KR20060024948A - A nitrogenous wastewater treatment process and system is included an organic nitrogen - Google Patents

Abstract

end. The technical field to which the invention described in the claims belongs.

The present invention relates to a method and a treatment system for nitrogen-based wastewater, and more particularly, to the treatment of total nitrogen (TN) of high concentration industrial wastewater containing a large amount of organic nitrogen.

I. The technical problem to be solved by the invention.

At present, the treatment of the nitrogen-based wastewater being carried out includes that most of the nitrogen contained in the wastewater is present as nitrate nitrogen (NO ₃ -N), and the rest is present as a small amount as ammonia nitrogen (NH ₄ -N). It is based on the presence.

Therefore, in this case, the denitrification reaction of NO ₃ -N through the anoxic process occurs in the first half, and then the nitrification of NH ₄ -N through the aerobic process occurs in the second half, and then returned to the anaerobic process in the first half. It is a treatment that circulates so that denitrification takes place so that the total nitrogen (TN) is removed.

However, in case of processing by the processing method for the industrial waste water containing a large amount of organic nitrogen, NO with an oxygen-free process of the first part due to the more large amount of nitrogen is present in the organic nitrogen than is present to NO ₃ -N ₃ Denitrification of -N can be easily carried out, but it causes the phenomenon of NH ₄ -N is rapidly increased, and the surging NH ₄ -N is leaked to the aerobic process in the later stage, so that the treatment due to the system overload is impossible. Eventually, the TN removal rate of the effluent could hardly be expected.

All. Summary of the Solution of the Invention.

Accordingly, the present invention allows the treatment of most of the nitrogen to be treated with an emphasis on organic nitrogen, and primarily organic matter through an anhydrous anoxic process that allows operation in aerobic state according to the characteristics of the incoming wastewater. After the stabilization of nitrogen, and secondly, the nitrification reaction of the converted NH ₄ -N to NO ₃ -N through the aerobic process is carried out, and then the third nitrified intermediate treated water through the anoxic process Denitrification and finally further decomposition of untreated excess organic nitrogen through an aerobic process takes place, which is then returned / recycled to an optional anoxic process for treatment.

la. Important uses of the invention

Method of treating nitrogen-based wastewater containing a large amount of organic nitrogen

Description

A nitrogenous wastewater treatment process and system is included an organic nitrogen}

       1 is a configuration of a processing system according to an embodiment of the present invention.

       2 is a block diagram of a processing system according to another embodiment of the present invention.

                       <Explanation of symbols for the main parts of the drawings>

       1: sludge return pump 2: air lift pump

       3: agitator 4: diffuser

       5: microbial carrier 6: effluent delivery piping

       7: Sludge pipe

       10: sump 20: random anaerobic tank

       30: Unit 1 40: Anaerobic Tank

       50: No. 2 tank 60: Settling tank

The present invention relates to a method and a treatment system for nitrogen-based wastewater, and more particularly, to the treatment of total nitrogen (TN) of high concentration industrial wastewater containing a large amount of organic nitrogen.

At present, the method for the treatment of nitrogen contained in wastewater is that the total nitrogen (TN) contained in the wastewater is mostly present in the form of nitrate nitrogen (NO ₃ -N) and the rest is ammonia nitrogen (NH ₄ -N). The system was designed with only a small amount in the form of).

Therefore, the treatment method for this purpose is to put an anoxic process in the first half to change the nitrogen (N) in the form of nitrate nitrogen (NO ₃ -N) to nitrogen (N ₂ ) gas to remove nitrogen by the denitrification reaction, The remaining traces of nitrogen (N) that are not removed are considered to be present in the form of ammonia nitrogen (NH ₄ -N) and are subjected to an aerobic process in the second half to convert ammonia nitrogen (NH ₄ -N) to nitrate nitrogen (NO). ₃ -N), and then the total nitrogen (TN) was removed by the treatment method to return to the oxygen-free process of the first half to denitrification.

However, in the case of treating industrial wastewater containing a large amount of organic nitrogen such as LCD manufacturing plants by applying this treatment method, the anoxic process in the first half because nitrogen is present in organic nitrogen more than that of NO ₃ -N. in the denitration reaction of NO ₃ -N it was easily made the concentration of the NO ₃ -N was significantly reduced, but this was based developer the concentration of NH ₄ -N rather be increased significantly occurs, thus increasing the NH ₄ -N state Intermediate treatment water was introduced into the aerobic process in the later stage, which could not be processed due to the overload caused by the increase of NH ₄ -N. As a result, the total nitrogen (TN) removal of the effluent could not be expected.

   As a result, the investigation revealed that TMAH (Tetra Methyl Amonium Hydro-oxide), which is a raw material used in LCD manufacturing plants, is a source of organic nitrogen, and the industrial wastewater generated in such a similar manufacturing process contains a large amount of organic nitrogen. Since organic nitrogen is converted into ammonia nitrogen by microorganisms and enzymatic action in anoxic or aerobic state, it causes the total nitrogen concentration to be increased. The design factor of the system for total nitrogen removal is more organic than nitrate nitrogen. There was a need for new treatment methods and systems that would be designed with greater emphasis on nitrogen.

Therefore, in the present invention, in the case of industrial wastewater in which a large amount of organic nitrogen is contained in a conventional treatment method consisting of anoxic and aerobic processes, the concentration of organic nitrogen in the effluent seems to be removed, but the concentration of total nitrogen is eventually increased. Is that organic nitrogen is NH ₄ -N ?? NO ₃ -N ?? N ₂ The phenomenon is caused by the fact that it is not completely removed through the sequential decomposition process but instead is left as NH ₄ -N, which is an intermediate state of decomposition, and flowed out untreated state. A new method and system for treating nitrogen-based wastewater, consisting of treatment processes and systems that are capable of decomposition, is devised.

To this end, the treatment method of the present invention is primarily to stabilize the organic nitrogen through an anhydrous anoxic process that allows the operation to aerobic state according to the characteristics of the incoming wastewater first, and then, secondly, the aerobic process After nitrification of the converted NH ₄ -N to NO ₃ -N is carried out, the third nitrified intermediate treated water is denitrated through an anoxic process to induce stable treatment through the sequential decomposition of organic nitrogen. Afterwards, the final decomposition of untreated excess organic nitrogen through the aerobic process takes place, and then the transfer / circulation back to the random anoxic process is performed so that the stepwise decomposition of organic nitrogen is performed to maximize the total nitrogen treatment. It is possible.

The nitrogen-based wastewater treatment method of the present invention first converts the organic nitrogen contained in the original wastewater into NH ₄ -N form through a noncultive anoxic process that allows the operation of the aerobic state according to the characteristics of the incoming wastewater. To stabilize and to remove NO ₃ -N through denitrification, and to further nitrate the converted NH ₄ -N to NO ₃ -N through the aerobic process, and nitrification. Denitrified intermediate treated water through an anoxic process to sequentially decompose most organic nitrogen contained in the raw wastewater to induce a stable treatment, and extra organic nitrogen untreated through an aerobic process. additional variations and NH ₄ -N of the fourth process stage the nitrification reaction to take place to be processed again by the conveying / circulating randomness anaerobic step of the first process step To ever processed through the process.

       At this time, the random anoxic process of the primary treatment step is aerobic conditions only when the nitrogen contained in the raw waste water is low in the organic nitrogen content in the initial stage, the ammonia nitrogen and nitrate nitrogen fractions are severely changed, so high ammonia nitrogen By operating in a non-oxygen condition in other or normal conditions, it is possible to efficiently treat according to the characteristics of the waste water generated.

       In addition, the microbial supply in the random anoxic process of the primary treatment step is the source of wastewater from sludge generated in the precipitation process included to precipitate and remove the sludge contained in the effluent generated after the fourth treatment step process. It is to return / circulate within 100% of the ratio.

       At this time, in the random anoxic process of the first treatment step, the aerobic process of the second treatment step, the anoxic process of the third treatment step, the aerobic process of the fourth treatment step to allow the microorganism to always adhere to the fixed rate by contacting the microorganisms It is possible to further increase the treatment efficiency by increasing the.

       In addition, the effluent water discharged from the aerobic process in the secondary treatment step and the effluent water discharged from the aerobic process in the fourth treatment step may contain trace amounts of undecomposed organic nitrogen and remain in a state converted to ammonia nitrogen. Depending on the treatment / operation situation, it can be returned / circulated to the random anaerobic process of the first treatment step and the anaerobic process of the third treatment step, respectively, so that the aerobic agitation-the aeration of the aeration is repeated / rotated several times to completely process the residual nitrogen. In this case, the return / circulation at this time is within 200% of the original wastewater.

At this time, the optional anoxic process of the first treatment step is a denitrification reaction of nitrate nitrogen (NO ₃ -N) contained in the raw wastewater or decomposition / conversion reaction of organic nitrogen to ammonia nitrogen (NH ₄ -N) and precipitated return sludge. The first anoxic process for inducing denitrification of nitrate nitrogen (NO ₃ -N) contained in the aerobic process, and the aerobic process of the second treatment step and the aerobic process of the fourth treatment step when the first anoxic process is operated aerobicly from bounce / are contained in the effluent is circulated, so a failure in maintaining the anaerobic conditions necessary for the denitrification of oxygen (O ₂₎ a nitrate nitrogen (NO ₃ -N) on the molecule to be introduced is expected to oxygen (O ₂₎ on these molecules A second anoxic to remove and to denitrate nitrogen nitrate (NO ₃ -N) or to decompose / convert organic nitrogen to ammonia nitrogen (NH ₄ -N) at the same time to remove by reaction with organic matter contained in the waste water Process and complete Nitrate nitrogen (NO ₃ -N) denitrification or organic nitrogen to ammonium nitrogen (NH ₄ -N) 3, separated by an oxygen-free process to ensure more effective by nitrogen done sequentially for ever degradation / conversion as in oxygen-free conditions It will be possible to process.

In other words, if the ratio of organic nitrogen and NO ₃ -N in the influent wastewater is high, the first anoxic process allows the organic nitrogen to be converted to NH ₄ -N by random microorganisms and at the same time NO ₃ -N. N may be converted to N _z gas to induce a denitrification reaction. On the other hand, when the ratio of NH ₄ -N in the influent wastewater is high, the first anoxic process is operated to be aerobic and NH ₄ -N After conversion to NO ₃ -N through nitrification by aerobic microorganisms, the second nitrogen-free process and the third anoxic process are always operated under anoxic conditions. Therefore, organic nitrogen is gradually converted into NH ₄ -N by anaerobic microorganisms. this conversion is to take place and, NO ₃ -N was ever to be an effective treatment of the aqueous phase of the incoming waste water can be removed by ever by the full-scale denitrification in N _z gas Is that.

On the other hand, organic nitrogen in the random anoxic process. Degradation / conversion to NH ₄ -N is produced by the LCD degradation / conversion of TMAH (Tetra Methyl Amonium Hydro-oxide ) of the raw materials to be used in a plant as randomness microorganism causative agent of organic nitrogen under anaerobic operating conditions NH ₄ the increase will -N, this denitrification process that occurs at the same time, the use of oxygen instead of NO ₃ when microorganisms decompose organic matter contained in waste water as an electron acceptor in denitrification it will be N ₂ gas as the reducing NO _3, NH ₄ The nitrification reaction in which -N is converted to NO ₃ -N is a reaction obtained by aerobic autotrophic microorganisms Nitrosomanas and Nitrobacter oxidizing ammonia using oxygen to synthesize NO ₃ -N under aerobic operating conditions.

In addition, in the aerobic process of the secondary treatment step, ammonia nitrogen (NH ₄ -N), which is increased in the effluent from the random anoxic process of the primary treatment step by the injection of oxygen, is oxidized to nitrate nitrogen (NO ₃ -N). When the concentration of organic nitrogen is kept high, the organic nitrogen is returned to the random anoxic process to minimize the oxygen contained therein, and then again in the anoxic process of the third tertiary treatment step. It intended to be efficiently guided to the degradation / conversion to the nitrogen (NH ₄ -N), thus by ammonium nitrogen to a reduction in residence time caused by the transport / rotation of the exhalation process of the secondary treatment stage (NH ₄ -N ) Is to prevent a decrease in the efficiency of nitrifying with nitrate nitrogen (NO ₃ -N).

The anoxic process of the tertiary treatment step is the denitrification of nitrate nitrogen (NO ₃ -N) increased in the effluent of the aerobic process of the second treatment step and decomposition / conversion of residual organic nitrogen to ammonia nitrogen (NH ₄ -N). In this case, the anaerobic process is operating in the range of 0.0 ~ 0.3PPM DO is not a complete anaerobic, in the present invention is called anoxic (Anoxic) state for distinction from anaerobic (Anabic), aerobic (Aerobic or Oxic) In practice, it is preferable to set the concentration range of the operating DO for the anoxic process to be in the range of 0.0 to 0.5 PPM.

       At this time, by returning / circulating the effluent of the aerobic process of the fourth treatment step to the anoxic process of the third treatment step, the untreated nitric acid and organic matter can be treated again in the aerobic process of the fourth treatment step.

       At this time, the aerobic process of the fourth treatment step is installed / arranged in order to treat / manage residual contaminants within the discharge standard within the final stage, and when organic nitrogen and ammonia nitrogen are above the total nitrogen (TN) management standard, In the case of random anoxic process of the first treatment step, when the nitrate nitrogen exceeds the total nitrogen (TN) standard and the organic pollutant exceeds the management standard, the influent wastewater flow to the anoxic process of the third treatment step, respectively It is possible to improve the processing efficiency by returning / circulating within 200% and repeating the treatment.

       Hereinafter, the system of the present invention will be described in more detail through an arrangement configuration according to the accompanying drawings.

       As shown in FIG. 1, the nitrogen-based wastewater treatment system of the present invention has a water collecting tank 10 for temporarily storing raw wastewater, and a selective agitation function for anoxic conditions and aerobic conditions depending on the characteristics of the incoming wastewater. Arbitrary anaerobic tank 20 equipped with the apparatus 3 and the aerobic apparatus 4, the first unit 30 equipped with the aerobic apparatus 4 for the operation function in aerobic conditions, and the operation in the anoxic condition Oxygen-free tank (40) equipped with a stirring device (3) for, the second unit tank (50) equipped with an air dispersing device (4) for operating in aerobic conditions, and included in the effluent of the second unit tank (50) The sedimentation tank (60) for separating the sludge from the supernatant and settling is configured in sequence.

       At this time, the settling tank (60) is connected to the sludge feed pipe (7) for returning / circulating the settling sludge to the random anoxic tank (20) by the sludge return pump (1), and the first unit (30) and The second water tank 50 is connected to the treated water transfer pipe 6 for returning / circulating the effluent to the random anoxic tank 20 and the anoxic tank 40 by the air lift pump 2, respectively. .

      Hereinafter, each reaction and role of the system arranged in the above manner will be described.

       First, the random anoxic tank 20 is characterized by the characteristics of industrial wastewater, the change of wastewater properties (particularly the components of the total nitrogen) is severe at the beginning of the product production process operation, so that the oxygen-free oxygen for smooth treatment of total nitrogen (TN) according to the characteristics of the wastewater It is possible to selectively operate under conditions of aerobic or aerobic conditions. In the initial stage, since the content of organic nitrogen is low and the ammonia nitrogen and nitrate nitrogen fractions are severely changed, the stirring device may be used only when the content of ammonia nitrogen is high. Both the 3) and the air dissipator 4 are operated to operate in an aerobic state, and in the other or normal state, only the stirring device 3 is possible to operate only in an oxygen-free state.

At this time, the optional anoxic tank 20 is denitrified of nitrate nitrogen (NO ₃ -N) contained in the original wastewater or decomposition / conversion of organic nitrogen to ammonia nitrogen (NH ₄ -N) as shown in FIG. When operating the first anaerobic tank 21 and the first anoxic tank 21 to induce denitrification of the nitrate nitrogen (NO ₃ -N) contained in the return sludge returned from the settling tank 60 and the aerobic tank, Oxygen-free conditions required for the denitrification of nitric acid nitrogen (NO ₃ -N) by molecular oxygen (O ₂ ) contained in the treated water returned / circulated from the first and second tanks 30 and 50 and expected to flow. It is difficult to maintain the oxygen, so that the oxygen (O ₂ ) on these molecules is removed by reaction with organic matter contained in the wastewater, and denitrification of nitrate nitrogen (NO ₃ -N) or organic nitrogen is carried out by ammonia nitrogen (NH). a second anoxic tank 22 to ever degradation / conversion in ₄ -N) , Nitrate-nitrogen in a completely oxygen-free conditions (NO ₃ -N) denitrification or organic nitrogen to ammonium nitrogen more efficiently nitrogen by ever separated by (NH ₄ -N), a third anoxic tank 23 to ever degradation / conversion to the To be able to handle

In other words, when the ratio of organic nitrogen and NO ₃ -N in the inflowing waste water is high, the first anoxic tank 21 is operated under anoxic conditions, so that organic nitrogen is converted into NH ₄ -N by random microorganisms and NO. ₃ -N can be converted to N _z gas to induce denitrification reaction, while when the ratio of NH ₄ -N in the incoming wastewater is high, the first anoxic tank 21 is allowed to operate in aerobic state _{After 4} -N is converted to NO ₃ -N through nitrification by aerobic microorganisms, and then, in the second anoxic tank 22 and the third anoxic tank 23, it is always operated under anoxic conditions, so that organic nitrogen is caused by anaerobic microorganisms. The conversion reaction to NH ₄ -N takes place in earnest, and NO ₃ -N allows removal by a full-scale denitrification reaction to N _z gas so that efficient treatment according to the characteristics of the influent wastewater is possible. Can be.

       In addition, the random anaerobic tank 20 is filled with a microbial carrier 5 for efficient treatment of high concentration organic nitrogen-based wastewater, thereby increasing the total MLSS concentration by the adherent MLSS in the tank, thereby reducing the reaction time and increasing the reaction rate. In addition, high processing efficiency can be expected.

On the other hand, organic nitrogen in the random oxygen-free tank 20 ?? Degradation / conversion to NH ₄ -N is produced by the LCD degradation / conversion of TMAH (Tetra Methyl Amonium Hydro-oxide ) of the raw materials to be used in a plant as randomness microorganism causative agent of organic nitrogen under anaerobic operating conditions NH ₄ the increase will -N, this denitrification process that occurs at the same time, the use of oxygen instead of NO ₃ when microorganisms decompose organic matter contained in waste water as an electron acceptor in denitrification it will be N ₂ gas as the reducing NO _3, NH ₄ The nitrification reaction in which -N is converted to NO ₃ -N is a reaction obtained by aerobic autotrophic microorganisms Nitrosomanas and Nitrobacter oxidizing ammonia using oxygen to synthesize NO ₃ -N under aerobic operating conditions.

In addition, the first gas tank 30 is injected into the oxygen by the oxygen storage device (4) and maintained in aerobic state, the ammonia nitrogen (NH ₄ -N) increased in the effluent from the random anoxic tank 20 It is for oxidizing / converting to nitrate nitrogen (NO ₃ -N). When the concentration of organic nitrogen is maintained high, the air lift pump (2) is used to the random anoxic tank (20) within 200% of the amount of influent wastewater. After minimizing the oxygen contained in the molecular by transport / circulation, it is intended to efficiently induce decomposition / conversion reaction of organic nitrogen to ammonia nitrogen (NH ₄ -N) again in the anoxic tank 40 disposed next. By reducing the residence time caused by the return / circulation of the first vessel 30 to prevent the reduction of the efficiency of nitrifying the ammonia nitrogen (NH ₄ -N) to nitrate nitrogen (NO ₃ -N) will be.

       At this time, if the microorganism carrier 5 is filled in the second vessel 30, of course, a higher treatment efficiency can be obtained.

The anoxic tank 40 is for denitrification of nitrogen nitrate (NO ₃ -N) increased in the effluent of the first tank 30 and the decomposition / conversion of residual organic nitrogen to ammonia nitrogen (NH ₄ -N). In this case, the anoxic tank 40 is not completely blocked because the reaction tank for maintaining an anoxic state is not completely blocked from the atmosphere and the surface is exposed to the atmosphere, so that the concentration of DO is operating in the range of 0.0 to 0.3PPM. In the present invention, it was determined to be anoxic to distinguish between anaerobic and aerobic (Aerobic or Oxic), and the concentration range of the DO for the anoxic process was set to 0.0 to 0.5PPM.

       At this time, the treated water is returned / circulated from the second tank 50, which is disposed later, to process untreated nitrogen nitrate and organic matter again in the second tank 50. Similarly, the microbial carrier 5 By charging additionally, higher processing efficiency can be expected.

       In addition, the second vessel 50 is installed / arranged to treat / manage the last remaining pollutants within the discharge standard, if the organic nitrogen and ammonia nitrogen is above the total nitrogen (TN) management standards of the above randomness When the oxygen-free tank 20, the nitrate nitrogen exceeds the total nitrogen (TN) standard and the organic pollutant exceeds the management standard, the inflow source using the air lift pump (2) to the oxygen-free tank (40), respectively The treatment efficiency can be improved by returning / circulating the wastewater within 200% of the waste water and repeating the treatment. Likewise, by further charging the microbial carrier 5, higher treatment efficiency can be expected.

       Hereinafter, the treatment effect of the nitrogen-based wastewater treated through the treatment method and treatment system of the present invention will be demonstrated in more detail through the following examples of measuring the removal efficiency of COD as well as total nitrogen.

       <Example 1>

      BATCH TEST

      1. Purpose of Experiment

      The purpose of the BATCH TEST was to examine the appropriate residence time and removal efficiency under anaerobic and arbitrary conditions as a preliminary step for the application of the PILOT TEST (arbitrary conditions: DO 0-0.5ppm, anoxic conditions). : DO 0-0.3 ppm)

      2 Experiment apparatus and method

      The experimental apparatus used for the BATCH TEST was manufactured so that the effective volume of the reactor was 20L using acrylic as shown in <Figure 2.1>. Agitator was installed in the reactor under anoxic condition (A condition), and in the reactor under random condition (condition B), the DO in the tank was properly adjusted, and one diffuser and one AIR TUBE in the tank were used for equal mixing of microorganisms and wastewater. Were installed respectively.

                  <Condition A-Anaerobic> <Condition B-Arbitrary>

                           <Figure 2.1> BATCH TEST Device

                 Table 2.1 Mixing Ratio of Wastewater and Microbial Concentrate

Condition Analysis frequency TN wastewater Microbial Concentrate (MLSS 6,000mg / L) MLSS concentration after mixing (mg / L) A (Anoxic) A-1 3rd time 5L 5L 3,000 A-2 3rd time 5L 10L 4,000 B (arbitrary) B-1 3rd time 5L 5L 3,000 B-2 3rd time 5L 10L 4,000

       The wastewater used in this experiment was TN wastewater from the LG Philips LCD wastewater treatment plant, and microorganisms were concentrated twice as much as sludge in the aeration tank with MLSS concentration of 3,000 mg / L (MLSS 6,000 mg / L) and then in the reactor A-1. MLSS 3,000 mg / L in the TEST of B-1, and MLSS 4,000 mg / L in the TEST of A-2 and B-2 were respectively injected.

       Table 2.1 shows the mixing ratio of wastewater and microbial concentrate. As shown in <Table 2.1>, BATCH TEST was conducted three times for each condition, and the mixing ratio of TN wastewater and microbial concentrate under conditions A-1 and B-1 was injected with 5L of microbial concentrate in 5L TN wastewater. In the A-2 and B-2 conditions, the experiment was performed by injecting 10 L of microbial concentrate into 5 L of TN wastewater.

       In addition, IPA (CODMn 700,000mg / L), DEVELOPER (TN 30,000mg / L) to keep the initial concentration (0hr) of the mixed solution constant under each condition (A-1, A-2, B-1, B-2) A small amount of industrial urea (UREA) and nitric acid (NO3-N 181,000mg / L) were added to adjust the concentration to TN 150mg / L, organic nitrogen 70mg / L, NH3-N 10mg / L and NO3-N 70mg / L. The experiment was carried out.

      In anoxic conditions, the DO concentration was adjusted to a range of 0.0 to 0.2 mg / L using a stirrer. In arbitrary conditions, the air injection amount was adjusted from time to time so that the DO concentration was in the range of 0.2 to 0.6 mg / L. It was operated as it is without adjustment of.

       3 Results and Discussion

       3.1 Changes in pH and DO Concentration

       <Figure 2.2> shows the change of pH and DO concentration by BATCH TEST of each condition. As shown in <Figure 2.2>, the pH of A-1 and A-2 increased rapidly from 6.7 to 8.6 during 0hr ~ 8hr, but gradually increased to 6.8 ~ 7.9 under B-1 and B-2.

       In the case of DO, the range of 0.1 ~ 0.2 (0.15) mg / L was shown under conditions A (A-1 and A-2), and 0.2 ~ 0.4 (0.3) mg under conditions B (B-1 and B-2). Both A and B conditions were found to be suitable for the anaerobic and random conditions.

                       <Figure 2.2> Changes in pH and DO Concentration

       3.2 Removal of Organics and Nitrogen

       <Table 2.2> shows the change of CODMn and nitrogen concentration and the removal efficiency of CODMn and nitrogen series according to time zone under A-1 condition, and <Figure 2.3> shows the change of concentration of CODMn and nitrogen series according to time slot. As shown in Table 2.2, the CODMn concentrations of 0hr, 4hr, 6hr and 8hr were 510.5mg / L, 345.7mg / L, 320.0mg / L, 269.0mg / L and 238.0mg / L, respectively. The removal efficiencies of 4hr, 6hr and 8hr were 32.3%, 37.3%, 47.3% and 53.4%.

       In addition, the concentration of TN (removal efficiency) was 150.3mg / L, 72.3mg / L (51.9%), 65.6mg / L (56.4%), 55.8mg / L (62.8%), 53.6mg / L (64.3%). The concentration of organic nitrogen (removal efficiency) was 71.1 mg / L, 35.5 mg / L (50.1%), 29.7 mg / L (58.2%), 23.4 mg / L (67.1%), and 22.6 mg / L (68.2%). NO3-N concentrations (removal efficiency) were 68.3 mg / L, 15.2 mg / L (77.7%), 11.8 mg / L (82.7%), 3.8 mg / L (94.4%), 1.4 mg / L ( 97.8%). At this time, NH4-N concentration was 10.9mg / L, 21.6 (-98.2%) mg / L, 24.1 (-121.1%) mg / L, 28.7 (-163.3%) mg / L, 29.6 (-171.1%) mg / L This is due to the fact that organic nitrogen was decomposed / converted into NH 4 -N.

       <Table 2.2> Changes in CODMn and Nitrogen Concentrations and Removal Efficiency by Time (A-1 Conditions)

       (UNIT: mg / L)

   Hours (hr) Item 0 One 2 3 4 5 6 7 8 REMARK MLSS 2980 CODMn 510.5 345.7 320.0 269.0 238.0 R, E ^* (%) - 32.3 37.3 47.3 53.4 T-N 150.3 72.3 65.6 55.8 53.6 R, E (%) - 51.9 56.4 62.8 64.3 Organic nitrogen 71.1 35.5 29.7 23.4 22.6 R, E (%) - 50.1 58.2 67.1 68.2 NO ₃ -N 68.3 15.2 11.8 3.8 1.4 R, E (%) - 77.7 82.7 94.4 97.8 NH ₄ -N 10.9 21.6 24.1 28.7 29.6 R, E (%) - -98.2 -121.1 -163.3 -171.5

 ※ R, E: Removal Efficiency for OHr

R · E : 0hr에 대*

R · E: vs 0hr

       <Figure 2.3> Changes in CODMn and Nitrogen Concentrations by Time Zone (A-1 Condition)

       <Table 2.3> shows the change of CODMn and nitrogen series concentration and removal efficiency by time zone under A-2 condition, and <Figure 2.4> shows the change of concentration of CODMn and nitrogen series by time slot. As shown in Table 2.3, the CODMn concentrations of 0hr, 4hr, 6hr and 8hr were 512.7mg / L, 343.2mg / L, 315.6mg / L, 261.0mg / L and 231.1mg / L, respectively. The removal efficiencies of 4hr, 6hr and 8hr were 33.1%, 38.4%, 49.1% and 54.9%.

       In addition, the TN concentrations (removal efficiency) were 151.7 mg / L, 70.2 mg / L (53.7%), 56.0 mg / L (63.1%), 52.3 mg / L (65.5%), and 49.5 mg / L (67.4%). , The concentration of organic nitrogen (removal efficiency) was 71.9 mg / L, 34.1 mg / L (52.6%), 25.1 mg / L (65.1%), 16.4 mg / L (77.2%), 9.4 mg / L (86.9%) The NO3-N concentration (removal efficiency) was 68.6 mg / L, 14.2 mg / L (79.3%), 5.3 mg / L (92.3%), 4.6 mg / L (93.3%), 3.4 mg / L (95.0). %). The NH4-N concentration was 11.2 mg / L, 21.9 (-95.5%) mg / L, 25.6 (-128.6%) mg / L, 31.3 (-179.5%) mg / L, 36.8 (-228.6%) mg / L As in A-1, organic nitrogen was decomposed / converted to increase the concentration of NH 4 -N.

       <Table 2.3> Changes in CODMn and Nitrogen Concentrations and Removal Efficiency by Time (A-2 Conditions)

  (UNIT: mg / L)

   Hours (hr) Item 0 One 2 3 4 5 6 7 8 REMARK MLSS 3850 CODMn 512.7 343.2 315.6 261.0 231.1 R, E ^* (%) - 33.1 38.4 49.1 54.9 T-N 151.7 70.2 56.0 52.3 49.5 R, E (%) - 53.7 63.1 65.5 67.4 Organic nitrogen 71.9 34.1 25.1 16.4 9.4 R, E (%) - 52.6 65.1 77.2 86.9 NO ₃ -N 68.6 14.2 5.3 4.6 3.4 R, E (%) - 79.3 92.3 93.3 95.0 NH ₄ -N 11.2 21.9 25.6 31.3 36.8 R, E (%) - -95.5 -128.6 -179.5 -228.6

* R · E: Removal Efficiency for 0hr

           <Figure 2.4> Changes in CODMn and Nitrogen Concentrations by Time Zone (A-2 Condition)

       <Table 2.4> shows the concentration change and removal efficiency of CODMn and nitrogen series by time zone under B-1 condition, and <Figure 2.5> shows the graph of CODMn and nitrogen concentration change by time zone. As shown in Table 2.4, the CODMn concentrations of 0hr, 4hr, 6hr and 8hr were 515.5mg / L, 330.2mg / L, 292.5mg / L, 240.0mg / L and 205.3mg / L, respectively. The removal efficiencies of 4hr, 6hr and 8hr were 35.9%, 43.2%, 53.4% and 60.2%.

       The TN concentrations (removal efficiency) were 148.7 mg / L, 70.5 mg / L (52.6%), 63.6 mg / L (57.2%), 55.8 mg / L (62.5%), and 52.8 mg / L (64.5%). The concentration of organic nitrogen (removal efficiency) is 69.7 mg / L, 33.5 mg / L (51.9%), 28.1 mg / L (58.2%), 16.4 mg / L (76.5%), 11.4 mg / L (83.6%) NO3-N concentrations (removal efficiency) were 69.5 mg / L, 16.5 mg / L (76.3%), 10.1 mg / L (85.5%), 6.1 mg / L (91.2%), and 4.2 mg / L (94.0). %). The NH4-N concentrations were 9.5 mg / L, 20.5 (-115.8) mg / L, 25.4 (-167.4) mg / L, 34.4 (-262.1) mg / L, and 37.2 (-291.6) mg / L. The concentration of NH4-N gradually increased due to degradation / conversion.

     <Table 2.4> Changes in CODMn and Nitrogen Concentrations and Removal Efficiency by Time (B-1 Condition)

(UNIT: mg / L)

   Hours (hr) Item 0 One 2 3 4 5 6 7 8 REMARK MLSS 2860 CODMn 515.5 330.2 292.5 240.0 205.3 R, E ^* (%) - 35.9 43.2 53.4 60.2 T-N 148.7 70.5 63.6 55.8 52.8 R, E (%) - 52.6 57.2 62.5 64.5 Organic nitrogen 69.7 33.5 28.1 16.4 11.4 R, E (%) - 51.9 58.2 76.5 83.6 NO ₃ -N 69.5 16.5 10.1 6.1 4.2 R, E (%) - 76.3 85.5 91.2 94.0 NH ₄ -N 9.5 20.5 25.4 34.4 37.2 R, E (%) - -115.8 -167.4 -262.1 -291.6

* R · E: Removal Efficiency for 0hr

           <Figure 2.5> Changes in CODMn and Nitrogen Concentrations by Time Zone (B-1 Condition)

       <Table 2.5> shows the change of CODMn and nitrogen series concentration and removal efficiency by time zone under B-2 condition, and <Figure 2.6> shows the change of concentration of CODMn and nitrogen series by time slot. As shown in Table 2.5, the CODMn concentrations of 0hr, 4hr, 6hr and 8hr were 512.1mg / L, 328.2mg / L, 276.7mg / L, 233.9mg / L and 197.2mg / L, respectively. The removal efficiencies of 4hr, 6hr and 8hr were 35.9%, 46.0%, 54.3% and 61.5%.

       In addition, the concentration of TN (removal efficiency) was 153.9 mg / L, 69.3 mg / L (54.9%), 61.4 mg / L (60.1%), 51.7 mg / L (66.4%), 48.8 mg / L (68.3%) The concentration of organic nitrogen (removal efficiency) was 76.2 mg / L, 29.3 mg / L (61.5%), 23.5 mg / L (69.2%), 7.5 mg / L (90.2%), 4.1 mg / L (94.6% NO3-N concentrations (removal efficiency) were 67.2 mg / L, 18.3 mg / L (72.8%), 13.8 mg / L (79.5%), 8.8 mg / L (86.9%), and 6.4 mg / L ( 90.5%). At this time, NH4-N concentration is 10.5mg / L, 21.7 (-106.7%) mg / L, 24.1 (-129.5%) mg / L, 35.4 (-237.1%) mg / L, 38.3 (-264.8%) mg / L As a result, the concentration of NH 4 -N was increased, which is considered to be a decomposition / conversion of organic nitrogen.

       <Table 2.5> Changes in CODMn and Nitrogen Concentrations and Removal Efficiency by Time (B-2 Conditions)

(UNIT: mg / L)

   Hours (hr) Item 0 One 2 3 4 5 6 7 8 REMARK MLSS 4050 CODMn 512.1 328.2 276.7 233.9 197.2 R, E ^* (%) - 35.9 46.0 54.3 61.5 T-N 153.9 69.3 61.4 51.7 48.8 R, E (%) - 54.9 60.1 66.4 68.3 Organic nitrogen 76.2 29.3 23.5 7.5 4.1 R, E (%) - 61.5 69.2 90.2 94.6 NO ₃ -N 67.2 18.3 13.8 8.8 6.4 R, E (%) - 72.8 79.5 86.9 90.5 NH ₄ -N 10.5 21.7 24.1 35.4 38.3 R, E (%) - -106.7 -129.5 -237.1 -264.8

* R · E: Removal Efficiency for 0hr

        <Figure 2.6> Changes in CODMn and Nitrogen Concentrations by Time Zone (B-2 Condition)

       In conclusion, the organic nitrogen of A-1 and B-1 was removed by 68.2% and 83.6%, respectively, when MLSS was 3,000mg / L. Nitrogen was removed by 86.4% and 94.6%, respectively, and NH4-N increased about 1.7 ~ 2.9 times compared to raw water under each condition. A-2 (DO 0.15ppm, MLSS 4,000ppm) and B-2 (DO 0.3ppm, MLSS 4,000ppm) conditions in the experiment through BATCH TEST are optimal for total nitrogen treatment of high concentration industrial wastewater containing organic nitrogen. Based on this, the conditions of PILOT TEST (continuous type) were set.

       In addition, it is judged that the use of RING LACE is effective based on the judgment that increasing the MLSS concentration can increase the treatment efficiency.

       Since industrial wastewater has a relatively high change in pollutant content and load, it is recommended to install a low-efficiency diffuser for maintaining random conditions and an agitator for maintaining anoxic conditions in order to cope with changes in conditions. Determined to be valid.

       Example 2

       PILOT TEST (Continuous Experiment)

       1. Purpose of Experiment

       Continuous experiments including an oxygen-free tank are performed at the appropriate residence time indicated by BATCH TEST to establish an optimal treatment system to facilitate the decomposition / conversion of organic nitrogen to ammonia nitrogen in nitrogen removal.

       2. Experiment apparatus and method

PILOT TEST에 사용된 실험 장치는 <그림 3.1>에서 보는 바와 같이 집수조, 임의성 무산소조(제1무산소조, 제2무산소조, 제3무산소조), 제1호기조(호기조-Ⅰ,Ⅱ), 무산소조(제4무산소조-Ⅰ,Ⅱ), 제2호기조(호기조-Ⅰ,Ⅱ,Ⅲ), 침전조로 구성되어 있으며, 각각의 반응조를 여러 개의 조로 분할한 것은 토목구조의 대규모 시설을 축소한 모형시설이기 때문이다.

The experimental apparatus used for the pilot test includes a collection tank, an arbitrary anoxic tank (first anoxic tank, a second anoxic tank, a third anoxic tank), a first tank (aerobic tanks I and II), and an anoxic tank (fourth anoxic tank). It consists of -I, II), No. 2 tank (Hogi-Ⅰ, II, III) and sedimentation tank, and the division of each reactor into several tanks is because it is a model facility with a large scale of civil engineering.

       P: PUMP E: Unit 1-I J: Unit 2-II

       A: Collection tank F: Unit 1-II K: Unit 2-III

       B: 1st anaerobic tank G: 4th anaerobic tank-ⅠL: Settling tank

       C: 2nd anaerobic tank H: 4th anaerobic tank -Ⅱ

       D: 3rd anaerobic tank I: 2nd key-Ⅰ

                        <Figure 3.1> Pilot Test Device

       Raw water TANK was installed in order to store TN wastewater in the pH adjustment tank of the wastewater treatment plant with a volume of 200L and transfer it to the random anaerobic tank. The anaerobic tank and the aerobic tank were made of PVC so that the effective volume of the tank was 15L with the width of 150mm, the length of 200mm and the height of 600mm. In addition, AGITATOR and AIR TUBE (low efficiency acid pipe; for the purpose of air agitation) were installed in the 1st anaerobic tank for proper DO concentration control and smooth mixing of waste water and microorganism, and 1 acid pipe and 1 AIR TUBE were installed in the aerobic tank. .

       Each reactor is equipped with a PVDC material suspension microorganism (RING LACE) based on the filling rate of 3-4% to increase the total MLSS concentration due to adherent MLSS. Microbial carriers were installed in each tank 40M in total by 4M RING LACE-35 standard.

       <Table 3.1> shows the operating conditions of the pilot device during the operation period. The volume of the anaerobic and aerobic tanks is 15 liters each, and the total volume of the bioreactor is 150 liters. The flow rate Q was 240 L / day, the total residence time of the bioreactor was 15 hr, and the MLSS concentration was based on the suspension of 4,000 mg / L of suspended MLSS concentration when no microbial carrier was installed. The total MLSS concentration obtained by adding 4,000 mg / L of suspended MLSS concentration and 1,500 mg / L of MLSS attached to the microorganism carrier was based on 5,500 mg / L.In order to maintain the microorganism concentration in the reactor, sludge returning was not performed. If not, the sludge residence time was maximized by operating based on 100% of the influent flow rate, and when the microbial carrier was installed based on 50% of the influent flow rate.

       In this case, the average volume load was based on 5.8kg-CODcr / ㎥.day, and the F / M ratio was based on an average of 0.9kg-CODcr / kg-MLSS.day when no carrier was installed. 0.65 kg-CODcr / kg-MLSS.day.

       In addition, the bioreactor is controlled to adjust the degree of agitation and air injection at any time to maintain anoxic and aerobic conditions so that the DO concentration is in the range of 0.1 to 0.8 mg / L, 0.0 to 0.2 mg / L, and 1.0 to 2.5 mg / L, respectively. The organic nitrogen was operated to facilitate the decomposition / conversion of ammonia nitrogen to ammonia nitrogen, and the pH was operated to be 7.4 ~ 8.2.

       <Table 3.1-1> Pilot Test Operation Conditions (No microbial carrier installed)

Item Operation condition Remarks Driving period  27 days flux 240L / DAY DO First and second anaerobic tanks 0.1 to 0.8 mg / L Third anoxic 0.0 to 0.2 mg / L Fourth Anaerobic 0.0 to 0.2 mg / L Aerobic 1.0 to 2.5 mg / L HRT 15 hr MLSS 4,000 mg / L pH 7.5 to 8.1

           <Table 3.1-2> Pilot Test Operation Conditions (Install Microbial Carrier)

Item Operation condition Remarks Driving period 27 days flux 240L / DAY DO First and second anaerobic tanks 0.1 to 0.8 mg / L Third anoxic 0.0 to 0.2 mg / L Fourth Anaerobic 0.0 to 0.2 mg / L Aerobic 1.0 to 2.5 mg / L HRT 15 hr MLSS 5,500 mg / L (4,000 / Float + 1,500 / fixed) With sticking MLSS pH 7.4 ~ 8.2

       3. Results and Discussion

       3.1 pH and DO Concentration Changes

       <Table 3.2> shows pH and DO concentration of each bioreactor, and <Figure 3.2> shows changes of pH and DO concentration of bioreactor. The pH of raw water was 7.4, the first oxygen-free tank 8.0, the third oxygen-free tank 8.1, the first tank-II 8.1, the fourth oxygen-free tank-II 7.7, the second tank-II 8.0 and the effluent 7.5 without the microbial carrier. The first anaerobic bath 0.5mg / L, the third anaerobic tank 0.1mg / L, No. 1 crude-II 1.9mg / L, No. 4 anaerobic -II 0.1mg / L, No. 2-crude 2.0-II 2.0mg / L.

       When the microorganism carrier was installed, the raw water was 7.4, the first anoxic tank 8.1, the third anoxic tank 8.2, the first anaerobic tank-II 8.1, the fourth anaerobic tank-II 7.8, the second aerobic tank-II 8.0, and the runoff water 7.8. If not installed, 1st tank 0.6mg / L, 1st anaerobic tank 0.25mg / L, 1st tank-II 1.9mg / L, 2nd anaerobic tank-Ⅱ 0.25mg / L, 2nd tank-II 2.0mg / L When the carrier was installed, the first arbitrary tank 0.5mg / L, the first anaerobic tank 0.1mg / L, the first anaerobic tank-II 1.9mg / L, the second anaerobic tank-II 0.1mg / L, the second anaerobic tank-II The case where the carrier was installed as 2.0 mg / L was found to be advantageous for maintaining oxygen-free conditions.

It is believed that the innermost part of the microbial membrane attached to the carrier is close to anaerobic, which counteracts the surface aeration effect expected in water surface.

   <Table 3.2.1> Changes in pH and DO Concentration (When Microbial Carriers Are Not Installed)

enemy First anaerobic tank Third anoxic 1st keynote-Ⅱ Fourth Anaerobic Tank-Ⅱ 2nd keynote-Ⅱ Runoff pH 6.8 ~ 7.9 (7.4) 7.4-8.7 (8.0) 7.3--9.4 (8.1) 7.2-8.6 (8.1) 7.4-8.8 (7.7) 7.5-8.4 (8.0) 7.3-8.2 (7.5) DO mg / L - 0.2 ~ 0.8 (0.6) 0.0 ~ 0.4 (0.25) 0.7 ~ 4.4 (1.9) 0.0 ~ 0.2 (0.25) 0.6 ~ 3.8 (2.0) -

 (): Average value

               <Figure 3.2.1> Changes in pH of influent and treated water

          <Table 3.2.2> Changes in pH and DO Concentration (In case of Microbial Carrier Installation)

enemy First anaerobic tank Third anoxic 1st keynote-Ⅱ Fourth Anaerobic Tank-Ⅱ 2nd keynote-Ⅱ Runoff

pH

pH 6.8 ~ 7.9 (7.4) 7.4-8.7 (8.1) 7.3 ~ 9.4 (8.2) 7.2-8.6 (8.1) 7.4-8.8 (7.8) 7.5-8.4 (8.0) 7.3-8.2 (7.8) DO mg / L - 0.1 ~ 0.8 (0.5) 0.0 ~ 0.2 (0.1) 0.7 ~ 4.4 (1.9) 0.0 ~ 0.2 (0.1) 0.6 ~ 3.8 (2.0) -

(): Average value

             <Figure 3.2.2> Changes in pH of influent and treated water

       3.2 CODcr concentration change and removal efficiency

       <Table 3.3> shows the CODcr removal efficiency and <Figure 3.3> shows the change of CODcr removal efficiency. The concentration of raw water was 2,655 ~ 4,954 (average 3,737) mg / L without microbial carrier, and the concentration of effluent was 510.2 ~ 1,856.3 (average 894.9) mg / L. The average treatment efficiency was 72.7%.

       The concentration of raw water ranged from 2,655 to 4,954 (average 3,737) mg / L when the microbial carrier was installed, and the concentration of effluent was 98.5 to 1,227 (average 398) mg / L. The CODcr removal efficiency was as low as 66.1% and as high as 97.1%. The treatment efficiency was 89.7%.

       Therefore, it was found that the case of installing the microbial carrier is excellent.

       <Table 3.3.1> CODcr Removal Efficiency (when no microorganism carrier is installed)

Experiment period Concentration (mg / L)  Removal efficiency (%) enemy Runoff 27 days 2,655-4,954 (3,599) 510.2-1,856.7 (894.9) 51.7 ~ 85.6 (72.7)

(): Average value

                   <Figure 3.3.1> Changes in CODcr Removal Efficiency

               <Table 3.3.2> CODcr Removal Efficiency (When Microbial Carrier is Installed)

Experiment period Concentration (mg / L)  Removal efficiency (%) enemy Runoff  27 days 2,655 ~ 4,954 (3,599) 95.8-1,227 (383) 66.1--97.1 (86.3)

(): Average value

                 <Figure 3.3.2> Changes in CODcr Removal Efficiency

       <Table 3.4> shows the CODcr concentration of the bioreactor and <Figure 3.4> shows the CODcr change of the bioreactor. If no microbial carrier is installed, the CODcr concentration of the bioreactor in the raw water is 2,134.2mg / L for the first anaerobic tank, 1,875.7mg / L for the third anaerobic tank, 1,498.5mg / L for the first vessel-II, and 1,178.5mg / L for the fourth anaerobic tank-II L, No. 2 tank-II 900.7 mg / L, and the CODcr concentration of the bioreactor when the carrier was installed was 1125 mg / L of the first anaerobic tank, 973 mg / L of the third anoxic tank, 681 mg / L of the first tank-II, No. 4 anoxic crude-II 560 mg / L, and 2nd basic crude-II 446 mg / L.

       The difference in the treatment efficiency of each step is related to the presence or absence of the installation of the carrier, but also determined that the total nitrogen (TN) as the denitrification consumed a large amount of organic matter.

<Table 3.4.1> CODcr Concentration by Bioreactor (if no microbial carrier is installed)

enemy First anaerobic tank Third anoxic No. 1 keynote -Ⅱ Fourth Anaerobic Tank-Ⅱ 2nd keynote-Ⅱ Runoff CODcr mg / L 2,655-4,954 (3,737) 1,947 ~ 3,643 (2,134.2) 1,573 ~ 3,276 (1,875.7) 1,103 ~ 2,991 (1,498.5) 780.2-2,523 (1,170.2) 514-1,897 (900.7) 510.2-1,856 (894.9)

             <Figure 3.4.1> CODcr Change in Bioreactor

        <Table 3.4.2> CODcr Concentration by Bioreactor (When Microbial Carrier is Installed)

enemy First anaerobic tank Third anoxic First Group -Ⅱ Fourth Anaerobic Tank-Ⅱ 2nd keynote-Ⅱ Runoff CODcr mg / L 2,655-4,954 (3,737) 138-2,233 (1,125) 173-2,098 (973) 58.2-1,591 (681) 40.2-1,523 (560) 114--1,347 (446) 98.5-1,227 (383)

(): Average value

                 <Figure 3.4.2> CODcr Change in Bioreactor

       3.3. CODMn concentration change and removal efficiency

       <Table 3.5> shows the CODMn removal efficiency and <Figure 3.5> shows the change of CODMn removal efficiency. The concentration of raw water was 919 ~ 1,286 (average 1,119) mg / L, and the concentration of effluent was 145.3 ~ 497.8 (average 258.6) mg / L without carrier. CODMn removal efficiency was 58.9%, 86.5%, and average. The treatment efficiency was 77.1%, and the CODMn removal efficiency was at least 71.9%, at most 97.5%, and the average treatment efficiency was 91.4%.

       It can be seen that it is likewise advantageous to install a microbial carrier.

        <Table 3.5.1> CODMn Removal Efficiency (when no microorganism carrier is installed)

Experiment period Concentration (mg / L)  Removal efficiency (%) enemy Runoff  27 days 919-1,286 (1,119) 145.3-497.8 (258.6) 58.9-86.5 (77.1)

(): Average value

                    <Figure 3.5.1> Changes in CODMn Removal Efficiency

           <Table 3.5.2> CODMn Removal Efficiency (When Microbial Carrier is Installed)

Experiment period Concentration (mg / L)  Removal efficiency (%) enemy Runoff  27 days 919-1,286 (1,119) 24.3 ~ 340 (99.3) 71.9-97.5 (91.4)

(): Average value

                    <Figure 3.5.2> Changes in CODMn Removal Efficiency

       <Table 3.6> shows the CODMn concentration of the bioreactor and <Figure 3.6> shows the CODMn change of the bioreactor. The CODMn concentration of the bioreactor for raw water is 889.5 mg / L for the first anaerobic tank, 542.1 mg / L for the third anaerobic tank, 465.8 mg / L for the first anaerobic tank II, and 354.2 mg / L for the fourth anaerobic tank-2 without the support , No. 2 tank-Ⅱ 266.8mg / L, and the carrier was installed when the first oxygen-free tank 416mg / L, the third oxygen-free tank 300mg / L, the first tank-II 277.6mg / L, the fourth oxygen-free tank-II 181.3mg / L L, No. 2 Gizo-II 106.8 mg / L.

                   <Table 3.6.1> CODMn Concentration by Bioreactor

enemy First anaerobic tank Third anoxic 1st keynote-Ⅱ Fourth Anaerobic Tank-Ⅱ 2nd keynote-Ⅱ Runoff CODMn mg / L 919-1,286 (1,119) 568.5-1,237 (846) 375.3-867 (663) 243.5-788 (578) 183.7--665 (386) 149.4 ~ 505.9 (267) 145.3-497.8 (258.6)

  (): Average value

                <Figure 3.6.1> CODMn Changes in Bioreactors

                <Table 3.6.2> CODMn Concentration by Bioreactor

enemy First anaerobic tank Third anoxic 1st keynote-Ⅱ Fourth Anaerobic Tank-Ⅱ 2nd keynote-Ⅱ Runoff CODMn mg / L 919-1,286 (1,119) 68.5 ~ 1,103 (416) 67.3 ~ 580 (300) 78.4-549 (278) 63.6-469 (181) 49.4-438 (107) 37.3-347 (99)

   (): Average value

               <Figure 3.6.2> CODMn Changes in Bioreactors

       3.4 T-N, Organic Nitrogen, NH3-N, NO3-N Concentration Changes and Removal Efficiency

       Table 3.7 shows the T-N removal efficiencies and Figure 3.7 shows the changes in T-N removal efficiencies. The concentration of raw water was 148 ~ 385 (average 257) mg / L, and without carrier, the concentration of effluent was 70.9 ~ 99.5 (average 87.3) mg / L, and the TN removal efficiency was 34.3%, 77.4%, average. The treatment efficiency was 64.3%, and the carriers were 7.0 ~ 68 (average 38.9) mg / L, the lowest TN removal efficiency was 76.5%, the highest 96.3%, and the average treatment efficiency was 84.9%.

       The significant difference in treatment efficiency is that not only is it advantageous to install a carrier, but also that the innermost part of the microbial membrane attached to the carrier is anaerobic, so that stable oxygen-free conditions can be maintained. Can be.

      <Table 3.7.1> T-N Removal Efficiency (when no microorganism carrier is installed)

Experiment period Concentration (mg / L)  Removal efficiency (%) enemy Runoff 27 days 148-385 (257) 70.9 ~ 99.5 (87.3) 34.3 ~ 77.4 (64.3)

 (): Average value

                    <Figure 3.7.1> Changes in T-N Removal Efficiency

        <Table 3.7.2> T-N removal efficiency (when microorganism carrier is installed)

Experiment period Concentration (mg / L)  Removal efficiency (%) enemy Runoff 27 days 148-385 (257) 7.0-68 (38.9) 76.5-96.3 (84.9)

  (): Average value

                   <Figure 3.7.2> Changes in T-N Removal Efficiency

       <Table 3.8> shows the T-N concentration of the bioreactor, and <Figure 3.8> shows the T-N change of the bioreactor. The TN concentration of the bioreactor for raw water is 154.2mg / L for the first anaerobic tank, 141.6mg / L for the third anaerobic tank, 139.6mg / L for the first anaerobic tank-II, and 115.6mg / L for the fourth anaerobic tank-2 without the support. , No. 2 tank-II 91.1 mg / L, and the carrier was installed 130 mg / L of the first anaerobic tank, 85.6 mg / L of the first anaerobic tank, 80.6 mg / L of the first anaerobic tank-II, 43.6 mg of the fourth anaerobic tank-Ⅱ / L, No. 2 vessel-II 40.2 mg / L.

       <Table 3.8.1> T-N Concentration by Bioreactor (if no microbial carrier is installed)

enemy First anaerobic tank Third anoxic 1st keynote-Ⅱ Fourth Anaerobic Tank-Ⅱ 2nd keynote-Ⅱ Runoff T-N (mg / L) 148-385 (257) 146.2--234 (154.2) 134.5-166 (141.6) 121.2--152 (139.6) 97.4-125 (115.6) 76.2-104 (91.1) 70.9 ~ 99.5 (87.3)

(): Average value

<Figure 3.8.1> T-N Changes in Bioreactors

<Table 3.8.2> T-N Concentration of Bioreactors (with Microbial Carrier)

enemy First anaerobic tank Third anoxic 1st keynote-Ⅱ Fourth Anaerobic Tank-Ⅱ 2nd keynote-Ⅱ Runoff T-N (mg / L) 148-385 (257) 66.3-144 (130) 40.5 ~ 101 (85.6) 31.2 ~ 95 (80.6) 21.7 ~ 87 (43.6) 10.2--75 (40.2) 7.0-68 (38.9)

(): Average value

                       <Figure 3.8.2> T-N Changes in Bioreactors

       <Table 3.9> shows the concentrations of organic nitrogen, NH4-N and NO3-N in the bioreactor, and <Figure 3.9> shows the changes of organic nitrogen, NH4-N and NO3-N in the bioreactor. The organic nitrogen concentration of the bioreactor in the raw water was 95.2mg / L for the first tank, 38.7mg / L for the first anaerobic tank, 27.7mg / L for the first tank-II, 25.6mg / L for the second tank-II, 15.6mg / L for the second tank-II -II 5.4mg / L, NH4-N concentration was 28.5mg / L for the first tank, 45.3mg / L for the first anaerobic tank, 17.6mg / L for the first tank-II, 25.5mg / L for the second anaerobic tank-II, No. 2 tank-Ⅱ 15.3mg / L, NO3-N concentration of 1st random tank 6.5mg / L, 1st anaerobic tank 1.6mg / L, 1st tank-II 35.3mg / L, 2nd anaerobic tank-II 2.5mg / L, No. 2 vessel-II 19.5 mg / L.

<Table 3.9.1> Organic Nitrogen, NH3-N, and NO3-N Concentrations by Bioreactor (No Carrier)

enemy First anaerobic tank Third anoxic 1st keynote-Ⅱ Fourth Anaerobic Tank-Ⅱ 2nd keynote-Ⅱ Runoff Organic Nitrogen (mg / L) 87.5-285 (157) 35.4-189 (95.2) 39.4-152 (88.7) 24.8 ~ 124 (76.7) 30.6 ~ 97 (65.6) 25.4 ~ 95.2 (56.3) 20.1 ~ 94.5 (54.2) NH ₄ -N (mg / L) 9.8-39.3 (19.9) 26.5 ~ 70.7 (48.5) 18.2 ~ 58.4 (45.3) 7.9 ~ 64.1 (27.6) 17.5-48.1 (45.5) 11.6 ~ 37.8 (20.3) 10.8 ~ 35.1 (20.0) NO ₃ -N (mg / L) 0.0 ~ 183 (80.1) 5.0 ~ 19.3 (10.5) 2.0 ~ 12.3 (7.6) 5.0-19.1 (35.3) 1.0 ~ 9.6 (4.5) 7.0-19.2 (14.5) 5.0-18.4 (13.1)

         <Figure 3.9> Changes in Organic Nitrogen, NH4-N, and NO3-N in Bioreactors

    <Table 3.9> Organic Nitrogen, NH3-N, NO3-N Concentrations by Bioreactors

enemy First anaerobic tank Third anoxic 1st keynote-Ⅱ Fourth Anaerobic Tank-Ⅱ 2nd keynote-Ⅱ Runoff

기성 질소 (mg/L)U

Ready Nitrogen (mg / L) 87.5-285 (157) 35.4 ~ 89 (55.2) 19.4--52 (38.7) 14.8 ~ 34 (27.7) 3.6-17 (5.6) 2.4 ~ 19.6 (5.4) 1.1-14.3 (5.3) NH ₄ -N (mg / L) 9.8-39.3 (19.9) 6.5 ~ 70.7 (28.5) 8.2 ~ 58.4 (45.3) 10.9-34.1 (17.6) 7.5 ~ 28.1 (25.5) 6.6-27.5 (15.3) 5.8-25.1 (15.1) NO ₃ -N (mg / L) 0.0 ~ 183 (80.1) 0.0 ~ 19.3 (6.5) 0.0 ~ 9.4 (1.6) 3.0-39.1 (35.3) 1.0-6.6 (2.5) 4.0 ~ 29.2 (19.5) 3.0-23.4 (18.5)

            <Figure 3.9> Changes in Organic Nitrogen, NH4-N, and NO3-N in Bioreactors

       From the results of the pilot test, the organic nitrogen removal efficiency of the first stage oxygen-free process (first, second, and third oxygen-free tanks) was about 75.3%, and NH4-N increased about 2.3 times. This result was superior to the TEST result of continuous PILOT PLANT TEST equipped with PVDC material RING LACE to increase the adherent MLSS. It can be seen that it is also applicable to the actual plant.

       4. Conclusion

       Through the BATCH TEST and the PILOT TEST including the randomization process, the results of organic nitrogen treatment were as follows.

       1. As a result of BATCH TEST with A condition (Anoxic) and B condition (Randomity) with MLSS maintained at 4,000mg / L, organic nitrogen removal rate was above 68% for both anoxic and random conditions at 8hr. It was confirmed that the decomposition / conversion of nitrogen to NH4-N first could be selected as an industrial wastewater treatment system containing a high concentration of total nitrogen.

       2. Based on the conditions shown in BATCH TEST, the pilot test resulted in removal of about 66.7% of TN and about 75.4% of organic nitrogen during the one-step anaerobic treatment process, and the removal efficiency of TN and organic nitrogen in the whole system. Were 84.9% and 96.6%, respectively.

       It was found that it is advantageous to install a hanging microorganism carrier (RING LACE) of PVDC material.

       3. As a result of the BATCH TEST and PILOT TEST, the oxygen free process is not only important for nitrogen removal but also organic nitrogen removal (decomposition / conversion to ammonia nitrogen) in the system combining 1st stage anoxic and aerobic processes, 2nd stage anoxic and aerobic processes. ) Was also very efficient.

       In particular, when the microbial carrier was installed in the anoxic treatment process in the first half, the industrial wastewater treatment of total nitrogen including organic nitrogen and high pollutant load was very efficient, and it was found that the system can effectively use organic pollutants contained in the original wastewater.

       In addition, it was found that the arrangement of anoxic and aerobic tanks filled with microbial carriers in the second half was efficient for stable management of the final treated water quality. I could see that.

 As described above, the present invention, in the case of high concentration industrial wastewater containing a large amount of organic nitrogen, it is possible to fully decompose the organic nitrogen to maximize the total nitrogen (TN: total Nitrogen) removal of the effluent.

Claims (11)

According to the characteristics of the incoming wastewater, the organic nitrogen contained in the raw wastewater is stabilized by changing to the form of NH ₄ -N through a random anoxic process that allows operation in aerobic state, and NO ₃ -N through denitrification. The first treatment step to enable the removal of, A secondary treatment step for nitrifying NH ₄ -N converted to NO ₃ -N through an arbitrary oxygen-free process of the primary treatment step,        A third treatment step of denitrifying the intermediate treated water in the aerobic process of the second treatment step through an anoxic process to sequentially decompose most organic nitrogen contained in the raw wastewater to induce a stable treatment; Through the aerobic process of the third treatment step, further change of untreated excess organic nitrogen and nitrification reaction of NH ₄ -N occur to be returned / circulated to the random anoxic process of the first treatment step so as to be treated. A method of treating nitrogen-based wastewater comprising a fourth treatment step.        The method for treating nitrogen-based wastewater according to claim 1, wherein the random anoxic process of the first treatment step is operated under aerobic conditions only when ammonia nitrogen in nitrogen contained in the raw wastewater is high.        The microorganism supply in the optional anoxic process of the first treatment step is characterized in that the sludge contained in the effluent generated after the fourth treatment step precipitates and returns / circulates. Method of Treating Nitrogen Wastewater.        The process of claim 1 or 2, wherein the random anaerobic process of the primary treatment step comprises a first anoxic process that allows operation in an aerobic state and a second anoxic process that allows operation in an anoxic state only. 3, a nitrogen-free waste water treatment method characterized in that the operation is carried out to sequentially perform an anoxic process.        The method of claim 4, wherein if the concentration of organic nitrogen in the effluent discharged from the random oxygen free process of the primary treatment step is maintained abnormally high, it is returned to / recycled to the second anoxic process of the primary treatment step Nitrogen-based wastewater treatment system.        According to claim 1, wherein the effluent discharged from the aerobic process of the fourth treatment step is the random anoxic of the first treatment step when the concentration of organic nitrogen and ammonia nitrogen exceeds the reference value of the total management target nitrogen (TN) concentration If the concentration of nitrate nitrogen exceeds the control target total nitrogen (TN) concentration and if the organic pollutant exceeds the control standard, return / circulate to the anoxic process of the tertiary treatment step. Nitrogen-based wastewater treatment system characterized in that.        A collection tank 10 for temporary storage of raw wastewater, an arbitrary anoxic tank 20 equipped with an agitator 3 and an acid generator 4, a first unit tank 30 equipped with an acid generator 4, and stirring Anaerobic tank 40 equipped with the apparatus 3, the second tank 50 is equipped with the air diffuser 4, and the sludge contained in the effluent of the second tank 50 is separated from the supernatant to settle. Nitrogen-based wastewater treatment system configured to sequentially arrange the settling tank (60).        The nitrogen system according to claim 7, wherein the settling tank (60) is connected with a sludge conveying pipe (7) for returning / circulating the settling sludge to the optional anoxic tank (20) by means of a sludge return pump (1). Wastewater Treatment System.        The method of claim 7, wherein the first and second tanks 30 and 50, the effluent is returned to the arbitrary anoxic tank 20 and the anoxic tank 40 by an air lift pump 2, respectively. Treatment system for nitrogen-based wastewater, characterized in that for the treatment water transfer pipe (8) is connected to each other.        8. The optional anoxic tank 20 according to claim 7, further comprising: a first anoxic tank 21 in which the stirring device 3 and the air dispersing device 4 are mounted, and a second anoxic tank 22 in which the stirring device 3 is mounted; , Nitrogen-based wastewater treatment system characterized in that it is divided into a third anoxic tank (23) equipped with a stirring device (3).        8. The nitrogen-based wastewater treatment system according to claim 7, wherein the random anaerobic tank (20) is filled with a microbial carrier (5).

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