CN214422480U - Heterogeneous ozone catalysis process units of processing waste water - Google Patents
Heterogeneous ozone catalysis process units of processing waste water Download PDFInfo
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- CN214422480U CN214422480U CN202120369464.5U CN202120369464U CN214422480U CN 214422480 U CN214422480 U CN 214422480U CN 202120369464 U CN202120369464 U CN 202120369464U CN 214422480 U CN214422480 U CN 214422480U
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Abstract
The application belongs to the technical field of waste water treatment, especially relates to a heterogeneous ozone catalysis process units who handles waste water. The process unit of the application comprises: an ozone generator and a heterogeneous ozone catalytic reaction column; the ozone aeration head of the ozone generator is communicated with the heterogeneous ozone catalytic reaction column, and the ozone generator enables ozone to be conveyed into the heterogeneous ozone catalytic reaction column; the heterogeneous ozone catalytic reaction column comprises a column body, a first heterogeneous ozone catalyst plate, a second heterogeneous ozone catalyst plate and a third heterogeneous ozone catalyst plate; heterogeneous ozone catalyst board sets up on the radial cross-section of cylinder for waste water passes heterogeneous ozone catalyst board through the water inlet of heterogeneous ozone catalytic reaction post, flows from the delivery port of heterogeneous ozone catalytic reaction post. The application provides a process units of handling waste water can effectively solve current waste water treatment process and have the problem that wastes time and energy, unable high efficiency, low price treatment livestock-raising waste water.
Description
Technical Field
The application belongs to the technical field of waste water treatment, especially relates to a heterogeneous ozone catalysis process units who handles waste water.
Background
The livestock breeding wastewater in south China contains high-concentration organic matters, ammonia nitrogen, suspended solids, a considerable amount of pathogens and toxic substances with specific structures, the biodegradability of the livestock breeding wastewater is poor, the water quality characteristics have strong regionality, and after the livestock breeding wastewater is treated by adopting the traditional anaerobic and aerobic process, the COD of the livestock breeding wastewater isCrAnd the chroma is still high, so advanced oxidation technology is needed to carry out advanced treatment on the livestock breeding wastewater, but the problems of high energy consumption, low utilization rate, high treatment cost and the like exist in practical application. Therefore, the existing wastewater treatment process has the problems of time and labor waste and incapability of efficiently and cheaply treating livestock breeding wastewater.
SUMMERY OF THE UTILITY MODEL
In view of this, the application provides a heterogeneous ozone catalysis process units of processing waste water, can effectively solve current waste water treatment process and have the problem that wastes time and energy, can't handle livestock-raising waste water high-efficiently, with low costs.
The present application provides in a first aspect a heterogeneous ozone catalytic process unit for treating wastewater, comprising:
an ozone generator and a heterogeneous ozone catalytic reaction column;
the ozone aeration head of the ozone generator is communicated with the heterogeneous ozone catalytic reaction column, and the ozone generator enables ozone to be conveyed to the inside of the heterogeneous ozone catalytic reaction column;
the heterogeneous ozone catalytic reaction column comprises a column body, a first heterogeneous ozone catalyst plate, a second heterogeneous ozone catalyst plate and a third heterogeneous ozone catalyst plate; the first heterogeneous ozone catalyst plate, the second heterogeneous ozone catalyst plate and the third heterogeneous ozone catalyst plate are arranged on the radial section of the column body, so that wastewater passes through a water inlet of the heterogeneous ozone catalytic reaction column to pass through the first heterogeneous ozone catalyst plate, the second heterogeneous ozone catalyst plate and the third heterogeneous ozone catalyst plate, and flows out from a water outlet of the heterogeneous ozone catalytic reaction column.
In another embodiment, the heterogeneous ozone catalytic process unit further comprises a movable assembly, the first, second or third heterogeneous ozone catalyst plates being disposed on a radial cross section of the column through the movable assembly, respectively, the movable assembly causing the first, second or third heterogeneous ozone catalyst plates to move radially inside the column.
In another embodiment, the heterogeneous ozone catalyst of the first heterogeneous ozone catalyst plate is selected from Mn-Fe-Ce/gamma-Al2O3A catalyst.
In another embodiment, the heterogeneous ozone catalyst of the second heterogeneous ozone catalyst plate is selected from Mn-Fe-Ce/gamma-Al2O3A catalyst.
In another embodiment, the heterogeneous ozone catalyst of the third heterogeneous ozone catalyst plate is selected from Mn-Fe-Ce/gamma-Al2O3A catalyst.
In another embodiment, the water inlet of the heterogeneous ozone catalytic reaction column is arranged at the bottom of the heterogeneous ozone catalytic reaction column.
In another embodiment, the water outlet of the heterogeneous ozone catalytic reaction column is arranged at the top of the heterogeneous ozone catalytic reaction column.
In another embodiment, the communication between the ozone aeration head of the ozone generator and the heterogeneous ozone catalytic reaction column specifically comprises: the ozone aeration head of the ozone generator is uniformly communicated with the bottom wall of the heterogeneous ozone catalytic reaction column.
In another embodiment, the first heterogeneous ozone catalyst plate, the second heterogeneous ozone catalyst plate, and the third heterogeneous ozone catalyst plate are disposed equidistant inside the column.
In another embodiment, the first heterogeneous ozone catalyst plate comprises an upper mesh separator plate, a lower mesh separator plate, and a heterogeneous ozone catalyst; the upper layer of reticular clapboard and the lower layer of reticular clapboard are aligned and fixed to form an accommodating cavity; the heterogeneous ozone catalyst is filled in the accommodating cavity;
the second heterogeneous ozone catalyst plate comprises an upper-layer reticular clapboard, a lower-layer reticular clapboard and a heterogeneous ozone catalyst; the upper layer of reticular clapboard and the lower layer of reticular clapboard are aligned and fixed to form an accommodating cavity; the heterogeneous ozone catalyst is filled in the accommodating cavity;
the third heterogeneous ozone catalyst plate comprises an upper-layer reticular clapboard, a lower-layer reticular clapboard and a heterogeneous ozone catalyst; the upper layer of reticular clapboard and the lower layer of reticular clapboard are aligned and fixed to form an accommodating cavity; the heterogeneous ozone catalyst is filled in the accommodating cavity.
In a second aspect, the present application provides a process flow of the heterogeneous ozone catalysis process device in practical application, comprising: the heterogeneous ozone catalytic process device is used together with the existing water collecting tank, deodorization tank and contact oxidation tank;
the method specifically comprises the following steps: the device comprises a water collecting tank, an ozone generator, a heterogeneous ozone catalytic reaction column, a deodorization tank and a contact oxidation tank;
the water outlet of the water collecting tank is connected with the water inlet of the heterogeneous ozone catalytic reaction column;
the water outlet of the heterogeneous ozone catalytic reaction column is connected with the water inlet of the deodorization tank;
the water outlet of the deodorization tank is connected with the water inlet of the contact oxidation tank;
the ozone generator is communicated with the heterogeneous ozone catalytic reaction column, and the ozone generator enables ozone to be conveyed to the inside of the heterogeneous ozone catalytic reaction column;
the heterogeneous ozone catalytic reaction column comprises a column body, a first heterogeneous ozone catalyst plate, a second heterogeneous ozone catalyst plate and a third heterogeneous ozone catalyst plate; the first heterogeneous ozone catalyst plate, the second heterogeneous ozone catalyst plate and the third heterogeneous ozone catalyst plate are arranged on the radial section of the column body, so that wastewater passes through a water inlet of the heterogeneous ozone catalytic reaction column to pass through the first heterogeneous ozone catalyst plate, the second heterogeneous ozone catalyst plate and the third heterogeneous ozone catalyst plate, and flows out from a water outlet of the heterogeneous ozone catalytic reaction column.
In another embodiment, the apparatus of the present application further comprises a reflow assembly; the backflow component comprises a backflow pump and a backflow pipeline, a water outlet of the contact oxidation pond is connected with a first end of the backflow pipeline through the backflow pump, and a second end of the backflow pipeline is connected with a water inlet of the heterogeneous ozone catalytic reaction column.
Specifically, the deodorization tank and the contact oxidation tank are both provided with water inlet at the bottom and water outlet at the upper end of an oblique angle.
Secondly, the heterogeneous ozone catalytic reaction post of this application device has 9 delivery ports, confirms the delivery port according to the play water demand.
In a third aspect, the present application provides a method of treating wastewater comprising:
the first, second and third heterogeneous ozone catalyst plates are provided with a heterogeneous ozone catalyst;
and 3, carrying out contact oxidation treatment on the second wastewater to obtain discharge water.
Specifically, the wastewater subjected to the tertiary sewage treatment is effluent of a biochemical sedimentation tank of a farm sewage treatment station subjected to the tertiary sewage treatment.
Specifically, the discharged water meets the livestock breeding industry wastewater discharge standard.
In another embodiment, the pH value of the wastewater subjected to the three-stage sewage treatment is adjusted to 8-10, and is preferably 9.
In another embodiment, the ozone aeration rate of the ozone treatment is 30 mg/L-120 mg/L; the time of ozone treatment is 20-50 min.
In another embodiment, the ozone treatment has an ozone aeration of 30 mg/L; the time of ozone treatment is 30 min.
In particular, the heterogeneous ozone catalysts on the first, second and third heterogeneous ozone catalyst plates may be conventional three-way heterogeneous ozone catalysts.
In another embodiment, the heterogeneous ozone catalyst of the first heterogeneous ozone catalyst plate is selected from Mn-Fe-Ce/gamma-Al2O3A catalyst;
the heterogeneous ozone catalyst of the second heterogeneous ozone catalyst plate is selected from Mn-Fe-Ce/gamma-Al2O3A catalyst;
the heterogeneous ozone catalyst of the third heterogeneous ozone catalyst plate is selected from Mn-Fe-Ce/gamma-Al2O3A catalyst.
In another embodiment, the heterogeneous ozone catalysts on the first, second and third heterogeneous ozone catalyst plates are added in an amount of 30g/L to 50 g/L.
In another embodiment, the time of the deodorization treatment is 1h to 2 h; the time of the contact oxidation treatment is 8-12 h.
In another embodiment, said step 3 further comprises a reflow process;
the reflow process includes:
and 6, carrying out contact oxidation treatment on the fifth wastewater to obtain reuse water.
Specifically, the application finds that the discharged water and the wastewater subjected to the three-stage sewage treatment are mixed and then subjected to ozone treatment, deodorization treatment and contact oxidation treatment by using three layers of heterogeneous ozone catalyst plates, so that the obtained recycled water meets the recycling standard. The reuse water meets the national regulation reuse standard.
In another embodiment, the reflux treatment is repeated for 1 to 3 times, i.e., step 5, step 6 and step 7 are performed in sequence.
In another embodiment, the volume ratio of the discharged water to the wastewater subjected to the three-stage sewage treatment is (1-3) to (1-2).
In another embodiment, the step 1 further comprises filtering the wastewater subjected to the tertiary sewage treatment.
Specifically, the filtering treatment is to introduce the wastewater subjected to the three-stage sewage treatment into a sand filter tank through a sand filter tank water inlet pump for filtering.
In another embodiment, the wastewater treatment methods disclosed herein can employ the heterogeneous ozone catalyzed process unit provided herein.
Specifically, the waste water through the tertiary treatment of sewage of this application is derived from breeding waste water.
The method can effectively reduce the content of organic matters in the wastewater, and the treated wastewater can reach the discharge standard or the recycling standard; the whole set of process equipment is environment-friendly, has low price, does not cause secondary pollution, greatly reduces the treatment cost, and canSubstitution for removal of CODCrThe chemical reagent has good practical application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a schematic diagram of a heterogeneous ozone catalytic process unit for wastewater treatment according to the present application.
FIG. 2 is a process flow of the heterogeneous ozone catalytic process unit for wastewater treatment of FIG. 1 in practical use.
FIG. 3 shows COD in raw water (wastewater after three-stage treatment of wastewater), ozone-catalyzed oxidation effluent and contact oxidation pond effluent (discharge water) provided by the embodiment of the present applicationCrAnd (4) value results.
FIG. 4 shows the results of a test for treating wastewater without using three layers of heterogeneous ozone catalyst plates as provided in comparative example 2 of the present application.
Detailed Description
The application provides a heterogeneous ozone catalysis process units of processing waste water for there is the technical defect who wastes time and energy, unable high efficiency, the low price of solving among the prior art handles livestock-raising waste water.
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it should be understood that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Referring to fig. 1 to 2, fig. 1 is a schematic structural diagram of a heterogeneous ozone catalytic process apparatus for treating wastewater according to the present application; FIG. 2 is a process flow of the heterogeneous ozone catalytic process unit for wastewater treatment of FIG. 1 in practical use.
As shown in figure 1, the heterogeneous ozone catalysis process unit for treating wastewater comprises: an ozone generator 2 and a heterogeneous ozone catalytic reaction column 3; an ozone aeration head 12 of the ozone generator is communicated with the heterogeneous ozone catalytic reaction column, and the ozone generator enables ozone to be conveyed into the heterogeneous ozone catalytic reaction column 3; the heterogeneous ozone catalytic reaction column comprises a column body 3-1, a first heterogeneous ozone catalyst plate 3-2, a second heterogeneous ozone catalyst plate 3-3 and a third heterogeneous ozone catalyst plate 3-4; the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4 are arranged on the radial section of the cylinder 3-1, so that wastewater passes through the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4 through a water inlet 3-5 of the heterogeneous ozone catalytic reaction column and flows out of a water outlet 3-6 of the heterogeneous ozone catalytic reaction column.
In another embodiment, the heterogeneous ozone catalytic process unit further comprises a movable assembly, the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4 are respectively arranged on the radial section of the column 3-1 through the movable assembly, and the movable assembly enables the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4 to move radially inside the column 3-1.
In particular, the movable component of the heterogeneous ozone catalytic process unit can be a conventional component capable of moving objects, such as a position adjusting component such as a pulley component. As shown in figure 1, the movable components of the device of the application comprise pulleys 6, stainless steel pipes, fixed valves and screws, sliding holes are symmetrically formed in the edges of a first heterogeneous ozone catalyst plate 3-2, a second heterogeneous ozone catalyst plate 3-3 and a third heterogeneous ozone catalyst plate 3-4, the stainless steel pipes are arranged in the sliding holes of the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4, an upper fixing valve and a lower fixing valve and screws are respectively arranged on the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4, the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4 are screwed and fixed on the stainless steel pipe; the pulley 6 is connected with the stainless steel pipe, and the pulley 6 adjusts the position of the stainless steel pipe in the cylinder 1, thereby adjusting the heights of the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4 in the cylinder 1.
Specifically, the pulley 6 is welded on the edge of the column body 3-1 through an iron column and is suspended at a position 1m away from the top outlet of the heterogeneous ozone catalytic reaction column 3, the pulley is connected with two stainless steel pipes with the diameter of 1cm, and the pulley 6 adjusts the position of the stainless steel pipes in the column body 1, so that the heights of the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4 in the column body 1 are adjusted; the symmetrical edges of the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4 are respectively provided with two sliding holes with the diameter of 0.5cm, the sliding holes are embedded into the two stainless steel pipes, the sliding holes of each heterogeneous ozone catalyst plate are provided with a fixing valve and a screw which can slide up and down, the stainless steel pipes can slide up and down, and the position of the corresponding heterogeneous ozone catalyst plate can be determined by adjusting the position of the fixing valve. The side wall of the heterogeneous ozone catalytic reaction column 3 is provided with 9 water outlets, the outside of each water outlet is provided with a switch valve, and the switch valves are transversely connected with a PVC plastic pipe with the specification of DN32 and are uniformly connected to a PVC plastic vertical pipe with the specification of DN32, and water is discharged through the vertical pipe.
The effective volume of the heterogeneous ozone catalytic reaction column 3 is 560L, the diameter of the column is 0.64m, the height of the column is 1.84m, and the effective height is 1.74 m. The first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4 are arranged on two aligned stainless steel tubes which are arranged in the heterogeneous ozone catalytic reaction column 3, the pulley 6 is connected with the stainless steel tube, the pulley 6 is welded on the top of the heterogeneous ozone catalytic reaction column 3 to adjust the height of the two stainless steel tubes on the heterogeneous ozone catalytic reaction column 3 in a lifting way, the heterogeneous ozone catalyst plate at the bottommost layer is always kept above the three titanium alloy microporous ozone aeration heads 12, the interval between three heterogeneous ozone catalyst boards can be adjusted according to the delivery port of difference to all the other above two-layer heterogeneous ozone catalyst boards, makes ozone can be fully contacted with heterogeneous ozone catalyst in heterogeneous ozone catalytic reaction post 3, improves ozone catalytic efficiency.
In another embodiment, the heterogeneous ozone catalyst of the first heterogeneous ozone catalyst plate is selected from Mn-Fe-Ce/gamma-Al2O3A catalyst. The heterogeneous ozone catalyst of the second heterogeneous ozone catalyst plate is selected from Mn-Fe-Ce/gamma-Al2O3A catalyst. The heterogeneous ozone catalyst of the third heterogeneous ozone catalyst plate is selected from Mn-Fe-Ce/gamma-Al2O3A catalyst.
As shown in figure 1, the water inlet 3-5 of the heterogeneous ozone catalytic reaction column is arranged at the bottom of the heterogeneous ozone catalytic reaction column.
As shown in figure 1, the water outlets 3-6 of the heterogeneous ozone catalytic reaction column are arranged at the top of the heterogeneous ozone catalytic reaction column.
In another embodiment, the communication between the ozone aeration head 12 of the ozone generator and the heterogeneous ozone catalytic reaction column 3 is specifically as follows: the ozone aeration head 12 of the ozone generator is uniformly communicated with the bottom wall of the heterogeneous ozone catalytic reaction column.
As shown in fig. 1, a first heterogeneous ozone catalyst plate 3-2, a second heterogeneous ozone catalyst plate 3-3 and a third heterogeneous ozone catalyst plate 3-4 are disposed at equal intervals inside the column 3-1.
Specifically, the heterogeneous ozone catalyst board of first heterogeneous ozone catalyst board 3-2, the heterogeneous ozone catalyst board of second 3-3 and the heterogeneous ozone catalyst board of third 3-4 of this application can be for having the baffle that the conventionality was equipped with heterogeneous ozone catalyst now, and this application provides a concrete structure.
In another embodiment, the first heterogeneous ozone catalyst plate 3-2 comprises an upper mesh partition plate, a lower mesh partition plate, and a heterogeneous ozone catalyst; the upper layer of reticular clapboard and the lower layer of reticular clapboard are aligned and fixed to form an accommodating cavity; the heterogeneous ozone catalyst is filled in the accommodating cavity; the second heterogeneous ozone catalyst plate 3-3 comprises an upper-layer mesh partition plate, a lower-layer mesh partition plate and a heterogeneous ozone catalyst; the upper layer of reticular clapboard and the lower layer of reticular clapboard are aligned and fixed to form an accommodating cavity; the heterogeneous ozone catalyst is filled in the accommodating cavity; the third heterogeneous ozone catalyst plate 3-4 comprises an upper-layer mesh partition plate, a lower-layer mesh partition plate and a heterogeneous ozone catalyst; the upper layer of reticular clapboard and the lower layer of reticular clapboard are aligned and fixed to form an accommodating cavity; the heterogeneous ozone catalyst is filled in the accommodating cavity.
Specifically, first heterogeneous ozone catalyst board 3-2, the heterogeneous ozone catalyst board of second 3-3 and the heterogeneous ozone catalyst board of third 3-4 are worked out by the stainless steel silk screen, and the hole of net silk is 1mm, and baffle thickness is 3-5cm, and the baffle divide into two parts from top to bottom, and the intermediate junction is fixed by the screw, can twist off the fixed screw when filling heterogeneous ozone catalyst, pours heterogeneous ozone catalyst into, and later twist on the screw and can accomplish filling heterogeneous ozone catalyst. This application adopts first heterogeneous ozone catalyst board 3-2, the layering mounting means in heterogeneous ozone catalytic reaction column 3's inside is installed to the heterogeneous ozone catalyst board 3-3 of second and the heterogeneous ozone catalyst board 3-4 equidistance layering of third, only need regularly wash first heterogeneous ozone catalyst board 3-2 with the water pipe, the heterogeneous ozone catalyst board 3-3 of second and the heterogeneous ozone catalyst board 3-4's of third surface, wash the delivery port discharge of water rethread heterogeneous ozone catalytic reaction column 3, can reach the effect of back flush, and the simple operation, thereby improve heterogeneous ozone catalyst and to ozone catalytic efficiency, prolong heterogeneous ozone catalyst life.
As shown in figure 2, the heterogeneous ozone catalysis process unit for treating wastewater has a process flow in practical application. The method comprises the following steps: the device comprises a water collecting tank 1, an ozone generator 2, a heterogeneous ozone catalytic reaction column 3, a deodorization tank 4 and a contact oxidation tank 5; the water outlet of the water collecting tank 1 is connected with the water inlet of the heterogeneous ozone catalytic reaction column 3; the water outlet of the heterogeneous ozone catalytic reaction column 3 is connected with the water inlet of the deodorization pool 4; the water outlet of the deodorization tank 4 is connected with the water inlet of the contact oxidation tank 5; the ozone generator 2 is connected with the bottom wall of the heterogeneous ozone catalytic reaction column 3, and the ozone generator 2 enables ozone to be conveyed into the heterogeneous ozone catalytic reaction column 3; the heterogeneous ozone catalytic reaction column 3 comprises a column body 3-1, a first heterogeneous ozone catalyst plate 3-2, a second heterogeneous ozone catalyst plate 3-3 and a third heterogeneous ozone catalyst plate 3-4; first heterogeneous ozone catalyst board, the heterogeneous ozone catalyst board of second and the heterogeneous ozone catalyst board of third set up on the radial cross-section of cylinder 3-1 for waste water passes first heterogeneous ozone catalyst board, the heterogeneous ozone catalyst board of second and the heterogeneous ozone catalyst board of third through the water inlet 3-5 of heterogeneous ozone catalytic reaction post, flows out from the delivery port 3-6 of heterogeneous ozone catalytic reaction post.
In another embodiment, the apparatus of the present application further comprises a reflow assembly; the backflow component comprises a backflow pump 7 and a backflow pipeline 8, the water outlet of the contact oxidation pond 5 is connected with the first end of the backflow pipeline 8 through the backflow pump 7, and the second end of the backflow pipeline 8 is connected with the water inlet of the heterogeneous ozone catalytic reaction column 3.
In another embodiment, the apparatus of the present application further comprises a sand filter tank feed pump 10 and a sand filter tank 9; the water outlet of the water collecting tank 1 is connected with the water inlet of a sand filtering tank 9 through a sand filtering tank water inlet pump 10; the water inlet of the sand filtration tank 9 is connected with the water inlet of the heterogeneous ozone catalytic reaction column 3.
In another embodiment, the apparatus of the present application further comprises a blower 11, and the blower 11 is connected to the contact oxidation tank 5.
As shown in figures 1-2, when in use, firstly, the ozone generator 2 is opened, the front end of an ozone vent of the ozone generator 2 is provided with a one-way check valve, the ozone generator 2 is connected with three titanium alloy ozone aeration heads 12, the titanium alloy ozone aeration heads 12 of the ozone generator 2 are communicated and connected with the heterogeneous ozone catalytic reaction column 3, ozone is introduced into the heterogeneous ozone catalytic reaction column 3 through the titanium alloy ozone aeration heads 12, and wastewater subjected to three-stage sewage treatment is introduced after the ozone is uniformly and continuously generated. Wastewater to be subjected to tertiary sewage treatment enters the heterogeneous ozone catalytic reaction column 3 through the water inlet 3-5 of the heterogeneous ozone catalytic reaction column, the external electromagnetic flow meter at the water inlet 3-5 of the heterogeneous ozone catalytic reaction column can accurately measure the flow and the flow speed of the wastewater, and the water inlet 3-5 of the heterogeneous ozone catalytic reaction column is internally connectedThe three-ring annular microporous water inlet pipe can ensure that water is uniformly fed and the liquid level rises at a constant speed. Selecting proper water outlets according to requirements, closing other water outlets, adjusting the positions of three layers of a first heterogeneous ozone catalyst plate 3-2, a second heterogeneous ozone catalyst plate 3-3 and a third heterogeneous ozone catalyst plate 3-4, keeping the catalyst partition plate at the bottommost layer on three titanium alloy microporous ozone aeration heads 12 all the time, keeping the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4 in three equal parts of the volume of the whole heterogeneous ozone catalytic reaction column 3, and the dosage of the heterogeneous ozone catalyst of the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4 is according to 1: 1:1, uniformly adding. After the effluent is stable, measuring the COD of the effluentCrAnd the like.
The raw materials and reagents used in the following examples are commercially available or self-made.
COD in wastewater in examples and comparative examples belowCrMeasuring by adopting a rapid digestion spectrophotometry; ammonia nitrogen is measured by adopting a nano-reagent spectrophotometry; the chroma is measured by a dilution multiple method.
The wastewater adopted in the following examples and comparative examples is the cow breeding wastewater, the cow breeding wastewater is derived from the effluent of a three-stage contact oxidation pond of a certain cow breeding base in Guangzhou city, the breeding base adopts the conventional process of 'anaerobic treatment, coagulation centrifugation, UASB (upflow anaerobic sludge blanket) + three-stage aerobic treatment and stabilization pond' to treat the cow breeding wastewater, the effluent of the three-stage contact oxidation pond is brownish red, the concentration of suspended solid is higher, the biochemical degradability is poor, and the problem cannot be solved by the conventional biological treatment process.
Example 1
The embodiment of the application discloses a method for treating wastewater, which comprises the following steps:
wastewater treatment was carried out using the apparatus described in figure 1.
and 6, carrying out contact oxidation treatment on the fifth wastewater to obtain reuse water.
The specific process comprises the following steps: the total effective volume of the heterogeneous ozone catalytic reaction column 3 is 560L, and the effective volume of the water collecting tank 1 and the effective volume of the deodorization tank 4 are both 1m3The effective volume of the contact oxidation pond 5 is 3m3Using Mn-Fe-Ce/gamma-Al2O3Mn-Fe-Ce/gamma-Al as heterogeneous ozone catalyst2O3Is filled in the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4, and the contact oxidation tank 5 is filled with polyester fiber.
The specific process flow is that a submersible pump pumps wastewater subjected to three-stage sewage treatment into a water collecting tank 1, the wastewater enters a heterogeneous ozone catalytic reaction column 3 after being filtered by a sand filter tank 9, ozone is controlled by an ozone generator 2 to be uniformly introduced into the heterogeneous ozone catalytic reaction column 3 through a titanium alloy microporous ozone aeration head 12 of the ozone generator 2, the wastewater is contacted with a first heterogeneous ozone catalyst plate 3-2, a second heterogeneous ozone catalyst plate 3-3 and a third heterogeneous ozone catalyst plate 3-4, the wastewater flows into a deodorization tank 4 through a water outlet at the top of the heterogeneous ozone catalytic reaction column after being subjected to an ozone catalytic reaction for 30 minutes, the wastewater flows into a contact oxidation tank 5 after being kept stand for 1 hour, the hydraulic retention time is 8 hours, discharge water is obtained, and part of the discharge water is refluxed to the heterogeneous ozone catalytic reaction column 3 for a secondary ozone catalytic reaction after being subjected to the contact oxidation treatment, additional discharge water is discharged.
Specifically, the ozone ventilation amount is adjusted to be 30g/h, the ozone catalytic reaction time is 30min, and the adding amount of the heterogeneous ozone catalyst of the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4 is 30 g/L. Pumping the discharged water of the contact oxidation tank 5 into a water collecting tank by a reflux pump 7, uniformly mixing the discharged water and raw water (wastewater subjected to tertiary sewage treatment) according to the volume ratio of 1:2, then performing secondary ozone catalytic reaction, automatically flowing the discharged water into a deodorization tank 4, performing deodorization treatment for 1 hour, introducing the deodorized water into the contact oxidation tank 5, obtaining recycled water after the contact oxidation treatment of the contact oxidation tank 5, and measuring the COD (chemical oxygen demand) of the recycled water after the discharged water is stableCrAnd obtaining the COD of the reuse water under the condition that the volume ratio of the discharged water to the raw water is 1:2CrAnd (4) comprehensive removal rate. The results are shown in Table 1.
Example 2
The embodiment of the application discloses a method for treating wastewater, which comprises the following steps:
referring to the method of example 1, except that the discharged water and the raw water (wastewater subjected to the tertiary treatment of wastewater) were uniformly mixed in a volume ratio of 1:1, the remaining steps were identical to example 1, and the COD of the reuse water was obtainedCrAnd obtaining the COD of the reuse water under the condition that the volume ratio of the discharged water to the raw water is 1:1CrAnd (4) comprehensive removal rate. The results are shown in Table 1.
Example 3
The embodiment of the application discloses a method for treating wastewater, which comprises the following steps:
referring to the method of example 1, except that the discharged water and the raw water (wastewater subjected to the tertiary treatment of wastewater) were uniformly mixed at a volume ratio of 2:1, the remaining steps were identical to example 1, and the COD of the reuse water was obtainedCrAnd obtaining the COD of the reuse water under the condition that the volume ratio of the discharged water to the raw water is 2:1CrAnd (4) comprehensive removal rate. The results are shown in Table 1.
Example 4
The embodiment of the application discloses a method for treating wastewater, which comprises the following steps:
referring to the method of example 1, except that the discharged water and the raw water (wastewater subjected to the tertiary wastewater treatment) were uniformly mixed at a volume ratio of 3:1, the remaining steps were identical to example 1, and the COD of the reuse water was obtainedCrAnd obtaining the COD of the reuse water under the condition that the volume ratio of the discharged water to the raw water is 3:1CrAnd (4) comprehensive removal rate. The results are shown in Table 1.
TABLE 1 COD of effluent from contact oxidation tank under different reflux ratiosCrComprehensive removal rate of
| Examples | Example 1 | Example 2 | Example 3 | Example 4 |
| COD of effluentCrValue of | 195mg/L | 171mg/L | 137mg/L | 132mg/L |
| CODCrComprehensive removal rate | 59.54％ | 65.59％ | 71.04％ | 71.49％ |
Example 5
The embodiment of the application discloses a method for treating wastewater, which comprises the following steps:
the wastewater COD treated by the three-stage sewage treatmentCrThe concentration of the wastewater is 581mg/L, the wastewater is respectively contacted with a first heterogeneous ozone catalyst plate, a second heterogeneous ozone catalyst plate and a third heterogeneous ozone catalyst plate, ozone is introduced for ozone treatment, and the ozone ventilation amount is 30g/h, so that the treated wastewater is obtained; the first heterogeneous ozone catalyst plate, the second heterogeneous ozone catalyst plate and the third heterogeneous ozone catalyst plate are provided with 30g/L heterogeneous ozone catalyst Mn-Fe-Ce/gamma-Al2O3. Measuring COD of treated wastewater after effluent is stableCrThe index is 287mg/L, CODCrThe removal rate was 50.60%.
Example 6
The embodiment of the application discloses a method for treating wastewater, which comprises the following steps:
wastewater treatment was carried out using the apparatus described in figure 1.
and 3, carrying out contact oxidation treatment on the second wastewater to obtain discharge water.
The specific process comprises the following steps: the total effective volume of the heterogeneous ozone catalytic reaction column 3 is 560L, and the effective volume of the water collecting tank 1 and the effective volume of the deodorization tank 4 are both 1m3The effective volume of the contact oxidation pond 5 is 3m3Using Mn-Fe-Ce/gamma-Al2O3Mn-Fe-Ce/gamma-Al as heterogeneous ozone catalyst2O3The heterogeneous ozone catalyst is filled in the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4, polyester fiber filler is adopted in the contact oxidation tank 5, and the adding amount of the heterogeneous ozone catalyst of the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4 is 30 g/L.
The specific process flow is that a submersible pump pumps wastewater subjected to three-stage sewage treatment into a water collecting tank 1, the wastewater enters a heterogeneous ozone catalytic reaction column 3 after being filtered by a sand filter tank 9, ozone is controlled by an ozone generator 2 to be uniformly introduced into the heterogeneous ozone catalytic reaction column 3 through a titanium alloy microporous ozone aeration head 12 of the ozone generator 2, the wastewater is in contact with a first heterogeneous ozone catalyst plate 3-2, a second heterogeneous ozone catalyst plate 3-3 and a third heterogeneous ozone catalyst plate 3-4, the ozone ventilation volume is 30g/h, the wastewater flows into a deodorization tank 4 through a water outlet at the top of the heterogeneous ozone catalytic reaction column after being subjected to an ozone catalytic reaction for 30 minutes, the wastewater flows into a contact oxidation tank 5 after standing for 1 hour, and the hydraulic retention time is 8 hours, so that the discharged water is obtained. Continuously running for 14 days, measuring COD at the positions of raw water (wastewater subjected to three-stage sewage treatment), ozone catalytic oxidation effluent and contact oxidation pond effluent (discharge water) at fixed time every day after effluent is stableCrThe value is obtained. The results are shown in FIG. 3. FIG. 3 shows COD in raw water (wastewater after three-stage treatment of wastewater), ozone-catalyzed oxidation effluent and contact oxidation pond effluent (discharge water) provided by the embodiment of the present applicationCrAnd (4) value results.
Comparative example 1
The application comparative example discloses a test that does not adopt heterogeneous ozone catalyst to handle waste water includes:
the wastewater COD treated by the three-stage sewage treatmentCr563mg/L, ozone is introduced for ozone treatment, and a heterogeneous ozone catalyst Mn-Fe-Ce/gamma-Al is not added in the ozone treatment process2O3And carrying out ozone catalytic reaction for 30 minutes with the ozone ventilation amount of 30g/h to obtain treated water. Measuring the COD of the effluent after the effluent is stableCrThe index is 479mg/L, CODCrThe removal rate was 14.92%.
By combining examples 5-6 with comparative example 1, it can be seen that no heterogeneous ozone catalyst Mn-Fe-Ce/γ -Al is used2O3The efficiency of removing organic matters in the wastewater by pure ozone oxidation is low.
After the device provided by the application is applied, the catalytic reaction efficiency, the ozone utilization rate and the CODCrThe removal rate is greatly improved, so that the device has good practical engineering application value.
As can be seen from FIG. 3, COD in the actual culture wastewaterCrAbout 500mg/L, and all are organic matters which are difficult to be biochemically degraded and can not be treated by the conventional biochemical method. By using the method, the COD of the effluent is obtained under the condition of continuous operation for 14 daysCrCan be stabilized at about 200mg/L, and meets the wastewater discharge standard of animal husbandry.
As can be seen from Table 2 and FIG. 3, COD was observed in the actual culture wastewaterCrThe value is higher, and when the emission requirement cannot be met only by using the ozone catalysis and biochemical method, the problem can be solved by using a reflux increasing method. Under the condition of reflux, on one hand, the COD of the wastewater entering the ozone catalytic reaction is reducedCrOn the other hand, the organic matters which are difficult to be biochemically degraded in the biochemical pond are subjected to secondary ozone catalytic reaction to improve the biodegradability, so that the COD of the effluent of the subsequent biochemical pondCrAnd decreases. The use of ozone is reduced by increasing the reflux, and the wastewater treatment cost can also be greatly reduced. The volume ratio of the discharged water to raw water (wastewater subjected to tertiary sewage treatment) in the method is (1-3): 1, the contact oxidation pond can stably discharge water after the reflux treatment under the mixing condition, and the COD of the discharged waterCrAll are stabilized below 200mg/L, CODCrThe comprehensive removal rates are 59.54%, 65.59%, 71.04% and 71.49% respectively. It can be seen that the larger the volume ratio of the discharged water to the raw water (wastewater subjected to the tertiary treatment of sewage) is, the better the relative treatment effect is. The method can effectively treat and deal with CODCrHigher culture wastewater.
Example 7
The embodiment of the application discloses a method for treating wastewater, which comprises the following steps:
wastewater treatment was carried out using the apparatus described in figure 1.
and 3, carrying out contact oxidation treatment on the second wastewater to obtain discharge water.
The specific process comprises the following steps: the total effective volume of the heterogeneous ozone catalytic reaction column 3 is 560L, and the effective volume of the water collecting tank 1 and the effective volume of the deodorization tank 4 are both 1m3The effective volume of the contact oxidation pond 5 is 3m3Using Mn-Fe-Ce/gamma-Al2O3Mn-Fe-Ce/gamma-Al as heterogeneous ozone catalyst2O3Is filled in the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate 3-4, and the contact oxidation tank 5 is filled with polyester fiber.
The specific process flow is that a submersible pump pumps wastewater subjected to three-stage sewage treatment into a water collecting tank 1, the wastewater enters a heterogeneous ozone catalytic reaction column 3 after being filtered by a sand filter tank 9, ozone is controlled by an ozone generator 2 to be uniformly introduced into the heterogeneous ozone catalytic reaction column 3 through a titanium alloy microporous ozone aeration head 12 of the ozone generator 2, the wastewater is contacted with a first heterogeneous ozone catalyst plate 3-2, a second heterogeneous ozone catalyst plate 3-3 and a third heterogeneous ozone catalyst plate 3-4, the wastewater flows into a deodorization tank 4 through a water outlet at the top of the heterogeneous ozone catalytic reaction column after being subjected to an ozone catalytic reaction for 30 minutes, the wastewater flows into a contact oxidation tank 5 after standing for 1 hour, and the hydraulic retention time is 8 hours, so that the discharged water is obtained.
Specifically, the ozone ventilation amount is adjusted to 120mg/L, the ozone catalytic reaction time is 30min, and the first heterogeneous ozone catalyst plate 3-2, the second heterogeneous ozone catalyst plate 3-3 and the third heterogeneous ozone catalyst plate are used for catalyzing ozoneThe dosage of the heterogeneous ozone catalyst of the catalyst plates 3-4 is 30 g/L. Determination of COD of discharged WaterCrThe results are shown in Table 3.
COD of the discharge waterCrThe comprehensive removal rate, the comprehensive chromaticity removal rate and the comprehensive ammonia nitrogen removal rate respectively reach 76.42 percent, 98.44 percent and 71.89 percent.
TABLE 3 Water quality index of discharged Water
Comparative example 2
The application comparative example discloses a test that does not adopt heterogeneous ozone catalyst board of three-layer to handle waste water includes:
referring to the method of example 7, except that no heterogeneous ozone catalyst was added to the three-layered heterogeneous ozone catalyst plate, the reaction time was 50min, and samples were taken every 10min to determine CODCrAmmonia nitrogen and chromaticity. The results are shown in FIG. 4. FIG. 4 shows the results of a test for treating wastewater without using three layers of heterogeneous ozone catalyst plates as provided in comparative example 2 of the present application.
As can be seen from FIG. 4, COD was observed during the test periodCrThe value is reduced from 563mg/L to 450mg/L, the ammonia nitrogen is reduced from 114mg/L to 102.5mg/L, and the chroma is reduced from 512 times to 32 times. Even if the reaction time is 50min, CODCrThe removal rate of ammonia nitrogen and the removal rate of ammonia nitrogen are both lower than 20 percent, and the effect of pure ozone oxidation is not obvious. Ozone oxidation for 50min, and introducing into contact oxidation tank to obtain CODCrThe values and the chroma did not change significantly.
The utility model provides a heterogeneous ozone catalysis + contact oxidation method can better handle the current system of breed waste water and go out water, and the treatment effect is stable, can replace former system end to be used for getting rid of CODCrThe chemical agent has great practical value and economic benefit.
In summary, the heterogeneous ozone catalytic moderate oxidation process method of the application is used for COD of actual aquaculture wastewaterCrThe removal has good treatment effect.
The foregoing is only a preferred embodiment of the present application and it should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.
Claims (10)
1. A heterogeneous ozone catalysis process units of handling waste water which characterized in that includes:
an ozone generator and a heterogeneous ozone catalytic reaction column;
the ozone aeration head of the ozone generator is communicated with the heterogeneous ozone catalytic reaction column, and the ozone generator enables ozone to be conveyed to the inside of the heterogeneous ozone catalytic reaction column;
the heterogeneous ozone catalytic reaction column comprises a column body, a first heterogeneous ozone catalyst plate, a second heterogeneous ozone catalyst plate and a third heterogeneous ozone catalyst plate; the first heterogeneous ozone catalyst plate, the second heterogeneous ozone catalyst plate and the third heterogeneous ozone catalyst plate are arranged on the radial section of the column body, so that wastewater passes through a water inlet of the heterogeneous ozone catalytic reaction column to pass through the first heterogeneous ozone catalyst plate, the second heterogeneous ozone catalyst plate and the third heterogeneous ozone catalyst plate, and flows out from a water outlet of the heterogeneous ozone catalytic reaction column.
2. The heterogeneous ozone catalytic process unit of claim 1 further comprising a movable assembly through which the first, second or third heterogeneous ozone catalyst plates are respectively disposed on a radial cross section of the column, the movable assembly causing the first, second or third heterogeneous ozone catalyst plates to move radially inside the column.
3. The heterogeneous ozone catalyst of claim 1Process unit, characterized in that the heterogeneous ozone catalyst of the first heterogeneous ozone catalyst plate is selected from the group consisting of Mn-Fe-Ce/γ -Al2O3A catalyst.
4. The heterogeneous ozone catalytic process unit of claim 1 wherein the heterogeneous ozone catalyst of the second heterogeneous ozone catalyst plate is selected from the group consisting of Mn-Fe-Ce/γ -Al2O3A catalyst.
5. The heterogeneous ozone catalytic process unit of claim 1 wherein the heterogeneous ozone catalyst of the third heterogeneous ozone catalyst plate is selected from the group consisting of Mn-Fe-Ce/γ -Al2O3A catalyst.
6. The heterogeneous ozone catalytic process unit of claim 1 wherein the water inlet of the heterogeneous ozone catalytic reaction column is disposed at the bottom of the heterogeneous ozone catalytic reaction column.
7. The heterogeneous ozone catalytic process unit of claim 6 wherein the water outlet of the heterogeneous ozone catalytic reaction column is disposed at the top of the heterogeneous ozone catalytic reaction column.
8. The heterogeneous ozone catalytic process unit according to claim 1, wherein the ozone aeration head of the ozone generator is in communication with the heterogeneous ozone catalytic reaction column, specifically: the ozone aeration head of the ozone generator is uniformly communicated with the bottom wall of the heterogeneous ozone catalytic reaction column.
9. The heterogeneous ozone catalytic process unit of claim 1 wherein the first heterogeneous ozone catalyst plate, the second heterogeneous ozone catalyst plate and the third heterogeneous ozone catalyst plate are positioned equidistant inside the column.
10. The heterogeneous ozone catalytic process unit of any one of claims 1 to 9 wherein the first heterogeneous ozone catalyst plate comprises an upper mesh partition plate, a lower mesh partition plate and a heterogeneous ozone catalyst; the upper layer of reticular clapboard and the lower layer of reticular clapboard are aligned and fixed to form an accommodating cavity; the heterogeneous ozone catalyst is filled in the accommodating cavity;
the second heterogeneous ozone catalyst plate comprises an upper-layer reticular clapboard, a lower-layer reticular clapboard and a heterogeneous ozone catalyst; the upper layer of reticular clapboard and the lower layer of reticular clapboard are aligned and fixed to form an accommodating cavity; the heterogeneous ozone catalyst is filled in the accommodating cavity;
the third heterogeneous ozone catalyst plate comprises an upper-layer reticular clapboard, a lower-layer reticular clapboard and a heterogeneous ozone catalyst; the upper layer of reticular clapboard and the lower layer of reticular clapboard are aligned and fixed to form an accommodating cavity; the heterogeneous ozone catalyst is filled in the accommodating cavity.
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| WO2023173715A1 (en) * | 2022-03-18 | 2023-09-21 | 中建三局绿色产业投资有限公司 | Ozone catalytic oxidation and flotation integrated system and method for using same |
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