KR100852760B1 - Apparatus and method for anaerobic ammonium oxidizing - Google Patents

Abstract

An apparatus and a method for anaerobic ammonium oxidizing is provided to cultivate anaerobic ammonium oxidizing microorganisms with difficult culture conditions to a high concentration, maintain a microorganism community stably, and increase the nitrogen removal efficiency. An apparatus for anaerobic ammonium oxidizing comprises a first reactor(1) for performing anaerobic ammonium oxidizing and a second reactor(3) for performing anaerobic ammonium oxidizing, wherein the first reactor is filled with a granular sludge of anaerobic ammonium oxidizing microorganisms, the granular sludge being adapted to high concentration wastewater in which ammonia nitrogen and nitrite as matrices have a concentration of 600 mg/L or more, treated water flows into the second reactor from the first reactor, the second reactor is filled with a nonwoven fabric(4) having a positive electric charge, and anaerobic oxidizing microorganisms of the treated water being attached to the nonwoven fabric. The apparatus further comprises a separation plate(2), an inflow pump(6), and an air inflow preventer(5).

Description

Anaerobic Ammonium Oxidation Apparatus and Method {APPARATUS AND METHOD FOR ANAEROBIC AMMONIUM OXIDIZING}

Figure 1 is a schematic diagram showing the configuration of the anaerobic ammonium oxidation apparatus according to an embodiment of the present invention.

2 is a schematic view showing a cross section of a nonwoven fabric of a second reactor in accordance with one embodiment of the present invention.

* Description of Signs of Main Parts of Drawings *

1: first reactor (granulation sludge reactor) 2: separation plate

3: second reactor (nonwoven biofilm reactor) 4: nonwoven fabric

5: air inflow protector 6: inflow pump

The present invention relates to an anaerobic ammonium oxidation apparatus and method capable of efficiently and economically treating livestock wastewater, landfill leachate, and sewage water generated after anaerobic treatment of sewage sludge with high concentration of ammonia nitrogen.

In detail, the present invention provides anaerobic ammonium oxidation step by step anaerobic ammonium oxide microbial granular sludge use process adapted to high concentration nitrogen wastewater and anaerobic ammonium oxide microorganisms adhered to low concentration nitrogen wastewater step by step anaerobic Ammonium oxidation apparatus and method.

Nitrogen removal is an important process for preventing eutrophication of water ecosystems in sewage and wastewater treatment processes.

Conventionally, the combination process of nitrification / denitrification reaction was most utilized for nitrogen removal.

Traditional nitric acid denitrification processes require long supply of air for nitrification and additional external carbon sources, such as methanol, for denitrification. Modifications of these nitric acid denitrification processes and other nitric acid denitrification processes are high in maintenance costs and difficult to expect improvement in treatment capacity.

Ammonium oxidation in anaerobic conditions was first presented by Broda et al. In 1977, and in 1995, Mulder et al., Of Delft University, the Netherlands, succeeded in cultivating on a laboratory scale. Subsequently, a continuous batch reactor was used as the optimal reactor type for environmental physiological studies of anaerobic ammonium oxide microorganisms.

Conventional ammonium oxidation was carried out by the activity of ammonium mono-oxygenase, an enzyme that requires oxygen as an electron donor, and was applied to the Planctomycetes phylum in an anaerobic fluidized denitrifying bed treating the effluent from the methane production reactor. The removal of ammonium by belonging microorganisms has been observed, providing the possibility that anaerobic ammonium oxidation will be widely applied in future sewage treatment systems.

In recent years, it has become clear that NO ₂ ⁻ is an important electron acceptor in the anaerobic ammonium oxidation process. The anaerobic ammonium oxidation process mechanism can be described by the following scheme.

_{^{1.0NH 4 + + 1.32NO 2 - +}} 0.066HCO 3 - + 0.13H + → 1.02N 2 + 0.26NO 3 - + 0.066CH 2 O 0.5 N 0.15 + 2.03H 2 O

Anaerobic ammonium oxidizing microorganisms are autotrophic, thus eliminating the need for the addition of an organic carbon source for the denitrification reaction, resulting in a very economical operating cost.

However, the anaerobic ammonium oxidizing microorganism is difficult to grow in a general natural environment because the growth rate is very slow as well as the growth time is about 2 weeks. Especially when oxygen and organics are introduced, the process becomes extremely unstable and difficult to recover.

Therefore, in the nitrogen removal process using anaerobic ammonium oxidizing microorganisms, above all, an anaerobic ammonium oxidation system capable of culturing the anaerobic ammonium oxidizing microorganisms at high concentration and stably maintaining a microbial community is required.

Therefore, the present invention is to solve the problems of the prior art as described above, an object of the present invention, cultivation of anaerobic ammonium oxidizing microorganisms with difficult culture conditions at a high concentration and can maintain a stable microbial community and nitrogen removal efficiency It is to provide an anaerobic ammonium oxidation apparatus and method that can be high.

The present invention for achieving the above object, an anaerobic ammonium oxidation apparatus capable of high-efficiency nitrogen removal, comprising a first reactor for performing anaerobic ammonium oxidation and a second reactor for performing anaerobic ammonium oxidation, the first The reactor is filled with granular sludge of anaerobic ammonium oxidizing microorganisms, the second reactor is filled with treated water from the first reactor and is filled with a positively charged nonwoven fabric, and the nonwoven fabric is attached with anaerobic oxidized microorganisms of the treated water. It is characterized by removing residual nitrogen in water.

In addition, the present invention for achieving the above object is an anaerobic ammonium oxidation method capable of high-efficiency nitrogen removal, one or two of ammonia nitrogen or nitrite nitrogen in the waste water by using the granular sludge of anaerobic ammonium oxide microorganisms First nitrogen gasification under anaerobic conditions (S1); And nitrogen gasification of one or two of ammonia nitrogen or nitrite nitrogen in the treated water by passing through the non-woven fabric having a positively charged discharged treated water after the step S1 (S2). Characterized in that it comprises a.

In one embodiment of the present invention, the granular sludge of the first reactor or the step S1 is preferably adapted in a high concentration of wastewater having a concentration of at least 600 mg / L of ammonia nitrogen and nitrite nitrogen as substrates.

In one embodiment of the invention, the granular sludge is preferably acclimatized for at least 6 months in the high concentration wastewater.

In one embodiment of the invention, it is preferred that the anaerobic ammonium oxidizing microorganism of the second reactor or step S2 is acclimatized in a low concentration wastewater in which the sum of the concentrations of ammonia nitrogen and nitrite nitrogen as substrates is less than 400 mg / L. .

In one embodiment of the present invention, the anaerobic ammonium oxidizing microorganisms are preferably adapted for at least one month in the low concentration wastewater.

In one embodiment of the present invention, the nonwoven fabric is preferably a radial nonwoven fabric for enhancing the contact between the substrate and the anaerobic ammonium oxidizing microorganism, and the material is preferably polypropylene.

In one embodiment of the present invention, the first reactor and the second reactor is preferably connected to each other with a perforated separator plate in order to separate the microbial community of each reactor, the separator plate is an elastic silicone Preferably, the separator is made of a material, and the hole of the separator is preferably 1 to 3 mm in diameter.

In one embodiment of the present invention, the first reactor and the second reactor are preferably connected to each other and form a single reactor as a whole.

In one embodiment of the present invention, in the first reactor or step S1, the treatment wastewater is preferably recycled for high integration of anaerobic oxidizing microorganisms and prevention of channeling of the substrate, and an upflow rate of 2 to 50 m / hour during the recycling. It is preferable to set it as (hr).

According to the above apparatus and method, it is possible to remove nitrogen at a rate of 0.5 kgN / m ³ -day within 1 month, and to remove nitrogen at a rate of 2 kgN / m ³ -day or more within 3 months.

That is, according to the present invention, in the short term, the commissioning period can be shortened within a month due to the granular sludge to which anaerobic ammonium oxide microorganisms are attached in the first reactor, and in the case of long term operation of 100 days or more, the nonwoven carrier of the second reactor is The attached anaerobic ammonium oxidizing microorganisms greatly increase the stability of nitrogen removal.

Hereinafter, an anaerobic ammonium oxidation apparatus and method according to the present invention will be described in detail.

Figure 1 is a schematic diagram showing the configuration of the anaerobic ammonium oxidation apparatus according to an embodiment of the present invention.

As shown in FIG. 1, the anaerobic ammonium oxidation device according to one embodiment of the present invention is a granulated sludge reactor 1 filled with granulated sludge of anaerobic oxidizing microorganisms, which is a first reactor, and a second reactor connected thereto. The nonwoven biofilm reactor 3 filled with phosphorus nonwoven fabric 4 is connected to form a single reactor.

The separator 2 is interposed between the first reactor 1 and the second reactor 3. The separator 2 is preferably drilled with a plurality of holes having a diameter of 1 to 3 mm.

Influent water flows into the first reactor (1) via an inlet pump (6) and the treated water outflow from the first reactor through the separation plate (2) to the second reactor (3) outflow of the second reactor Part is returned to the inlet pump (6) and the other part is discharged after passing through the air inlet protector (5).

Referring to the method of the present invention, in the present invention, firstly, the first treatment is performed in the first reactor 1 using anaerobic granular sludge formed by the biological self-immobilization phenomenon of microorganisms (S1).

In general, anaerobic oxidizing microorganisms growing in a bottom-up anaerobic reactor have the property of self-aggregating, thereby forming granular sludge nuclei, and attaching other microorganisms around them to maintain long solid residence time in a continuous reactor. "Granular sludge of anaerobic oxidizing microorganisms") is produced. Anaerobic ammonium oxides with extremely slow growth rates can provide growth conditions that allow stable growth through long solid residence times as described above.

Granular sludge from anaerobic ammonium oxidizing microorganisms maintains a stable microbial community structure in the upflow anaerobic reactor, thus reducing the process recovery time from the influx of oxygen, organic matter, interferences and impacts from high concentration substrates.

In the present invention, as the granular sludge of the anaerobic ammonium oxidizing microorganism, in particular, by using granular sludge that is acclimatized in a high concentration of wastewater having a sum of ammonia nitrogen and nitrite nitrogen as substrates of 600 mg / L or more (300 mg / L or more, respectively). In the short term, high efficiency nitrogen removal can be expected. In particular, in the case of using the high-concentration wastewater that has been acclimated for at least 6 months, it is possible to perform stable treatment even under the conditions of 0.4 kg / m ³ -day, which is the existing nitrogen design load.

On the other hand, in the long-term operation in the above-described primary treatment, the stickiness of the anaerobic ammonium forms a highly integrated sludge aggregate having a diameter of 5 cm or more, and deteriorates the nitrogen removal performance due to the substrate delivery rate limitation. The passage of is fixed in one place, resulting in a problem of limited substrate contact.

In order to solve this phenomenon, the present invention maintains the suspended state by allowing the granular sludge to flow by the waste water by maintaining the recycle of the waste water in the first reactor to perform the primary treatment. As such, when the suspended state is maintained, microbial aggregates and channeling phenomena may be prevented (a phenomenon in which granular sludge flows from the first reactor to the second reactor) and the nitrogen gas may be easily discharged.

In the recirculation, when the upflow speed is 2 to 50 m / hr, the microbial aggregates and the channeling phenomenon can be prevented and nitrogen gas can be easily discharged. However, if the upflow speed exceeds 50m / hour (hr), the granular sludge is destroyed by the shear force may adversely affect the performance of the anaerobic ammonium oxidation process itself.

After the first treatment, the wastewater exits the first reactor 1 and enters the second reactor 3 for the second treatment.

In the present invention, it is preferable to use a whole single reactor in which the first reactor 1 and the second reactor 3 are connected, and the separator 2 between the first reactor 1 and the second reactor 3. Intervene). The separator 2 serves to separate the microbial community between both reactors 1 and 3. Holes having a diameter of 1 to 3 mm are drilled in the separation plate 2 to prevent inflow of particulate sludge, rather than wastewater, into the second reactor 3.

In particular, when the material of the separator 2 is made of an elastic material such as silicone, it is possible not only to alleviate the impact on the glass reactors, but also to prevent leakage of waste water at the connection part and to prevent oxygen from flowing. Can be performed.

However, in the case of a full-scale reactor, it is not necessary to use an elastic body, and sealing is performed to prevent leakage of waste water or inflow of oxygen.

In the second reactor 3, a second treatment for effective nitrogen removal is performed (S2).

The second reactor 3 is filled with, for example, a nonwoven fabric 4 made of polypropylene, and the positively charged nonwoven fabric 4 made of polypropylene is subjected to anaerobic ammonium oxide under negative charge in the wastewater introduced from the first reactor 1. It serves to effectively fix and fix the microorganism, thereby minimizing the loss of anaerobic ammonium oxidizing microorganisms in the treated water flowing out of the first reactor (1).

The anaerobic ammonium oxidizing microorganism attached to the nonwoven fabric 4 in the second reactor 3 preferably has a low concentration of less than 400 mg / L (each less than 200 mg / L) of the sum of the concentrations of ammonia nitrogen and nitrite nitrogen as substrates. More preferably in the waste water is granulated sludge that has been acclimated for at least one month. When the anaerobic ammonium oxidizing microorganisms attached to the nonwoven fabric 4 are adapted to low concentrations as described above, it is possible to contribute to a particularly stable nitrogen treatment.

For reference, it is necessary to maintain an appropriate concentration (concentration of nitrous acid in the reactor of 50 mg / L or less) so that there is no inhibition in the compliance of the anaerobic ammonium oxidizing microorganisms in the first reactor or the second reactor as described above.

2 is a schematic view showing a cross section of a nonwoven fabric of a second reactor in accordance with one embodiment of the present invention.

As shown in Fig. 2, as the nonwoven fabric 4 of the second reactor, it is preferable to use a nonwoven fabric having a radial shape in order to facilitate the movement of the wastewater and the contact with the substrate.

As described above, in the present invention, two anaerobic ammonium oxide microbial communities, in particular, the stability and efficiency of the anaerobic ammonium oxidation process can be simultaneously achieved by the stepwise treatment of high concentration nitrogen wastewater utilizing a microbial community adapted under different conditions. In particular, anaerobic granular sludge in the primary reactor, which has been acclimated for 6 months or more in high concentration nitrogen wastewater, efficiently fixes the microbial community, thereby normalizing the processes disturbed by oxygen inflow, organic inflow, and impact by high concentration substrate in a short time. Secondary reactions with microorganisms attached to them greatly enhance nitrogen removal. In addition, both the primary reactor filled with anaerobic granular sludge and the secondary reactor filled with nonwoven fabric maintain high concentrations of anaerobic ammonium oxidizing microorganisms with a slow doubling time in a continuous process. In addition, the technique of maintaining a high recycle rate of the first reactor can prevent the high integration of the charged anaerobic granular sludge to significantly lower the process failure rate. Therefore, the anaerobic ammonium oxidation process according to the present invention can promote its commercial development.

Hereinafter, the present invention will be described in more detail by explaining preferred embodiments of the present invention. However, the present invention is not limited to the following examples, and various forms of embodiments can be implemented within the scope of the appended claims, and the following examples are only common in the art while making the disclosure of the present invention complete. It is intended to facilitate the implementation of the invention to those with knowledge.

<Example>

As shown in FIG. 1, a single set of continuous reactors was constructed comprising a first reactor (V ₁ = 1 L) and a second reactor (V ₂ = 1.35 L). The continuous reactor was produced with a total effective volume of 3.35 L. A continuous reactor was fabricated to test the applicability of the granular anaerobic ammonium oxide microorganisms to the synthetic wastewater.

The bottom of the first reactor, or continuous reactor, is a bottom-up anaerobic ammonium oxidation reactor, and the top of the second, or continuous reactor, is an anaerobic ammonium oxidation reactor filled with radial nonwovens.

The microorganisms planted in the first reactor were granular anaerobic ammonium oxidizing bacteria which were acclimated in high concentration wastewater (the sum of the concentrations of the substrate ammonia nitrogen and nitrite nitrogen 600 mg / L) for 6 months, and the filling volume was 0.5 L.

In order to control the temperature of the reactor, a constant temperature system equipped with a PID-controlled heater in a box of 127 cm (width) × 70 cm (height) × 151 cm (height) was constructed, and the pH affecting the growth of anaerobic ammonium oxide microorganisms. Automatic computers (Model IMC61, Isteck Inc.) and computers for constant monitoring of temperature, ORP, etc. were installed and operated.

The generated gas was separated by GSS (Gas Solid Separator) in the upper part of the reactor, and even a small amount of generated gas was accurately measured by a wet gas meter (TG05 type, Ritter), and a minute pump (Model QSY with RH, Fluidmetering Inc.) was measured. The return water was introduced.

The hydraulic residence time was operated for 1 day, and the treated water was recycled at a flow rate of 2-30 meters / hour (hr) by adjusting the internal circulation rate using a micro pump.

The initial inlet nitrogen load was operated under the condition of 0.1 kg N / m ³ -day, and it was operated in the condition of 0.6 kgN / m ³ -day from 23 days of operation by increasing the nitrogen concentration of the influent.

The constant temperature system was operated so that the temperature in the reactor was 35 ± 1 ° C., which is a medium temperature condition.

Effluent and microorganisms were collected periodically to observe the nitrogen removal and anammox reaction of the microorganisms during the continuous culture. In addition, the nitrogen gas composition change in the effluent gas was monitored 2-3 times a week.

The synthetic wastewater composition used in this example is shown in Table 1 below.

Tap water (g / L) Target con. (Mg / L) (NH ₄ ) ₂ SO ₄ 0.23-2.37 50-500 NaNO ₂ 0.25-2.47 50-500 NaHCO ₃ 0.504 72 KH ₂ PO ₄ 0.027 6 MgSO _{4 7} H ₂ O 0.123 12 CaCl ₂ · 2H ₂ O 0.176 48 Trace Component Solution I * 1ml / L Trace Component Solution II ** 1ml / L Trace Component Solution I * EDTA 5 FeSO ₄ 7H ₂ O 5 Trace Component Solution II ** ZnSO ₄ · 7H ₂ O 0.430 CoCl ₂ · 6H ₂ O 0.240 MnCl ₂ 4H ₂ O 0.990 CuSO ₄ · 5H ₂ O 0.250 Na ₂ MoO ₄ 2H ₂ O 0.220 NiCl ₂ · 6H ₂ O 0.190 Na ₂ SeO ₄ · 10H ₂ O 0.210 H ₃ BO ₃ 0.014

As shown in Table 1, for continuous culture of anaerobic ammonium oxidizing microorganisms, ammonia nitrogen and nitrite nitrogen in the influent were changed to 50 to 500 mg / L and 50 to 500 mg / L, respectively. As the sodium bicarbonate was added to maintain the alkalinity to 300 ~ 500 mg / L. Meanwhile, microorganisms such as iron and manganese required for microbial growth were added to maintain optimum growth conditions.

As a result of performing about 100 days of operation on the synthetic wastewater, it showed excellent reaction characteristics showing nitrogen removal rate of 0.50 kg N / m ³ -day under the condition of 0.6 kgN / m ³ -day within 30 days of operation. It was.

The removal efficiency of ammonia nitrogen showed excellent removal characteristics in the range of 82 ~ 88% when the inflow concentration was gradually increased from 50 to 500 mg / L, and in the case of nitrous nitrogen, more than 99% in all operating conditions. Excellent removal properties were shown.

The system showed surprising results at a high rate of nitrogen removal over 2 kgN / m ³ -day (five times the conventional nitrogen design load) within three months of operation at an inlet total nitrogen concentration of 1,000 mg / L.

According to the present invention can be cultured in a high concentration of anaerobic ammonium oxidizing microorganisms with difficult culture conditions and can maintain a stable microbial community and increase the nitrogen removal efficiency.

Claims (11)

In the anaerobic ammonium oxidation unit, A first reactor for carrying out anaerobic ammonium oxidation and a second reactor for carrying out anaerobic ammonium oxidation, The first reactor is filled with granular sludge of anaerobic ammonium oxidizing microorganisms, and the granular sludge is adapted to high concentration wastewater having a concentration of at least 600 mg / L of ammonia nitrogen and nitrite nitrogen as substrates. Treated water from the first reactor is introduced into the second reactor, a positively charged nonwoven fabric is filled, and anaerobic ammonium oxidation apparatus characterized in that the anaerobic oxidizing microorganism of the treated water is attached to the nonwoven fabric. delete The method of claim 1, The granular sludge has been acclimatized in the high concentration wastewater for at least 6 months. The method of claim 1, The anaerobic ammonium oxidation microorganism of the second reactor is an anaerobic ammonium oxidation device characterized in that the sum of the concentration of ammonia nitrogen and nitrite nitrogen as a substrate is a low concentration of wastewater less than 400mg / L. The method of claim 4, wherein The anaerobic ammonium oxidation microorganism is characterized in that the low concentration of the waste water is acclimatized for at least one month. The method of claim 1, Anaerobic ammonium oxidation apparatus, characterized in that the nonwoven fabric is a radial nonwoven fabric. The method of claim 1, Wherein said first reactor and said second reactor are connected to each other with a perforated separator therebetween. The method of claim 1, Anaerobic ammonium oxidation apparatus, characterized in that the wastewater in the first reactor is recycled. The method of claim 8, Anaerobic ammonium oxidation apparatus, characterized in that the upflow speed during the recycle is 2 ~ 50m / h (hr). The method of claim 1, The apparatus is anaerobic ammonium oxidation device, characterized in that to remove nitrogen at 0.5 kgN / m ³ -day within 1 month, and to remove nitrogen at 2 kgN / m ³ -day or more within 3 months. In the anaerobic ammonium oxidation method, Using granular sludge of anaerobic ammonium oxidizing microorganisms, one or both of ammonia nitrogen or nitrite nitrogen in wastewater is first nitrogenized under anaerobic conditions, and the granular sludge has a concentration of 600 mg of ammonia nitrogen and nitrite nitrogen as substrates. Step (S1), characterized in that it is adapted to a high concentration of wastewater of more than / L; And After passing through the step S1 to pass through the nonwoven fabric having a positively charged treated water flowing out one or two of ammonia nitrogen or nitrite nitrogen in the treated water in a second anaerobic nitrogen gas (S2); Anaerobic ammonium oxidation method comprising a.

Images