Removal of residual organic matter, phosphates and ammonium from thermofilically digested pig manure

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1 Removal of residual organic matter, phosphates and ammonium from thermofilically digested pig manure D. Karakashev, J. E. Schmidt and I. Angelidaki* Institute of Environment & Resources DTU, Technical University of Denmark Bygningstorvet, Building 113, DK-2800, Kgs Lyngby, Denmark * Corresponding author. Phone: (+45) , Fax: (+45) , 1 dbk@er.dtu.dk 2 jes@er.dtu.dk 3 dbk@er.dtu.dk Abstract Full-scale anaerobic digestion of pig manure often resulted in liquid effluents with considerably high organic matter, ammonia and phosphates content. If not enough agricultural land is available, the disposal of this effluent requires additional treatment. Different process scheme for reduction of the organic matter and nutrients from thermofilically digested pig manure were tested in full-scale and lab-scale conditions. The steps tested were membrane microfiltration, anaerobic post-digestion, phosphates removal as struvite (PRS), partial oxidation and oxygen-limited autotrophic nitrification-denitrification (OLAND) process. However, microfiltration was unsuitable for treatment of digested pig manure due to membrane clogging Combination of thermophilic anaerobic digestion with sequential separation by decanter centrifuge and post digestion in UASB reactor reduced the organic content by 80 %. PRS process employing MgO for struvite formation was used for almost complete removal (96 %) of phosphates from digested pig manure. OLAND process succeeded to remove ammonium only from highly diluted digested manure with low organic matter content (around 2.5 g COD/L). Based on the results obtained, a conceptual scheme for treatment of pig manure is suggested. Keywords: anaerobic, digested pig manure, UASB, PRS, OLAND Introduction Pig farming is a major EU agricultural industry. Nowadays, farmers in the EU are confronted with an increasing number of environmental regulations concerning the application of the produced manure as a direct fertilizer on agricultural land. Other sustainable solutions for pig manure treatment need to be implemented with respect to environmental and agricultural benefits. Anaerobic codigestion of pig manure with other organic wastes in full-scale biogas plants offer several advantages such as renewable energy (methane) production, reducing pollution, odours and recycling of nutrients back to the soil (Verstraete and Vandevivere 1999). Due to stringent environmental regulation on animal waste in European Union, digested pig manure is regarded as potential environmental risk with respect to its still high biodegradable organic matter, phosphate and ammonium content. In order to manage this waste properly, the digested manure should be treated as wastewater to meet discharge standards. Up until now, only process schemes for anaerobic treatment of raw pig manure containing wastewaters have been developed (Sanchez et al., 1995; Hwang et al., 2006; Beal et al., 1999). Most advanced processes studied for organic matter (in means of chemical oxygen demand, COD), phosphates and ammonium removal were upflow anaerobic sludge blanket (UASB), phosphates removal as struvite (PRS, a process developed by Colsen BV in cooperation with Geochem, prof. Olaf Schuiling) (The removal of phosphates from anaerobic treated wastewater or effluent from digesters, through the production of usable fertilizer struvite ) and OLAND (oxygen-limited autotrophic nitrification-denitrification) (Kuia and Verstraete, 1998) respectivelly. UASB reactor technology has already been demonstrated for removal of organic matter from highly diluted (to 8 g COD.L -1 ) piggery waste supernatant (Sanchez et al., 2005). However this technology was not tested for direct treatment of digested undiluted manure with high COD content (more than 20 g COD.L -1 ). PRS was proved as a relatively simple and fast method compared to biological methods for phosphorus removal. Main advantage is that the nutrients (phosphates and ammonium) are also recovered as struvite (magnesium ammonium phosphate hexahydrate) which is commonly used as fertilizer. OLAND is a novel, promising, low-cost alternative to conventional denitrification systems where ammonium is converted to dinitrogen gas with nitrite as electron acceptor. OLAND offer advantages as energy saving, less sludge production and no extra organic carbon source needed.

2 It has never been used directly for ammonium removal from wastes with high organic content such as animal manures. Up until now, a feasible process for treatment of digested pig manure is not developed yet. Innovative technologies need to be implemented in order to find sustainable solution for removal of residual organic matter and nutrients from digested pig manure. The aim of the present investigation was to study possibility for COD, phosphates and ammonia removal from digested pig manure The processes used were membrane microfiltration and UASB process (COD removal), PRS process (phosphates removal), and OLAND process (ammonium removal) Materials and methods Substrate Anaerobically digested pig manure was obtained from a thermophilic (55 o C) full-scale biogas plant (Hegndal, Hemmet, Denmark). Plant treated pig manure together with small amount of fishprocessing industrial waste. Effluent was collected after decanter centrifuge operated at 5000 g to separate fibers from the liquid fraction. This substrate was used separately in the experiments for removal of organic matter, phosphates and ammonia. The average characteristics of the substrate are presented in Table1. Table 1. Characteristics of the digested pig manure Parameters Unit Average Value ± SD ph ± 0.1 TS g/l 21. 0± 0.9 SS g/l 5.2 ± 1.0 COD (total) g/l 23.0 ± N-NH 4 g/l 3.5 ± 0.4 N-total g/l 4.3 ± 0.08 P-total g/l 0.7 ± P-PO 4 g/l 0.3 ± 0.02 Equipment Submerged capillary membrane microfiltration unit (MRC SUR 2342, Mitsubishi, Japan) was installed in close proximity to biogas plant. The technical specifications of the unit were: membrane flux (max.)13.6 L.m -2.hr - 1, membrane surface1.5 m 2, flow per membrane10.2 L.hr - 1, element size 1,035 x 446 x13 mm. A lab-scale UASB reactor operated in semi-continuous mode was used for COD removal. The reactor operational parameters were: temperature 55 o C, total volume 334 ml, operating volume 255 ml, HRT 6 days. Reactor was inoculated with 0.05 L anaerobic granular sludge obtained from a potato factory (Kruiningen, Netherlands). Average organic loading rate of the reactor was 3.8 g COD.L -1.day -1. For removal of phosphates, PRS process was employed as described elsewhere (Beal et al., 1999). MgO was used for struvite formation. For removal of ammonium, OLAND process was employed using lab-scale UASB reactor (250 ml) operated in semi-continuous mode. OLAND reactor was seeded with sludge from an oxygenlimited autotrophic nitrification-denitrification (OLAND) process. The inoculum was supplied by Laboratory of Microbial ecology (Ghent University,Belgium). The reactor was operated at 35 o C with a working volume of 200 ml and HRT of 1 d. For start-up, the reactor was fed with a synthetic wastewater (Chamchoi and Nitisoravut, 2007) containing ammonia, nitrite and nitrate. Addition of pig manure digested to artificial wastewater was done gradually in 5 % increments to avoid inhibition of autotrophic ammonia-oxidizing bacteria to high organic loads. In order to increase the part of

3 manure that could be treated by OLAND process, a partial aeration step was tested. This part of the research is still on-going. Methane potential Determination of methane potential of the digested manure was done by DTU method, where acumulated methane in the headspace of closed vials was analysed by GC (Angelidaki and Sanders, 2004). Calculation of theoretical methane potential of digested manure was made according to COD content and Buswells formula (Buswell and Neave, 1930). Analyses Analytical determination of total COD, total solids (TS), suspended solids (SS), volatile solids (VS), volatile suspended solids (VSS), total- and ammonium nitrogen, total phosphorus, phosphates and ph was carried out according to Standard Methods (APHA, 1998). Results and discussion Anaerobically digested pig manure had still high COD, ammonium and phosphates content (Table 1) with respect to EU environmental legislations (Council Directive 96/61/EC concerning integrated pollution prevention and control). In order to find a sustainable solution for treatment of this waste membrane, microfiltration method was tested first. This method is widely used for removal of soluble nutrients from particles in wastewater treatment (Cheremisinoff 1994). Microfiltration was tested as a possible way to separate the digested manure into filtrate with low COD and suspended solids, containing mainly nutrients (nitrogen and phosphorus) and concentrate with high organic matter and solids content. The filtrate could be further treated to remove nitrogen and phosphorus while the concentrate could be rejected into anaerobic digester in order to maximize the methane production. A lot of technical difficulties on installation and start-up of the membrane were resolved successfully. Results obtained show that microfiltration lead to considerable reduction of TS - 50 %, total TSS- 98 %, VS 40 %, VSS - 95 % and total COD - 30 %. Slight decreases of total phosphorus, ammonium and total nitrogen was also observed. No reduction of soluble phosphorus was noticed. Maximal obtained outflow rate was 12 L filtrate per hour. However aeration of the membrane created foaming after 12 h of operation. Complete clogging of the membrane was observed after 3-4 days of operation. Back flushing with water failed to completely remove accumulated particles. Data obtained showed that the membrane was unsuitable for practical application. This resulted in a need to find another options for treatment of digested pig manure in order to remove residual COD, ammonium and phosphates. UASB reactor technology was tested for removal of organic matter from digested manure. In order to evaluate performance (organic matter removal efficiency) of the UASB reactor, methane potential experiments were carried out. Theoretical methane potential of the digested manure was 8 m 3 CH 4.m -3 waste. As the maximum methane potential obtained in this study was 5.5 m 3 CH4.m -3 waste, anaerobically degradable organic matter in the digested manure was around 70 %. This value was used to calculate degradable COD removal efficiency (Figure 1) according to detected COD removal values. Results obtained for steady state (Figure 1) showed high degradable COD removal efficiency, around 70 %. This proved UASB technology as a good option for organic matter removal from digested manure. Combination of thermophilic anaerobic digestion with sequential separation by decanter centrifuge and post digestion in UASB reactor resulted in 80 % organic matter removal from pig manure. This value is comparable with removal (90-95 %) of organic mater from wastewaters using UASB process (Metcalf and Eddy, 2003). However the UASB effluent had a still high organic content-around 10 g COD.L -1 and ammonium concentration around 1 g.l -1. No reduction in phosphate concentration was registered. Additional treatment of digested manure was needed to reduce phosphate and ammonia levels.

4 Degradable COD removal efficiency (%) Days Figure 1. Degradable COD removal efficiency of the UASB reactor. PRS process was employed for phosphates removal through chemical precipitation. Results obtained showed a very high phosphate removal, about 96 %. This was in agreement with other study showed a good PRS performance for removing phosphate in the effluents from anaerobic digestion (Yoshino, et al., 2003).At the same time, partial ammonia and total nitrogen removal (around 6 %) was observed. According to stoichiometrical equation of struvite formation, ammonia consumption by struvite formation reaction was lower than the reduction of ammonium probably due to ammonia stripping Ammonium (NH 4 ) can be easily converted into ammonia (NH 3 ) when ph increased during chemical precipitation. COD decreased slightly over the process and practically no change in total solids and suspended solids was noticed. For removal of ammonium OLAND process was used. In our experiments, ammonium removal varied between 80 and 90 % when up to 10 % solution of digested manure in nitrite containing artificial wastewater was used. OLAND processed failed to remove ammonium when 20 % solution of digested manure was introduced. This was due to the increased C: N ratio resulted in inhibition of the autotrophic ammonia oxidizers. Presently we are testing a partial aeration step, previous to OLAND step. This process is developed by Ughent and Colsen and is patented as NAS (new activated sludge) process. During this step, excess organic matter will be removed and partial oxidation of ammonia to nitrite will take place. More attempts and strategies are needed in order to adapt anaerobic ammonia-oxidizing bacteria to real manure wastewaters. On the results obtained for removal of COD, ammonium and phosphates, a principal flowchart for whole process of pig manure treatment is suggested (Figure 2). After anaerobic digestion and decantation, liquid manure fraction could be processed in a UASB reactor for reduction of residual COD combined with biogas production. The effluent from this step could further be processed for complete removal of phosphates as struvite. Finally, residual ammonium (after partial aeration step for nitrite formation) could be degraded to dinitrogen gas in OLAND process by anaerobic ammoniaoxidizing bacteria adapted to high organic loads. However, more investigations are needed to clarify the economical feasibility of such a process scheme.

5 Biogas Residual biogas Air Dinitrogen gas Anaerobic digestion Decantation UASB PRS Partial aeration OLAND Pig manure Fibers Struvite Effluent Figure 2. Principal flowchart of a possible pig manure treatment process. Conclusions Anaerobic digestion of pig manure resulted in digested effluents with high organic matter, phosphates and ammonium content. UASB technology can be applied as a method for removal of residual COD combined with renewable energy (methane) production. PRS treatment was found to be an excellent process for almost complete removal of phosphates. However, more attempts are needed in order to find a way for adaptation of anaerobic ammonia oxidizers to high organic content of digested manure. Acknowledgements The financial support of PIGMAN project (grant SME ) is gratefully acknowledged. We also would like to thank Emiliano Bruni, Francesc Juan Roca and Zhenwei Zhu for their participation in the experimental work. References Angelidaki I. and Sanders W. (2004) Assessment of the anaerobic biodegradability of macropollutants. Reviews in Environmental Science and Bio/Technology, 3, Beal L.J, Burns R.T., Stalder K.J. (1999). Effect of anaerobic digestion on struvite production for nutrient removal from swine waste prior to land application. ASAE Annual international Meeting, July 18-21, Toronto, Canada. Buswell E.G., Neave S.L. (1930). Laboratory studies of sludge digestion. Illinois Division of State Water Survey, Bulletin No. 30. Chamchoi N, and Nitisoravut S. (2007).Anammox enrichment from different conventional sludges. Chemosphere, 66 (11), Cheremisinoff P.N.(1994). Handbook of water and wastewater treatment technology. Marcel Dekker Inc. Council Directive 96/61/EC of 24 September 1996 concerning integrated pollution prevention and control. (accessed 21 March 2007). Hwang L.S., Min K.S., Choi E., and Yun Z. (2006). Resource recovery and nitrogen removal from piggery waste using the combined anaerobic processes. Wat. Sci. Technol., 54 (8), Kuai L. and Verstraete W. (1998). Ammonium Removal by the Oxygen-Limited Autotrophic Nitrification- Denitrification System. Appl. Env. Microb. 64 (11), Metcalf and Eddy (2003). Wastewater engineering: treatment and reuse. 4 th edition, McGraw-Hill, Canada. Sanchez E., Borja R., Travieso L., Martin A., Colmenarejo M.F. (2005). Effect of organic loading rate on the stability, operational parameters and performance of a secondary upflow anaerobic sludge bed reactor treating piggery waste. Biores. Technol., 96, Sanchez E., Monroy O., Canizares R.O., Travieso L. (1995). Comparative study of piggery waste treatment by upflow sludge beds anaerobic reactors and packed bed reactors. J. Agric. Eng. Res., 62, The removal of phosphates from anaerobic treated wastewater or effluent from digesters, through the production of usable fertilizer struvite. Flyer_alternative_phosphorus_removal_by_Anphos.pdf (accessed 21 March 2007). Verstraete W., and Vandevivere P. (1999). New and Broader Applications of Anaerobic Digestion. Crit. Rev. Env. Sci. Tech.29 (2),

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