CN108623096B - Treatment process of high-concentration degradation-resistant sewage - Google Patents
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- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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Abstract
The invention relates to a treatment process of high-concentration refractory organic sewage, wherein the sewage to be treated sequentially passes through a first-stage carbon adsorption treatment area, a pre-ozone catalytic oxidation area, an MBBR biochemical treatment area, a second-stage carbon adsorption treatment area, a post-ozone catalytic oxidation area and a third-stage carbon adsorption treatment area; the first level carbon adsorption treatment zone, the second level carbon adsorption treatment zone and the third level carbon adsorption treatment zone all include the active carbon adsorption zone, and the active carbon of third level carbon adsorption treatment zone exhaust flows back to the active carbon adsorption zone in first level carbon adsorption treatment zone and/or the second level carbon adsorption treatment zone, and surplus ozone in preceding ozone catalytic oxidation and the back ozone catalytic oxidation is used for the active carbon adsorption zone in the first level carbon adsorption treatment zone. The sewage treatment process can greatly improve the sewage treatment efficiency, reduce the cost and has stable process.
Description
Technical Field
The invention relates to the field of industrial sewage treatment, in particular to a treatment process of high-concentration degradation-resistant sewage.
Background
With the rapid development of industry, the number of types of wastewater is rapidly increased, and the pollution to water is also becoming serious. The composition and type of industrial wastewater are more complex and more difficult to treat.
For example, municipal sludge anaerobic ammonia oxidation effluent and landfill leachate are high-concentration, high-pollution and degradation-resistant organic wastewater. The water contains aerobic organic pollutants and various metals and ammonia nitrogen compounds, and the concentration of COD and BOD in the water is as high as tens of thousands and is far higher than that of urban sewage.
In addition, non-chlorinated aromatic compounds such as naphthalene and phenanthrene, chlorinated aromatic compounds, phosphate esters, phthalate esters, phenolic compounds, aniline compounds, and the like, which are difficult to biodegrade, are contained in such sewage. The quality of the sewage becomes worse with the lapse of time, and the BOD/COD is less than 0.1, and the sewage has almost no biodegradability.
The current treatment methods for such wastewater include: adsorption, chemical precipitation, density separation, catalytic oxidation, reverse osmosis, gas stripping, and wet oxidation. The efficiency of removing COD by a physical method can reach 50-80%, but the cost is higher, and the method is not suitable for treating a large amount of sewage.
Disclosure of Invention
The invention aims to provide a treatment process of high-concentration degradation-resistant organic sewage, which has the characteristics of improving the sewage treatment efficiency, reducing the cost and having stable process.
The technical purpose of the invention is realized by the following technical scheme: a treatment process of high-concentration refractory organic sewage comprises the steps of sequentially passing sewage to be treated through a first-stage carbon adsorption treatment area, pre-ozone catalytic oxidation, MBBR biochemical treatment, a second-stage carbon adsorption treatment area, post-ozone catalytic oxidation and a third-stage carbon adsorption treatment area; the first-stage carbon adsorption treatment area, the second-stage carbon adsorption treatment area and the third-stage carbon adsorption treatment area all comprise activated carbon adsorption areas, activated carbon exhausted from the carbon adsorption treatment area leaning on the back stage flows back to the activated carbon adsorption area leaning on any one of the front-stage carbon adsorption treatment areas, and residual ozone in the front ozone catalytic oxidation and the back ozone catalytic oxidation is used for the activated carbon adsorption areas in the first-stage carbon adsorption treatment areas.
The invention adopts a mode of combining physical adsorption and chemical treatment to treat the sewage difficult to degrade, the sewage to be treated enters a first-stage carbon adsorption treatment area in advance, and the active carbon in the first-stage carbon adsorption treatment area adsorbs organic matters in the sewage in advance. The sewage is further treated by adopting a pre-ozone catalytic oxidation method, so that organic matters in the sewage are greatly reduced, and the biodegradability of the sewage is improved; the former ozone catalytic oxidation is matched with MBBR biochemical treatment, so that the content of organic matters in the sewage is further reduced, and the content of COD in the sewage is reduced. And then the sewage is treated again by combining the second-stage carbon adsorption treatment area, the post ozone catalytic oxidation treatment area and the third-stage carbon adsorption treatment area, so that organic residues in the sewage are reduced.
When the sewage reaches the third-stage carbon adsorption treatment area, the activated carbon in the third-stage carbon adsorption treatment area is not saturated yet, and the sewage can flow back to the first-stage carbon adsorption treatment area or the second-stage carbon adsorption treatment area for repeated use. At the moment, the residual ozone of the front ozone catalytic oxidation and the residual ozone of the back ozone catalytic oxidation can flow back to the active carbon adsorption area in the first-stage carbon adsorption treatment area, the ozone is used for carrying out oxidation treatment on the sewage to be treated, the biodegradability of the sewage to be treated is improved, the usage amount of the active carbon is reduced, the ozone does not need to be additionally introduced into the active carbon adsorption area, and the ozone usage amount is saved.
Further, the first-stage carbon adsorption treatment area comprises a coagulation area, a flocculation area and a precipitation area which are sequentially connected with the active carbon adsorption area; the second-stage carbon adsorption treatment area comprises an active carbon adsorption area, an active carbon precipitation area, a coagulation area, a flocculation area and a precipitation area, and the third-stage carbon adsorption treatment area is the same as the second-stage carbon adsorption treatment area.
By adopting the technical scheme, when the sewage to be treated is treated in the first-stage carbon adsorption treatment area, the contents of sludge, organic pollutants and the like in the sewage to be treated are relatively large, and the sewage to be treated is directly coagulated and flocculated for sedimentation after being adsorbed by activated carbon. When sewage enters the second-stage carbon adsorption treatment area and the third-stage carbon adsorption treatment area, the content of sludge and organic pollutants in the sewage is greatly reduced, and the sewage needs to be subjected to precipitation treatment after being adsorbed by activated carbon.
Further, oxygen generated in the first-stage carbon adsorption treatment area is used for the ozone preparation system.
By adopting the technical scheme, after residual ozone generated in the processes of front ozone catalytic oxidation and rear ozone catalytic oxidation is introduced into the first-stage carbon adsorption treatment area, ozone and sewage are in contact oxidation to generate a large amount of oxygen, and the oxygen generated in the process is reintroduced into the ozone preparation system, so that the ozone utilization rate is improved, and the ozone preparation cost is reduced.
And further, 80-90% of the total amount of the active carbon discharged from the third-stage carbon adsorption treatment area flows back to the first-stage carbon adsorption treatment area and/or the second-stage carbon adsorption treatment area.
By adopting the technical scheme, in the whole sewage treatment system, fresh activated carbon is directly put into the third-stage carbon adsorption treatment area, and the activated carbon which does not reach saturation in the third-stage carbon adsorption treatment area can flow back to the previous-stage carbon adsorption treatment area, so that the utilization rate of the activated carbon is improved.
Furthermore, the retention time of the sewage in the activated carbon adsorption zone is 20-50 min.
Further, 10-20% of the total amount of the activated carbon generated in the activated carbon precipitation zone in the second stage carbon adsorption treatment zone and the third stage carbon adsorption treatment zone flows back to the activated carbon adsorption zone.
By adopting the technical scheme, in the same-stage carbon adsorption treatment area, a small amount of activated carbon in the activated carbon precipitation area flows back to the activated carbon adsorption area, and the activated carbon which does not reach saturation in the next-stage carbon adsorption treatment area act together with the sewage to be treated, so that the utilization rate of the activated carbon is further improved. In addition, the active carbon flows back in the same-stage carbon adsorption treatment area, and the stirrer can play a role in stirring, so that the effective contact between the active carbon and sewage is improved.
Further, the pre-ozone catalytic oxidation comprises three stages of contact zones, the contact time of each stage of contact zone is 20-30min, and an alumina catalyst is placed in the third stage of contact zone.
Furthermore, the post-ozone catalytic oxidation comprises a two-stage fluidized bed, the catalyst selects hydrogen peroxide with the concentration of 30%, and the retention time of the sewage to be treated is 50-80 min.
Furthermore, the sludge reflux amount of the sedimentation zone in the first stage carbon adsorption treatment zone, the second stage carbon adsorption treatment zone and the third stage carbon adsorption treatment zone is 4-8% of the total amount of the inlet water, and the sludge is refluxed to the flocculation zone.
By adopting the technical scheme, the returned sludge enhances the flocculation effect, can be rapidly precipitated and produces larger and more uniform alum flocs.
In conclusion, the invention has the following beneficial effects:
1. the ozone used in the first-stage carbon adsorption treatment area is residual ozone generated by the pre-ozone catalytic oxidation and the post-ozone catalytic oxidation, so that the utilization rate of the ozone is improved; ozone and sewage to be treated are mixed in a first-stage carbon adsorption treatment area, so that the content of organic pollutants in the sewage to be treated is reduced, and the properties and the structure of macromolecular organic matters are changed, thereby being beneficial to activated carbon adsorption;
2. ozone in the first-stage carbon adsorption treatment area reacts with sewage to be treated to generate oxygen which can be used as an oxygen source of an ozone preparation system for producing ozone, and the ozone and the oxygen form a circulating system, so that the use of liquid oxygen is reduced, and the operation cost is reduced;
3. for sewage with poor biochemical property of BOD/COD less than 0.1, ozone catalytic oxidation, MBBR biochemical reaction and three-level activated carbon adsorption treatment area are adopted to match, so that the biochemical property of the sewage is improved;
4. the front ozone catalytic oxidation, the multi-stage carbon adsorption treatment area and the rear ozone catalytic oxidation are matched, so that organic pollutants in sewage can be removed to the maximum extent;
5. the sewage reacts with a catalyst in the ozone catalytic oxidation to reduce the content of organic pollutants in the sewage; in the post-ozone catalytic oxidation, an internal circulating fluidized bed technology is adopted to fully mix the hydrogen peroxide catalyst with the sewage, so that the utilization rate of ozone is improved, the generation of hydroxyl radicals is promoted, and the treatment efficiency of the sewage is improved;
6. the three-stage carbon adsorption treatment area is provided with the backflow of the waste activated carbon, so that the adsorption characteristic of the activated carbon is fully utilized, the using amount of the activated carbon and the adding amount of ozone are reduced, and the operation cost is reduced;
7. sludge backflow is arranged in the flocculation area and the sedimentation area in the three-stage carbon adsorption treatment area, so that the sludge concentration of the flocculation area is increased, the collision probability of alum floc is increased, the adding amount of a coagulant and a flocculant is reduced, and the operation cost is reduced.
Drawings
FIG. 1 is a process diagram of treatment of high-concentration degradation-resistant sewage.
Detailed Description
The present invention will be described in further detail with reference to examples.
The first embodiment is as follows: a treatment process of high-concentration degradation-resistant sewage combines a figure 1 and comprises a first-stage carbon adsorption area, a pre-ozone catalytic oxidation area, an MBBR biochemical treatment area, a second-stage carbon adsorption treatment area, a post-ozone catalytic oxidation area and a third-stage carbon adsorption treatment area which are sequentially connected.
The first-stage carbon adsorption treatment area comprises an active carbon adsorption area, a coagulation area, a flocculation area and a precipitation area which are sequentially connected; the second-stage carbon adsorption treatment area and the third-stage carbon adsorption treatment area respectively comprise an activated carbon adsorption area, an activated carbon precipitation area, a coagulation area, a flocculation area and a precipitation area.
The anaerobic ammonia oxidation effluent of a certain sewage treatment plant is treated by adopting the process, and the water quality condition of the sewage is shown in table 1.
TABLE 1 anammox effluent from a wastewater treatment plant
| Detecting items | PH | COD(mg/L) | SS(mg/L) |
| Water inflow index | 6-9 | 1000 | 196 |
| Index of water discharge | 6-9 | 60 | 10 |
(1) Carrying out first-stage carbon adsorption treatment on the sewage to be treated: the sewage to be treated is in contact oxidation with residual ozone in the previous ozone catalytic oxidation and the subsequent ozone catalytic oxidation in an active carbon adsorption zone, and simultaneously the sewage to be treated is mixed with the active carbon which flows back from a second-stage carbon adsorption zone in the active carbon adsorption zone (the back flow is 90 percent, and the specific surface area of the active carbon is 650 m)2And/g) to adsorb organic pollutants in the wastewater and improve the biodegradability of the sewage to be treated. Ozone is oxidized by contacting with the sewage to be treated to generate oxygenIn an ozone production system.
(2) Fully mixing the sewage to be treated with the activated carbon, wherein the hydraulic retention time of an activated carbon adsorption zone is 30min, allowing the sewage subjected to activated carbon adsorption to enter a coagulation zone, and adding a coagulant PAC (50 mg/L) into the coagulation zone for rapidly stirring and mixing for 3 min. PAC and organic pollutants in the sewage to be treated are mixed to form floccule sediment with smaller particle size. Then, the sewage to be treated enters a flocculation area, a flocculating agent PAM (the adding amount is 1.0mg/L) is added into the flocculation area, the mixture is stirred and mixed for 12min at a low speed, meanwhile, the backflow sludge is injected into the flocculation area, the flocculation effect is enhanced, and larger and more uniform alum flocs can be generated. And finally, the sewage enters a settling zone, sludge is concentrated to the concentration of 50-200g/L by a mud scraper, and the sludge continuously flows back to the flocculation zone with the sludge backflow amount of 6%.
(3) The sewage in the first-stage carbon adsorption treatment area is subjected to ozone catalytic oxidation (the introduction amount of ozone is 300mg/L), the ozone catalytic oxidation is set to be three-stage, and the wastewater is subjected to ozone catalytic oxidation treatment, so that organic matters are further degraded, and the biodegradability of the wastewater is improved.
(4) The biodegradability of the sewage subjected to ozone catalytic oxidation is improved, then MBBR biochemical treatment is carried out, and the carrier filler subjected to biofilm formation floats in the sewage under the action of blast aeration, so that microorganisms in the biofilm are fully contacted with organic matters and oxygen in the sewage, and pollutants are easily adsorbed and degraded by the microorganisms. Because the concentration of the microorganisms on the biomembrane is very high, the concentration of the microorganisms in the MBBR is also very high, and the degradation of high-concentration nondegradable pollutants in the sewage is facilitated. The hydraulic retention time in the MBBR tank is 5 h.
(5) Performing secondary carbon adsorption treatment on the sewage subjected to the MBBR biochemical treatment, and enabling the sewage to enter an active carbon adsorption tank, wherein the hydraulic retention time of an active carbon adsorption area is 30 min; then, the sewage enters an active carbon sedimentation tank, and the hydraulic retention time of the active carbon sedimentation tank is 20 min; 90 percent of the total amount of the precipitated active carbon flows back to the active carbon adsorption area of the first-stage carbon adsorption treatment, and 10 percent of the total amount of the precipitated active carbon flows back to the active carbon adsorption area of the present-stage carbon adsorption treatment. The sewage enters a coagulation zone, and a coagulant PAC (the adding amount is 50mg/L) is added to be rapidly stirred and mixed for 3 min. The sewage after coagulation treatment enters a flocculation area, and a flocculating agent PAM (the adding amount is 1.0mg/L) is added to be slowly stirred and mixed for 12 min. The flocculated sewage enters a settling zone for settling separation, the settled sludge is concentrated to the concentration of 50-200g/L, and the sludge reflowing amount is 6 percent and reflows to the flocculation tank.
(6) And (3) carrying out post ozone catalytic oxidation treatment on the sewage subjected to the second-stage carbon adsorption treatment, adding 30% hydrogen peroxide as a catalyst into a post ozone catalytic oxidation system, wherein the sewage and the catalyst (the adding amount of the catalyst is 0.6g/L) and the hydraulic retention time of the sewage is 60 min.
(7) And (3) carrying out third-stage activated carbon adsorption treatment on the sewage treated in the step (6), stirring and mixing the sewage and the activated carbon in an activated carbon adsorption area, keeping the hydraulic retention time in an adsorption tank for 30min, fully stirring the sewage and the activated carbon, then carrying out precipitation in an activated carbon precipitation area, keeping the hydraulic retention time in the precipitation area for 20min, refluxing 90% of the total amount of the precipitated activated carbon to the activated carbon adsorption area subjected to the second-stage activated carbon adsorption treatment, and refluxing 10% of the total amount of the activated carbon to the activated carbon adsorption area subjected to the first-stage activated carbon adsorption treatment. The sewage enters a coagulation zone, a coagulant PAC (the adding amount is 50mg/L) is added to the sewage for rapid stirring and mixing for 3min, the sewage after coagulation treatment enters a flocculation zone, and a flocculating agent PAM (the adding amount is 1.0mg/L) is added to the sewage for slow stirring and mixing for 12 min. And (3) precipitating and separating the flocculated sludge, wherein the concentration of the concentrated sludge is 50-200g/L, and the reflux amount of the sludge is 6% and then the sludge flows back to the flocculation tank.
The difference between the other embodiments and the first embodiment is the process parameters, which are specifically shown in table 2.
TABLE 2 Process parameters for the examples
The process of the above embodiments is adopted to detect the quality of the effluent, and the detection results of the quality of the effluent are shown in table 3.
TABLE 3 effluent quality test results of the wastewater to be treated
| Item | PH | COD(mg/L) | SS(mg/L) |
| Example one | 6-9 | 49 | 8.6 |
| Example two | 6-9 | 51 | 8.5 |
Comparative example: the existing method for treating high-concentration organic wastewater difficult to degrade combines MBR + RO advanced treatment. The process comparison with the present invention is shown in table 4.
Table 4 process comparison results:
due to the characteristic of high-concentration degradation-resistant organic wastewater, the conventional MBR + RO process is inconvenient for long-term operation of a system, RO concentrated water needs to be continuously treated, and the treatment difficulty is higher. The membrane is easily polluted due to high water quality fluctuation, the service life of the membrane is influenced, and the membrane backwashing is frequent. And the investment cost is higher in the early stage and the operation cost is higher. Compared with the prior art, the process has the advantages of long-term stable operation, low investment cost and low operation cost.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (6)
1. A treatment process of high-concentration refractory organic sewage is characterized by comprising the following steps: the sewage to be treated sequentially passes through a first-stage carbon adsorption treatment area, a pre-ozone catalytic oxidation area, an MBBR biochemical treatment area, a second-stage carbon adsorption treatment area, a post-ozone catalytic oxidation area and a third-stage carbon adsorption treatment area; the first-stage carbon adsorption treatment area comprises an active carbon adsorption area, a coagulation area, a flocculation area and a precipitation area which are sequentially connected; the second-stage carbon adsorption treatment area and the third-stage carbon adsorption treatment area respectively comprise an active carbon adsorption area, an active carbon precipitation area, a coagulation area, a flocculation area and a precipitation area which are sequentially connected; residual ozone in the front ozone catalytic oxidation and the rear ozone catalytic oxidation is used in an active carbon adsorption area in the first-stage carbon adsorption treatment area; 80-90% of the activated carbon in the activated carbon precipitation zone in the third-stage carbon adsorption treatment zone reflows to the activated carbon adsorption zone in the second-stage carbon adsorption treatment zone; 80-90% of the active carbon in the active carbon precipitation zone in the second-stage carbon adsorption treatment zone reflows to the active carbon adsorption zone of the first-stage carbon adsorption treatment zone; 10-20% of the total amount of the activated carbon generated in the activated carbon precipitation zones in the second-stage carbon adsorption treatment zone and the third-stage carbon adsorption treatment zone flows back to the activated carbon adsorption zones in the same-stage carbon adsorption treatment zone.
2. The process for treating high-concentration refractory organic sewage according to claim 1, wherein the process comprises the following steps: the oxygen generated in the first-stage carbon adsorption treatment area is used for an ozone preparation system.
3. The process for treating high-concentration refractory organic sewage according to claim 1, wherein the process comprises the following steps: the retention time of the sewage in the active carbon adsorption zone is 20-50 min.
4. The process for treating high-concentration refractory organic sewage according to claim 1, wherein the process comprises the following steps: the front ozone catalytic oxidation comprises three stages of contact zones, the contact time of each stage of contact zone is 20-30min, and an alumina catalyst is placed in the third stage of contact zone.
5. The process for treating high-concentration refractory organic sewage according to claim 1, wherein the process comprises the following steps: the ozone catalytic oxidation comprises a two-stage fluidized bed, the catalyst selects hydrogen peroxide with the mass concentration of 30%, and the retention time of the sewage to be treated is 50-80 min.
6. A process for treating high-concentration refractory organic sewage according to any one of claims 1 to 5, which comprises the following steps: the sludge reflux amount of the sedimentation zone in the first stage carbon adsorption treatment zone, the second stage carbon adsorption treatment zone and the third stage carbon adsorption treatment zone is 4-8% of the total volume of the water inlet volume, and the sludge is refluxed to the flocculation zone.
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