SBR System for Agrochemical Industry - Feasibility & Implementation Pravin Manekar, Rima Biswas & Tapas Nandy CSIR-National Environmental Engineering Research Institute, Nagpur 440 020, India [email protected]; [email protected]; [email protected] Abstract Feasibility of sequential batch reactor (SBR) was investigated to treat an agrochemical effluent by overcoming factor affecting process stability such as microbial imbalance and substrate sensitivity. The full-scale aerobic process was evaluated under the existing operating condition lead to non-optimal performance. Laboratory study was conducted in a bench scale SBR system stage-I&II model. SBR system stage-I&II achieved biooxidation at 6 days hydraulic retention time in an extended aeration mode. The maximum removal of chemical oxygen demand (COD) and biochemical oxygen demand (BOD) by heterotrophic bacteria in the first stage reactor was 87% and 90%, respectively. Removal of toxic ammoniacal-nitrogen by autotrophic bacteria in a second stage bio-oxidation was 97%. SBR system stage-I&II showed a great promise for improving the process stability and treating the agrochemical effluent. SBR system stage-I&II was implemented at full-scale level to treat the agrochemical effluent. Key words: Agrochemical industry; SBR; bio-oxidation process; implementation 1 Introduction Agrochemical industries consume enormous water for producing the pesticides, insecticides, herbicides and fungicides and generate multi-stream complex effluents. Discharging of untreated or partially treated agrochemical effluent render adverse effects on receiving water bodies (Delorenzo et al., 2001). Chemicals present in agrochemical effluent are often toxic to aquatic life. Agrochemical effluents are typically characterized with high concentrations of COD and ammonia. Treatment technologies for high COD concentration and ammonia comprise physico-chemical and biological processes. However, unlike chemical treatment biological process does not produce a huge quantity of sludge and thus are more environmentally friendly. Biological processes such as ASP, SBR, anaerobic–aerobic (A/O) biofilm reactors, moving bed membrane bioreactor, packed-bed biofilm reactor and pre-denitrification can effectively remove carbonaceous and nitrogenous pollutants (Kim et al., 2009; Yang and Yang, 2011; Karkare and Murthy, 2012). The SBR has been successfully employed in the treatment of both municipal sewage and industrial effluent (Mace and Mata-Alvarez, 2002). It is simple in process engineering, design and requires less foot print (Vazquez et al., 2006). This technology is a cyclic batch process operated in a sequence of fill, react, settle and decant for effective removal of pollutants (Akin and Ugurlu, 2005) and best suitable for accommodating multiple microbial reaction in a single reactor. However, carbon and nitrogen removal can suffer from disagreement of demand and supply of substrates between two metabolically different groups of microorganism namely the heterotrophsand the autotrophs often lead to failure. The competition become more intense when complex industrial effluent are treated such as effluent from steel industry, coal carbonization, and municipal leachates, etc. (Marttinen et al., 2002; Manekar et al., 2011b). To overcome the incompatibility between heterotrophic and autotrophic bacteria in a single stage reactor or multiple-stage processes is often advocated for treating high strength effluent (Kim et al., 2013). This 1 paper addressed the feasibility and implementation SBR system stage-I&II for carbon and nitrogen removal from agrochemical industry. Thus, the work aimed for feasibility and implementation of the SBR system for treating the agrochemical effluent. 2 Methodology 2.1 Effluent segregation and quantification The agrochemical industry is located in the southern part of India. The production capacity of the industry is 12.5 tonnes per day. The production unit comprises four process blocks designated I-IV, and produces a comprehensive range of pesticides, technical, formulations and custom manufactured fine chemicals. The complex process effluents generated from the four manufacturing units (namely block I-IV) were segregated into three main streams, and designated as stream A-C. The stream A was generated after product separation; ejector condensates from all the process blocks were channelized in the stream B. Stream C, highly organic in nature was left over solvent separation. The quantum of streams A, B and C generated were 250, 300 and 30 m3d-1, respectively. 2.2 Treatment facility Stream A was treated in evaporative system, and condensate obtained was stripped in an air stripper. The stripped effluent was further combined with stream B before feeding to aerobic system. The sludge from biological process and concentrate from the evaporator system were dried separately, the dried sludge and concentrate were disposed off to a treatment storage and disposal facility. Hourly samples were collected in polypropylene bottles and composited for 24 h at different stages of the effluent treatment plant (ETP). The composite samples were analyzed as referred in the Standard Methods (APHA, 2005). 2.3 Sequential batch reactor Ammonia stripped effluent was treated in a bench scale SBR system consists of two cubical acrylic tanks of size (30×30×30 cm3). The SBR stage-I was inoculated with the biomass collected from the existing ETP of the agrochemicals industry. Biomass to be inoculated in SBR stage-II was obtained from an industrial nitrification unit and acclimatized with domestic sewage. The SBR stage-I was fed with stripped effluent (pH 7.2) at different HRTs in an extended aeration mode. The SBR stage-I&II was operated in a cyclic batch mode having a time schedule as follows: 4 h-filling, 18 h-filling and aeration (both oxic); 2 h-settling, 4 h-decanting (both anoxic). The SBR stage-I&II was optimized by operating reactors at different HTRs (1-4 d). Air was supplied to maintain a DO concentration 2.5 mgl-1 and to ensure proper contact of substrates and microorganisms during fill and aeration mode. 3 Results and discussion 3.1 Physico-chemical characterization of effluents A detailed physico-chemical characterization of streams A and B, generated from the different process blocks I-IV was carried out, and the results are summarized in Table 1. TDS and COD concentrations of stream A (from process blocks I-IV) were very high in the range 160,000-253,000 and 56,280-84,000 mgl-1, respectively and hence stream A was characterized as high TDS and high COD effluent. The COD concentration of stream B (from process blocks I-IV) was 5-7 times more than its TDS concentration. Therefore, it was characterized as low TDS and high COD effluent. Additionally, ammonia and SS concentrations in stream A were much higher than stream B. In totality, all the stream from agrochemical effluent was characterized high strength 2 effluent containing high concentration of organic, inorganics and ammonia. The process effluents were found to be free from pesticides, herbicides, fungicides and insecticides. 3.2 Assessment of existing aerobic system Performance of the aerobic system and treated effluent quality as per the stipulated discharge norms into Inland Surface Waters is summarized in Table 2. The influent to SBR was high in ammonia concentration (305-385 mgl-1). The DO concentration during the fill and the aeration period was found to be less than 1 mgl-1. The mixed liquor volatile suspended solid (MLVSS) and mixed liquor suspended solid (MLSS) concentrations were 1452-2000 and 2100-2500 mgl-1, respectively. 3.3 SBR stage-I In the existing aerobic system, 59-65% SS, 72-83% BOD and 68-77% COD removals were achieved. Ammonia removal was not taking place even after operating the reactor at an extremely high HRT of 24 days. The treated water quality from the existing aerobic system did not conform to the Indian Inland Surface Waters (ISW) standard discharged with respect to BOD, COD and ammonia concentration (Table 2). Laboratory studies were carried out in a 24 h cyclic SBR stage-I bio-oxidation reactor at mixed liquor suspended solid (MLSS) concentration of 3200-3500 mgl-1 with varying HRTs (1-4 days). Biological process depends on the bacterial growth/decay rate and HRT that yield desired treatment efficiency. The characteristic of FSSBR feed was as follows: pH: 7.07.3; TDS: 2700 mgl-1; COD: 3000 mgl-1; BOD: 2500 mgl-1 and ammonia 200mgl-1. The results from this set of the experiments are presented in Fig. 1.The removal of the major pollutant parameters such as COD and BOD at HRT 1 day was 70% and 75%, respectively. When the reactor was operated at higher HRTs, the increase in the removal of pollutants (COD and BOD) was observed. However, at HRT greater than 3 days, COD and BOD removal efficiency dropped to 80% and 86%, respectively. The highest removal of carbonaceous substrate was obtained at 3 d (72 h) HRT with more than 90% removal efficiency. Maranon et al. (2008b) reported a very similar COD removal efficiency at HRT of 115 h in a single stage SBR for treatment coke effluent. The treated effluent characteristics from the SBR stage-I were as follows: COD: 400 mgl1 ; BOD 250 mgl-1; ammonia nitrogen: 200 mgl-1. The results obtained were comparatively better than the existing aerobic system. However, treated effluent did not meet the Indian ISW discharge standards. Therefore, further treatment was necessary to meet the regulatory norms. 3.4 SBR stage-II The SBR stage-II was targeted for nitrification of SBR stage-I effluent. Therefore, to develop nitrifying activity in SBR stage-II biomass from a full-scale nitrifying reactor was acclimatized with SBR stage-I effluent. After acclimatization, which lasted for around 3 months it was found 18% and 7% of biomass was composed of ammonia oxidizing bacteria (AOB) and nitrite oxidizing bacteria (NOB) with bacterial count of 5-27×107 and 2-10×07 CFU ml-1, respectively. The nitrification performance of SBR stage-II was observed at different HRTs (Fig. 2). At lower HRT, the removal efficiency of the ammonia was inefficient. Removal efficiency increased with increase in HRT up to 3 d. However, further increase in HRT resulted in decrease in removal of ammonia. Peak 97% removal efficiency of ammonia was obtained at 3 d HRT in an extended aeration mode. Many researchers have reported a minimum of 2.5-8 d for more than 70% nitrification efficiency (Maranon et al., 2008a; Biswas et al., 2010; Manekar et al., 2011b). At 3 d optimal HRT, the SBR stage-II treated effluent had the following 3 characteristics COD ≤110 mgl-1, BOD≤ 50 mgl-1, ammonia ≤10 mgl-1, nitrite: BDL and nitrate≤ 7mgl-1. Thus, along with ammonia removal, the COD of 72.5% and BOD of 80% removals were also observed in SBR stage-II. Heterotrophic bacteria oxidized the carbonaceous substrate to more than 90% efficiency. Autotrophic bacteria in the SBR stage-II effectively oxidized ammonia concentration to 97% and thus, improved the stability of nitrification process. The stage separation provided separate environmental condition for optimum activities of heterotrophic and autotrophic bacteria (Vazquez et al., 2006; Biswas et al., 2010). Thus, fends off the competition between heterotrophic and autotrophic bacteria, improves the process stability for substrate sensitivity through active interaction of substrates and renders the optimum environmental conditions to microbes for effective oxidation of carbonaceous and nitrogenous substrates. Effective carbon-nitrogen removal in the SBR stage I&II was achieved at an optimal HRT of 6 d. The final effluent from the SBR stageII met the discharge standards for ISW, with respect to all parameters. 3.5 Full-scale SBR system design & implementation The full-scale SBR stage-I&II was designed for a flow rate of 600 m3d-1 to operate in a cyclic batch mode with a time schedule as described earlier. The yield coefficient (Y) of the SBR stage-I&II cycle was 0.4 gg-1, while the endogenous respiration coefficient (kd) was: 0.035 d-1.The full-scale SBR stage-I&II was designed with 6 days total HRT and 3 days at each stage, operating in an extended aeration mode with 2 Nos. each for SBR stage-I(14.2×14.2 ×5.5) and SBR stage-II(13.5×13.5×5.5). The loading rates for SBR stage I&II were 0.750 and 0.083 kgBODm-3d-1, respectively. The oxygen demand for stage-I and stage-II was 2220 and 565 kgd-1O2-1, respectively. The power requirement to meet the oxygen demand of SBR stage-I&II was 150 kW. Conclusions Agrochemical effluent is composed of high concentration of ammonia-nitrogen, organic and inorganic matter. The effluent poses serious threat on aquatic on discharge environment, and hence essentially requires an effective bio-oxidation process. Feasibility of SBR system in two stages has studies, designed and implemented on full scale. Carbon management in the first-stage SBR and nitrogen in the second-stage SBR fends off microbial competition and improves the process stability through active interaction of substrates and bacteria that a single-stage conventional process often suffers. The full scale implementation demonstrates that the sequential batch reactor system is a techno-economically viable for treating agrochemical effluent. References 1. Akin, B.S., Ugurlu, A., 2005. Monitoring and control of biological nutrient removal in a sequencing batch reactor. Process Biochem. 40, 2873-2878. 2. APHA, 2005. Standard Methods for the Examination of Water and Wastewater, 21st ed. American Public Health Association, Washington, DC, USA. 3. Biswas, R., Bagchi, S., Urewar, C., Gupta, D., Nandy, T., 2010. Treatment of wastewater from a low-temperature carbonization process industry through biological and chemical oxidation processes for recycle/reuse: a case study. Water Sci. Technol. 61 (10), 2563-2573. 4. Delorenzo, M.E., Scott, G.L., Ross, P.E., 2001. Toxicity of pesticides to aquatic microorganisms: a review. Environ. Toxicol. Chem. 20, 84-98. 4 5. Karkare, M.V., Murthy, Z.V.P., 2012. Kinetic studies on agrochemicals wastewater treatment by aerobic activated sludge process at high MLSS and high speed agitation. J. Ind. Eng. Chem. 18 (4), 1301-1307. 6. Kim, Y.M., Park, D., Lee, D.S., Jung, K.A., Park, J.M., 2009. Sudden failure of biological nitrogen and carbon removal in the full-scale pre-denitrification process treating cokes wastewater. Bioresour. Technol. 100, 4340-4347. 7. Kim, Y.M., Park, H., Choc, K.H., Park, J.M., 2013. Long term assessment of factors affecting nitrifying bacteria communities and N-removal in a full-scale biological process treating high strength hazardous wastewater. Bioresour. Technol. 134, 180189. 8. Mace, S., Mata-Alvarez, J., 2002. Review of SBR technology for wastewater treatment: an overview. Ind. Eng. Chem. Res. 41, 5539-5553. 9. Manekar, P., Biswas, R., Manikavasagam, K., Nandy, T., 2011b. Novel two stage biooxidation and chlorination process for high strength hazardous coal carbonization effluent. J. Hazard. Mater. 189, 92-99. 10. Maranon, E., Vazquez, I., Rodríguez, J., Castrillon, L., Fernandez, Y., 2008a. Coke wastewater treatment by a three-step activated sludge system. Water Air Soil Pollut. 192, 155-164. 11. Maranon, E., Vazquez, I., Rodríguez, J., Castrillon, L., Fernandez, Y., Lopez, H., 2008b. Treatment of coke wastewater in a sequential batch reactor (SBR) at pilot plant scale. Bioresour. Technol. 99, 4192-4198. 12. Marttinen, S.K., Kettunen, R.H., Sormunen, K.M., Soimasuo, R.M., Rintala, J.A., 2002. Screening of physical–chemical methods for removal of organic material, nitrogen and toxicity from low strength landfill leachate. Chemosphere 46, 851-858. 13. Vazquez, I., Rodriguez, J., Maranon, E., Castrillon, L., Fernandez, Y., 2006. Study of the aerobic biodegradation of coke wastewater in a two and three-step activated sludge process. J. Hazard. Mater. 137, 1681-1688. 14. Yang, S., Yang, F., 2011. Nitrogen removal via short-cut simultaneous nitrification and denitrification in an intermittently aerated moving bed membrane bioreactor. J. Hazard. Mater. 195, 318-323. Table1:Physico-chemical characteristics (range) of Low TDS&high COD and high TDS & high COD Multi-streams effluent Parameters Low TDS and high COD High TDS and high COD 5 I&II 10.6-11.3 416-1270 2-68 1290-2020 7120-13760 4000-8780 280-616 2-15 pH Alkalinity SS TDS COD BOD Ammonia Phenols Process block IV 8.1-8.6 150-1860 2-74 1420-2120 1360-2880 2400-3166 11.2-56 10-114 III 9.1-10.3 184-1480 2-4 348-2370 3360-6640 2000-2800 380-716 10-119 I-IV 10.4-11.3 5300-14730 1650-6110 160000-253000 56280-84000 2114-3220 - All values are expressed in mgl-1, except pH. Table 2: Performance of existing Aerobic system vis-à-vis Inland Surface Waters discharge standard norms a Parameters Aerobic system Discharge Standard Inlet outlet pH 10.0-10.7 6.7-8.1 5.5-9.0 SS 100-200 41 -70 100 550-1502 250 COD 1750-6400 250-505 30 BOD 892-2995 Phenol 2.2-20.9 BDL-2.0 5 172 -400 50 Total NH3 -N 305-385 Indian Standards for discharge into Inland Surface Waters; All values are in mgl−1, except pH. a Effluent COD±65 Effluent BOD±20 Effluent Ammonia±40 BOD removal Effluent COD±25 Effluent Ammonia±4 Nitrite: BDL COD removal COD removal 100 25 days operation for each set of HRT 160 -1 600 500 80 400 300 70 200 60 100 0 50 2 3 140 120 90 100 80 80 60 40 70 20 0 4 60 1 HRT, days Per cent removal Effluent average concentration, mgl 90 1 100 25 days operation for each set of HRT Per cent removal Effluent average concentration, mgl -1 700 Effluent BOD±15 Nitrate±1 BOD removal Ammonia removal 2 3 4 HRT, days Fig.1. Performance of SBR stage-I at different HRTs. Fig.2. Performance of SBR stage-II at different HRTs. 6
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