CN109775896B - Device and method for deeply purifying biochemical tail water by coupling ozone catalytic oxidation and coagulating sedimentation - Google Patents
Device and method for deeply purifying biochemical tail water by coupling ozone catalytic oxidation and coagulating sedimentation Download PDFInfo
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 109
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 230000003647 oxidation Effects 0.000 title claims abstract description 90
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 90
- 238000004062 sedimentation Methods 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 65
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 34
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- 238000010168 coupling process Methods 0.000 title claims abstract description 25
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 25
- 230000001112 coagulating effect Effects 0.000 title claims description 35
- 238000005345 coagulation Methods 0.000 claims abstract description 74
- 230000015271 coagulation Effects 0.000 claims abstract description 74
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 239000000701 coagulant Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 21
- 239000010802 sludge Substances 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 230000014759 maintenance of location Effects 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000002356 single layer Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- CYUOWZRAOZFACA-UHFFFAOYSA-N aluminum iron Chemical compound [Al].[Fe] CYUOWZRAOZFACA-UHFFFAOYSA-N 0.000 claims description 2
- 239000010865 sewage Substances 0.000 abstract description 10
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention belongs to the technical field of advanced sewage treatment, and particularly relates to a device and a method for deeply purifying biochemical tail water by ozone catalytic oxidation coupling coagulation sedimentation, wherein the device is divided into three functional areas: the oxidation area, the coagulation area and the sedimentation area are communicated with each other; the water inlet and the air inlet at the bottom of the oxidation zone are connected with a gas-liquid mixing ejector, and a catalyst layer is arranged in the gas-liquid mixing ejector; a coagulant adding device, a tubular mixer and a vertical folding baffle unit are arranged in the coagulation zone; the sedimentation zone is internally provided with an inclined plate unit; mud discharging systems are arranged at the bottoms of the coagulation zone and the sedimentation zone; firstly, removing heterocyclic compounds, humic acids and the like from biochemical tail water through an oxidation zone, and deeply removing soluble microorganism byproducts and the like in the biochemical tail water through a coagulation zone and a sedimentation zone after the formed ozone-containing effluent; the device and the method for treating biochemical tail water have small occupied area and short reaction time, can effectively improve the utilization rate of ozone and catalyst, and reduce the consumption of coagulant.
Description
Technical Field
The invention belongs to the technical field of advanced sewage treatment, and particularly relates to a device and a method for deeply purifying biochemical tail water by ozone catalytic oxidation coupling coagulation sedimentation.
Background
The chemical wastewater has wide sources, complex components, high salt content and great treatment difficulty, and becomes a public focus in recent years. At present, a mode of combining enterprise pretreatment and centralized treatment of a park comprehensive sewage treatment plant is mainly adopted for the wastewater, but the treatment mode does not consider the complexity of wastewater components, and a large amount of nitrogen heterocycles, polycyclic aromatic hydrocarbons and nitrobenzene organic matters are strong in toxicity and are difficult to remove by a traditional biochemical method. Therefore, how to realize the advanced treatment of the biochemical tail water of the chemical wastewater has important environmental significance.
The coagulating sedimentation method is the most common advanced treatment method for sewage treatment plants in China, but the coagulating sedimentation process focuses on the removal of total phosphorus, and the removal efficiency of organic matters is limited due to the influence of complex water quality. In practical application, the coagulating sedimentation method is generally combined with other advanced treatment technologies, such as adsorption method, membrane separation method, fenton oxidation, ozone oxidation and the like. Chinese patent application No. 201810017810.6 discloses a method for treating artificial stone wastewater by gradient coagulation and adsorption, wherein the artificial stone wastewater is treated by a combined process of a three-stage coagulation sedimentation tank and an adsorption sedimentation tank, and the method has the advantages of large drug consumption, large sludge yield and large equipment occupation area. As another example, chinese patent application No. 201520535667.1 discloses a combined wastewater treatment system of coagulation treatment and membrane separation, and the method still has difficulty in solving the problems of membrane pollution and membrane flux reduction caused by organic matters, thereby increasing the operation cost to a certain extent.
In the prior art, although China patent application No. 201721163647.1 discloses a wastewater treatment system based on an ozone catalytic oxidation and coagulating sedimentation method. However, the method has only simple addition of ozone catalytic oxidation and a coagulating sedimentation method to remove the organic matters, and no synergistic removal effect on the organic matters is seen. Chinese patent application No. 201610367055.5 discloses an ozone coagulation interaction synergistic method for improving the removal efficiency of organic matters, and oxidation and coagulation are simultaneously realized in the same system, and the method needs to prepare ozone water under the condition of ph=3, has complex operation, and is mainly suitable for the advanced treatment of low-concentration biochemical tail water/drinking water.
In summary, the combined technology of the existing coagulating sedimentation method and other advanced treatment technologies can improve the removal effect of the organic matters to a certain extent, but the problems of long process flow, large medicament consumption, complex operation and the like exist, and in addition, the removal effect of the organic matters is only the simple addition of the combined technology.
The ozone catalytic oxidation technology is a high-grade oxidation technology based on strong oxidizing property of ozone, adsorption and catalytic performance of a catalyst, and the oxidation mechanism is mainly that the reaction of hydroxyl groups on the surface of the catalyst and ozone accelerates the generation of hydroxyl free radicals, and has better removal capability on refractory organic matters in water. Coagulant such as aluminum, ferric salt and the like can form hydroxyl polynuclear complex after being dissolved in water, and meanwhile, the zeta potential of colloid particles in the water can be weakened in an ozone environment. Based on the method, the device and the method for deeply purifying the biochemical tail water by ozone catalytic oxidation coupling coagulating sedimentation are developed, the process flow is simplified, the occupied area is reduced, the reaction time is shortened, the energy consumption in the reaction process is reduced, the utilization rate of ozone and catalyst and the removal rate of organic matters in the tail water are effectively improved, and the device and the method have great environmental significance for the advanced treatment process of the biochemical tail water.
Disclosure of Invention
The invention solves the technical problems in the prior art and provides a device and a method for deeply purifying biochemical tail water by ozone catalytic oxidation coupling coagulation sedimentation.
In order to solve the problems, the technical scheme of the invention is as follows:
the device for deeply purifying biochemical tail water by ozone catalytic oxidation coupling coagulation sedimentation comprises a shell, wherein an oxidation area, a coagulation area and a sedimentation area are arranged in the shell;
the bottom of the oxidation zone is provided with a water inlet, an air inlet and a gas-liquid mixing jet device, the water inlet and the air inlet are connected with the gas-liquid mixing jet device, a catalyst layer is arranged in the oxidation zone, and the top of the oxidation zone is provided with an ozone reflux device and a tail gas absorbing device;
the coagulation zone is provided with a tubular mixer, the tubular mixer is provided with a coagulant adding device, the coagulation zone is communicated with the oxidation zone through the tubular mixer, and a vertical folding baffle unit is arranged in the coagulation zone;
the sedimentation area is communicated with the coagulation area through the bottom, an inclined plate unit is arranged in the sedimentation area, an overflow weir is arranged on the side wall of the sedimentation area, and a water outlet guide pipe is arranged at the bottom of the overflow weir;
and mud discharging systems are arranged at the bottoms of the coagulation zone and the sedimentation zone.
Preferably, the number of the tube mixers is 2; the number of the vertical folding baffle units is 6, and the vertical folding baffle units are used for increasing the turbulence of the water body and improving the flocculation effect.
Preferably, the pitch of the sloping plate units is 60-150 mm, and the sloping plate units are used for accelerating the flocculation precipitation.
Preferably, the catalyst used in the catalyst layer is a particle catalyst of metal-supported particle activated carbon, and the metal is a combination of any two or more metals of iron, cerium, manganese, zinc, copper and aluminum.
Preferably, the number of the catalyst layers is one or more, and the addition amount of the single-layer catalyst is 2-4 g/L.
Preferably, the sludge discharge system comprises a sludge hopper and a sludge discharge pipe; and an outlet at the bottom of the sludge hopper is connected with a sludge discharge pipe.
Preferably, a tail gas outlet pipeline is arranged at the top of the oxidation zone, an ozone detector is arranged on the tail gas outlet pipeline, and the tail gas outlet pipeline is respectively connected with the ozone reflux device and the tail gas absorption device through three-way valves.
Preferably, the air inlet is provided with a gas mixing device, and the ozone reflux device is connected into the gas mixing device.
A method for deeply purifying biochemical tail water by coupling ozone catalytic oxidation and coagulating sedimentation comprises the following steps:
step 1: the biochemical tail water and ozone are respectively introduced into a gas-liquid mixing ejector through a water inlet and an air inlet, and then introduced into an oxidation zone;
step 2: the biochemical tail water containing ozone treated in the step 1 is mixed with a coagulant through a tubular mixer and then enters a coagulation zone;
step 3: and (3) enabling the water treated in the coagulation zone in the step (2) to enter a precipitation zone, and discharging the water reaching the standard through a floc sedimentation separation process.
According to the concentration and components of organic matters in the biochemical tail water, the types and layers of the catalyst, the ozone concentration and the coagulant adding amount are regulated. Firstly, removing heterocyclic compounds, humic acids and the like from biochemical tail water through an oxidation zone, and then, deeply removing soluble microbial products and the like in the biochemical tail water through a coagulation zone and a sedimentation zone after ozone-containing effluent is formed.
Preferably, the COD concentration of the inflow water of the oxidation zone ranges from 50mg/L to 200mg/L.
Preferably, the concentration of the ozone in the oxidation zone is 4.0-6.0 mg/min; the hydraulic retention time of the oxidation zone is 10-30 min.
Preferably, the coagulant is any one of aluminum-based, iron-based and aluminum-iron-based inorganic coagulant, and the adding amount is 80-150 mg/L.
Preferably, the hydraulic retention time of the coagulation zone is 5-10 min.
Preferably, the hydraulic retention time of the precipitation zone is 15-30 min.
The advantages of the present invention over the prior art are as follows,
(1) The device for deeply purifying the biochemical tail water by ozone catalytic oxidation coupling coagulation sedimentation has the advantages of small occupied area, short reaction time, simple operation and high organic matter removal rate, is suitable for the biochemical tail water containing various complex and difficult-to-degrade organic matters, is not easily influenced by the fluctuation of the water quality and the salinity of the tail water, and has broad spectrum.
(2) The device for deeply purifying biochemical tail water by coupling ozone catalytic oxidation and coagulating sedimentation can fully utilize ozone in the water discharged from an oxidation zone by placing the three functional zones in the same reaction device, remarkably improve the utilization rate of ozone and coagulant, reduce the consumption of coagulant, and compared with a conventional coagulation and ozone combination method, the device can improve the removal rate of organic matters in the tail water by 20% -30% under the condition of the same ozone and catalyst addition, reduce the consumption of coagulant by 20% -30%, and effectively remove different types of organic matters in different functional zones.
(3) According to the method for deeply purifying biochemical tail water by coupling ozone catalytic oxidation and coagulating sedimentation, on one hand, zeta potential of colloid particles in water is reduced in an ozone environment, and the degree of hydrolytic polymerization of a coagulant is increased, so that colloidal particles are destabilized to form large and heavy floccules, and on the other hand, hydroxyl groups formed by hydrolysis of the surfaces of a catalyst and the coagulant promote ozone to generate hydroxyl free radicals, so that organic matters are effectively removed.
(4) The catalyst layer can be arranged into one or more layers according to the water quality of the inlet water and the outlet water of the ozone catalytic oxidation area, so that the catalyst utilization rate is remarkably improved, the wastewater treatment effect can be further improved by optimizing the ratio of the carrier to the metal of the catalyst, and the catalyst has a wide application prospect in the aspect of treating the biochemical tail water containing complex organic matters.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for deeply purifying biochemical tail water by ozone catalytic oxidation coupling coagulation sedimentation;
in the figure: 1. a water inlet; 2. an air inlet; 3. a gas-liquid mixing jet device; 4. a catalyst layer; 5. coagulant adding device; 6. a tube mixer; 7. a vertical folding baffle unit; 8. a swash plate unit; 9. a sludge hopper; 10. a mud pipe; 11. an overflow weir; 12. a water outlet guide pipe; 13. an ozone detector; 14. an ozone reflux device; 15. a tail gas absorbing device; 16. a gas mixing device; 17. a housing.
Fig. 2 is a partial structure of the plan view of fig. 1.
FIG. 3 shows the coagulant dosage in the coagulating sedimentation zone according to the invention compared with the coagulant dosage in a single coagulation process.
FIG. 4 is a comparison of the zeta potential of colloidal particles in the water of the oxidation zone of the present invention with the zeta potential of raw water.
FIG. 5 is a graph showing the comparison of the floc size in the coagulating sedimentation zone of the present invention with the floc size in a single coagulation process.
Detailed Description
Example 1
A device and a method for deeply purifying biochemical tail water of an ozone catalytic oxidation coupling coagulation sedimentation are provided, wherein COD (chemical oxygen demand) of the biochemical tail water of a sewage treatment plant in a chemical industrial park is 95 mg/L.
The device for deeply purifying biochemical tail water by coupling ozone catalytic oxidation with coagulation sedimentation comprises a shell 17, wherein an oxidation area, a coagulation area and a sedimentation area are arranged in the shell 17;
the bottom of the oxidation zone is provided with a water inlet 1, an air inlet 2 and a gas-liquid mixing jet device 3, the water inlet 1 and the air inlet 2 are connected into the gas-liquid mixing jet device 3, the inside of the oxidation zone is provided with a catalyst layer 4, and the top of the oxidation zone is provided with an ozone reflux device 14 and a tail gas absorbing device 15; preferably, a tail gas outlet pipeline is arranged at the top of the oxidation zone, an ozone detector 13 is arranged on the tail gas outlet pipeline, and the tail gas outlet pipeline is respectively connected with an ozone reflux device 14 and a tail gas absorption device 15 through three-way valves; the gas inlet 2 is provided with a gas mixing device 16, and the ozone reflux device 14 is connected with the gas mixing device 16;
the coagulation zone is provided with a tubular mixer 6, the tubular mixer 6 is provided with a coagulant adding device 5, the coagulation zone is communicated with the oxidation zone through the tubular mixer 6, and a vertical folding baffle unit 7 is arranged in the coagulation zone; preferably, the number of the tube mixers 6 is 2; the number of the vertical folding baffle units 7 is 6, and the vertical folding baffle units are used for increasing the turbulence of the water body and improving the flocculation effect;
the sedimentation area is communicated with the coagulation area through the bottom, an inclined plate unit 8 is arranged in the sedimentation area, an overflow weir 11 is arranged on the side wall of the sedimentation area, and a water outlet guide pipe 12 is arranged at the bottom of the overflow weir 11; preferably, the distance between the sloping plate units 8 is 60-150 mm, so as to accelerate the flocculation precipitation;
mud discharging systems are arranged at the bottoms of the coagulation zone and the sedimentation zone; preferably, the sludge discharge system comprises a sludge hopper 9 and a sludge discharge pipe 10; the bottom outlet of the sludge hopper 9 is connected with a sludge discharge pipe 10.
The device is divided into three functional areas: the oxidation area, the coagulation area and the sedimentation area are communicated. Wherein, the water inlet 1 and the air inlet 2 at the bottom of the oxidation zone are connected with the gas-liquid mixing ejector 3, and a catalyst layer 4 is arranged inside the oxidation zone. The oxidation zone is provided with a catalyst layer 4, the catalyst is granular active carbon loaded by iron and cerium, the single-layer catalyst dosage is 2.0g/L, ozone is prepared by a high-voltage discharge type ozone generator, generated ozone is introduced into the oxidation zone from bottom to top through a microporous aeration head through a gas-liquid mixing jet device 3, an exhaust outlet is provided with an ozone detector 13, and part of ozone gas enters an ozone reflux device 14 according to the concentration of the ozone at an air outlet and is mixed with ozone through a gas mixing device 16; part of the ozone gas enters the tail gas absorption device 15. Ozone concentration was 4.0mg/min and hydraulic retention time was 20min. Biochemical tail water enters from the water inlet and is introduced into the oxidation zone through the gas-liquid mixing ejector 3.
The coagulation zone is communicated with the oxidation zone through tubular mixers, effluent with ozone concentration of 0.7mg/L formed in the oxidation zone enters the coagulation zone, 2 tubular mixers 6 are arranged in the coagulation zone, each mixer is provided with a coagulant adding device 5 for adding coagulant, and 6 hydraulic mixing vertical folding baffles 7 are arranged inside the mixer. The sedimentation area is communicated with the coagulation area through the bottom, an inclined plate unit 8 is arranged in the sedimentation area, the interval between the inclined plates is 110mm, and a water outlet guide pipe 12 is arranged at the bottom of the side wall overflow weir 11. The water treated by the coagulation zone enters a precipitation zone and is discharged after reaching standards in the process of floc sedimentation and separation; the bottoms of the coagulation area and the sedimentation area are provided with a sludge hopper 9 and a sludge discharge pipe 10. The adding amount of the 10% polyaluminium chloride solution (10% is mass fraction, the same applies below) in the coagulation zone is 80mg/L, the flow rate of the tubular mixer is 1.0m/s, and the hydraulic retention time is 8min. The treated water is discharged after reaching the standard in the process of floc sedimentation separation, and the sedimentation time is 20min.
Example 2:
the device and the method for deeply purifying biochemical tail water by coupling ozone catalytic oxidation with coagulating sedimentation in the embodiment change various operation parameters by adopting the same device as in the embodiment 1, and specifically operate as follows: the oxidation zone is provided with two catalyst layers, the single-layer catalyst dosage is 3g/L, the ozone concentration is 4.8mg/min, and the hydraulic retention time is 25min. The coagulation zone is communicated with the oxidation zone through a tubular mixer, and effluent with ozone concentration of 0.8mg/L formed in the oxidation zone enters the coagulation zone. The adding amount of the 12% polyaluminium chloride solution in the coagulation zone is 100mg/L, the flow rate of the tubular mixer is 1.0m/s, and the hydraulic retention time is 8min. The treated water is discharged after reaching the standard in the process of floc sedimentation separation, and the sedimentation time is 25min.
Example 3:
the device and the method for deeply purifying biochemical tail water by coupling ozone catalytic oxidation with coagulation sedimentation in the embodiment change the operation parameters by adopting the same device as in the embodiment 1, and specifically operate as follows: the ozone catalytic oxidation zone is provided with two layers of catalyst layers, the catalyst is granular activated carbon loaded by three metals of iron, cerium and zinc, the single-layer catalyst dosage is 4g/L, the ozone concentration is 5.6mg/min, and the sewage residence time is 30min. The coagulation zone is communicated with the oxidation zone through a tubular mixer, and effluent with ozone concentration of 0.9mg/L formed in the oxidation zone enters the coagulation zone. The adding amount of the 15% polyaluminium chloride solution in the coagulation zone is 120mg/L, the flow rate of the tubular mixer is 1.0m/s, and the hydraulic retention time is 10min. The treated water is discharged after reaching the standard in the process of floc sedimentation separation, and the sedimentation time is 30min.
Example 4:
the device and the method for deeply purifying biochemical tail water by coupling ozone catalytic oxidation with coagulation sedimentation in the embodiment are used for treating the biochemical tail water of a sewage treatment plant in a chemical industry park, the COD is 160mg/L, and the device and the method adopt the same device as in the embodiment 1, change various operation parameters and specifically operate as follows: the ozone catalytic oxidation zone is provided with two layers of catalyst layers, the catalyst is granular activated carbon loaded by three metals of manganese, copper and aluminum, the single-layer catalyst dosage is 4g/L, the ozone concentration is 5.0mg/min, and the sewage residence time is 20min. The coagulation zone is communicated with the oxidation zone through an overflow port, and effluent with ozone concentration of 0.8mg/L formed in the oxidation zone enters the coagulation zone. The adding amount of the 15% polyaluminium chloride solution in the coagulation area is 110mg/L, the flow rate of the tubular mixer is 1.0m/s, and the hydraulic retention time is 10min. The treated water is discharged after reaching the standard in the process of floc sedimentation separation, and the sedimentation time is 25min.
The removal of organic matters from wastewater in each of examples 1 to 4 is shown in Table 1.
Table 1 removal of organics from wastewater units: mg/L
As shown in Table 1, the ozone catalytic coupling coagulating sedimentation process can effectively treat biochemical tail water with different sources and different organic pollutant loads, and the COD of the treated effluent can completely reach the first-level discharge standard of urban sewage treatment plants.
The amounts of coagulant used in the coagulating sedimentation zone in each of examples 1 to 4 are shown in FIG. 3.
As shown in figure 3, the coagulant dosage is reduced by 20-27% compared with the single coagulation process.
The zeta potential of the colloidal particles in the oxidized regions in each example is shown in FIG. 4 by examples 1 to 4.
As shown in FIG. 4, compared with untreated biochemical tail water, ozone can change the electrification condition of the surface of colloidal particles in the biochemical tail water, the zeta potential of the colloidal particles is reduced by 2.7-7.1 mV, and then the hydration film on the surface of the colloidal particles is weakened, so that the destabilization of the colloidal particles is facilitated.
The particle diameters of the flocs formed in the coagulating sedimentation regions in examples 1 to 4 are shown in FIG. 5.
As shown in FIG. 5, compared with the single coagulation process, the particle size of the floccule formed by the polyaluminum chloride coagulant is increased by 40-70%.
Example 5:
comparative examples: the invention is compared with the conventional combination method of coagulation and ozone.
The COD of the biochemical tail water of a sewage treatment plant in a chemical industry park is 95mg/L, and the conventional coagulation and ozone combination method is adopted, and the specific steps are as follows: and the coagulating sedimentation area and the oxidation area are sequentially connected along the flowing direction of the wastewater. The adding amount of the 10% polyaluminum chloride solution in the coagulating sedimentation zone is 80mg/L. The stirring process in the coagulating sedimentation tank is divided into two stages, wherein the stirring speed is 100r/min, and the stirring time is 1min in the first stage; in the second stage, the stirring speed is 20r/min, and the stirring time is 8min. The flocculated water is subjected to solid-liquid separation by an inclined plate sedimentation tank, and the sedimentation time is 20min. And the water inlet of the oxidation zone is communicated with the water outlet of the precipitation zone. The oxidation zone is provided with a catalyst layer, the catalyst is granular active carbon loaded by iron and cerium, the single-layer catalyst dosage is 2g/L, ozone is prepared by a high-voltage discharge type ozone generator, the generated ozone is introduced into an ozone catalytic oxidation tower from bottom to top through a hole aeration head, an ozone detector is arranged at a tail gas outlet, and part of ozone gas enters an ozone reflux device according to the concentration of ozone at a gas outlet and is mixed with ozone through a gas mixing device; part of ozone gas enters the tail gas absorbing device. Ozone concentration was 4.0mg/min and hydraulic retention time was 20min. The water is collected again.
Example 6:
comparative examples: the invention is compared with the conventional combination method of coagulation and ozone.
The COD of the biochemical tail water for treating certain chemical pharmaceutical wastewater is 147mg/L, the conventional coagulation and ozone combination method is adopted, the device and the flow are the same as those of the embodiment 4, and each operation parameter is changed, and the specific operation is as follows: the adding amount of the 12% polyaluminum chloride solution in the coagulating sedimentation zone is 100mg/L. The stirring process in the coagulating sedimentation tank is divided into two stages, wherein the stirring speed is 120r/min, and the stirring time is 1min in the first stage; in the second stage, the stirring speed is 20r/min, and the stirring time is 8min. The flocculated water is subjected to solid-liquid separation by an inclined plate sedimentation tank, and the sedimentation time is 25min. The oxidation zone is provided with two catalyst layers, the single-layer catalyst dosage is 3g/L, the ozone concentration is 4.8mg/min, and the hydraulic retention time is 25min.
Example 7:
comparative examples: the invention is compared with the conventional combination method of coagulation and ozone.
The COD of biochemical tail water of a petrochemical wastewater is 190mg/L, a conventional coagulation and ozone combination method is adopted, the device and the flow are the same as those of the embodiment 4, and each operation parameter is changed, and the specific operation is as follows: the adding amount of the 15% polyaluminum chloride solution in the coagulating sedimentation zone is 120mg/L. The stirring process in the coagulating sedimentation tank is divided into two stages, wherein the stirring speed is 130r/min, and the stirring time is 1min in the first stage; in the second stage, the stirring speed is 20r/min, and the stirring time is 10min. The flocculated water is subjected to solid-liquid separation by an inclined plate sedimentation tank, and the sedimentation time is 30min. The oxidation zone is provided with two catalyst layers, the catalyst is granular activated carbon loaded by iron, cerium and zinc, the single-layer catalyst dosage is 4g/L, the ozone concentration is 5.6mg/min, and the hydraulic retention time is 30min.
The removal of organic matters from wastewater in each of examples 5 to 7 is shown in Table 2.
Table 2 organic matter removal from wastewater unit: mg/L
As shown in Table 2, under the condition that the quality of the inlet water and the operation parameters are kept consistent, the removal rate of organic matters in a coagulating sedimentation zone in the conventional coagulating+ozone combination method is lower than 10%, and the total COD removal rate is only 30% -47%. The present invention (Table 1, examples 1-3) is compared with conventional coagulation+ozone combination methods (Table 2, examples 5-7): the ozone oxidation zone can promote the removal effect of the subsequent coagulating sedimentation zone on organic matters, and the total COD removal rate is improved by 24-28%.
It should be noted that the above-mentioned embodiments are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and the equivalents or alternatives made on the basis of the above description are all included in the scope of the present invention.
Claims (8)
1. The method for deeply purifying biochemical tail water by coupling ozone catalytic oxidation and coagulating sedimentation is characterized by comprising the following steps of:
step 1: the biochemical tail water and ozone are respectively introduced into a gas-liquid mixing ejector through a water inlet and an air inlet, and then introduced into an oxidation zone;
step 2: the biochemical tail water containing ozone treated in the step 1 is mixed with a coagulant through a tubular mixer and then enters a coagulation zone;
step 3: the water treated by the coagulation zone in the step 2 enters a precipitation zone and is discharged after reaching standards through a floc sedimentation separation process;
the device adopted by the method comprises a shell, wherein an oxidation area, a coagulation area and a sedimentation area are arranged in the shell;
the bottom of the oxidation zone is provided with a water inlet, an air inlet and a gas-liquid mixing jet device, the water inlet and the air inlet are connected with the gas-liquid mixing jet device, a catalyst layer is arranged in the oxidation zone, and the top of the oxidation zone is provided with an ozone reflux device and a tail gas absorbing device; the catalyst adopted by the catalyst layer is a granular catalyst of metal-loaded granular active carbon, and the metal is a combination of any two or more metals of iron, cerium, manganese, zinc, copper and aluminum;
the coagulation zone is provided with a tubular mixer, the tubular mixer is provided with a coagulant adding device, the coagulation zone is communicated with the oxidation zone through the tubular mixer, and a vertical folding baffle unit is arranged in the coagulation zone;
the sedimentation area is communicated with the coagulation area through the bottom, an inclined plate unit is arranged in the sedimentation area, an overflow weir is arranged on the side wall of the sedimentation area, and a water outlet guide pipe is arranged at the bottom of the overflow weir;
and mud discharging systems are arranged at the bottoms of the coagulation zone and the sedimentation zone.
2. The method for deeply purifying biochemical tail water by ozone catalytic oxidation coupled coagulation sedimentation according to claim 1, wherein the number of the tubular mixers is 2; the number of the vertical folding baffle units is 6; the pitch of the sloping plate units is 60-150 mm.
3. The method for deeply purifying biochemical tail water by ozone catalytic oxidation coupling coagulating sedimentation according to claim 1, wherein the number of the catalyst layers is one or more, and the addition amount of a single-layer catalyst is 2-4 g/L.
4. The method for deeply purifying biochemical tail water by ozone catalytic oxidation coupling coagulating sedimentation according to claim 1, wherein the sludge discharge system comprises a sludge hopper and a sludge discharge pipe; and an outlet at the bottom of the sludge hopper is connected with a sludge discharge pipe.
5. The method for deeply purifying biochemical tail water by ozone catalytic oxidation coupling coagulating sedimentation according to claim 1, wherein a tail gas outlet pipeline is arranged at the top of the oxidation zone, an ozone detector is arranged on the tail gas outlet pipeline, and the tail gas outlet pipeline is respectively connected with an ozone reflux device and a tail gas absorption device through a three-way valve; the air inlet is provided with a gas mixing device, and the ozone reflux device is connected into the gas mixing device.
6. The method for deeply purifying biochemical tail water by ozone catalytic oxidation coupling coagulating sedimentation according to claim 1, wherein the COD concentration of the inflow water in the oxidation zone ranges from 50mg/L to 200mg/L.
7. The method for deeply purifying biochemical tail water by ozone catalytic oxidation coupling coagulating sedimentation according to claim 1, wherein the concentration of ozone in the oxidation zone is 4.0-6.0 mg/min; the hydraulic retention time of the oxidation zone is 10-30 min; the hydraulic retention time of the coagulation area is 5-10 min; the hydraulic retention time of the precipitation area is 15-30 min.
8. The method for deeply purifying biochemical tail water by ozone catalytic oxidation coupling coagulating sedimentation according to claim 1, wherein the coagulant is any one of aluminum-based, iron-based and aluminum-iron-based inorganic coagulants, and the adding amount is 80-150 mg/L.
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