Process Biochemistry 40 (2005) 177–182 Wastewater treatment with combined upflow anaerobic fixed-bed and suspended aerobic reactor equipped with a membrane unit B. Kocadagistan a , E. Kocadagistan a,∗ , N. Topcu b , N. Demircioǧlu a a Faculty of Engineering, Department of Environmental Engineering, University of Ataturk, Erzurum, Turkey b Faculty of Education, University of Celal Bayar, Manisa, Turkey Received 14 August 2003; accepted 29 November 2003 Abstract A combined upflow anaerobic fixed-bed (UAF-B), using pumice as a biofilter material, and a suspended aerobic activated sludge bioreactor (SAR) equipped with a microfiltration (MF) unit has been designed. This system exhibited high performance on the removal of organic matter. COD removal efficiencies were in the range of 94–98.7% with organic loading rates (OLR) of 3.67–16.56 kg COD m−3 per day. Phosphorous and nitrogenous materials were removed from the wastewater as well as COD. High PO4 -P removal efficiencies (96–97%) were achieved in this study. NO2 -N and NO3 -N concentrations in the effluent of MF were less than 1.0 mg l−1 through most experiments. Suspended solid concentrations measured in the effluent were below the detectable levels. Biofilm development and microbial communities were investigated using scanning electron microscopy (SEM). © 2004 Elsevier Ltd. All rights reserved. Keywords: Pumice; Membrane; Upflow anaerobic fixed-bed (UAF-B); Biofilter; Phosphate removal 1. Introduction Fixed-film anaerobic reactors have been widely used for the treatment of high strength wastewaters. In fixed-film anaerobic reactors, large amount of biomass remains in the filter to secure solid retention despite a short hydraulic retention times. These reactors have several advantages over aerobic and anaerobic reactors such as higher organic loadings, lower hydraulic retention times and smaller reactor volumes. Lower sludge and suspended solid quantities can also be achieved in these reactors. Many different materials have been studied as filter support media including baked clay [1], RPF sheets [2], plastic tubes with diameter of 2 cm and length of 1.5–2 cm [3], PVC Raschig rings with a diameter of 2 cm and a specific surface area of 228 m2 /m3 [4], ceramic Raschig rings, wind ball and circular pipes [5]. The surface state of filter bed material, the pore size and the media geometries have been found to be important factors in treatment efficiencies of anaerobic ∗ Corresponding author. Tel.: +90-442-231-4808; fax: +90-442-231-4808. E-mail address: [email protected] (E. Kocadagistan). 0032-9592/$ – see front matter © 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.procbio.2003.11.055 fixed-bed reactors [6–9], while specific surface area and media porosities have been only minor [10–12]. Several studies have been performed by anaerobic filters for the treatment of high strength industrial wastewaters from the dairy, fermentation and sugar refining industries [12–14]. All these reports have shown that anaerobic fixed-film reactors were capable of treating high strength wastewaters. Furthermore, for the biological removal of nitrogenous, phosphorous and carbonaceous matter, combined systems should be used including anaerobic–aerobic fixed-bed and anaerobic expanded-bed reactors [15]. For this purpose many different treatment systems have been used. A combined anaerobic–aerobic fixed-film bioreactor has been tested for organic matter removal for 133 days and 92% removal efficiencies of organic matter removal achieved at an average of 0.39 kg COD/m−3 per day organic loading rates [16]. A bioreactor integrated to a membrane module system is usually referred to as a membrane bioreactor (MBR) [17]. Because MBRs have several advantages over conventional biological reactors, they have been found as convenient for water and wastewater treatment in the last decade. The MBR processes can be especially suitable for reuse and recycling 178 B. Kocadagistan et al. / Process Biochemistry 40 (2005) 177–182 of wastewater owing to their high-quality and disinfected effluents [17]. This article is focused on treatment of a synthetically prepared, high strength wastewater with a combined laboratory scale system consist of an anaerobic fixed-bed reactor filled with pumice as a filter bed media and an aerobic suspended sludge activated sludge bioreactor equipped with a crossflow microfiltration membrane unit. 2. Materials and method 2.1. Wastewater The wastewater, employed in this study, was prepared synthetically at various COD concentrations in the range between 250 and 5000 mg COD l−1 . The initial concentration of phosphorous and nitrogenous materials were also modified by altering the composition of wastewater (Table 1). 2.2. Reactors The experimental system is given in Fig. 1. It was composed of an up flow anaerobic fixed-bed reactor, a suspended aerobic activated sludge reactor (SAR) equipped with an MF unit. The synthetic wastewater was fed to the bottom of the Table 1 Composition of synthetic wastewater Chemical Amount (mg l−1 ) C6 H12 O6 CO(NH2 )2 MgSO4 CaCl2 KH2 PO4 K2 HPO4 FeCl3 COD 1000 227 100 7.5 52.7 107 0.5 1007 Fig. 1. Schematic view of experimental system. Table 2 The authentic characteristics of pumice used in this study [18] Parameters Values Chemical compound (%) SiO2 AlO2 Fe2 O3 Na2 O K2 O TiO2 Uniformity coefficient (D60 /D10 ) Effective grain size, D10 (mm) Porosity (%) Density (0.5–1.0 mm grain size) (g cm−3 ) 72.07 13.50 1.21 1.60 11.27 0.35 1.35 0.59 69.24 0.689 UAF-B reactor. The UAF-B reactor was a circular polyester column with an inner diameter of 10 cm and a total height of 100 cm. The working volume of this reactor was varied from 1 to 5 l depending on the hydraulic retention time. During the experiments nitrogen gas was used in the UAF-B reactor to strip oxygen and maintain anaerobic conditions. The dissolved O2 (DO) concentrations of UAF-B were measured as 0.1 mg l−1 during the experiments. This reactor was filled with pumice, which was supplied by Ercis, Turkey, as filter bed material. Pumice is used as a biofilm support material in water and wastewater treatment because of its high porosity and large surface area. It is a light and porous volcanic rock material formed during explosive eruptions. Pumice is riddled with pores of irregular or oval shape, which are usually not connected to each other. Italy, is the biggest pumice producer in the world (% 44 in total) and Turkey is the second (9% in total) [18]. The chemical composition of the pumice, obtained from an Electron Probe Microscopic Analyzer (EPMA), is given in Table 2. The SEM picture of pumice, before use in the UAF-B reactor, is shown in Fig. 2. Effluent, taken from the upper level of the UAF-B reactor, then passed to the SAR and aerated for achieving Fig. 2. SEM picture of pumice before filling to the reactor (upsizing: 400×). B. Kocadagistan et al. / Process Biochemistry 40 (2005) 177–182 aerobic digestion and phosphorus uptake with an airflow of 40–60 l h−1 [19]. The SAR has similar construction properties to the UAF-B and operated according to the principles of suspended growth activated sludge reactors. Because adequate mixing occurred in the SAR by the recycled water of the membrane unit (retentate), no mixing was applied to this reactor. While the UAF-B was operated under mesophilic conditions (35 ± 1 ◦ C) the SAR temperature was kept in the range between 18 and 20 ◦ C. Both the reactors were jacketed and temperature controlled by a Lauda thermostatic water bath. The SAR contents then taken from the bottom and recycled to the upper side of the reactor after passing through the crossflow MF unit with the aid of a circulating pump (1400 d min−1 , 0.75 kW centrifuge pump). The MF unit permeate is the effluent of the entire system. The influent rates were adjusted as equal to the MF permeate rate (in the range of 1–5 ml min−1 ) during all experiments, hence the wastewater inlet pump (Masterflex, L/S model peristaltic pump) was turned on after the permeate reached a stationary flow rate. Consequently, the working volumes of both UAF-B and SAR were fixed to required levels. A denitrified wastewater recycle line was placed to the UAF-B from the SAR to accomplish denitrification in the UAF-B reactor (1–4 times influent flow). The OLR of the UAF-B and SAR were in the range from 3.67 to 16.56 and 0.33 to 2.92 kg COD m−3 per day, respectively, in this study. The membrane filtration unit, manufactured in-house, was a flat type module with an effective surface area of 50 cm2 and the pore diameter of this cellulose acetate membrane sheet, produced by Schleicher & Schuel was 0.45 m. The pressure difference (P) used as driving force was required for the formation of crossflow regime and adjusted with two valves placed at the inlet and outlet line of the MF unit. The pressure differences were in the range from 0.2 to 1 kg cm−2 and the permeate fluxes obtained with this membrane module were 12 and 60 l m−2 h−1 for 1 and 5 ml min−1 effluent flow rates, respectively, in this study. 2.3. Experimental Samples were taken from the permeate flow of the membrane unit (the effluent of the experimental system) for evaluating the entire system performance and from the effluent of both reactors for evaluating each reactor performance. NO3 -N, NO2 -N, PO4 -P, COD and SS analyses were accomplished according to the Standard Methods [20]. pH, temperature and dissolved O2 were measured with a WTW, Multi 340i model multi parameter measurement apparatus. COD analyses were made by the aid of Dr. Lange, LT100 model thermo reactor and all of the analyses were carried out with an UV spectrophotometer (Shimadzu UV-160 A). The pH was manually controlled close to neutral pH by addition of 1.0 M of HCl or NaOH solutions. 179 2.4. Start-up period The UAF-B reactor was filled with pumice which was ground and sieved to 0.5–1 mm granule diameters. The UAF-B was first fed with a mixture of 1 l dewatered activated sludge taken from the wastewater treatment plant of Erzincan City of Turkey and synthetic wastewater as inoculum (1/1, volume/volume ratio). Nitrogen gas was injected with a diffuser system to the bottom of the UAF-B to maintain anaerobic conditions. Biogas production and biofilm formation were observed for 7 and 45 days, respectively, after this inoculation. Biofilm formation can be seen from the SEM picture of pumice (Fig. 3). The UAF-B reactor OLR values were increased progressively (in the range from 0.5 to 5 kg COD m−3 per day) to adapt the reactor microorganisms to high organic loading rates. The SAR was also filled with the above mentioned mixture and aerated continuously. The start-up period continued for 60 days. 3. Results and discussion The experimental system exhibited excellent performance for COD removal from the wastewater. 98.70% of COD removal efficiency was achieved (Fig. 4) under the following conditions: initial COD of 1150 mg l−1 and organic loading rate for UAF-B reactor of 4.14 kg COD m−3 per day. Because the influent COD concentrations of the SAR (effluent of the UAF-B) varied according to the treatment performance of UAF-B, the organic loading rates of SAR also fluctuated. When UAF-B was filled with pumice to a level of 4 l (51 cm height of the UAF-B), 0.8 l of wastewater was able to penetrate to the reactor and the hydraulic retention time was determined by considering this wastewater volume, existent in the UAF-B. Consequently, the hydraulic retention times (HRT) were 2.66 h for UAF-B and 13.33 h for SAR (the volume of SAR was 4 l), respectively, at 5 ml min−1 flow rate. As the OLR, applied to the UAF-B, was increased, there was a slight decrease in the COD removal of the system (Fig. 5). However, results showed that the removal rates were higher than those of classical systems although the OLR values increased up to the 16.56 kg COD m−3 per day. These COD removal rates were 98.39, 98.35, 97.88 and 94.00% for 5.58, 7.20, 9.00 and 16.56 kg COD m−3 per day organic removal rates, respectively. High removal rates at high OLR values achieved with membrane bioreactors were also reported by many researchers [21–23]. The PO4 -P concentrations of influent wastewater were varied (in the range 4–84 mg PO4 -P l−1 ) with altering the concentrations of KH2 PO4 and K2 HPO4 , in the synthetic wastewater. Phosphate release and uptake rates in the UAF-B and SAR are shown in Fig. 6. PO4 -P values increased from 5 to 115 mg l−1 , while the COD decreased from 634 to 254 mg l−1 in the UAF-B. SAR COD and 180 B. Kocadagistan et al. / Process Biochemistry 40 (2005) 177–182 Fig. 4. COD removal performance of the reactors. Fig. 5. The effect of OLR on COD removal efficiencies. PO4 -P concentrations were observed as 26 and 0.6 mg l−1 , respectively, at the end of the 24 h. COD and PO4 -P removal efficiencies of the entire system were determined as 97.4 and 96.25%, respectively. Similar data were observed in all the other experiments. PO4 -P removal efficiencies achieved in this study are given in Fig. 7. Nitrogenous matter removal performance of the entire system was evaluated with NO2 -N and NO3 -N concentrations of both UAF-B and SAR. NO2 -N concentrations of SAR Fig. 3. SEM pictures of pumice taken from UAF-B reactor after 2 months of operation (upsizing: a, 300×; b, 400×; c, 3000×; d, 8000×). Fig. 6. PO4 -P release and uptake together with COD removal (initial COD = 1000 mg l−1 ; initial PO4-P = 16 mg l−1 ). B. Kocadagistan et al. / Process Biochemistry 40 (2005) 177–182 181 4. Conclusions Fig. 7. The effect of initial PO4 -P concentrations on the PO4-P removal efficiencies. (MF effluent) decreased from 1.73 to 0.38 mg l−1 , while the concentration of UAF-B was 8.2 to 2.14 mg l−1 (Fig. 8). NO3 -N concentrations in both UAF-B and SAR decreased from 4.43 to 1.65 and 6.16 to 0.31 mg l−1 , respectively, in a period of 1.25 when the recycle flow from SAR to UAF-B was four times the influent flow rate (Fig. 8b). When no recycle was applied to the system (Fig. 8a), the effluent NO2 -N and NO3 -N concentrations were, respectively, 1.241 and 8 mg l−1 for SAR and 0.11 and 0.412 mg l−1 for UAF-B at the end of the same time period above. The influent nitrogen concentration was determined theoretically from CO(NH2 )2 which was the unique nitrogen source in the synthetic wastewater. Biological removal of carbonaceous, phosphorous and nitrogenous materials was investigated in a combined upflow anaerobic fixed-bed and suspended aerobic bioreactor equipped with a membrane unit. The following conclusions were drawn from this study. The experimental system was capable of simultaneous removal of the carbonaceous, phosphorous and nitrogenous materials. The COD removal efficiencies above 94% even though the OLR values were 16.56 kg COD m−3 per day. The best COD removal efficiency was 98%. These removal efficiencies were achieved with short HRT in the range 2.66–13.33 h. Since a high biomass content could be held in the UAF-B reactor, the volume of reactor was minimized and the hydraulic retention times were short. Phosphorous and nitrogenous materials were removed from the wastewater with this system as well as COD. PO4 -P removal efficiencies were obtained up to 99% and during most experiments NO2 -N and NO3 -N concentrations were low (in the range from 0.1 to 1 mg l−1 ) as compared with influent theoretical nitrogen concentrations. The recycle flow between SAR and UAF-B has an important role in the removal of nitrogen because the denitrification process cannot occur in the absence of NO3 . The denitrified water recycle line from SAR to UAF-B was connected to the system to supply NO3 to the UAF-B reactor. Since suspended solids and most of the bacteria cannot pass through the membrane filter, these parameters were not observed in the effluent (MF effluent) during the experiments. The pumice used in this study is a very cheap and readily available material in Turkey. Furthermore, it exhibited good performance as a fixed-bed material for microorganisms. It seems that, pumice is a practicable biofilter material. Consequently, it was considered that, the combined upflow anaerobic fixed-bed, formed with pumice, and suspended aerobic activated sludge bioreactor equipped with a crossflow membrane unit designed for this study is a useful system to treat high strength wastewaters. Acknowledgements This research was supported by the project (BAP-2001/43) of the Research Fund of Ataturk University and performed in the laboratories of Ataturk University, Engineering Faculty, Environmental Engineering Department. The authors would like to thank to the personnel of Scanning Electron Microscopy Laboratory of Engineering Faculty. References Fig. 8. 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