Experience from start-ups of the first ANITA Mox Plants M. Christensson1, S. Ekström1, A. Andersson Chan2, E. Le Vaillant1 and R. Lemaire3 1 AnoxKaldnes AB, Klosterängsvägen 11A, 226 47 Lund, Sweden ([email protected]; [email protected]; [email protected]). 2 Tekniska Förvaltningen, Box 1222 351, Växjö, Sweden ([email protected]) 3Veolia Water Technical Department, 1 rue Giovanni Battista Pirelli, 94417 St-Maurice, France ([email protected]) Abstract ANITA Mox is a new 1-stage deammonification MBBR developed for partial nitrification to nitrite and autotrophic N-removal from N-rich effluents. This deammonification process offers many advantages such as dramatically reduced oxygen requirements, no COD requirement, lower sludge production, no pre-treatment or requirement of chemicals and thereby being an energy and cost efficient nitrogen removal process. An innovative seeding strategy, the “BioFarm concept” has been developed in order to decrease the start-up time of new ANITA Mox installations. New ANITA Mox installations are started with typically 3-15% of the added carriers being from the “BioFarm”, with already established anammox biofilm, the rest being new carriers. The first ANITA Mox plant, started up in 2010 at Sjölunda WWTP in Malmö, Sweden, proved this seeding concept, reaching an ammonium removal rate of 1.2 kgN/m3.d and approximately 90% ammonia removal within 4 months from start-up. This first ANITA Mox plant is also the BioFarm used for forthcoming installations. Typical features of this first installation were low energy consumption, 1.5 kW/NH 4Nremoved, low N2O emissions, <1% of the reduced nitrogen and a very stable and robust process towards variations in loads and process conditions. The second ANITA Mox plant, started up at Sundets WWTP in Växjö, Sweden, reached full capacity with more than 90% ammonia removal within 2 months from start-up. By applying a nitrogen loading strategy to the reactor that matches the capacity of the seeding carriers, more than 80% nitrogen removal could be obtained throughout the start-up period. Keywords Anammox, ANITA Mox, Deammonification, MBBR, Sidestream treatment INTRODUCTION With the raising awareness on energy savings, anaerobic sludge digestion is now one of the key processes leading towards energy-neutral or even energy producing WWTP. The drawback is the increased ammonium concentration in the sidestream reject water that is recycled to the inlet of the WWTP, which may constitute up to 20-30% of the overall incoming N load. In order to prevent costly extension of the aeration capacity and the size of aerobic/anoxic tanks, together with increased consumption of expensive external carbon sources, dedicated sidestream treatment processes using autotrophic N-removal through anaerobic ammonium oxidation (anammox) have gained increased popularity seen as a long-term solution, especially when considering energy- and cost-effectiveness. Compared to conventional nitrification/denitrification processes, autotrophic Nremoval processes (i.e. anammox-type processes) offer many advantages such as (i) 60% reduction of O2 demand, (ii) no COD requirement and (iii) lower sludge production. Due to the very slow growth rate of anammox bacteria, different biofilm N-removal processes, with or without support material, have been developed as 2-stage systems, such as combined SHARON / Anammox-granular process (Abma, 2007) and 1-stage systems, also referred to as “Deammonification” process, such as granular Sequencing Batch Reactors (SBR) (Wett, 2007; Vlaeminck, 2008; Vazquez-Padin, 2009) or Moving-Bed Biofilm Reactors (MBBR) (Rosenwinkel, 2005; Cema, 2009). The ANITA Mox process is a 1-stage MBBR deammonification process where partial nitrification to nitrite by ammonia oxidizing bacteria (AOB) and autotrophic N-removal by anammox bacteria occur simultaneously within the aerobic and anoxic zones of the biofilm resulting from oxygen mass transfer limitation under limited dissolved oxygen (DO) condition. The biological processes taking place inside the biofilm developed on the plastic carriers are illustrated in Figure 1. NH4+ Liquid N2 Nitritation AOB NO2 Anammox Biofilm Carrier - O2 Aerobic Anoxic Figure 1. Schematic of 1-stage nitritation/anammox biological processes occurring inside a carrier’s biofilm. AOB oxidize NH4 to NO2 in the aerobic zone of the biofilm (i.e. outer part) while anammox bacteria located in the anoxic zone of the biofilm (i.e. inner part) consume NO2 produced by AOB together with the excess NH4. The very slow growth of anammox bacteria and sensitivity towards high concentrations of oxygen, nitrite/free nitrous acid and free ammonia during the start-up phase has been widely reported and therefore limit a widespread application of anammox type processes. To shorten the start-up phase, new ANITA Mox processes are seeded with a small fraction of colonized carriers, which reduce the time required for the development of a mature deammonification biofilm on the brand new carriers. The concept of seeding has proven to dramatically decrease the start-up time from up to a year down to 2-3 months depending on the amount of seeding (Christensson et al., 2011, Lemaire et al., 2011) and are in contradiction with studies by Schneider et al. (2009) reporting that seeding with fully functional deammonification biofilm was not an efficient start-up strategy for MBBR deammonification systems. To meet the request for seeding carriers, the first ANITA Mox full-scale plant at Sjölunda WWTP is used as a nursery for anammox bacteria growing on suspended carriers, referred to as the “BioFarm”. An add-on feature to the ANITA Mox is the real-time DO control strategy, where nitrite production is maximised without nitrite being further oxidized to nitrate. A control loop continuously calculates the amount of NO3-Nprod/NH4-Nrem. based on signals from online sensors in the inlet and outlet of the reactor. If the NO3-Nprod/NH4-Nrem.-ratio is higher than 11% it indicates that there is oxygen available in excess favouring nitrite oxidizing bacteria, why DO set-point should be decreased, and vice-versa, if the NO3-Nprod/NH4-Nrem.-ratio is lower than 11%, DO set-point should be increased to further increase NH4-removal. This paper presents experiences from start-up and operation of the first ANITA Mox implemented in full-scale at Sjölunda WWTP in Malmö and from the second installation at Sundet WWTP in Växjö. The Sjölunda WWTP (550,000 PE) has a total capacity of 40 tBOD7/d and a maximum hydraulic capacity of 4.4 m3/s to the biological treatment (Mases et al. 2010). Approximately 60% of the reject water is treated by an existing SBR (1,920m3) operated in nitritation mode only and the remaining 40% representing around 200 kgN/d is today treated by a full-scale ANITA Mox plant (200m3). The Sundet WWTP (80 000 PE) has a total capacity of 5.5 tBOD7/d and a maximum hydraulic capacity of 0.8 m3/s to the biological treatment. Today, only primary sludge and biological sludge are digested in two mesophilic anaerobic digesters, but in a near future external substrates (food residuals) will be co-digested, hygienizated and digested a second time in a newly built digester. After dewatering, all reject water is treated in the ANITA Mox process. METHODS Design parameters of full-scale ANITA Mox plant at Sjölunda WWTP and Sundet WWTP The full-scale plant at Sjölunda WWTP consists of 4 MBBR with a total volume of 200m3. The individual 50m3 reactors are 6m high, made of fibre glass, fully covered and insulated and can be operated independently or in series. BiofilmChip™M K3 and Anox™ K5 carriers (AnoxKaldnes, Sweden) have so far been used in these MBBRs. NH4+, NO3-, pH and TSS are measured on-line (WTW, Germany) in the reject water feed and inside each reactor. Airflow and dissolved oxygen (DO) are also measured and controlled in each reactor. An off-gas online analyser (Horiba, Japan) was used for oxygen transfer trials and determination of potential N2O emission. The main design and operating parameters of the ANITA Mox reactors are presented in Table 1 and the reject water composition and sludge dewatering operation are detailed in Table 2. Table 1 Design and operating parameters of full-scale ANITA Mox MBBRs Parameters ANITA Mox Sjölunda ANITA Mox Sundet Volume 4 x 50m3 (=200m3) 350m3 Design N-load 200 kgN/d 320 kgN/d (first phase) 430 kgN/d (second phase) Carrier type BiofilmChip™ M / K3 / Anox™ K5 Anox™ K5 Temperature 22-33 °C (no control) 22-33 °C (no control) pH 6.7-8.0 (no control) 6.7-7.5 (no control) DO 0.5-1.5 mgO2/L (advanced 0.5-1.5 mgO2/L (advanced DO control DO control strategy) strategy) Start-up August 2010 November 2011 The full-scale plant at Sundet consists of a single 350m3 covered reactor. It is a refurbished SBR, using the existing fine-bubble aeration system and with two 4 kW STAMO mixers. 43% Anox™ K5 carriers was added to meet the first design phase. NH4+ and pH are measured on-line (WTW, Germany) in the inlet reject water feed and NH4+, NO3-, pH, DO inside the reactor. Table 2. Reject Water characteristics at Sjölunda WWTP and Sundet WWTP Characteristics Units Sjölunda Reject Water Sundet Reject Water Type of sludge digested -primary + secondary sludge primary, secondary and 20% external sludge Total flow m3/d 650 (160 ; 126)* 144 1) * NH4 mgN/L 855 (148 ; 75) 1,043 1) * CODs mg/L 257 (67 ; 22) BOD7 mg/L 147 (73 ; 16)* HCO3 mg/L 4,570 (130 ; 111)* 4,6502) TSS mgSS/L 330** 355 2) * mean (SD ; sample number); ** mean (from operator since 2006) 1) mean 2009-2011, 2) mean 2011, Analysis Mixed liquor samples were filtered at 1.6 µm before analysis for NH4+, NO3-, NO2- and soluble COD using Dr Lange kits (Hach Lange, Germany). TSS were analysed according to the standard methods (APHA, 1995). RESULTS AND DISCUSSION Due to limitations of seeding media available and in order to optimize the start up procedure, the 4 ANITA Mox reactors at Sjölunda WWTP were started up at different time. In 2010 the first 50m3 ANITA Mox full-scale reactor (MBBR1) was filled with 40% BiofilmChip M (BCM) carriers and seeded with 0.9m3 pre-colonised carriers with anammox activity corresponding to 3% of the overall volume. After 3 months of operation, effluent NH4 was typically below 100 mgN-NH4/L except after occasional incidents of power failure (e.g. day 280), see Figure 2. The nitrate level in the outlet was also on average below 100 mgN-NO3/L and the ratio NO3-produced : NH4-removed was in the range of 8-22% (Figure 2c) which is close to the stoechiometric ratio (i.e. 11%) if nitrate was only produced by anammox bacteria with no further oxidation of nitrite into nitrate by the nitrite oxidizing bacteria (NOB) and no reduction of nitrate by heterotrophic denitrifiers. The real-time DO control strategy developed for the ANITA Mox process was very successful in limiting the activity of NOB in the system and therefore ensuring that most of the nitrite produced by the AOB is actually used by the anammox bacteria. The nitrite concentration in the outlet was always very low (i.e. < 5 mgN-NO2/L) although transitory accumulations of nitrite up to 120 mgN-NO2/L were observed during the start-up period with no real impact on the MBBR performances. The fact that nitrite was barely present in the MBBR indicates that the system was likely NO2 limited and that the anammox activity was limited by the supply of NO2 from the AOB. The N-loading and NH4-removal rate was increased steadily from the start-up as shown in Figure 2b. After only 4 months operation and with only 3% of seeding material, NH4-removal rate reached 1.2 kgN/m3react.d (Figure 2b) with approximately 90% NH4 removal efficiency (Figure 2c). These performances were obtained (i) without any pre-treatment of the reject water, (ii) without any chemical addition of methanol, acid or base solution, (iii) with no need for mechanical mixers in the MBBR (i.e. continuous aeration strategy sufficient for mixing carriers) and (iv) without any heating system even during the winter months in Sweden. Between operation day 280-450 the N-loading and removal rate decreased to 0.70 – 1.1 kgN/m3day and then increased back to its initial capacity of 1.2 kgNH4-N/m3d, Figure 2b. The period with lower N-loading and removal rates coincides with issues with reject water supply but also with the warmer summer months where the process temperature increases from around 27-29 °C up to 33 °C. It seems like the better performances that are observed from operation day 450 are also related to the process temperature returning to below 30 °C from mid November 2011 (operation day 450). In spite of variation in N-load the NH4removal stayed high, typical > 90% for the entire operation period. Long term operation of the MBBR1 at Sjölunda WWTP has proven the ANITA Mox to be a robust and stable process towards variations in loads of reject water supply, variations in suspended solids, power failure and pump issues typical encountered at treatment plants and still maintaining high ammonium removal capacity. High energy efficiency, with a power consumption of 1.45-1.75 kWh/kgNH4-N, and low carbon footprint, with average N2O emissions in the range of 0.2 – 0.9% of the reduced nitrogen, were obtained in MBBR1 making the ANITA Mox a sustainable solution (Christensson et al., 2011). 50 100 150 200 250 300 350 400 450 500 550 600 1,2 30 1,0 25 0,8 20 0,6 15 0,4 NH4-N load NH4-N removal Temp 0,2 0,0 NO3-N, NO2-N out (mgN/L) 5 0 80 600 45 40 70 35 90 0 % NH4-N & TN removal 10 50 100 150 200 250 300 350 400 450 60 500 550 % NH4-N removal % TN removal % NO3-N produced 50 40 30 25 20 30 15 20 10 10 5 0 % NO3-N produced N-load & removal rate (kgN/m3.d) 0 260 240 220 200 180 160 140 120 100 80 60 40 20 0 35 Temp C NH4-N in NH4-N out NO3-N out NO2-N out NH4-N in & out (mgN/L) 1300 1200 1100 1000 900 800 700 600 500 400 300 200 100 0 1,4 0 0 50 100 150 200 250 300 Days 350 400 450 500 550 600 1,4 35 1,2 30 1,0 25 0,8 20 NH4-N load NH4-N removal Temp 0,6 15 0,4 10 0,2 5 0,0 Temp C N-load & removal rate (kgN/m3.d) Figure 2. Performances of the first 50m3 MBBR filled with 40% BCM since start-up: NH4, NO3 and NO2 measured in inlet and outlet (a); NH4 loading and removal rates (kgN-NH4/m3reactor.d) and T°C in the MBBR (b); % TN and NH4 removal and ratio NO3-produced : NH4-removed in % (c). 0 0 20 40 60 80 100 120 140 160 180 Days Figure 3. Temperature, NH4-N load and removal rates in MBBR4 from the BioFarm during restart after 20m3 of colonised K5 carriers were taken out to seed the ANITA Mox process at Sundet WWTP. During 2010-2011 the remaining ANITA Mox reactors at Sjölunda were taken into operation using different carriers and seeding percentage. Figure 3 shows the N-loading and removal rate after the second start-up of MBBR 4 on Day 308 when 20m3 of Anox K5 carriers (i.e. corresponding to 80% of the total media amount in the reactor) were taken out in order to seed the reactor at Sundet WWTP for fast start-up. When 20m3 of new K5 carriers were added to the remaining 5m3 of precolonized anammox carriers left in the reactor, removal rate reached back to 1 kgN/m3d after only 2 months of operation and is still increasing to more than 1.2 kgN/m3d (Figure 3). NH4-N in NH4-N out NO3-N out NO2-N out 40 60 80 100 120 140 160 180 35 1,2 30 1,0 25 0,8 20 NH4-N load 0,6 15 0,4 10 0,2 5 90 0 20 40 60 80 100 120 140 160 0 180 45 80 40 70 35 60 % NH4-N removal % TN removal % NO3-N produced 50 40 Temp C 20 0,0 % NH4-N & TN removal 260 240 220 200 180 160 140 120 100 80 60 40 20 0 30 25 20 30 15 20 10 10 5 0 % NO3-N produced N-load & removal rate (kgN/m3.d) NH4-N in & out (mgN/L) 1300 1200 1100 1000 900 800 700 600 500 400 300 200 100 0 1,4 0 NO3-N, NO2-N out (mgN/L) Performance of ANITA™ Mox full-scale plant at Sundet WWTP The ANITA Mox process was started up at Sundet WWTP by seeding with 20m3 K5 carriers from the BioFarm on the 6th of December 2011. The seeding media corresponds to 13% of total carrier filling degree. Since the process was started up during the coldest winter months, the temperature was kept around 28°C by batch wise heating of water when needed during the first month of operation. To promote growth of anammox bacteria the reactor was fed with an amount of reject water corresponding to an ammonium load slightly higher than the capacity of the seeding media. The influent flow was continuously increased and the total amount of reject water was treated in the ANITA Mox process after only 2 months of operation. Influent ammonium concentration to the ANITA Mox reactor varied between 820-1100 mgNH4-N/L.From the first day of operation the effluent NH4-N concentration has always been below 220 mgNH4-N/L with an average NH4-N removal of 88% (Figure 4a&c). Nitrate concentrations in the MBBR outlet have been in the range of 16-88 mgNO3-N/L which corresponds to a ratio 2-8.2% of produced NO3-N to NH4-N removed, see (Figure 4a&c). One nitrite peak, corresponding to 60 mgNO2-N/L has been observed during the operation period, otherwise the effluent NO2-N have an average concentration of 2.9 mgNO2-N/L (Figure 4a). 0 0 20 40 60 80 100 120 140 160 180 Days Figure 4. Operation results ANITA Mox Sundets WWTP, NH4, NO3 and NO2 measured in inlet and outlet (a); NH4 loading and removal rates (kgN-NH4/m3reactor.d) and T°C in the MBBR (b); % TN and NH4 removal and ratio NO3-produced : NH4-removed in % (c). The nitrogen load on the process has increased from 0.01 to 0.83 kgN/m3d, which corresponds to an increasing nitrogen removal from 0 to 0.63 kgN/m3d, (Figure 4b). An overall nitrogen removal over 84% has been maintained since the process start-up (Figure 4c). Relatively low loading and removal rates in kgN/m3d at Sundet WWTP are explained with present shortage of reject water supply at the WWTP compared to the design load and not due to poor process performance as could be seen at the restart of MBBR4 where the seeded carriers original came from (Figure 3). N2O measurements performed during 10 days in May 2012 shows that the N2O emissions from the ANITA Mox unit at Sundet WWTP corresponds to an average of 0.75% of nitrogen removed. The highest N2O emission recorded during the period equals to 3.1% of nitrogen removed and N2O in the off gas varied between 0-163 ppm. The study shows that the process tends to emit least N2O during stable operation without any disturbances and a DO concentration > 1 mgO2/L. Daily averages shows that operation at a DO concentration < 1 mgO2/L can give rise to N2O emissions corresponding up to 2.15% of nitrogen removed while stable operation with a DO concentration > 1 mgO2/L can allow low daily averages of N2O emissions down to 0.06% of reduced nitrogen. Figure 5 illustrates emitted N2O in percentage of nitrogen removed together with effluent NH4-N, NO3-N and DO concentrations in mg/L during two 24 hour periods from the 23rd to 24th and from the 29th to 30th of May. The graphs of DO and emitted N2O from the first 24 hour period indicates that the aeration of the process is disturbed and that the disturbance occurs more frequently between midnight of the 23rd and noon on the 24th (four times) where N2O emissions above 1% of reduced nitrogen are measured directly after the unaerated period. The disturbance in aeration occurs less frequently after noon until midnight of the 24th (two times) and Figure 5a shows that the N2O emissions tend to decrease as the process is operated during longer periods without disturbances, the N2O emissions measured after noon on the 24th have peaks corresponding to 0.8% of nitrogen removed and low concentrations of less then 0.1% is recorded through longer periods. Figure 5b shows a 24 hour period where aeration of the process is undisturbed and the N2O emissions are low in the range of 0.04-0.16% of nitrogen removed. 80 NH4-N out NO3-N out % NO2-N produced DO conc. 2 60 50 40 1 30 20 % N₂O-N prod, DO conc. NH4-N & NO3-N out 70 10 2012-05-23 12:00 Days 2012-05-23 18:00 0 2012-05-24 00:00 2 NH4-N & NO3-N out 130 120 110 100 90 80 70 60 50 40 30 20 10 0 2012-05-29 18:28 2012-05-23 06:00 1 2012-05-30 00:28 2012-05-30 06:28 Days 2012-05-30 12:28 % N₂O-N prod, DO conc. 0 2012-05-23 00:00 0 2012-05-30 18:28 Figure 5. Typical concentrations of effluent NH4-N, NO3-N, DO and emitted N2O given in percentage of reduced nitrogen during two 24 hour periods from the ANITA Mox plant at Sundet WWTP. CONCLUSION • The ANITA Mox process is a very robust MBBR deammonification technology to address issues of increasing N-load on WWTP coming from advanced sludge treatment processes while reducing the overall carbon footprint and tending towards energy-sufficiency. • The specific start-up strategy, where carriers with already colonized anammox biofilm were seeded to the ANITA Mox process, shortened start-up time to 2 months at Sundet WWTP and 4 months at Sjölunda WWTP, reaching a N-removal rate of 1.2 kgN-NH4/m3reactor.d with 90% NH4 removal efficiency • Carriers with very large protected surface area, such as BiofilmChip M and Anox K5, are well suited for deammonification processes as it creates a dense and compact biofilm with high anammox activity allowing for smaller reactor design. • The average N2O-emissions from the ANITA Mox process (i.e. 0.2-0.9% of N-removed) is in the low range of what has been previously reported from different full-scale sidestream anammox processes. ACKNOLEDGMENTS The authors would like to acknowledge all the personnel at Sjölunda WWTP (Malmö, Sweden) and Sundet WWTP for their kindly assistance with the ANITA Mox operation. REFERENCES APHA (1995). Standard methods for the examination of water and wastewater. 19th edn, American Public Health Association, Washington DC, USA. Abma W., Schultz C., Mulder J., van der Star W., Strous M., Tokutomi T. and van Loosdrecht M. (2007). Fullscale granular sludge Anammox process. Wat. Sci. Tech., 55(8/9), 27-33. Cema G. (2009). Comparative study on different Anammox systems. PhD Thesis, KTH Stockholm. Christensson M., Ekström S., Lemaire R., Le Vaillant E., Bundgaard E., Chauzy J., Stålhandske L., Hong Z., and Ekenberg M. (2011). ANITA Mox -A BioFarm solution for fast start-up of deammonifying MBBRs. Conference Proceedings WEFTEC 2011, Los Angeles. 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