JP2022032878A - Biofilm reactor for advanced purification of sewage and operating method therefor - Google Patents

Abstract

To provide a biofilm reactor for advanced purification of sewage and an operating method therefor.SOLUTION: A biofilm reactor 1 for advanced purification of sewage has a rectangular structure. The biofilm reactor 1 has sequentially from bottom to top a backwash member 2, a water passing area 3, a boulder layer 4, a ceramic site layer 5 and a functional filter layer 6 made of alumina and titanium dioxide, and an overflow weir 7 is provided on the outside of the top of the biofilm reactor 1. If the water flow is too large, the water passing area 3 is placed below the backwash member 2, thereby distributing the water passing evenly by the backwash member 2 and reducing impact on the boulder layer 4.SELECTED DRAWING: Figure 1

Description

The present invention belongs to the technical field of biofilm sewage treatment, and specifically relates to a biofilm reactor for highly purifying sewage and an operation method thereof.

With the continuous improvement of sewage treatment wastewater standards, the removal of pollutants such as total nitrogen and total phosphorus in sewage poses major challenges for sewage treatment plants, and new pollutants and other substances are gradually attracting attention to sewage. As such, the reduction of biological toxicity of wastewater through advanced sewage treatment and safe reuse is one of the research hotspots in sewage treatment.

Traditional activated sludge processes are difficult to meet increasingly stringent sewage emission standards,
The biofilm denitrification filter process is becoming more and more widely applied due to its simple operation, small footprint, low cost, and deep denitrification. Sulfur independent nutrition-heterotrophic denitrification and other methods are gradually being applied to the denitrification filter process due to the lower cost compared to adding carbon sources, but compared to traditional heterotrophic denitrification. Then, when the denitrification rate is low and the temperature of the operating environment is relatively low, the denitrification process in the denitrification filter is inhibited, the denitrification efficiency is significantly reduced, and the denitrification rate is effectively increased. Is one of the main problems faced in its application. Generally speaking, the methods of increasing the denitrification rate of the denitrification filter are mainly to improve the carrier, improve the design of the nitrifying device, add a bioenricher, raise the operating temperature, etc., for example. The Chinese invention patent "Multipoint Enhanced Denitrification and Denitrification Biological Filter""Pool" (public number CN208200506U) is a unit time by arranging multiple water supply and carbon source administration pumps to distribute and administer water. The purpose of reducing the water head loss per unit and improving the efficiency of the denitrification filter can be achieved, but the equipment cost is high and the equipment cost is high.
The operation became difficult, and the Chinese invention patent "Preparation and application of ecological matrix particles for enhanced denitrification in river water" (publication number CN106365305B) is a highly permeable porous material, inorganic binder, corn. Consists of sustained-release carbon sources such as the cob of the ecological matrix particles are used for ecological filters and slow release of carbon sources in artificial wetlands, thereby achieving the purpose of nitrogen removal. However, the substrate strength of such particles is generally high and their effect gradually changes with the release of sustained-release carbon sources, requiring intermittent replenishment of fillers to maintain the effect. In recent years, some quinones have improved the efficiency of electron transfer between microorganisms by acting as electron carriers, thereby effectively increasing the rate of microorganisms removing nitrates and nitrites, resulting in traditional heterotrophic denitrification. Although showing applicability to nitrification filters, a new type of sulfur independent nutrition-heterotrophic denitrification filter provides new ideas for enhanced denitrification of biochemical tailwater treatment.

From the point of view of advanced phosphorus removal, with the advancement of technology, aluminum compounds have shown relatively good performance in total phosphorus removal, but the conventional method of adding aluminum and iron compounds to the filter is a filter. The use of solid-mounted aluminide filter media to affect the operation and cost of the product and remove total phosphorus has become a potentially feasible method, as well as titanium dioxide or micro / nanocatalytic oxidation in confined spaces. The use of can effectively decompose trace amounts of new contaminants remaining in tail water such as endocrine disruptors, reduce the toxicity of final wastewater such as personal care products, and reuse treated wastewater. Ensure safety. Therefore, by setting up a functional filter layer that simultaneously improves the purification effect of the denitrifying filter on biochemical wastewater and the new pollutant total phosphorus, a potentially effective technique for advanced treatment of the denitrifying filter. Simultaneous removal of total phosphorus and new pollutants has become a means and an important development direction, and is rarely described in existing patent literature.

At the same time, the "sludge" formed during the biofilm aging process also has a certain adverse effect on the operation of the denitrification filter system, which is detrimental to the advanced removal of contaminants by the reactor, and the biofilter is regularly used. Backwashing and restoring the biofilm activity of the system is also an important means for improving the advanced purification efficiency of biofilm reactors and energy-saving operations.

The present invention is a denitrification filter when purifying sewage to a high degree in the total nitrogen, total phosphorus removal process.
Solving the problems of operational burden due to the addition of drugs or carbon sources and low denitrification efficiency due to low temperature conditions,
Considering the reduction of toxicity during sewage treatment, we provide new equipment (biofilm reactor, biofilm reactor) for highly purifying and safe reuse of sewage and how to operate the equipment.

The technical solution of the present invention is as follows. Biofilm reactors for highly purifying sewage
It has a rectangular parallelepiped structure, launching area from bottom to top, backwash member, boulder layer, ceramic site layer,
And a biofilm reactor comprising a functional filter layer consisting of an alumina and titanium dioxide or a polyhydroxycomplex modified montmorillonite layer with an overflow weir on the outside of the apex.
An inlet pool for storing sewage, which is connected to the launch area via a launch pipe equipped with a launch pump and has a stirrer inside.
A first reagent storage box for storing storage quinone redox mediators, a second for storing sulfur sources, connected to an inlet pool via a reagent addition tube equipped with a metering pump.
Reagent storage box, and a third reagent storage box for storing carbon sources,
It is connected to the overflow dam via a water discharge pipe, is also connected to the backwash member via a backwash pipe equipped with a backwash pump, and a water discharge port with a valve is provided above the backwash member to purify water. With an exit pool for storing
Includes a PLC controller, which is electrically connected to the launching pump, stirrer, metering pump, and backwash pump to control the operation of the entire device.

In addition, the backwash member includes the filter bricks and the shelves located under the filter bricks, the bottom of the shelves and the biofilm reactor is the backwash water distribution area to which the backwash water pump is connected, and the backwash water. A backwash gas pipe located in the distribution area is provided and the backwash gas pipe is connected to the outlet pool via a backwash pipe with a backwash water pump.
On both sides of the filter brick, there are connecting cylinders and connecting columns that are connected to the adjacent filter bricks and separate the adjacent filter bricks with slits of equal width, and diagonal dividers are provided at the four corners inside the filter bricks. Multiple water / gas pipes are provided on the four diagonal dividers, and the four diagonal dividers are divided into a hexagonal column cavity centered inside the filter brick and a cavity at the four corners, and the upper layer. The tops of the two cavities are provided with a first backwash hole that vertically penetrates the filter bricks, and the sides of the two lower cavities are provided with a second backwash hole that horizontally penetrates the filter bricks.
Inside the hexagonal column cavity, a partition plate for dividing the hexagonal column cavity into an upper gas distribution cavity and a lower water distribution cavity is horizontally arranged, and a launching cut is provided at the bottom of the water distribution cavity. ,
The shelf board is located under the water distribution cavity and a launch groove is opened to communicate with the cut, and the backwash water is introduced into the water distribution cavity and sequentially passes through the water / gas distribution pipe of the lower diagonal partition plate to the lower layer. It enters the two cavities and distributes the secondary water, and finally flows from the first backwash hole on both sides to the slit between the two adjacent filter bricks, backwashes upward through the slit, and the backwash gas pipe. Multiple gas cross nozzles are provided on the top, and the gas cross nozzles sequentially pass upward through the preliminary holes on the shelf plate and the partition plate and extend into the gas distribution cavity, and the backwash airflow is introduced into the gas distribution cavity in sequence. It passes through the water / gas distribution pipe of the upper diagonal partition plate, reaches the upper two cavities, distributes the secondary gas, and is finally discharged from the second backwash hole at the top of the filter brick to reverse the gas in the filter layer. Wash. Gas and water are distributed individually or simultaneously during backwashing. The inside of the filter brick of the present invention is made by pouring concrete, and a diagonal partition plate and a reinforcing rib for resisting an impact force are provided inside the partition plate.

Further, the method for producing the functional filter layer includes the following steps.
The method for producing the functional filter layer includes the following steps.
Step 1: Prepare an aluminum sulfate solution with aluminum ions at a concentration of 10-12 g / L, add sodium hydroxide to adjust the pH of the solution to about 7.0, and stir for 5-10 minutes.
After forming an aluminum hydroxide precipitate by the reaction, 1 to 2 g / L titanium dioxide powder is added to the solution, stirred uniformly, placed in a closed container and heated to 100 to 110 ° C., and 24-36.
h Shake to form an aluminum sulfate-titanium dioxide mixture having a particle size of 20 to 30 μm.
Step 2: Porous ceramic sites obtained by sintering 5 to 10% by weight of fly ash are added to the aluminum sulfate-titanium dioxide mixture, washed, and then immersed in the prepared solution for 20 to 30 minutes. After removal, molecular strength is used to attach micron-level aluminum sulphate and nano-level titanium dioxide to the pore structure of the ceramic site and allow it to dry naturally.

The present invention further provides a functional filter layer composed of a polyhydroxycomplex-modified montmorillonite layer, wherein the montmorillonite in the polyhydroxycomplex-modified montmorillonite layer is 65.5% SiO2, 14.3% Al2O3, 1. 78% Fe
It consists of 2O3, 1.08% CaO, 1.42% MgO, 0.2% K2O and 0.19% TiO2.
The method for producing a polyhydroxycomplex-modified montmorillonite comprises the following steps.
Step 1: A montmorillonite suspension with a solid-liquid ratio of 1: 100 is swollen for 24 hours at 22 kHz.
Disperse for 5 min under ultrasonic waves.
Step 2: Add 0.1MNaOH solution to 0.1MFeCl3 solution and [OH] / [Fe] =
Set to 2.0 to form an iron polyhydroxy complex and prepare a modified solution.
Step 3: Add the modified solution to the clay suspension so that the ratio of iron to clay is 1.0 mmol / g, hold the mixed suspension solution at room temperature for 24 hours, centrifuge the clay, and distill water. Wash until chlorine-free, dry at room temperature, and bake at 500 ° C. for 2 hours.

The present invention further provides a method of operation for highly purifying sewage using the biofilm reactor, which comprises the following steps.
S1: Detect biochemical wastewater to be treated, measure its carbon-nitrogen ratio, calculate the total nitrogen load for launch according to the launch status, and according to the calculation result, heterotrophic denitrification mode or autotrophic sulfur. The nutrition-heterotrophic denitrification mode is selected and treated, and the successor treatment and drug addition to the biofilter (1) is carried out according to the selected treatment method.
S2: When treating wastewater by selecting the heterotrophic denitrification mode, after the filter is started normally, 50 to 120 nM quinone redox mediator is continuously or intermittently added to the water depending on the operating environment temperature.
When treating wastewater by selecting the autotroph-heterotrophic denitrification mode of sulfur, a certain amount of sulfur source was added according to the carbon-nitrogen ratio in the wastewater, the biofilm was cultured, and the filter was normally disclosed. Later, 70-150 nM quinone redox mediator is added to the water continuously or intermittently depending on the operating environment temperature to achieve the purpose of enhancing denitrification.

Further, the biochemical wastewater is one of the biochemical wastewater and the biochemical wastewater of the industrial wastewater of the urban sewage treatment plant, and the total nitrogen concentration is 30 mg / L or less.

Further, the heterotrophic denitrification mode is selected under the conditions that COD / TN ≧ 3, and the launching total nitrogen load designed by launch is 0.25 to 0.60 kg · TN / (m3 · d). ,
The condition that the autotroph-heterotrophic denitrification mode of sulfur is COD / TN <3 and the total nitrogen load of the launch designed by launch is 0.05 to 0.35 kg · TN / (m3 · d). Is selected by.
Further, in the heterotrophic denitrification mode, when the temperature is 15 to 25 ° C., the quinone redox mediator is added every other day, the addition concentration is 80 to 120 nM, and the temperature is 10 to 10 to.
When the temperature is 15 ° C., the dose is continuously administered, and the administration concentration is 50 to 100 nM. The quinone redox mediator is sodium anthraquinone-2-sulfonate, 1,2-naphthoquinone-4-sodium sulfonate, anthraquinone-2. , Any one of disodium 6-disulfonate.

Further, in the autonomous-heterotrophic denitrification mode of sulfur, in the heterotrophic denitrification mode, the sulfur source is any one of the elemental sulfur, sodium sulfide or sodium thiosulfate.
The ratio of the amount to remove total nitrogen by heterotrophic denitrification and autotrophic denitrification is 1: 1 to 1: 1:
The ratio of the dose of the sulfur source to the amount of total nitrogen removed by autotrophic denitrification of sulfur is 3
~ 5kg elemental sulfur / kg · TN, 5 ~ 6kg sodium sulfide / kg · TN, 8 ~ 10kg
Administer at a ratio of sodium thiosulfate / kg · TN.

The beneficial effects of the present invention are as follows.
(1) The present invention uses sulfur autotroph-dependent nutrition denitrification to compensate for the high cost defects caused by the addition of carbon sources, and is a trace quinone redox mediator that basically does not change the conditions of the inflowing organic matter concentration. Using the addition of, under the condition of limited carbon source concentration, improve the denitrification capacity of the denitrification filter, achieve the purpose of strengthening denitrification, increase the total nitrogen, increase the removal rate, carbon Effective cost savings compared to adding sources.
(2) The present invention uses alumina and carbon dioxide serum sites as a functional filter material layer consisting of a filter material layer or a polyhydroxy complex modified montmorillonite layer, which greatly simplifies the drug administration system and is totally simplified. The effect of removing phosphorus is improved, and the toxicity of water is effectively reduced.
(3) The present invention can significantly improve the removal of total nitrogen, total phosphorus, and biological toxicity in the sewage treatment process of a biofilm reactor, has a large high purification effect, and is safe for reusing sewage after treatment. Is improved.
(4) With the backwash member of the present invention, the uniformity of water distribution reaches 90% or more, and the energy consumption of backwash is reduced by 30% to 40%.

It is a schematic of the whole structure of the apparatus of this invention. It is sectional drawing of the filter brick of this invention. It is a top view of the filter brick of this invention. It is a right side view of the filter brick of this invention. It is a plan view of the partition plate of this invention. It is a schematic assembly drawing of the backwash member of this invention. It is an operation effect diagram which purifies the secondary wastewater highly by the heterotrophic denitrification filter under the enhanced normal temperature condition of this invention. It is an operation effect diagram which purifies the secondary biochemical wastewater of industrial wastewater highly by the autotrophs-heterotrophic denitrification filter of sulfur under the enhanced low temperature condition of this invention. It is an operation effect diagram of the secondary biochemical wastewater denitrification which purifies urban wastewater highly by the heterotrophic denitrification filter under the enhanced low temperature condition of this invention. The operational effect diagram of highly purifying the secondary biochemical wastewater of an urban sewage treatment plant by the autotrophic-heterotrophic denitrification filter of sulfur under the enhanced normal temperature condition of the present invention.

[Explanation of code]
1 Biofilm Reactor 2 Backwash member 21 Filter brick 22 Shelf board 23 Backwash water pump 24 Backwash water distribution area 25 Backwash gas pump 26 Backwash gas pipe 27 Connection cylinder 28 Connection pillar 29 Diagonal partition plate 210 Water / gas distribution pipe 211 Hexagonal pillar cavity 212 Cavity 213 First backwash hole 214 Second backwash hole 215 Partition plate 216 Gas distribution cavity 217 Water distribution cavity 218 Trigger 219 Launch groove 220 Gas cross nozzle 221 Preliminary hole 3 Launch area 4 Ball stone layer 5 Ceramic site layer 6 Functional filter layer 7 Overflow dam 8 Injection inlet pool 9 Launch pump 10 Launch tube 11 Stirrer 12 First reagent storage box 13 Second reagent storage box 14 Measuring pump 15 Reagent addition tube 16 Exit Pool 161 Water discharge port 17 Backwash pipe 18 PLC controller 19 Water discharge pipe 20 Third reagent storage box

In order to further understand the contents of the present invention, the present invention will be described in detail with reference to the following examples.
Example 1
As shown in FIG. 1, the biofilm reactor for highly purifying sewage is a biofilm reactor 1 having a rectangular parallelepiped structure, and the biofilm reactor 1 is a backwash member 2 and a launch region 3 in order from bottom to top. , A ball stone layer 4, a ceramic site layer 5, and a functional filter layer 6 composed of alumina and titanium dioxide, an overflow dam 7 is provided on the outside of the top of the biofilm reactor 1, and if the water flow is too large, the launch region 3 Is installed below the backwash member 2, whereby the launch water is evenly distributed by the backwash member 2 and the impact on the ball stone layer 4 is reduced.
As shown in FIGS. 1, 2, 3, 3, 4, 5, and 6, the backwash member 2 is a filter brick 2.
1 and a shelf 22 located below the filter brick 21 are included, and the bottom of the shelf 22 and the biofilm reactor 1 is a backwash water distribution region 24 to which the backwash pump 23 is connected.
A backwash gas pipe 26 located in the backwash water distribution area 24 is provided, and the backwash gas pipe 26 is connected to the outlet pool 16 via a backwash pipe 17 provided with a backwash water pump 23.
A connecting cylinder 27 and a connecting pillar 28 connected to the adjacent filter bricks 21 on both sides of the filter brick 21 and dividing the adjacent filter bricks 21 into slits of the same width are provided, and each of the four corners inside the filter brick 21 is provided. An inclined diagonal partition plate 29 is provided, a plurality of water / gas distribution pipes 210 are provided on the four diagonal partition plates 29, and the four diagonal partition plates 29 are hexagonal pillar cavities centered on the inside of the filter brick 21. It is divided into 211 and four corner cavities 212, and a second backwash hole 214 that vertically penetrates the filter brick 21 is provided at the top of the two cavities 212 in the upper layer, and on the side surface of the two cavities 212 in the lower layer. A first backwash hole 213 that horizontally penetrates the filter brick 21 is provided.
Inside the hexagonal column cavity 211, a partition plate 215 for dividing the hexagonal column cavity 211 into an upper gas distribution cavity 216 and a lower water distribution cavity 217 is horizontally arranged, and water is launched at the bottom of the water distribution cavity 217. A cut-out 218 is provided for this purpose, and a launch groove 219 is opened in which the shelf board 22 is located below the water distribution cavity 217 and communicates with the cut-out 218. It passes through the water / gas distribution pipe 210 of 29, reaches the lower two cavities 212, distributes secondary water, and finally has a slit between two adjacent filter bricks 21 from the first backwash holes 213 on both sides. A plurality of gas cross nozzles 220 are provided on the backwash gas pipe 26, and the gas cross nozzles 220 sequentially upwardly form the shelf plate 22 and the preliminary hole 221 on the partition plate 215. It passes through and extends to the gas distribution cavity 216, and the backwash airflow is introduced into the gas distribution cavity 216, and the water / gas distribution pipe 2 of the upper diagonal partition plate 29 is sequentially introduced.
It passes through 10 and reaches the upper two cavities 212, distributes the secondary gas, and is finally discharged from the second backwash hole 214 at the top of the filter brick 21 to backwash the filter layer with gas. Gas and water are distributed individually or simultaneously during backwashing. The inside of the filter brick 21 of the present invention is made by pouring concrete, and reinforcing ribs for resisting an impact force are provided inside the diagonal partition plate 29 and the partition plate 215.
As shown in FIG. 1, the inlet pool 8 for storing sewage is connected to the launch region 3 via a launch pipe 10 provided with a launch pump 9, and a stirrer 11 is provided in the inlet pool 8. The first reagent storage box 12 for storing the quinone redox mediator and the second reagent storage box 13 for storing the sulfur source are provided as the first reagent storage box 12 and the second.
The reagent storage box 13 and the third reagent storage 20 of the above are connected to the inlet pool 8 via the reagent addition pipe 15 provided with the measuring pump 14, respectively, and the outlet pool 16 for storing purified water.
Is connected to the overflow dam 7 via the water discharge pipe 19, the outlet pool 16 is also connected to the backwash member 2 via the backwash pipe 17 provided with the backwash water pump 23, and a valve at the top of the outlet pool. A water discharge port 161 is provided, and the treated waste water is immediately discharged, sufficient backwash water is secured in the outlet pool 16, and the PLC controller 18 for controlling the operation of the entire device is advanced. It is electrically connected to the water pump 9, the stirrer 11, the measuring pump 14, and the backwash water pump 23.
The operation method of this device is as follows. First, wastewater is detected, and the detection target is COD concentration, T.
N concentration, nitrate nitrogen concentration, ammonia nitrogen concentration, nitrite nitrogen concentration, total phosphorus, pH, and environmental temperature are included. Select the nitrification mode from COD / TN, COD / TN ≧ 3, launching designed by launch When the total nitrogen load is 0.25 to 0.60 kg · TN / (m3 · d), heterotrophic denitrification Select mode, COD / TN <3, launch designed by launch Total nitrogen load is 0
.. For 05-0.35 kg · TN / (m3 · d), select the sulfur autotroph-heterotrophic denitrification mode.
When the wastewater is introduced into the inlet pool 8 for water storage and the dependent nutrient denitrification mode is selected, the metering pump 14 of the first reagent storage box 12 is opened and the Kinon Redox mediator is continuously or intermittently applied as needed. Is administered to the inlet pool 8 and uniformly stirred and mixed by the stirrer 11, and the wastewater in the inlet pool 8 is discharged from the launch pipe 10 to the launch region 3 via the launch pump 9.
The wastewater is transported to the A area 221 of the above, overflows upward to the B area 222 through the communication pipe 223, and sequentially passes through the ball stone layer 4, the ceramic site layer 5, and the functional filter layer 6 to be purified and filtered together with the layers. After the purified water flows into the overflow dam 7, it flows into the outlet pool 16 from the water discharge pipe 19, and when the total amount of nitrogen in the reactor does not meet the drainage requirement, the third reagent storage box 20 is opened as needed and carbon is used. Administer the source.
When the autotroph-heterotrophic denitrification mode of sulfur is selected, the metering pump 14 of the second reagent storage box 13 is first opened, a certain amount of sulfur source is added according to the carbon-nitrogen ratio in the waste water, and the biofilm is formed. After culturing, the launch pump 9 is opened to start pouring water into the biofilm reactor 1, and the metering pump 14 of the first reagent storage box 12 is selectively opened according to the operating environment temperature to continuously or intermittently enter the launch. Add Kinon Redox Mediator to Achieve the purpose of strengthening denitrification.
When it is necessary to backwash the biofilm reactor 1 after a certain period of time, the launch pump 9 is closed and the launch is stopped, and at the same time, the backwash pump 17 is opened and the stored purified water in the outlet pool 16 is B. It is sent to area 222, and at the same time, the backwash pump 25 is opened, purified water and backwash gas are circulated through the water flow path 211 of the filter brick 21, distributed outward from the flow control gap 212, and between the two adjacent filter bricks 21. Water and gas are evenly distributed upward from the gap, and backwashing is performed. At the same time, during the period when purified water flows through the water flow path 211, the upper filter medium is squeezed through the backwashing hole 214 opened at the top of the filter brick 21. Backwash evenly. The filter brick 21 is fixedly connected to the communication pipe 223 of the shelf board 22 via the connection hole 216, and the displacement of the filter brick 21 can be prevented. Launching and backwashing in different areas can effectively prevent filter brick clogging, increase backwashing efficiency, and reduce backwashing energy consumption.

Example 2
This embodiment relates to a method of adding a quinone redox mediator to enhance denitrification when the denitrification filter employs a heterotrophic denitrification method to highly purify secondary biochemical wastewater.
As a result of detecting the secondary biochemical wastewater to be treated, the COD concentration is 50 to 65 mg / L, the TN concentration is 16 to 19 mg / L, the nitrate nitrogen concentration is 14 to 17 mg / L, and the ammonia. The oxygen demand concentration is 0.4 to 0.6 mg / L, and the nitrite nitrogen concentration is 0.2 to 0.2.
It is 0.8 mg / L, total phosphorus is 0.50 to 0.58 mg / L, and pH is 7.4 to 7.
.. 6 and the environmental temperature is 18 ° C. As can be seen from the detection result, the COD / TN exceeds 3, the hydraulic pressure holding time is 1.0 h, and the launching total nitrogen load is 0.5 kg · TN / (m3).
-D) Select the heterotrophic denitrification filter treatment, and since the temperature is normal temperature, the intermittent administration method is adopted and the denitrification filter is operated by the upward method.
Two sets of nitrification devices, a comparative group and a test group, are installed to treat wastewater, and the comparative group operates with the device without the functional filter layer 6 in Example 1. In the test group, the nitrification device provided with the functional filter layer 6 in Example 1 is used.
The method for producing the functional filter layer 6 is as follows. Prepare a 10 g / L (with aluminum ion) aluminum sulfate solution (Al2 (SO4) 3.18H2O), add sodium hydroxide to adjust the solution pH to about 7.0, stir for 6 minutes, and then 1.8 g. / L Titanium dioxide (TiO2) powder was added to the solution, the solution was heated to 100 ° C. in a closed container, shaken for 24 hours, and then the porous ceramic site mixed with 5 wt% fly ash was selected and washed. Immerse in the prepared solution for 30 minutes, then remove and allow to air dry to obtain a functional filter layer.
As for the operating period of the nitrifying device and the water quality of the water in which all nitrogen enters and exits, as shown in FIG. 7, after 70 days of operation, the drainage of the nitrifying device was relatively stable, and as a result of detecting the denitrification filter drainage, the result was found. The wastewater TN concentration was 8 to 11 mg / L, and the total nitrogen removal rate was relatively low.
After detecting the wastewater TOC and TN concentration and adding a redox mediator during the operation for the following 35 days, the TOC concentration in the wastewater hardly changed, and the total nitrogen concentration in the wastewater was 3.5-8.
It is 5 mg / L, and the average total nitrogen removal rate is improved by 3.75 mg / L as compared with the comparative group.
The total nitrogen removal rate was improved by 24.6%, and the purpose of enhancing denitrification was achieved. At the same time, the total wastewater phosphorus was 0.20 to 0.28 mg / L, and from the biological toxicity test using luminescent bacteria. As can be seen, the relative suppression rate of wastewater in the test group was 26% to 32% lower than that in the comparative group. The mass of sodium acetate required to remove total nitrogen per unit mass is 6 g sodium acetate / gTN
Then, it is necessary to add 22.5 mg / L of sodium acetate, the price of sodium acetate is 2500 yuan / ton, and the price of 1,2-naphthoquinone-4-sodium sulfonate is 220.
Calculated as 0 yuan / kg (95% purity), the cost can be saved by 0.022 yuan / m3 and the carbon source administration cost can be saved by 38.7%. The water distribution uniformity of the backwash member reached 93% and the backwash energy consumption was reduced by 34%.

Example 3
In this example, the denitrification filter employs an autotroph-heterotrophic denitrification method of sulfur to purify the secondary biochemical wastewater of industrial wastewater (spun wastewater) at low temperatures with a quinone redox mediator. In addition, it relates to a method for enhancing denitrification.
As a result of detecting the secondary biochemical wastewater to be treated, the COD concentration is 30 to 35 mg / L, the TN concentration is 15 to 18 mg / L, the nitrate nitrogen concentration is 13 to 15 mg / L, and the ammonia. The oxygen demand concentration is 0.1 to 0.3 mg / L, and the nitrite nitrogen concentration is 0.1 to 0.3 mg / L.
It is 0.4 mg / L, total phosphorus is 0.15 to 0.26 mg / L, and pH is 7.5 to 7.
.. 8 and the environmental temperature is 10 ° C. Since the COD / TN is less than 3, the hydraulic pressure holding time is 2.0 h, and the launching total nitrogen load is 0.15 kg · TN / (m3 · d).
Using the autotroph-heterotrophic denitrification filter treatment of sulfur, the temperature is low, so the continuous administration method is used, the denitrification filter is operated in the upward method, and the hydraulic pressure retention time is 2.0.
Since h is selected and sodium sulfide is selected as the sulfur source and added in a ratio of heterotrophic denitrification to autotrophic reverse digestion 1: 1, the concentration of sodium sulfide added is 40 mg / L.
Two sets of nitrification devices, a comparative group and a test group, are installed to treat wastewater, and the comparative group operates with the device without the functional filter layer 6 in Example 1. In the test group, the nitrification device provided with the functional filter layer 6 in Example 1 is used.
The method for producing the functional filter layer 6 is as follows. By weight%, 65.5% SiO2, 1
4.3% Al2O3, 1.78% Fe2O3, 1.08% CaO, 1.42% MgO, 0
.. Montmorillonite is composed of 2% K2O and 0.19% TiO2, and its solid-liquid ratio is 1: 100.
The montmorillonite suspension is inflated for 24 hours and dispersed for 5 min under 22 kHz ultrasonic waves. A 0.1 MNaOH solution was added to the 0.1 MFeCl3 solution to make [OH] / [Fe] = 2.0, and an iron polyhydroxy complex was used to prepare a modified solution. The modified solution was added dropwise to the clay suspension so that the ratio of iron to clay was 1.0 mmol / g, and the mixed suspension solution was added to the clay suspension at room temperature for 24 hours.
Retained. Centrifuge the clay, wash with distilled water until chlorine-free, dry at room temperature, 5
After firing at 00 ° C. for 2 hours, a functional layer filter medium is obtained.
As shown in FIG. 8, the operation result of the reactor is that after operating for 70 days, the drainage of the reactor is relatively stable, and as a result of detecting the drainage of the denitrification filter, the drainage TN concentration is 9 to 12 m.
At g / L, the total nitrogen removal rate was low. At this time, in the test group, 70 mM anthraquinone-2,6-disulfonate disodium was continuously administered, and the wastewater TOC and TN concentration were detected. During the operation for the following 35 days, the redox mediator was added, the wastewater TOC concentration hardly changed, and the total wastewater nitrogen concentration was 5.8 to 9.6 mg / L. The rate is improved by 3.10 mg / L, the total nitrogen removal rate is improved by 18.2%, the purpose of strengthening denitrification is achieved, and at the same time, the total wastewater phosphorus is 0.08 to 0.14 mg / L and emits light. As can be seen from the biological toxicity test using bacteria, the relative suppression rate of wastewater from the test group was reduced by 48% to 52% compared to the comparative group. Assuming that the mass of sodium acetate required to remove total nitrogen per unit mass is 6 g sodium acetate / gTN, sodium acetate is 18.6 m.
It is necessary to add g / L, and if the price of sodium acetate is 2500 yuan / ton and the anthraquinone-2,6-disodium dissulfonate is calculated as 1200 yuan / kg (90% purity), the cost is 0.020 yuan. / M3 can be saved, and the carbon source administration cost can be saved by 42.3%. The uniformity of water distribution of the backwash member reaches 94.5% and the backwash energy consumption is 35%.
It was reduced.

Example 4
This embodiment relates to a method of adding a quinone redox mediator to enhance denitrification when the denitrification filter uses a heterotrophic denitrification method to purify secondary biochemical wastewater of highly urban wastewater at low temperatures. ..
As a result of detecting the urban wastewater to be treated, the COD concentration is 40 to 60 mg / L, the TN concentration is 14 to 16 mg / L, the nitrate nitrogen concentration is 13 to 15 mg / L, and the ammonia nitrogen concentration is. It is 0.4 to 0.6 mg / L and the nitrite nitrogen concentration is 0.2 to 0.5 mg.
/ L, total phosphorus is 0.56 to 0.64 mg / L, pH is 7.0 to 7.2, and the environmental temperature is 12 ° C. Since the COD / TN exceeds about 3, the hydraulic pressure holding time is 1.
.. Since it is 5 hours and the total nitrogen load of the launch is 0.4 kg ・ TN / (m3 ・ d), the heterotrophic denitrification filter treatment is used, and the temperature is low, so the continuous administration method is used. Then, the denitrification filter is operated by the gravity flow method.
Two sets of nitrification devices, a comparative group and a test group, are installed to treat wastewater, and the comparative group operates with the device without the functional filter layer 6 in Example 1. In the test group, the functional filter layer 6 in Example 1
Operates on a nitrifying device equipped with.
The method for producing the functional filter layer 6 is as follows. Prepare a 10 g / L (with aluminum ion) aluminum sulfate solution (Al2 (SO4) 3.18H2O), add sodium hydroxide to adjust the solution pH to about 7.0, stir for 6 minutes, and then 1.0 g. / L Titanium dioxide (TIM2) powder was added to the solution, the solution was heated to 105 ° C. in a closed container, shaken for 48 hours, then selected and washed with porous ceramic sites mixed with 10 wt% fly ash.
After soaking in the prepared solution for 30 minutes, it is taken out and air-dried to obtain a functional filter layer.
As shown in FIG. 9, the reactor operation results show that the wastewater is relatively stable after 70 days of operation, and as a result of detecting the denitrification filter wastewater, the wastewater TN concentration is 9 to 11 mg / L, and the total nitrogen removal rate is high. At this time, in the test group, 80 mM sodium anthraquinone-2-sulfonate was continuously administered in the running water, the effluent TN concentration was detected, and then during the operation for 35 days, the redox mediator was added, and then the total effluent was drained. The nitrogen concentration is 4.5 to 6.4 mg / L, and the average total nitrogen removal rate is improved by 4.55 mg / L and the total nitrogen removal rate is 42.5 when compared with the comparative group.
Achieves the purpose of improving% and strengthening denitrification, and at the same time, total phosphorus in wastewater is 0.26 to 0.36 mg /
When it reached L, as can be seen from the biological toxicity test using luminescent bacteria, the relative effluent suppression rate of the test group was reduced by 18% to 24% compared to the comparative group. Assuming that the mass of sodium acetate required to remove total nitrogen per unit mass is 6 g sodium acetate / gTN, sodium acetate 27
.. It is necessary to add 3 mg / L, and if sodium acetate is 2500 yuan / ton and anthraquinone-2-sulfonate sodium is 1600 yuan / kg (92% purity), the cost can be saved by 0.028 yuan / m3 and carbon. The source administration cost was saved by 41.8%. The water distribution uniformity of the backwash member reached 95% and the backwash energy consumption was reduced by 38%.

Example 5
In this example, if the denitrification filter uses an autotroph-heterotrophic denitrification method of sulfur to purify secondary biochemical wastewater from an urban sewage treatment plant at high temperature at room temperature, a quinone redox mediator is added. On how to enhance denitrification.
First, the polyhydroxycomplex-modified montmorillonite was prepared as the functional filter layer 6, and the production method thereof is as follows.
As a result of detecting microsewage on the ground to be treated, the COD concentration was 20 to 30 mg / L.
The TN concentration is 15 to 20 mg / L, the nitrate nitrogen concentration is 14 to 19 mg / L, the ammonia nitrogen concentration is 0.2 to 0.3 mg / L, and the nitrite nitrogen concentration is 0.2 to 0. At 4 mg / L, total phosphorus is 0.20 to 0.28 mg / L, pH is 7.4 to 7.6, and the environmental temperature is 22 ° C.
Is. Since its COD / TN is less than 3, the autotroph-heterotrophic denitrification filter treatment of sulfur is used, and since the temperature is normal temperature, it is administered intermittently and the denitrification filter is operated by the gravity flow method. , The hydraulic retention time is 2.5 h, elemental sulfur is selected as the sulfur source, heterotrophic denitrification and autotrophic backdigestion 1: 1.5 are added, and the amount of elemental sulfur added is 80 mg.
/ L.
Two sets of nitrification devices, a comparative group and a test group, are installed to treat wastewater, and the comparative group operates with the device without the functional filter layer 6 in Example 1. In the test group, the functional filter layer 6 in Example 1
Operates on a nitrifying device equipped with.
The method for producing the functional filter layer 6 is as follows. The functional filter layer 6 is composed of a polyhydroxy complex modified montmorillonite layer, and the montmorillonite in the polyhydroxy complex modified montmorillonite layer is 65.5% SiO2, 14.
3% Al2O3, 1.78% Fe2O3, 1.08% CaO, 1.42% MgO, 0.2
It consists of% K2O and 0.19% TiO2.
The method for producing a polyhydroxycomplex-modified montmorillonite comprises the following steps. A montmorillonite suspension having a solid-liquid ratio of 1: 100 is swollen for 24 hours and dispersed for 5 min under 22 kHz ultrasonic waves. Add 0.1M NaOH solution to 0.1MFeCl3 solution and add [OH].
/ [Fe] = 2.0 to form an iron polyhydroxy complex to prepare a modified solution. The modified solution is added dropwise to the clay suspension so that the ratio of iron to clay is 1.0 mmol / g, and the mixed suspension solution is held at room temperature for 24 hours. The clay is centrifuged, washed with distilled water until chlorine is not contained, dried at room temperature, and then calcined at 500 ° C. for 2 hours to obtain a functional filter layer.
As shown in FIG. 10, the results of the reactor show that after operating for 70 days, the wastewater is relatively stable, and as a result of detecting the denitrification filter wastewater, the wastewater TN concentration is 10 to 13 mg / L, and the total nitrogen removal rate is high. At this time, the test group went into water, and every other day, 120 mM anthraquinone-2,
Disodium 6-disulfonate was administered, its wastewater TN concentration was detected, and after 35 days of operation, after adding a redox mediator, the total wastewater nitrogen concentration was 5.8 to 7.6 mg /.
It is L, and compared with the comparative group, the average total nitrogen removal is improved by 4.8 mg / L, the total nitrogen removal rate is improved by 41.7%, the purpose of strengthening denitrification is achieved, and at the same time, the total phosphorus in the wastewater is reduced. 0.12-0.1
It reached 6 mg / L, and as can be seen from the biological toxicity test using luminescent bacteria, the relative effluent suppression rate of the test group was reduced by 12% to 20% compared to the comparative group. Assuming that the mass of sodium acetate required to remove total nitrogen per unit mass is 6 g sodium acetate / gTN, it is necessary to add 28.8 mg / L of sodium acetate, and the sodium acetate is 2500 yuan / ton.
Calculating anthraquinone-2,6-disodium disulfonate as 1800 yuan / kg (95% purity) saves 0.032 yuan / m3 in cost and 44.8% in carbon source administration cost. The water distribution uniformity of the backwash member reached 96% and the backwash energy consumption was reduced by 40%.

It should be noted that a person skilled in the art can directly conceive some modifications from the disclosed contents and common wisdom of the present invention based on the idea and specific examples of the present invention, and the details thereof will be omitted, but other methods, Alternatively, the functions and effects of the present invention can be similarly achieved by substantive changes such as replacement of well-known techniques of the prior art and various combinations of features, each of which is within the scope of protection of the present invention.

Claims (8)

It has a rectangular parallelepiped structure, and is a functional filter layer composed of a launching region (3), a backwash member (2), a boulder layer (4), a ceramic site layer (5), and alumina and titanium dioxide in order from bottom to top. A functional filter layer (6) composed of a polyhydroxycomplex-modified montmorillonite layer.
), And a biofilm reactor (1) provided with an overflow weir (7) on the outside of the top.
A stirrer (11) is provided inside the launching area (3) via a launching pipe (10) provided with a launching pump (9), and an inlet pool (8) for storing sewage. When,
A first reagent storage box (12) for storing the storage quinone redox mediator connected to the inlet pool (8) via a reagent addition tube (15) equipped with a metering pump (14).
), A second reagent storage box (13) for storing the sulfur source, and a third reagent storage box (20) for storing the carbon source.
It is connected to the overflow weir (7) via a water discharge pipe (19) and is connected to a backwash water pump (23).
) Is connected to the backwash member (2) via a backwash pipe (17), and a water discharge port (161) with a valve is provided above the backwash member (2), and an outlet pool (161) for storing purified water is provided. 16) and
A PLC controller (18) that is electrically connected to the launching pump (9), stirrer (11), metering pump (14), and backwash pump (23) to control the operation of the entire device, and
A biofilm reactor for highly purifying sewage, characterized by containing. The method for producing the functional filter layer composed of alumina and titanium dioxide is as follows.
Step 1: Prepare an aluminum sulfate solution having a concentration of 10 to 12 g / L with aluminum ions, add sodium hydroxide to adjust the pH of the solution to 7.0, stir for 5 to 10 minutes, and react to aluminum hydroxide by reaction. After forming a precipitate, 1 to 2 g / L of titanium dioxide powder is added to the solution, stirred uniformly, placed in a closed container and heated to 100 to 110 ° C. for 24-36 h.
Shaking to form an aluminum sulfate-titanium dioxide mixture having a particle size of 20 to 30 μm.
Step 2: Porous ceramic sites obtained by sintering 5 to 10% by weight of fly ash are added to the aluminum sulfate-titanium dioxide mixture, washed, and then immersed in the prepared solution for 20 to 30 minutes. After taking it out, micron level aluminum sulfate and nano level titanium dioxide are attached to the pore structure of the ceramic site by molecular force and dried.
The biofilm reactor for highly purifying sewage according to claim 1, wherein the biofilm reactor comprises. The method for producing the functional filter layer composed of the polyhydroxycomplex-modified montmorillonite layer is as follows.
Montmorillonite in the polyhydroxycomplex modified montmorillonite layer is 65.5% SiO2, 14.3% Al2O3, 1.78% Fe2O3, 1.08% Ca by weight.
Prepared with O, 1.42% MgO, 0.2% K2O, 0.19% TiO2,
Step 1: A montmorillonite suspension with a solid-liquid ratio of 1: 100 is swollen for 24 hours at 22 kHz.
Disperse for 5 min under ultrasonic waves,
Step 2: Add 0.1MNaOH solution to 0.1MFeCl3 solution and [OH] / [Fe] =
To 2.0, form an iron polyhydroxy complex and prepare a modified solution,
Step 3: Add the modified solution to the clay suspension so that the ratio of iron to clay is 1.0 mmol / g, hold the mixed suspension solution at room temperature for 24 hours, centrifuge the clay, and distill water. The biofilm reactor for highly purifying sewage according to claim 1, wherein the mixture is washed to a chlorine-free state, dried at room temperature, and fired at 500 ° C. for 2 hours. It is an operation method for highly purifying sewage by using the biofilm reactor (1) according to any one of claims 1 to 3.
S1: Detect the biochemical wastewater to be treated, measure its carbon-nitrogen ratio, calculate the total nitrogen load of the launch according to the launch situation, and according to the calculation result, the heterotrophic denitrification mode or the independence of sulfur. Performing a successor treatment and drug addition to the biofilm reactor (1), depending on the treatment method selected, the nutrition-heterotrophic denitrification mode selected.
S2: When treating wastewater by selecting the heterotrophic denitrification mode, after the filter is started normally, 50 to 120 nM quinone redox mediator is continuously or intermittently added to the water depending on the operating environment temperature.
When treating wastewater by selecting the autotroph-heterotrophic denitrification mode of sulfur, a certain amount of sulfur source was added according to the carbon-nitrogen ratio in the wastewater, the biofilm was cultured, and the filter was normally disclosed. A method of operation comprising adding 70-150 nM quinone redox mediator to water continuously or intermittently depending on the operating environment temperature to enhance denitrification. The biochemical wastewater is any one of the biochemical wastewater of the urban sewage treatment plant and the biochemical wastewater of the industrial wastewater, and the total nitrogen concentration is 30 mg / L or less. Item 4. The operation method according to Item 4. The heterotrophic denitrification mode is selected under the conditions that COD / TN ≧ 3, and the launching total nitrogen load designed by launch is 0.25 to 0.60 kg · TN / (m3 · d).
The condition that the autotroph-heterotrophic denitrification mode of sulfur is COD / TN <3 and the total nitrogen load of the launch designed by launch is 0.05 to 0.35 kg · TN / (m3 · d). The operation method according to claim 4, wherein the operation method is selected in. In the dependent nutrient denitrification mode, quinone redox mediator is added every other day when the temperature is 15 to 25 ° C, and continuously when the addition concentration is 80 to 120 nM and the temperature is 10 to 15 ° C. It was administered and the administration concentration was 50 to 100 nM, and the quinone redox mediator was contained in sodium anthraquinone-2-sulfonate, sodium 1,2-naphthoquinone-4-sulfonate, and disodium anthraquinone-2,6-disulfonate. The operation method according to claim 4, wherein the operation method is any one of the above. In the autonomous-heterotrophic denitrification mode of sulfur, claim 4 is characterized in that, in the heterotrophic denitrification mode, the sulfur source is any one of elemental sulfur, sodium sulfide or sodium thiosulfate. The described operation method.

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