CN111825200A - Ozone catalytic fluidized bed device and method for treating high-concentration nonbiodegradable organic wastewater - Google Patents
Ozone catalytic fluidized bed device and method for treating high-concentration nonbiodegradable organic wastewater Download PDFInfo
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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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses an ozone catalytic fluidized bed device for treating high-concentration nonbiodegradable organic wastewater, which relates to a sewage treatment technology in the field of environmental protection, and has the structure that: comprises an organic wastewater conveying pipeline and a dissolved gas water conveying pipeline which are used for connecting a sewage storage tank, a sewage pressurizing pump, an ozone generating device, a dissolved gas pump, a fluidized bed reactor and a plurality of control valves; the top of the fluidized bed reactor is provided with a top dissolved gas water distribution pipe which is communicated with a dissolved gas water distribution head for conveying dissolved gas water; also discloses a method for treating the organic wastewater, which comprises the following steps: adding organic wastewater into a sewage storage tank, starting an ozone generating device, and filling a catalyst at the bottom of a fluidized bed reactor; mixing at least a part of ozone generated by the ozone generating device with the organic wastewater, and then conveying the mixture to the dissolved air pump to generate dissolved air water; the gas-dissolving water enters the bottom of the fluidized bed reactor through a pipeline from the gas-dissolving water distribution pipe at the top to the gas-dissolving water distribution head and contacts with the granular catalyst to generate catalytic degradation reaction.
Description
Technical Field
The invention relates to the field of ecological environment protection sewage treatment, in particular to advanced oxidation equipment and a treatment method in the field of high-concentration nonbiodegradable industrial sewage treatment equipment, and specifically relates to an ozone catalytic fluidized bed device and a treatment method for treating high-concentration nonbiodegradable organic wastewater.
Background
According to the national annual book of Chinese statistics in 2018 of the State statistics office, the total amount of the national wastewater discharge in 2017 is 699.66 tons, and the emission amount of industrial wastewater in 31 main urban wastewater is 239.16 hundred million tons. The analysis report of the domestic industrial sewage treatment industry in 2019, namely the evaluation of market operation situation and development prospect shows that the industrial sewage treatment industry in China just steps into a rapid growth period in the field of industrial sewage treatment, and the market scale can keep higher accelerated development. By 2024, the market scale of industrial wastewater in China is expected to break through the 3500 hundred million Yuan major customs. The industrial sewage is relatively complex in pollutant, contains a large amount of toxic and harmful substances which are difficult to degrade by microorganisms, and has relatively large difference in pollutant types and concentrations in sewage discharge of different types of industrial enterprises, thereby providing higher technical requirements for the treatment of the industrial sewage.
For such industrial wastewater, advanced oxidation technology is currently generally adopted as pretreatment, final advanced treatment or both pretreatment and final treatment. The advanced oxidation technology widely used in engineering mainly includes Fenton series method, ozone catalytic oxidation and wet catalytic oxidation method. The advanced oxidation technology is mainly used for treating the industrial wastewater difficult to biodegrade and has two purposes, namely directly oxidizing and degrading organic components in the wastewater, improving the biodegradability of the wastewater, namely improving the B/C value of effluent, and combining a microorganism treatment unit to ensure that the wastewater treatment meets the requirements of national relevant discharge standards. The Fenton series method is easy to generate a large amount of sludge and frequently adjust the pH value in the application process; wet catalytic oxidation is not widely used because of the high temperature and pressure involved in the operation process, which places high demands on the equipment materials and operation.
Ozone oxidation is an efficient water treatment technology, and ozone has higher oxidation-reduction potential (2.07ev) than common oxidants such as chlorine gas, hydrogen peroxide and the like, so that most organic pollutants in water can be oxidized and decomposed to achieve the aim of purifying water. Ozone oxidation presents several problems in practical engineering applications, mainly expressed as: (1) low ozone utilization rate, and (2) incomplete decomposition of organic matters, which is not suitable for treating high-concentration wastewater difficult to biodegrade. In response to the above problems with ozone oxidation, ozone catalytic oxidation technology has been developed. The catalytic oxidation of ozone promotes the generation of hydroxyl free radicals (. OH) in the reaction process under the action of a catalyst, and increases the oxidative degradation capability and the mineralization capability of organic pollutants. Generally, the catalytic ozonation technology for treating low-concentration wastewater difficult to biodegrade is mature and widely applied in engineering, but is greatly limited due to the form of a reactor and the development of a catalyst in treating high-concentration wastewater (such as COD greater than 5000 mg/L).
Disclosure of Invention
The invention provides an ozone catalytic fluidized bed device for treating high-concentration organic wastewater difficult to biodegrade, which solves the problems of low ozone utilization rate, easy catalyst hardening, low organic matter mineralization degree and the like of a traditional packed tower reactor when treating high-concentration organic wastewater.
The technical scheme of the invention is as follows:
an ozone catalytic fluidized bed device for treating high-concentration nonbiodegradable organic wastewater comprises an organic wastewater conveying pipeline and a dissolved gas water conveying pipeline which are used for connecting a sewage storage tank, a sewage pressurizing pump, an ozone generating device, a dissolved gas pump, a fluidized bed reactor and a plurality of control valves;
the dissolved air pump is used for mixing the organic wastewater from the organic wastewater conveying pipeline and the ozone from the ozone generating device to generate dissolved air water;
the organic wastewater conveying pipeline is arranged at the upstream of the dissolved air pump; the dissolved gas water delivery pipeline is arranged at the downstream of the dissolved gas pump; the organic wastewater conveying pipeline is sequentially provided with a first junction joint, a second junction joint and a third junction joint in sequence by taking the flow direction of organic wastewater as a sequence;
the top of the fluidized bed reactor is provided with a top dissolved gas water distribution pipe which is communicated with at least one dissolved gas water distribution head arranged at the bottom and used for conveying the dissolved gas water treated by the dissolved gas pump into the fluidized bed reactor through the dissolved gas water distribution head;
and a water outlet is formed in the upper part of the side wall of the fluidized bed reactor and used for discharging the wastewater treated by the fluidized bed reactor.
In the technical scheme, the top of the fluidized bed reactor is provided with a pool top ozone distribution pipe, the bottom of the fluidized bed reactor is provided with a fluidized bed bottom gas distribution gallery, and at least one bottom ozone gas dissolving head arranged in the fluidized bed bottom gas distribution gallery; the outlet of the pool top ozone distribution pipe is communicated with the bottom ozone dissolved air head and is used for conveying ozone from the ozone generating device to the fluidized bed reactor through the pool top ozone distribution pipe and the bottom ozone dissolved air head;
the outlet pipeline of the ozone generating device is connected with a branched pipeline, wherein a first branched pipeline of the ozone generating device is connected with the ozone distributing pipe at the top of the tank, and a second branched pipeline of the ozone generating device is converged with the organic wastewater conveying pipeline at the second converging connection part.
In the technical scheme, a water return pipe is arranged at the lower part of the fluidized bed reactor, and a pipeline connected with an outlet of the water return pipe is converged with the organic wastewater conveying pipeline at the first converging connection part;
preferably said sewage pressurization pump is disposed upstream of said first junction connection on said organic wastewater delivery conduit;
a gas-water separator and a pressure stabilizing tank are arranged on the gas-dissolved water conveying pipeline;
the gas-water separator is used for removing redundant gas.
Preferably, the third junction of the organic wastewater conveying pipeline is connected with an air interface, and the flowing air is conveyed to the dissolved air pump and the fluidized bed reactor through the air interface.
In the technical scheme, a return pipe is arranged on the side wall of the fluidized bed reactor, the upper part of the return pipe is communicated with the upper part of the fluidized bed reactor, and a return water port of the return pipe is communicated with the lower part of the fluidized bed reactor; the water outlet is arranged at the upper part of the return pipe; the top of the return pipe is connected with a tail gas decomposer for receiving and decomposing ozone dissolved out from the treated sewage.
Preferably, the water distribution head for dissolved gas water and the ozone dissolved gas head at the bottom are both multiple and are uniformly distributed at the bottom of the fluidized bed reactor.
Another aspect of the present invention provides a method for treating high concentration organic wastewater difficult to biodegrade using at least one set of catalytic ozonated bed apparatus as set forth in any one of claims 1 to 6, comprising the steps of:
adding organic wastewater into a sewage storage tank, starting an ozone generating device, and filling a catalyst at the bottom of a fluidized bed reactor;
mixing at least a part of ozone generated by the ozone generating device with the organic wastewater, and then conveying the mixture to the dissolved air pump to generate dissolved air water;
the gas-dissolving water enters the bottom of the fluidized bed reactor through a pipeline from the gas-dissolving water distribution pipe at the top to the gas-dissolving water distribution head and fully contacts with the granular catalyst to generate catalytic degradation reaction.
In the technical scheme of the method for treating the organic wastewater, the ozone quantity generated by an ozone generating device can be regulated and controlled; and can provide the following treatment modes for organic wastewater with different concentrations:
when low-concentration organic wastewater is treated, the ozone generating device and the outlet pipeline thereof are controlled, all ozone generated by the ozone generating device and the organic wastewater are mixed and then are conveyed to the dissolved air pump to generate dissolved air water, and then enter the fluidized bed reactor through the pipeline from the top dissolved air water distribution pipe to the dissolved air water distribution head to fully contact with the catalyst and generate catalytic oxidation; or controlling the ozone generating device and the outlet pipeline thereof to ensure that all ozone generated by the ozone generating device is directly introduced into the fluidized bed reactor through the ozone gas distribution pipe at the top of the tank and the ozone gas dissolving head at the bottom of the tank to fully contact with the catalyst and generate catalytic oxidation;
when high-concentration organic wastewater is treated, the ozone generating device and the outlet pipeline thereof are controlled, part of generated ozone is mixed with the organic wastewater and then is conveyed to the dissolved air pump to generate dissolved air water, and then enters the fluidized bed reactor through the pipeline from the top dissolved air water distribution pipe to the dissolved air water distribution head to fully contact with the catalyst and generate catalytic oxidation; the other part is directly introduced into the fluidized bed reactor through an ozone gas distribution pipe at the top of the tank and an ozone gas dissolving head at the bottom to fully contact with the catalyst and generate catalytic oxidation;
when higher-concentration organic wastewater is treated, the ozone generating device and the outlet pipeline thereof are controlled, so that part of generated ozone is mixed with the organic wastewater and then is conveyed to the dissolved air pump to generate dissolved air water, and the other part of generated ozone is directly introduced into the fluidized bed reactor through the ozone gas distribution pipe at the top of the tank through the ozone gas dissolving head at the bottom to be fully contacted with the catalyst and generate catalytic oxidation; and through the third confluence joint and the air interface, air is fully mixed by the dissolved air pump and then enters the fluidized bed reactor through the top dissolved air water distribution pipe and the dissolved air water distribution head so as to ensure that the granular catalyst filled in the fluidized bed reactor is in a fluidized state.
In the technical scheme, when the concentration of organic matters in the water discharged from the water outlet after being treated by the fluidized bed reactor does not meet the effluent water quality requirement, another set of ozone catalytic fluidized bed device as claimed in any one of claims 1 to 6 is additionally arranged for carrying out next-stage repeated treatment, wherein the water discharged from the water outlet of the previous-stage ozone catalytic fluidized bed device is used as organic wastewater of the next-stage ozone catalytic fluidized bed device; the treatment is repeated until the designed effluent quality requirement is met.
Preferably, in the above technical solution,
controlling the sewage entering the fluidized bed reactor to stay for 1-3 hours;
the unit dosage of ozone is 1-4g per liter of water per hour;
the usage amount of the granular catalyst is 10-20% of the volume of the fluidized bed reactor.
A large number of application experiments prove that sewage containing a large number of toxic and harmful organic matters which are difficult to biodegrade cannot meet the technical requirements by adopting advanced oxidation technologies such as electrocatalytic oxidation and Fenton reagent methods and a method for directly adding an oxidant. After the ozone catalytic fluidized bed device and the process are adopted for treatment, the COD removal rate is ideal, the B/C value is obviously improved, and the requirement of a subsequent process/treatment unit on the water quality of inlet water is met. The embodiments section provides a partial application data example application effect.
Compared with the prior art, the process has the following advantages:
(1) the reactor form of the fluidized bed is adopted, so that the contact reaction area of ozone and the granular catalyst is increased, the utilization rate of the ozone is increased, and the organic load of the whole system and the removal rate of organic pollutants in sewage are improved.
(2) The reactor form of the fluidized bed is adopted, so that the problem that the traditional packed tower loses efficacy due to the fact that a catalyst is hardened under the condition that the concentration of water inlet organic matters is too high is solved.
(3) Ozone generated by the ozone generating device can enter the fluidized bed reactor through two modes of the ozone gas dissolving head and the gas dissolving pump. The dissolving amount and the reflux amount of the ozone are increased, and simultaneously, sufficient power is provided for fluidization of the particle catalyst.
(4) Different operation modes can be flexibly adopted according to the concentration of pollutants in the sewage, and the current situation that the traditional ozone catalytic equipment is only suitable for treating low-concentration sewage is changed.
(5) The device and the process are superior to the prior advanced oxidation technologies such as electrocatalysis, Fenton reagents, wet catalytic oxidation processes and the like in treatment effect, investment and operation cost.
Drawings
FIG. 1 is a schematic view showing the construction of an ozone catalytic fluidized bed apparatus in a typical example of the present invention.
Fig. 2 is a schematic view of the structure of the fluidized bed reactor of fig. 1.
FIG. 3 is a top view of the bottom gas distribution gallery of the fluidized bed of FIG. 2;
reference numerals: the device comprises a sewage storage tank (1), a sewage pressure pump (2), an ozone generating device (3), a dissolved air pump (4), an air-water separator (5), a pressure stabilizing tank (6), a fluidized bed reactor (7), a water return pipe (8), a pool top ozone gas distribution pipe (9), a fluidized bed bottom gas distribution gallery (10), a dissolved air water distribution head (11), a top dissolved air water distribution pipe (12), a bottom ozone gas dissolution head (13), a return pipe (14), a water outlet (15), a return water port (16), a tail gas decomposer (17), a pool top inspection port (18), a granular catalyst (19) and an air inlet (20).
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples. The following examples are given by way of illustration and description of the present invention and are not intended to limit the scope of the present invention.
Example 1
In all embodiments of the invention, an ozone catalytic fluidized bed device for treating high-concentration nonbiodegradable organic wastewater is provided, which structurally comprises an organic wastewater conveying pipeline, a dissolved gas water conveying pipeline, a sewage pressurizing pump 2, an ozone generating device 3, a dissolved gas pump 4, a fluidized bed reactor 7 and a plurality of control valves; the ozone generating device 3 is used for generating ozone; the dissolved air pump 4 is used for mixing the organic wastewater from the organic wastewater conveying pipeline and the ozone from the ozone generating device 3 to generate dissolved air water; the organic wastewater conveying pipeline is arranged at the upstream of the dissolved air pump 4; the dissolved gas water delivery pipeline is arranged at the downstream of the dissolved gas pump 4; the organic wastewater conveying pipeline is sequentially provided with a first junction, a second junction and a third junction in sequence by taking the flow direction of the organic wastewater as the sequence.
As shown in fig. 2, a top water distribution pipe 12 for dissolved gas water is arranged at the top of the fluidized bed reactor 7, the top water distribution pipe 12 for dissolved gas water is communicated with at least one water distribution head 11 for dissolved gas water arranged at the bottom, and the water distribution head 11 for dissolved gas water is used for conveying the dissolved gas water treated by the dissolved gas pump 4 into the fluidized bed reactor 7; the upper part of the side wall of the fluidized bed reactor 7 is provided with a water outlet 15 for discharging the wastewater treated by the fluidized bed reactor 7.
In some embodiments, as shown in fig. 2, wherein the fluidized bed reactor 7 is further provided with a tank top ozone distribution pipe 9 at the top, a fluidized bed bottom distribution corridor 10 at the bottom, and at least one bottom ozone dissolving head 13 arranged in the fluidized bed bottom distribution corridor 10; the outlet of the pool top ozone distributing pipe 9 is communicated with the bottom ozone dissolving head 13 and is used for conveying the ozone from the ozone generating device 3 to the fluidized bed reactor 7 through the pool top ozone distributing pipe 9 and the bottom ozone dissolving head 13.
The outlet pipeline of the ozone generating device 3 is connected with a branched pipeline, wherein the first branched pipeline is connected with the ozone distributing pipe 9 at the top of the tank, and the second branched pipeline is converged with the organic wastewater conveying pipeline at the second converging joint.
In some embodiments, the lower part of the fluidized-bed reactor 7 is provided with a water return pipe 8, and the pipe to which the outlet of the water return pipe 8 is connected merges with the organic wastewater conveying pipe at a first merging connection.
In some embodiments, a sewage pressurization pump 2 is disposed on the organic wastewater transport conduit upstream of the first confluence junction.
In some embodiments, a gas-water separator 5 and a surge tank 6 are provided between the dissolved air pump 4 and the top dissolved air water distributor 12.
In some embodiments, the third junction of the organic wastewater delivery conduit is connected to an air connection 20 for delivering the motive air to the dissolved air pump 4 and to the fluidized bed reactor 7.
In most embodiments, a return pipe 14 is provided on the side wall of the fluidized bed reactor 7, the upper portion of the return pipe 14 communicates with the upper portion of the fluidized bed reactor 7, and a return water port 16 of the return pipe 14 communicates with the lower portion of the fluidized bed reactor 7; the water outlet 15 is arranged at the upper part of the return pipe 14; the top of the return pipe 14 is connected with a tail gas decomposer 17 for receiving and decomposing ozone dissolved in the treated sewage.
In most embodiments, as shown in fig. 3, the water distribution head 11 for dissolved gas water and the ozone dissolved gas head 13 at the bottom are both multiple and are uniformly distributed at the bottom of the fluidized bed reactor 7.
The ozone catalytic fluidized bed device can also comprise a sewage storage tank 1, or not, and can be directly communicated with the outlet of the existing sewage storage tank of a user.
Example 2
In a preferred embodiment of the present invention as shown in fig. 1, the ozone catalytic fluidized bed apparatus comprises a sewage storage tank 1, a sewage pressurizing pump 2, an ozone generating device 3, a dissolved air pump 4, an air-water separator 5, a surge tank 6, a fluidized bed reactor 7, a water return pipe 8, a tank top ozone distribution pipe 9, a fluidized bed bottom air distribution gallery 10, a dissolved air water distribution head 11, a top dissolved air water distribution pipe 12, a bottom ozone dissolved air head 13, a return pipe 14, a water outlet 15, a return water port 16 and a tail gas decomposer 17 which are connected by pipes. In which a fluidized bed reactor 7 is packed with a particulate catalyst 19. The top of the fluidized bed reactor 7 is provided with a tank top inspection port 18.
Wherein, a part of the ozone generated by the ozone generating device 3 passes through the ozone gas distribution pipe 9 at the top of the tank, and the bottom ozone gas dissolving head 13 arranged at the bottom of the tank is directly introduced into the fluidized bed reactor 7 to be fully contacted with the granular catalyst 19 filled in the fluidized bed and generate catalytic oxidation, thereby playing the function of degrading organic matters in the sewage. And the other part of ozone and the sewage in the sewage storage tank 1 enter the dissolved air pump 4 together with the sewage which flows back from the water return pipe 8 at the bottom of the fluidized bed reactor 7 through the sewage pressurizing pump 2 for full dissolved air mixing, and then enter the bottom of the fluidized bed reactor 7 through the water distribution pipe 12 for connecting the top dissolved air water to fully contact with the granular catalyst 19, so that the purpose of degrading organic pollutants in the sewage and the effect of fluidizing the granular catalyst 19 are achieved.
In the preferred embodiment of the present invention, especially when treating high concentration organic wastewater, a part of the ozone generated by the ozone generator 3 is mixed with the wastewater in the wastewater storage tank 1 and the wastewater returned through the water return pipe 8 by the dissolved air pump 4, and the mixed solution is fed into the fluidized bed reactor 7. The purpose of mixing with the return water is to reduce the concentration of organic matters in the sewage entering the fluidized bed reactor 7, reduce the design load of the fluidized bed reaction and improve the sewage treatment efficiency.
In a preferred embodiment of the invention, the treated water outlet 15 of the fluidized bed reactor 7 is arranged in the upper part of the return pipe 14 of the fluidized bed reactor 7. Part of the granular catalyst 19 flowing out of the fluidized bed reactor 7 and part of the treated sewage reenter the bottom of the fluidized bed reactor 7 through the backflow water port 16 and the water distribution head 11 for dissolved gas water at the bottom of the pool to release the sewage dissolved with ozone, the ozone dissolved in the ozone dissolving head 13 is fully mixed and generates catalytic oxidation reaction, the concentration of organic matters in the inlet water can be reduced, and the granular catalyst 19 can be prevented from losing.
In the preferred embodiment of the present invention, if the concentration of organic matters in the sewage entering the fluidized bed reactor 7 through the sewage storage tank 1 is low, all the ozone generated by the ozone generating device 3 can be directly and fully mixed with the sewage in the sewage storage tank 1 through the dissolved air pump 4, and then enter the fluidized bed reactor 7 through the top dissolved air water distribution pipe 12 and the dissolved air water distribution head 11.
In the preferred embodiment of the present invention, if the concentration of organic matters in the wastewater entering the fluidized bed reactor 7 through the wastewater storage tank 1 is low, all ozone generated by the ozone generating device 3 can be directly released into the fluidized bed reactor 7 through the ozone gas distribution pipe 9 on the top of the tank through the ozone gas dissolving head 13 on the bottom by the control valve, and fully contacts with the granular catalyst 19 in the fluidized bed reactor 7 to generate catalytic oxidation reaction.
In order to ensure that the granular catalyst 19 in the fluidized bed reactor 7 is in a fluidized state, the sewage in the sewage storage tank 1 and the air from the air interface 20 are fully mixed by the dissolved air pump 4, then reach the dissolved air water distribution head 11 through the top dissolved air water distribution pipe 12, and then enter the fluidized bed reactor 7 so as to ensure that the granular catalyst 19 filled in the fluidized bed reactor 7 is in a fluidized state.
In the preferred embodiment of the present invention, if the concentration of organic matters in the sewage from the sewage storage tank 1 is too high, the concentration of organic matters in the effluent from the water outlet 15 is still high, and the effluent from the fluidized bed reactor 7 through the water outlet 15 can be further treated by adding the first-stage fluidized bed reactor until the designed effluent quality requirement is met. The secondary fluidized bed reactor operates in the same manner as the fluidized bed reactor 7 can alternatively operate.
Wastewater treatment was carried out using the apparatus of example 2:
wherein the used granular catalyst 19 is a commercial ozone catalyst particle which is purchased from Lontai environment-friendly; and other similar products can be used for substitution without limitation.
Application example 1:
high-concentration medical wastewater in a certain pharmaceutical park in Sichuan contains a large amount of toxic and harmful organic matters which are difficult to biodegrade. The wastewater is relatively deep in chroma, is black and is accompanied by foul odor, the COD content is about 58000mg/L, the pH value is 7-8, and the TDS: 20000 mg/L-30000 mg/L. The sewage is treated by advanced oxidation technologies such as electrocatalytic oxidation and Fenton reagent method and a method for directly adding an oxidant, and the technical requirements are not met.
The amount of the particulate catalyst 19 used was 20% by volume of the fluidized bed reactor 7.
In the application example, all ozone generated by the ozone generating device 3 is directly and fully mixed with sewage in the sewage storage tank 1 through the dissolved air pump 4, and then enters the fluidized bed reactor 7 through the top dissolved air water distribution pipe 12 and the dissolved air water distribution head 11. A first stage fluidized bed reactor is used.
After raw water is diluted according to the ratio of 1:1, adding the raw water into a sewage storage tank 1, starting an ozone generating device 3, testing the adding amount of ozone under the running state, and determining the optimal adding amount according to the effluent quality judgment.
And respectively recording the states of the water sample in the retention time of 1h, 2h and 3h, and sampling for detection. The results are shown in Table 1.
TABLE 1 COD content and removal rate of pharmaceutical wastewater at different reaction times
| Serial number | Catalytic reaction time of ozone | COD(mg/L) | Removal Rate (%) | B/C value |
| 1 | 0 | 28700 | --- | 0.30 |
| 2 | 1hr | 16370 | 42.96 | --- |
| 3 | 2hr | 14700 | 48.78 | --- |
| 4 | 3hr | 11860 | 58.67 | 0.46 |
Under the condition that the adding amount of ozone is 2g/L ∙ h, COD in the wastewater can be effectively reduced through the catalytic oxidation reaction of the ozone, and the removal rate of the COD reaches 58.67% after 3 hours of oxidation. The B/C value of the wastewater after the ozone catalytic oxidation treatment is obviously improved (reaching 0.46, the B/C value of raw water is 0.30), the biodegradability is greatly improved, and the water quality requirement of the subsequent process inlet water is met. The treatment effect is superior to that of advanced oxidation technologies such as electrocatalysis, Fenton reagent, wet catalytic oxidation process and the like.
Application example 2:
the sewage generated by the center is recovered and refined from the waste engine oil in Sichuan. The water contains partial suspended matters, has deep chroma, is accompanied by foul smell, has high organic pollutant concentration and COD content up to 35000mg/L, and is difficult to treat by adopting the conventional process.
The granular catalyst 19 is a granular catalyst of an ozone reactor which is a commercially available product and contains a transition metal, a rare earth metal and an oxidation metal as effective catalyst components, and the amount of the granular catalyst is 15% of the volume of the fluidized bed reactor.
In the embodiment of the application, all ozone generated by the ozone generating device 3 is directly and fully mixed with sewage in the sewage storage tank 1 through the dissolved air pump 4, and then enters the fluidized bed reactor 7 through the top dissolved air water distribution pipe 12 and the dissolved air water distribution head 11. A first stage fluidized bed reactor is used. And testing the ozone adding amount under the running state, and determining the optimal adding amount.
And respectively recording the states of the water sample in the retention time of 1h, 2h and 3h, and sampling for detection. The results are shown in Table 2.
Through the treatment of the ozone catalytic fluidized bed device, the adding amount of ozone is adjusted to be 1.6 g/L.h, the hydraulic retention time is controlled to be 3h, the COD content of raw water is reduced from 35000mg/L to 15820mg/L, the overall removal rate of the COD content in the water reaches 54.8 percent, and the technical requirement of subsequent process treatment is met.
TABLE 2 COD content and removal rate of the waste oil recovered sewage in different reaction times
| Serial number | Catalytic reaction time of ozone | COD(mg/L) | Removal Rate (%) |
| 1 | 0hr | 35000 | --- |
| 2 | 1hr | 23940 | 31.6 |
| 3 | 2hr | 18480 | 47.2 |
| 4 | 3hr | 15820 | 54.8 |
Application example 3:
condensate water obtained after desalting hydrazine hydrate wastewater generated by a Yibin chemical plant is colorless and transparent in water quality, has pungent odor, and has the pH value of 9-10 and the COD: 1155mg/L, B/C:0.21, biodegradability is poor.
The granular catalyst 19 is a commercially available product, and is an ozone reactor granular catalyst containing transition metal, rare earth metal, and oxidation metal as effective catalyst components, and is used in an amount of 10% by volume of the fluidized bed reactor 7.
In the embodiment of the application, all the ozone generated by the ozone generating device 3 directly passes through the ozone gas distribution pipe 9 at the top of the tank and the ozone gas dissolving head 13 at the bottom, and directly enters the fluidized bed reactor 7 to fully contact with the granular catalyst 19 in the fluidized bed reactor 7 and generate catalytic oxidation reaction. And testing the ozone adding amount under the running state, and determining the optimal adding amount.
And respectively recording the states of the water sample in the retention time of 1h, 2h and 3h, and sampling for detection. The results are shown in Table 3.
TABLE 3 COD content and removal rate of condensate after desalination of hydrazine hydrate wastewater at different reaction times
| Serial number | Catalytic reaction time of ozone | COD(mg/L) | Removal Rate (%) | B/C |
| 1 | 0.0hr | 1155 | --- | 0.21 |
| 2 | 0.5hr | 811.8 | 29.71 | -- |
| 3 | 1.0hr | 699.6 | 39.42 | -- |
| 4 | 1.5hr | 574.2 | 50.28 | -- |
| 5 | 2.0hr | 455.4 | 60.57 | -- |
| 6 | 2.5hr | 389.4 | 66.28 | 0.36 |
Ozone unit dosage: 0.38 g/L.h, the COD in the wastewater can be effectively reduced by ozone catalytic oxidation, and the removal rate of the COD reaches 66.28% after 2.5h of oxidation; the B/C value of the wastewater after the catalytic oxidation treatment of the ozone is improved from 0.21 to 0.36, and the technical requirements of subsequent treatment units are met.
Claims (10)
1. An ozone catalytic fluidized bed device for treating high-concentration organic wastewater difficult to biodegrade is characterized in that:
comprises an organic wastewater conveying pipeline and a dissolved gas water conveying pipeline which are used for connecting a sewage storage tank (1), a sewage booster pump (2), an ozone generating device (3), a dissolved gas pump (4), a fluidized bed reactor (7) and a plurality of control valves;
the dissolved air pump (4) is used for mixing the organic wastewater from the organic wastewater conveying pipeline and the ozone from the ozone generating device (3) to generate dissolved air water;
the organic wastewater conveying pipeline is arranged at the upstream of the dissolved air pump (4); the dissolved gas water delivery pipeline is arranged at the downstream of the dissolved gas pump (4); the organic wastewater conveying pipeline is sequentially provided with a first junction joint, a second junction joint and a third junction joint in sequence by taking the flow direction of organic wastewater as a sequence;
the top of the fluidized bed reactor (7) is provided with a top dissolved gas water distribution pipe (12), and the top dissolved gas water distribution pipe (12) is communicated with at least one dissolved gas water distribution head (11) arranged at the bottom and used for conveying the dissolved gas water treated by the dissolved gas pump (4) into the fluidized bed reactor (7) through the dissolved gas water distribution head (11);
and a water outlet (15) is arranged at the upper part of the side wall of the fluidized bed reactor (7) and is used for discharging the wastewater treated by the fluidized bed reactor (7).
2. The catalytic ozonation fluid bed apparatus of claim 1,
wherein the top of the fluidized bed reactor (7) is provided with a tank top ozone distribution pipe (9), the bottom of the fluidized bed reactor is provided with a fluidized bed bottom gas distribution gallery (10), and at least one bottom ozone dissolving head (13) arranged in the fluidized bed bottom gas distribution gallery (10); the outlet of the pool top ozone distributing pipe (9) is communicated with the bottom ozone dissolving head (13) and is used for conveying ozone from the ozone generating device (3) to the fluidized bed reactor (7) through the pool top ozone distributing pipe (9) and the bottom ozone dissolving head (13);
the outlet pipeline of the ozone generating device (3) is connected with a branched pipeline, wherein the first branched pipeline of the ozone generating device is connected with the ozone distributing pipe (9) at the top of the tank, and the second branched pipeline of the ozone generating device is converged with the organic wastewater conveying pipeline at the second converging connection part.
3. The catalytic ozonation fluid bed apparatus of claim 2,
a water return pipe (8) is arranged at the lower part of the fluidized bed reactor (7), and a pipeline connected with an outlet of the water return pipe (8) is converged with the organic wastewater conveying pipeline at the first converging connection part;
preferably said sewage pressurization pump (2) is disposed upstream of said first confluence connection on said organic wastewater delivery conduit;
a gas-water separator (5) and a pressure stabilizing tank (6) are arranged on the dissolved gas-water conveying pipeline;
the gas-water separator (5) is used for removing redundant gas.
4. The catalytic ozonation bed apparatus according to claim 1, wherein the third junction of the organic wastewater delivery pipes is connected with an air interface (20), and the air interface (20) is used for delivering flowing air to the dissolved air pump (4) and the fluidized bed reactor (7).
5. The catalytic ozonation fluid bed apparatus according to claim 1, wherein a return pipe (14) is arranged on the side wall of the fluidized bed reactor (7), the upper part of the return pipe (14) is communicated with the upper part of the fluidized bed reactor (7), and a return water port (16) of the return pipe (14) is communicated with the lower part of the fluidized bed reactor (7); the water outlet (15) is arranged at the upper part of the return pipe (14); the top of the return pipe (14) is connected with a tail gas decomposer (17) which is used for receiving and decomposing ozone dissolved out in the treated sewage.
6. The catalytic ozonation fluid bed apparatus according to any one of claims 2 to 5, wherein the water distribution head (11) for dissolved air water and the ozone dissolution head (13) at the bottom are both multiple and uniformly distributed at the bottom of the fluidized bed reactor (7).
7. A method for treating high-concentration organic wastewater difficult to biodegrade, which is characterized by adopting at least one set of ozone catalytic fluidized bed device as claimed in any one of claims 1 to 6, and comprising the following steps:
adding organic wastewater into a sewage storage tank (1), starting an ozone generating device (3), and filling a catalyst (19) at the bottom of a fluidized bed reactor (7);
mixing at least a part of ozone generated by the ozone generating device (3) with the organic wastewater, and then conveying the mixture to the dissolved air pump (4) to generate dissolved air water;
the gas-dissolving water enters the bottom of the fluidized bed reactor (7) through a pipeline from the gas-dissolving water distribution pipe (12) at the top to the gas-dissolving water distribution head (11) and fully contacts with the granular catalyst (19) to generate catalytic degradation reaction.
8. The method according to claim 7, wherein the amount of ozone generated by the ozone generating device (3) is controlled; and can provide the following treatment modes for organic wastewater with different concentrations:
when low-concentration organic wastewater is treated, the ozone generating device (3) and an outlet pipeline thereof are controlled, all ozone generated by the ozone generating device is mixed with the organic wastewater and then is conveyed to the dissolved air pump (4) to generate dissolved air water, and then enters the fluidized bed reactor (7) through a pipeline from the top dissolved air water distribution pipe (12) to the dissolved air water distribution head (11) to fully contact with the catalyst (19) and generate catalytic oxidation; or the ozone generating device (3) and the outlet pipeline thereof are controlled to ensure that all ozone generated by the ozone generating device is directly introduced into the fluidized bed reactor (7) through the ozone gas distribution pipe (9) at the top of the tank and the bottom ozone gas dissolving head (13) to be fully contacted with the catalyst (19) and generate catalytic oxidation;
when high-concentration organic wastewater is treated, the ozone generating device (3) and an outlet pipeline thereof are controlled, part of generated ozone is mixed with the organic wastewater and then is conveyed to the dissolved air pump (4) to generate dissolved air water, and then enters the fluidized bed reactor (7) through a pipeline from the top dissolved air water distribution pipe (12) to the dissolved air water distribution head (11) to be in full contact with the catalyst (19) and generate catalytic oxidation; the other part is directly introduced into the fluidized bed reactor (7) through an ozone gas distribution pipe (9) at the top of the tank and a bottom ozone gas dissolving head (13) to fully contact with the catalyst (19) and generate catalytic oxidation;
when higher-concentration organic wastewater is treated, the ozone generating device (3) and an outlet pipeline thereof are controlled, part of generated ozone is mixed with the organic wastewater and then is conveyed to the dissolved air pump (4) to generate dissolved air water, and the other part of generated ozone is directly introduced into the fluidized bed reactor (7) through the ozone gas distribution pipe (9) at the top of the tank through the ozone gas dissolving head (13) at the bottom to fully contact with the catalyst (19) and generate catalytic oxidation; and through the third junction and the air interface (20), air is fully mixed by the dissolved air pump (4) and then enters the fluidized bed reactor (7) through the top dissolved air water distribution pipe (12) and the dissolved air water distribution head (11) to ensure that the granular catalyst (19) filled in the fluidized bed reactor (7) is in a fluidized state.
9. The method according to claim 7 or 8, characterized in that when the concentration of organic matters in the water discharged through the water outlet (15) after being treated by the fluidized bed reactor (7) does not meet the effluent quality requirement, another set of ozone catalytic fluidized bed device according to any one of claims 1 to 6 is added for the next-stage repeated treatment, wherein the water discharged from the water outlet (15) of the previous-stage ozone catalytic fluidized bed device is used as organic wastewater of the next-stage ozone catalytic fluidized bed device; the treatment is repeated until the designed effluent quality requirement is met.
10. The method according to any one of claims 7 to 9,
controlling the sewage entering the fluidized bed reactor (7) to stay for 1-3 hours;
the unit dosage of ozone is 1-4g per liter of water per hour;
the usage amount of the granular catalyst is 10-20% of the volume of the fluidized bed reactor (7).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113651458A (en) * | 2021-09-07 | 2021-11-16 | 广东驰佑生物科技有限公司 | Ozone disinfection water treatment method and equipment |
| US11485661B2 (en) | 2021-06-21 | 2022-11-01 | Zhejiang Gongshang University | Device for advanced degradation of organic wastewater and application thereof |
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