; when the reflux ratio is 25%, 50%, 75% and 100%, the COD removing rate of the whole process is increased from 61% to 64.8%. The method has the defects that the biochemical effluent reflux is mainly used for improving the COD removal rate of the post-ozone oxidation, and when the reflux ratio is improved from 25% to 100%, the overall COD removal rate is only improved from 61% to 64.8%. And the ozone addition amount is 2kgO3The dosage of ozone is still higher; when further improvement of COD is requiredThe removal rate needs to be increased, and the ozone adding amount needs to be increased so that the removal rate of the post-ozone COD is increased to 50 percent.
In summary, ozonation-biochemistry is a related whole process system, and under the same process effect condition, the change of a certain parameter in the system can achieve partial target, but may cause other problems. Therefore, the development of an economic and efficient ozone oxidation-biochemical synergistic treatment process has important significance in that the investment cost and the occupied area are not increased or even reduced on the basis of reducing the adding amount and the operating cost of water treatment ozone.
Disclosure of Invention
The invention aims to solve the technical problem that the ozone oxidation-biochemical method in the existing water treatment technology has higher treatment cost and the new technical problem generated by improving the method:
(1) the technical improvement reduces the ozone adding amount, but the whole operation cost is not increased;
(2) the technical improvement reduces the ozone adding amount, but increases the investment and land occupation of the system;
(3) the technical improvement adopted reduces the ozone dosage, but the stable operation capability of the system for coping with the fluctuation of water quality and treatment load is reduced.
The invention aims to provide an ozone oxidation-biochemical coupling water treatment method which is suitable for advanced purification treatment (namely water supply treatment), sewage pretreatment and sewage advanced treatment of micro-polluted water. By utilizing respective technical advantages and cost characteristics of ozone oxidation and biochemical treatment, the synergistic coupling effect of the ozone oxidation and the biochemical treatment is fully exerted, and the aims of reducing the ozone consumption, reducing the ozone-biochemical operation cost and not increasing the ozone-biochemical system investment are fulfilled.
The "advanced purification treatment of micro-polluted water" in the invention refers to the advanced purification treatment of micro-polluted water sources such as surface water and drinking water sources to meet the occasions with high requirements on water quality, such as ecological restoration, advanced purification of drinking water sources, purification treatment of tap water and the like.
The term "pretreatment of wastewater" as used herein means that the wastewater is not subjected to biochemical treatment, has a high concentration of pollutants and low biodegradability and high toxicity, or has other factors affecting the biochemical treatment of wastewater, and needs to adopt physical and chemical methods to reduce the concentration of pollutants, reduce the toxicity of wastewater, and improve the biodegradability of wastewater. For example: industrial wastewater such as pesticide wastewater, pharmaceutical wastewater, printing and dyeing wastewater, electroplating wastewater, fine chemical wastewater and the like needs to be pretreated before biochemical treatment of wastewater.
The 'advanced sewage treatment' in the invention means that the sewage is subjected to front-end treatment, especially biochemical treatment, and pollutants, especially organic matters, in the wastewater can not be biodegraded any more; further treatment is needed to reach the discharge standard. The corresponding concepts generally include:
(1) the third-stage treatment (the first-stage treatment refers to grating-sand setting, and the second-stage treatment refers to biochemistry) in the urban sewage treatment.
(2) In the industrial wastewater treatment, the biochemical effluent is further treated.
(3) The sewage treatment functional unit added on the basis of the existing sewage treatment facilities and equipment also belongs to the category of sewage advanced treatment under general conditions.
The technical problem to be solved by the invention is realized by the following technical scheme:
the ozone oxidation-biochemical coupled water treatment method is characterized in that the sewage is sequentially subjected to front-end ozone oxidation treatment and back-end biochemical treatment, and the wastewater treatment capacity of an ozone oxidation-biochemical system is Q (unit: m)3H) the COD of the feed water is SCOD(unit: g/m)3) The ozone adding concentration is m (unit: g/m3) (ii) a After the sewage is treated by ozone oxidation-biochemical treatment, biochemical effluent is treated according to the flow rate q (unit: g/m)3) Flows back to the ozone oxidation water inlet end, and
and the adding amount of the ozone m is less than or equal to SCOD.
Wherein, the ozone oxidation-biochemical coupling water treatment method is preferable, the return flow q of the effluent is controlled, so that
The ozone oxidation-biochemical coupled water treatment method is further preferable, and the water outlet reflux quantity q is controlled so that
The ozone oxidation-biochemical coupling water treatment method is further preferable, and the water outlet reflux quantity q is controlled, so that
The ozone oxidation-biochemical coupled water treatment method is preferably used for leading the ozone oxidation-biochemical coupled water treatment method to achieve the same treatment effect
The ozone dosage can be reduced.
The ozone oxidation-biochemical coupled water treatment method is further optimized under the condition of achieving the same treatment effect
The ozone dosage can be further reduced.
The ozone oxidation-biochemical coupling water treatment method is further preferable, under the condition of achieving the same treatment effect, so that
The ozone dosage can be further reduced.
The ozone oxidation-biochemical coupling water treatment method is further preferable, under the condition of achieving the same treatment effect, so that
The ozone dosage can be further reduced.
The ozone oxidation-biochemical coupled water treatment method is particularly preferred, under the condition of achieving the same treatment effect, so that
The ozone dosage can be further reduced.
In the above improved technical scheme of the present invention, the ozone oxidation process is an ozone advanced oxidation process or an ozone catalytic oxidation process, and the ozone advanced oxidation process is selected from O3、O3/H2O2、O3UV or O3And (4) catalytic oxidation.
In the above improved technical scheme of the invention, the ozone oxidation can also be UV oxidation or UV/H2O2Electrocatalytic oxidation, Fenton oxidation or other advanced oxidation processes. Ozone oxidation and ozone catalytic oxidation belong to advanced oxidation processes and can generate hydroxyl radicals; thus, the advanced oxidation process UV oxidation, UV/H, which also generates hydroxyl radicals2O2The combined process of electrocatalytic oxidation, Fenton oxidation and other advanced oxidation and biochemical formation can also adopt a method of returning biochemical effluent to oxidation influent to reduce the operation cost of the oxidation section.
In the above improved technical scheme of the present invention, the biochemical process may be an activated sludge process, a biofilm process, a biofilter process or a combination thereof, depending on the treatment object and the treatment target.
The activated sludge process may be anaerobic, hydrolytic acidification, aerobic, A/O, A2O, SBR, MBR, oxidation ditch or combination process thereof. The biofilm process may be a biological contact process, a biological fluidized bed process, an MBBR, or a combination thereof. The biological filter method is a high-load biological filter, a low-load biological filter, a tower biological filter, an activated carbon filter or an aeration biological filter.
In the above improved technical solution of the present invention, the biological contact method may be a biological contact carbon oxidation tank, a nitrification contact tank, or a denitrification contact tank, or a combination thereof.
In the above improved technical scheme of the present invention, the MBBR tank may be an MBBR carbon oxidation tank, an MBBR nitrification tank, an MBBR denitrification tank, or a combination thereof.
In the improved technical scheme of the invention, the biological aerated filter can be a carbon oxidation filter, a nitrification filter, a denitrification filter or a combined process thereof.
According to the technical scheme and the improved technical scheme, when organic pollutants such as COD (chemical oxygen demand) and the like are taken as main treatment targets, the biochemical process can be an aerobic process, an anaerobic process, an MBR (membrane bioreactor), an oxidation ditch, a biological contact carbon oxidation process, an MBBR (moving bed biofilm reactor) carbon oxidation process, an aeration biological filter or a process combination thereof; when using COD and NH3The N reaches the standard as the main treatment target, and the biochemical process can be A/O, SBR, nitrification contact, MBBR nitrification, a nitrification filter or other processes with nitrification capacity and combined processes; when using COD and NH3N, TN the main treatment target is to reach standard, a biological denitrification process or a process combination with nitrification/denitrification capability is adopted.
When the biochemical process selects a biological filter process, the filtering speed of the biological filter is 3-20 m/h, preferably 10-16 m/h; the height of the filter bed of the biological filter is 2.0-4.5 m, preferably 2.0-2.5 m; the liquid level difference between the ozone oxidation pond and the carbon oxidation biological filter is not less than 2.0m, and preferably not less than 3.0 m.
When the biochemical process selects an activated sludge method, a secondary sedimentation tank and sludge reflux are required to be arranged after the activated sludge method, the surface load of the secondary sedimentation tank is 0.5-2.0 m3/(m2.h), preferably 1.0-2.0 m3/(m2.h), the sludge reflux ratio is 50-150%, and the sludge concentration is 2000-6000 mg/L. Suspended filler carriers or suspended rope biological filler carriers can be added into the activated sludge tank.
When the biochemical process is a biofilm process, the filling materials in the biofilm tank include but are not limited to MBBR filling materials, contact oxidation filling materials, activated carbon particles and hollow spherical filling materials, so that a sludge membrane process is formed. The filling ratio of the filler is 30-70 percent, and the preferable filling ratio of the suspended filler is 30-50 percent; the preferable filling ratio of the fixed suspension type filler is 40-70%, and the installation distance is 50-200 mm.
According to technical specifications of sewage treatment engineering by a biofilter method (HJ2014-2012), the filtering speed of the carbon oxidation filter is 2-10 m/h, the filtering speed of the nitrification filter is 3-12 m/h, and the filtering speed of the denitrification filter is 8-12 m/h; the height of the filter bed is 2.5-4 m, and the height difference of the inlet and outlet water liquid levels is not less than 1.8 m. Under the condition that the effluent of the biological filter tank flows back and the reflux ratio Q/Q is 0.5-3, the filtration rate of the biological filter tank is increased to the original (Q + Q)/Q, and if the biological filter tank is designed according to the technical specification, the size of the corresponding filter tank is increased by Q/Q compared with that of the filter tank without backflow, so that the investment is increased.
In order to ensure the filtering effect of the filter and the relative stability of a filter material layer, the method of the invention is also adopted to circulate the effluent of the biological filter to ozone oxidation treatment, the filtering speed is increased to 10-16 m/h, the height of the filter bed is reduced to 2-2.5 m, and the liquid level height difference is increased to more than 3m, so that the biological filter can normally operate under the working condition of high filtering speed of the method of the invention.
The principle of the invention is as follows:
for the ozone oxidation-biochemical coupled system, the function of the ozone oxidation stage includes selective oxidation of organic matter and non-selective oxidation of organic matter. The selective oxidation of ozone generally means that ozone or hydroxyl free radicals act on organic matters containing unsaturated bonds or functional groups to change the chemical structure of the organic matters so that the organic matters which are difficult to biodegrade are converted into biodegradable organic matters; the non-selective oxidation of ozone mainly is that ozone or hydroxyl free radicals directly act on organic matters to completely degrade or mineralize the organic matters. The selective oxidation of ozone consumes a smaller amount of ozone, while the non-selective oxidation of ozone consumes a larger amount of ozone. The selective oxidation and the non-selective oxidation of the ozone exist in the ozone oxidation system at the same time, and because the selective oxidation rate of the ozone is higher and the consumed ozone amount is less, the selective oxidation of the ozone is mainly used in the initial stage of the ozone oxidation of the water (namely the stage with lower ozone adding amount); in the middle and later stages of ozone oxidation (i.e. the stage with higher ozone dosage), the non-selective oxidation of ozone is mainly used. Under the condition that the total ozone adding amount is not changed, the ratio of the ozone adding amount for selective oxidation to the ozone adding amount for non-selective oxidation determines the treatment effect of the ozone oxidation-biochemical system. Therefore, in the water treatment system, ozone is added in a segmented and batched manner, water after ozone oxidation is added each time enters the next-stage ozone oxidation and biochemical system after being treated in the biochemical stage, and the treatment effect can be improved under the condition that the total adding amount of the ozone is not changed; the ozone adding amount can be saved under the condition of unchanged treatment effect. Theoretically, the treatment effect of the continuous multi-stage ozone oxidation-biochemical system is generally better than that of the one-stage ozone oxidation-biochemical system.
For the ozone oxidation-biochemical coupled water treatment system, the biochemical effluent at the rear end flows back to the ozone oxidation influent at the front end, so that the circulating treatment of water in the ozone oxidation-biochemical system can be realized; in the ozone oxidation stage of water each time, organic matters which are difficult to degrade are converted into oxidation products which can be biodegraded, and then the oxidation products are degraded or mineralized in the biochemical stage; organic matters which can not be completely mineralized in the biochemical stage change chemical structures under the metabolism of microorganisms, and are easier to be selectively oxidized by ozone after returning to the ozone oxidation stage through backflow to form oxidation products which are easy to biodegrade. Therefore, the biochemical effluent flows back to the ozone oxidation water inlet end, so that the treatment effect of the multi-section ozone oxidation-biochemical system can be realized; the higher the reflux ratio is, the more fully the synergistic coupling effect of the ozone oxidation and the biochemical treatment can be exerted, and the ozone adding amount is saved.
By the reflux ratio
The control of the ozone oxidation-biochemical coupling system can realize the circulation times of water in the ozone oxidation-biochemical coupling system.
Is equivalent to a two-section ozone oxidation-biochemical treatment system;
equivalent to a three-section ozone oxidation-biochemical treatment system;
equivalent to a four-section ozone oxidation-biochemical treatment system;
equivalent to a six-section type ozone oxidation-biochemical treatment system;
corresponding to a seven-section ozone oxidation-biochemical treatment system. The higher the reflux ratio is, the more fully the synergistic coupling effect of ozone oxidation and biochemical treatment in water treatment can be exerted, and the ozone adding amount is reduced. However, if the reflux ratio is too high, the energy consumption cost increased by the reflux pump is also higher, and the benefit generated by saving the ozone adding amount is gradually reduced, so that the benefit caused by the too high reflux ratio is not obvious.
Compared with the water treatment method of post-ozone reflux secondary oxidation disclosed by 201511020280.3, the water treatment method has the advantages and disadvantages that:
compared with the prior art, the invention has the beneficial technical effects that:
(1) the biochemical effluent flows back, so that the treatment effect of a multi-section ozone oxidation-biochemical system can be realized in the one-section ozone oxidation-biochemical system, and the ozone adding amount can be generally saved by more than 20%.
(2) Through biochemical effluent backflow, the treatment effect of a multi-section ozone oxidation-biochemical system is realized in a one-section ozone oxidation-biochemical system, and the floor area and the investment cost of the whole system can be generally saved by more than 50% compared with those of the multi-section ozone oxidation system.
(3) The water inlet flow of the ozone oxidation device is Q + Q through biochemical effluent backflow, and the concentration of ozone in the ozone oxidation pond is lower than that of ozone in the case that the total ozone adding amount is reduced
Under the condition of the ozone concentration, the ozone is more used for non-selective oxidation, and the ozone oxidation-biochemical synergistic treatment effect is further enhanced.
(4) The water inlet flow of the ozone oxidation device is Q + Q through biochemical effluent backflow, and the concentration of ozone in the ozone oxidation pond is lower than that of ozone in the case that the total ozone adding amount is reduced
Under the condition of low ozone adding concentration, the dissolving efficiency and the utilization efficiency of ozone can be improved, the concentration of ozone in the ozone tail gas can be reduced, and the design and the use scale of an ozone tail gas damage device can be reduced; because the concentration of ozone in the outlet water of the ozone oxidation pond is further reduced, the adverse effect of the outlet water of the ozone carrying the ozone on the back-end biochemical treatment is also reduced to the maximum extent.
(5) The biochemical effluent is refluxed to dilute the influent water, so that the influent water quality is more stable, and the load impact resistance of the ozone oxidation-biochemical system is improved.
(6) In the ozone oxidation device in the prior art, a circulating pump of an ozone oxidation pond is often arranged in the design to improve the dissolving effect of ozone; in the prior art, a biochemical device after ozone oxidation is generally an aeration biological filter, and a circulating pump is often arranged to improve the water distribution uniformity of the aeration biological filter. The typical internal circulation biological aerated filter is the product. The effluent of the biochemical device flows back to the ozone oxidation device for water inlet, so that the requirements of self-circulation treatment of the ozone oxidation device and circulation treatment of the biochemical device can be met without increasing the investment of a circulating pump. The established ozone oxidation-biochemical sewage advanced treatment system can realize the technical scheme and the effect required by the invention under the condition of only changing a pipeline without increasing equipment and operation cost.
(7) The biochemical effluent flows back to the ozone oxidation device for water inlet, and engineering implementation, popularization and application are easy to carry out no matter a new device or the existing device is modified, no matter the field of micro-polluted water deep purification or the field of sewage treatment.
(8) In the prior art, an ozone catalytic oxidation tank filled with a solid catalyst is often adopted in an ozone oxidation process, an aeration biological filter tank filled with a filter material is often adopted in a biochemical process, and the change of the reflux ratio of biochemical effluent can cause the change of hydraulic conditions, such as the change of the filter speed, the loss of a filter head, the loss of the filter material and the like, so that the poor treatment effect is caused. When the ozone oxidation-biochemical system adopts an ozone oxidation device-biochemical device with a non-filter structure, for example, an ozone contact tank is adopted in the ozone oxidation process, and a biofilm process such as a fluidized bed with large porosity, an MBBR (moving bed biofilm reactor), a biological contact tank and the like is adopted in the biochemical process, the biochemical effluent backflow has little influence on the hydraulic conditions of the ozone oxidation tank and the biochemical tank, and the ozone dissolution efficiency of the ozone oxidation tank and the mass transfer conditions of pollutants and biofilms in the biochemical tank can be improved.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a graph showing the effect of UV254 and COD treatment under different ozone adding conditions
Detailed Description
The embodiments of the present invention will be further described with reference to the accompanying drawings so as to facilitate the further understanding of the present invention by those skilled in the art, and do not limit the right thereto.
The method A is an ozone oxidation-biochemical coupling water treatment process of the invention: the water to be treated is sequentially subjected to ozone oxidation treatment at the front end and biochemical treatment at the rear end, and the wastewater treatment capacity of an ozone oxidation-biochemical system is Q (unit: m)3H) the COD of the feed water is SCOD(unit: g/m)3) The ozone adding concentration is m (unit: g/m3) (ii) a The method is characterized in that: after the water to be treated is treated by ozone oxidation-biochemical treatment, the biochemical effluent is treated according to the flow rate q (unit: g/m)3) Reflows to the ozone oxidation water inlet end.
Method B is ozone oxidation-biochemical water treatment process in the prior art
Method C is ozone oxidation-biochemistry-ozone oxidation-biochemistry water treatment process
Example 1 ( claims 1, 2, 3, 4, 5, 6, 7 and technical Effect (r))
A tail water after two-stage biochemical treatment, COD150mg/L, SS30mg/L and TDS11000mg/L, is respectively treated by method A, method B and method C, the scale Q of waste water treatment is 1m3The reaction time of the ozone is 60min, and the retention time of the biochemical device is 2 h; the reflux quantity q of the ozone oxidation-biochemical coupling device is 1-6 m3The ozone dosage is 50mg/L, and the wastewater treatment effects under different conditions of different methods are shown in the following tableAs shown.
TABLE 1 effect of ozone oxidation-biochemical treatment under various conditions
When the total ozone adding amount is the same, the COD concentration of the effluent is lower in the method A (external reflux ozone oxidation-biochemistry) and the method B (external reflux-free ozone oxidation-biochemistry); compared with the method C (multi-stage ozone oxidation-biochemistry), the method has the same effect.
Example 2 (technical effects of claims 1, 2, 3, 4, 5, 6, 7-
A tail water after two-stage biochemical treatment, COD150mg/L, SS30mg/L and TDS11000mg/L, is respectively treated by method A and method C, and the scale Q of waste water treatment is 1000m3The reaction time of the ozone is 60min, and the retention time of the biochemical device is 2 h; the reflux quantity q of the ozone oxidation-biochemical coupling device is 1000-3000 m3The ozone adding amount is 50mg/L, and the occupied area and the investment cost under different conditions of different methods are shown in the table below.
TABLE 2 treatment Effect of ozonation-Biochemical Process under different conditions
Example 3 (claims 5, 6, 7, 8, 9)
Tail water after two-stage biochemical treatment, COD150mg/L, SS30mg/L and TDS11000mg/L, adopts methods A of different conditions to treat waste water, and the scale Q of waste water treatment is 1m3The reaction time of the ozone is 60min, and the retention time of the biochemical device is 2 h; the reflux quantity q of the ozone oxidation-biochemical coupling device is 0.11-2.3 m3The ozone dosage is 50mg/L, and the wastewater treatment effect of the method A under different conditions is shown in the table below.
TABLE 3 treatment Effect of ozonation-Biochemical Process under different conditions
Example 4 (claim 8)
Tail water after two-stage biochemical treatment, COD150mg/L, SS30mg/L and TDS11000mg/L, adopts methods A of different conditions to treat waste water, and the scale Q of waste water treatment is 1m3The reaction time of the ozone is 60min, and the retention time of the biochemical device is 2 h; reflux quantity q of ozone oxidation-biochemical coupling device is 3m3The ozone dosage is 50 mg/L.
The ozone oxidation process is O respectively3Contact oxidation, O3/H2O2Oxidation, O3UV oxidation and ozone catalytic oxidation, wherein the total adding amount of ozone m is 150mg/L (related to Q only), the front adding amount of ozone m1 is 100mg/L, and the rear adding amount of ozone m2 is 50 mg/L. Wherein:
①O3pall ring packing is filled in the contact oxidation pond, and the filling ratio is 30 percent;
②O3/H2O2the ratio of the adding amount of the oxidized hydrogen peroxide to the adding amount of the ozone is 0.5;
③O3selecting ultraviolet rays at 254nm in UV oxidation, and irradiating for 15min with UV light;
④O3the catalyst is prepared by selecting an Al catalyst doped with Mn and Ti through catalytic oxidation, and the filling ratio of the catalyst is 30 percent.
The effect of wastewater treatment in method A under different conditions is shown in the following table.
TABLE 4 effect of ozonation-Biochemical treatment under different conditions
Example 5 (claims 9, 10, 11, 12, 13, 14)
Tail water after two-stage biochemical treatment, COD150mg/L, SS30mg/L and TDS11000mg/L, adopts methods A of different conditions to treat waste water, and the scale Q of waste water treatment is 1m3The reaction time of the ozone is 60min, and the retention time of the biochemical device is 2 h; reflux quantity q of ozone oxidation-biochemical coupling device is 3m3The ozone dosage is 50 mg/L.
Carbon oxidation filter pond: the height of the filter bed is 2m, the designed filtering speed is 15m/h, and the difference between the designed filtering speed and the liquid level of the ozone oxidation tank is 3 m.
Carbon oxidation contact cell: the biological rope filler has the installation distance of 100mm and the filling ratio of 60 percent.
MBBR packing: modified MBBR suspended filler, 25mm 10mm, filling ratio 40%.
The effect of wastewater treatment in method A under different conditions is shown in the following table.
TABLE 5 effect of ozonation-Biochemical treatment under different conditions
When the biochemical device is a carbon oxidation biological filter, a carbon oxidation contact tank and an MBBR, the standard discharge of the COD of the secondary biochemical effluent can be realized.
Example 6 (claims 9, 10, 11, 12, 13, 14)
Tail water after two-stage biochemical treatment, COD150mg/L, NH3-N16.8mg/L, SS30mg/L, TDS11000mg/L, treating wastewater by adopting a method A with different conditions, wherein the wastewater treatment scale Q is 1m3The reaction time of the ozone is 60min, and the retention time of the biochemical device is 2 h; reflux quantity q of ozone oxidation-biochemical coupling device is 3m3The ozone dosage is 50 mg/L. Wherein:
a nitrification filter tank: the height of the filter bed is 2.5m, the designed filtering speed is 12m/h, and the liquid level difference between the designed filtering speed and the designed filtering speed is 3 m.
A nitrification contact tank: the biological rope is 50mm in filler, 100mm in installation distance, 60% in filling ratio and 4m in installation height.
The effect of wastewater treatment in method A under different conditions is shown in the following table.
TABLE 6 effect of ozonation-biochemical treatment under different conditions
The device can realize NH in water when the device is a nitrification filter tank and a nitrification contact tank3-emission on standard of N.
Example 7 (claims 9, 10, 11, 12, 13, 14)
The tail water after two-stage biochemical treatment has the following inlet water quality: the pH value is 6-9, the COD is less than or equal to 60mg/L, the SS is less than or equal to 20mg/L, the TN is less than or equal to 2.5mg/L, and the TP is less than or equal to 0.5 mg/L. Treating the wastewater by adopting a method A under different conditions, wherein the wastewater treatment scale Q is 1m3The reaction time of the ozone is 60min, and the retention time of the biochemical device is 2 h; reflux quantity q of ozone oxidation-biochemical coupling device is 3m3The ozone dosage is 50 mg/L.
A denitrification filter tank: the height of the filter bed is 2.5m, the designed maximum filtering speed is 15m/h (related to Q + Q), and the liquid level difference of the ozone oxidation pond is 3.5 m.
A denitrification contact tank: the biological rope is 50mm in filler, 80mm in installation distance, 70% in filling ratio and 4.5m in installation height.
The effect of wastewater treatment in method A under different conditions is shown in the following table.
TABLE 7 effect of ozonation-Biochemical treatment under different conditions
And when the biochemical device is a denitrification filter tank and a denitrification contact tank, standard discharge of the secondary biochemical effluent TN can be realized.
Example 8 (pretreatment of wastewater)
A sewage treatment plant mainly treats printing and dyeing washing industrial wastewater in an industrial park, COD is 1000mg/L, the wastewater is treated by a method A and a method B respectively, and the wastewater treatment scale Q is 1m3/h。
Ozone oxidation all adopts O3In the contact oxidation process, the retention time of an ozone oxidation tank is 1h, and the adding concentration m of ozone is 100mg/L (only related to Q).
The biochemical process adopts hydrolysis acidification-aerobic process. Wherein the hydrolytic acidification residence time is 4 hours, and the aerobic sludge process is adopted for aerobic treatment and the residence time is 4 hours.
The reflux quantity q of the ozone oxidation-biochemical coupling device is 0.5-3 m3The effect of wastewater treatment under different conditions in different processes is shown in the following table.
TABLE 8 treatment Effect of different ozone oxidation-hydrolytic acidification-aerobic processes
When the total ozone adding amount is the same, the printing and dyeing wastewater is pretreated by adopting the ozone oxidation-hydrolytic acidification-aerobic coupling process, and the COD removal rate is obviously higher than that of the ozone oxidation-biochemical coupling treatment process without backflow.
Example 9 (pretreatment of wastewater)
The comprehensive waste water from production of agricultural chemicals is obtained by acid separation, slag removal and air floatation oil removal, and its COD is 1000mg/L, BOD is 50mg/L, and contains toxic pollutants of phenol and aniline, etc., and can not be directly treated by adopting biochemical method. The wastewater was subjected to pretreatment tests using methods a and B. The wastewater treatment scale of the test device is Q1 m3/h。
(1) Both method A and method B adopt O3/H2O2And (3) oxidation, wherein the adding concentration of ozone is 100mg/L (only related to Q), the adding concentration of hydrogen peroxide is 60mg/L (only related to Q), and the ozone reaction time is 60 min.
(2) The method A and the method B adopt a sludge film process for biochemistry, the sludge concentration is 6000mg/L, MBBR filler is added, the filling ratio is 45 percent, and the biochemical retention time is 24 hours; the sludge reflux ratio of the secondary sedimentation tank is 100 percent, and the surface load of the secondary sedimentation tank is 2.0m3/(m2.h)。
(3) Method A. the reflux quantity q of the ozone oxidation-biochemical coupling device is 0.5-3 m3/h
The different reflux ratio conditions of Process A and the wastewater treatment effect of Process B are shown in the following table.
TABLE 9 treatment Effect of ozone oxidation-activated sludge Process under different conditions
Under the condition of the same total ozone adding amount, the pesticide wastewater is pretreated by adopting the ozone oxidation-activated sludge coupling method, and the COD removal rate is obviously higher than that of the ozone oxidation-biochemical coupling treatment method without backflow.
Example 10 (pretreatment of wastewater)
The printing and dyeing wastewater is the wastewater after oil removal and flocculation air flotation oil removal, the average COD is about 600mg/L, the average BOD is about 100mg/L, the azo refractory macromolecular organic matter is contained, a hydrolysis acidification-aerobic process is adopted, the retention time of a hydrolysis acidification tank is 24 hours, the retention time of an aerobic tank is 24 hours, and the COD of the effluent can be below 150 mg/L. The sewage station of a certain enterprise is built and has the design processing capacity of 200m3The hydrolysis acidification tank is used for 24 hours, and the aerobic tank is used for 24 hours; the upgrading and transformation reach the discharge standard of pollutants for textile dyeing and finishing industry water (GB4287-2012), wherein COD is less than or equal to 100 mg/L. The production scale of enterprises is increased, and the amount of wastewater is 200m3Increase to 400m3The method is adopted for modification, namely an ozone oxidation tank is added, wastewater is subjected to ozone oxidation treatment and then biochemical treatment, a hydrolysis acidification tank and an aerobic tank are modified into a mud film process, the total retention time is shortened from 48h to 24h, MBBR suspended fillers are added into the hydrolysis tank and the aerobic tank, the MBBR suspended fillers are cylindrical fillers made of modified PP and having the diameter of 25mm × 10mm, and the sludge concentration is 2000-4000 mg/L:
(1) by the use of O3Catalytic oxidation with α -Al as catalyst2O3The catalyst loaded with noble metals such as Cu, Mn, Ti and the like has a catalyst filling ratio of 30 percent and a filling height of 2 m. The effective retention time of the ozone reaction tower is 60 min. The ozone adding concentration is 120mg/L (only related to Q).
(2) The method A and the method B adopt a sludge film method for biochemistry, the sludge concentration is 6000mg/L, and MBBR filler is addedThe filling ratio is 45 percent, and the biochemical retention time is 24 hours; the sludge reflux ratio of the secondary sedimentation tank is 100 percent, and the surface load of the secondary sedimentation tank is 2.0m3/(m2.h)。
(3) Method A. the reflux quantity q of the ozone oxidation-biochemical coupling device is 0.5-3 m3H is used as the reference value. Performing a characteristic biofilm culturing test and sludge acclimation for about 40 days after ozone oxidation.
The different reflux ratio conditions of Process A and the wastewater treatment effect of Process B are shown in the following table.
TABLE 10 treatment Effect of different ozone oxidation-activated sludge Process
When the total ozone adding amount is the same, the printing and dyeing wastewater is treated by adopting the ozone oxidation-activated sludge process coupling device, and when the ozone adding amount is 120mg/L and the reflux ratio reaches 3, the COD (chemical oxygen demand) of biochemical effluent is 90mg/L, so that the COD emission limit requirement in the discharge standard of pollutants for textile dyeing and finishing industry water (GB4287-2012) is met.
Example 11 (comparison with CN 201511020280)
The secondary sedimentation tank effluent of the refining and chemical wastewater has COD of 120-140 mg/L, and three sets of devices are adopted to perform a wastewater treatment effect test with the test scale of 1m3/h。
Test a was treated using method a of the invention: the designed filtering speed of the carbon oxidation biological filter is 16m/h, the height of a filter bed is 2m, and the liquid level difference between the ozone oxidation tank and the biological filter is 3 m. The retention time of the ozone oxidation tank is 45min, the retention time of the biological filter tank is 2h, the ozone adding concentration m is 80mg/L, and the biochemical effluent reflux quantity q is 0.5-3 m3/h。
Test B was processed using method B: and in the method B, a carbon oxidation biofilter process is adopted as a biochemical process, the retention time of an ozone oxidation pond is 45min, the retention time of the biofilter is 2h, and the ozone adding concentration m is 80-100 mg/L.
Test D was carried out using a front ozonation-biological aerated filter-rear ozonation-clean water basin device (method D) of chinese patent application No. CN 201511020280: the technological parameters of the ozone oxidation pond are the same as those of the test A, the ozone reaction time is 45min before ozone reaction, and the ozone reaction time is 45min after ozone reaction; but the ozone adding amount is as follows; the retention time of the biological filter is 2 hours. The reflux amounts of the clean water tank are respectively 0.25, 0.5, 0.75 and 1m3/h。
The retention time of the biological aerated filter device is 2 hours; the reflux quantity q of the ozone oxidation-biological aerated filter coupling device is 1-6 m3The ozone adding concentration m is 50mg/L (only related to Q), and the wastewater treatment effects under different conditions of different methods are shown in the following table.
TABLE 11 treatment Effect of different ozonation-biological aerated filter processes
Compared with the method D, the method A has the advantage that the ozone dosage is reduced from 154mg/L to 130mg/L under the condition that the ozone dosage is reduced and the reflux ratio is 100 percent in order to achieve the same wastewater treatment effect.
When the reflux ratio was increased from 0 to 50%, 100%, 200%, 300%, the COD removal rate was increased from 53.8% to 68.0%, 71.3%, 73.7% and 76.8% compared to method B.
Example 12 (purification treatment of drinking water source)
A process for purifying and treating river water as drinking water source includes coagulating deposition, intermediate water pool, ozone oxidizing pool, biological activated carbon filter pool, disinfecting unit, etc. its treating scale is 5 ten thousand m3/d, and it is composed of 8 ozone oxidizing and 8 activated carbon filter pools. The average value of the CODmn of the inlet water quality is 6mg/L, and the treatment is carried out until the CODmn is less than or equal to 2 mg/L. Designing the maximum adding amount of ozone to be 3mg/L, the retention time of an ozone reaction tank to be 20min, and the adding amount of the actually operated ozone to be 2 mg/L; the retention time of the biological activated carbon filter is 30min, and the designed filtration speed of the activated carbon filter is 8 m/h; .
1 group of ozone oxidation tanks and biological activated carbon filter tanks are modified into the ozone oxidation-activated carbon filter tank coupling process of the method, and the reflux ratio of the activated carbon filter tanks is 0.5-2.
The following table shows the treatment effect of the method and the ozone-biological activated carbon filter device in the water plant.
TABLE 12 treatment effect of different ozonation-biological aerated filter processes
Example 13 (method for determining ozone addition amount and reflux amount)
The secondary sedimentation tank effluent of the refining and chemical wastewater has COD of 120-140 mg/L and adopts an ultraviolet-visible spectrophotometer with COD 140mg/L, TOC 54.2mg/L, UV2540.389, 60 times chroma.
(1) Ozone oxidation test device, ozone oxidation device is once only added to waste water.
(2) Ozone prepared by the liquid oxygen source ozone generator is added into the ozone oxidation device at the adding speed of 1.5 mg/(L.min). Samples were taken at 0, 1, 2, 5, 10, 20, 30, 50, 80, 120, 150, 180min for UV254 and COD values. Calculating SUVA-UV 254-1000/COD
(3) The test results are shown in the following table:
TABLE 13 treatment effect of different ozone addition amounts on UV254 and COD of wastewater
As can be seen from FIG. 2, in the stage of small ozone dosage, the removal rate of UV254 is greater than that of COD, and in this stage, ozone is mainly selectively oxidized, so that the biodegradability of wastewater is improved, and the ozone consumption is low.
The above examples are only for describing the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should be made within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (15)
1. The water to be treated is sequentially treated by front-end ozone oxidation treatment and back-end biochemical treatment, and the water treatment capacity of the ozone oxidation-biochemical treatment system is Q (unit: m)3H) the COD of the feed water is SCOD(unit: g/m)3) The ozone adding concentration is m (unit: g/m3) (ii) a The method is characterized in that: after the water to be treated is treated by ozone oxidation-biochemical treatment, biochemical effluent is treated according to the flow rate q (unit: g/m)3) Refluxing to the ozone oxidation water inlet end; and is
m≤SCOD。
2. The water treatment method according to claim 1, characterized in that:
3. the water treatment method according to claim 2, characterized in that:
4. a water treatment method according to claim 3, characterized in that:
5. the water treatment method according to claim 1, characterized in that:
6. water according to claim 5The processing method is characterized by comprising the following steps:
7. the water treatment method according to claim 6, characterized in that:
8. the water treatment method according to any one of claims 1 to 7, characterized in that: the ozone oxidation process is an ozone advanced oxidation process or an ozone catalytic oxidation process, and the ozone advanced oxidation process is selected from O3、O3/H2O2、O3UV or O3And (4) catalytic oxidation.
9. The water treatment method according to any one of claims 1 to 7, characterized in that: the biochemical process is an activated sludge method, a biofilm method, a biological filter method or a combined process thereof.
10. The water treatment method according to claim 9, characterized in that: the activated sludge process comprises anaerobic treatment, hydrolytic acidification, aerobic treatment and A/O, A2O, SBR, MBR, oxidation ditch or other activated sludge process.
11. The water treatment method according to claim 9, characterized in that: the biofilm method is a contact oxidation method, a biological fluidized bed method, MBBR or other biofilm processes.
12. The water treatment method according to claim 11, characterized in that: the contact oxidation is a biological contact carbon oxidation tank, a nitrification contact tank or a denitrification contact tank; the MBBR pool is an MBBR carbon oxidation pool, an MBBR nitrification pool or an MBBR denitrification pool.
13. The water treatment method according to claim 9, characterized in that: the biological filter method is a high-load biological filter, a low-load biological filter, a tower biological filter, an activated carbon filter or an aeration biological filter.
14. The water treatment method according to claim 13, characterized in that: the aeration biological filter is a carbon oxidation filter, a nitrification filter or a denitrification filter.
15. The water treatment method according to claim 1, characterized in that: the ozone oxidation can also be UV catalytic oxidation, UV/H2O2Electrocatalytic oxidation, Fenton oxidation or other advanced oxidation processes.
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| CN201910231730.5A CN111747600A (en) | 2019-03-26 | 2019-03-26 | Ozone oxidation-biochemical coupling water treatment method |
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| CN112645538A (en) * | 2020-12-14 | 2021-04-13 | 安徽纬纶环保科技有限公司 | Well-flushing waste liquid integrated treatment device |
| CN113003850A (en) * | 2020-11-13 | 2021-06-22 | 四川全息生态环境技术产业有限公司 | Advanced oxidation method and device |
| CN116986770A (en) * | 2023-09-06 | 2023-11-03 | 轩昂生态环境建设有限公司 | Method and device for treating landfill leachate concentrated solution in sanitation field |
| CN117566901A (en) * | 2023-12-19 | 2024-02-20 | 上海勘测设计研究院有限公司 | Ozone and MBBR combined pretreatment equipment and pretreatment process thereof |
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