Performance of an integrated fixed bed membrane bioreactor (FBMBR) applied to pollutant removal from paper-recycling wastewater

Performance of an integrated fixed bed membrane bioreactor (FBMBR) applied to pollutant removal from paper-recycling wastewater

Water Resources and Industry 21 (2019) 100111 Contents lists available at ScienceDirect Water Resources and Industry journal homepage: www.elsevier...

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Water Resources and Industry 21 (2019) 100111

Contents lists available at ScienceDirect

Water Resources and Industry journal homepage: www.elsevier.com/locate/wri

Performance of an integrated fixed bed membrane bioreactor (FBMBR) applied to pollutant removal from paper-recycling wastewater

T

Ali Izadia, Morteza Hosseinia,∗, Ghasem Najafpour Darzia, Gholamreza Nabi Bidhendib, Farshid Pajoum Shariatic a

Department of Chemical Engineering, Babol Noshirvani University of Technology, Babol, P.O.B. 484, Iran Faculty of Environment, University of Tehran, Tehran, Iran c Department of Chemical Engineering, Science and Research Branch, Islamic Azad University, Tehran, Iran b

A R T IC LE I N F O

ABS TRA CT

Keywords: Fixed bed membrane bioreactor (FBMBR) Membrane fouling Transmembrane pressure (TMP)

Recently, new technologies regarding water and wastewater treatment have been developed and among these processes, the fixed bed biofilm reactor combined with membrane bioreactor is the recent alternative solution to conventional technologies. In this research, an integrated fixed bed membrane bioreactor (FBMBR) with a hydraulic retention time (HRT) of 36 h was developed to remove pollutants from real paper-recycling wastewater. The removal efficiencies of chemical oxygen demand (COD), ammonium, nitrite, nitrate and total nitrogen (TN) for permeate and supernatant were in the range of 92–99%, 59–97%, 78–97%, 59–98% and 68–92%, respectively. In addition, the membrane fouling was evaluated by transmembrane pressure (TMP) monitoring during experimental period at a constant flux of 12 l m−2.h−1, and the TMP increasing rate was 2 mbar/day. The results as a whole indicated that the FBMBR can be applied effectively to removal of pollutants from real paper-recycling wastewater.

1. Introduction Regarding the increase in human population, the demand for industrial establishments will increase. This event will cause some problems, such as over-exploitation of resources, which leads to environmental pollution [1]. Pulp and paper plants are a main sources of aquatic pollution and are considered the third most water intensive ones after metals and chemicals industries [2–4]. At different steps of pulp and paper production, more than 250 chemicals are produced and consequently observed in the wastewater. In addition, some serious environmental problems are caused by discharging untreated pollutants into the environment [1,5]. Different treatment technologies, which vary among mills, have been used in the processes of pulp and paper mills to diminish the negative effects of effluents on the environment [6–8]. The conventional method for treatment of paper mill wastewater includes a balance tank, a first sedimentation tank, an anoxicaerobic tank and a secondary sedimentation tank. In general, the conventional treatment could not fulfill the standards of water quality for the process of paper making and the final effluent has more than 40% organics with low biodegradability in the total organic matter content. Hence, the integrated membrane bioreactor has been applied in order to treat wastewater from paper mills



Corresponding author. E-mail addresses: [email protected] (A. Izadi), [email protected] (M. Hosseini), [email protected] (G.N. Darzi), [email protected] (G.N. Bidhendi), [email protected] (F.P. Shariati). https://doi.org/10.1016/j.wri.2019.100111 Received 6 December 2018; Received in revised form 13 April 2019; Accepted 15 April 2019 2212-3717/ © 2019 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/BY/4.0/).

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[9,10]. The application of this technology for both municipal and industrial wastewater treatment has been increased due to the need for more advanced wastewater treatment, stricter laws and scarcity of fresh water resources [11]. An MBR system integrates a physical separation with an activated sludge process by a membrane. This technique has a lot of benefits in comparison with conventional activated sludge (CAS) treatment, such as, high quality effluent, high disinfection ability, lower net sludge production, small footprint and also improved nutrient removal [12,13]. One of the most important advantages of a membrane bioreactor system is the complete biomass retention by the membrane, enabling the handle of sludge retention time (SRT) independently of the HRT [14]. Qu et al. [15] mentioned that an optimal value for COD removal from pulp and paper wastewater was the HRT of 1.1 ± 0.1 days and the main mechanism of membrane fouling was cake formation. To treat kraft pulp mill foul condensates, Dias et al. [16] used an MBR with an HRT of 19 h, and the results proved the technical feasibility and potential acceptability of this method at high temperatures for industrial applications. It was indicated that the treated wastewater by the integrated membrane process can fulfill all the standards of process water of paper mills and could be used again in paper manufacturing process [9]. The application of a thermophilic submerged anaerobic membrane bioreactor for kraft evaporator condensate treatment was investigated. The results revealed that this treatment process is a feasible way for biogas production and organic matter removal [17]. Membrane fouling is the main disadvantage of the application of MBR systems and considered as a function of operation condition [18,19]. In this phenomenon, the soluble and small particles penetrate into the membrane, and along with other inorganic and organic matters, are adsorbed into the membrane pores, reducing the permeate flux [20,21]. Therefore, extensive attempts have been made to explore mechanisms and consequently mitigation of membrane fouling in MBR systems. Studies show that membrane fouling results from interactions between foulants and membranes. Among complicated interactions, interfacial interactions have a particular importance because they directly determine the adhesion/deposition of various foulants on the surface of membrane, which is considered as the main source of fouling [22,23]. Evaluation of these interfacial interactions is crucial to understanding and controlling adhesion process and membrane fouling [24,25]. Quantification of interfacial interactions between particles provides a way to regulate the interface behaviors of particles related to adhesion, aggregation, flocculation and membrane fouling. Although existing methods are based on assumptions of smooth particles (although real particle surfaces are rather rough), a new method for randomly rough membrane surface modeling was proposed to quantify interfacial interactions between two rough particles, and it was found that ripple frequency and particle radius had profound effects on the interfacial interaction [26–28]. Moreover, the mechanisms of fouling caused by the gel layer has been investigated. Agar, which has a network structure, has been used as a model foulant for gel layer formation, and filtration resistance of gel layers was evaluated. The results showed that gel layer, as compared with cake layer, had unusually high specific filtration resistance (SFR) and high measured porosity. Its filtration resistance was independent of pH and ionic strength but linearly increased with gel thickness. From chemical potential viewpoint, a new mechanism was proposed to explain the high SFR of gel layer. The estimation based on Flory-Huggins theory showed that the filtration resistance induced by mixing chemical potential variation was comparable to that of the agar gel. The results suggested that the proposed mechanism is the major cause of high filtration resistance of the gel layer [29,30]. The effect of Ca2+ on the filtration behaviors of the alginate solution and its underlying mechanisms was evaluated. The filtration resistance of the formed gel layer and SFR of alginate solution showed a unimodal pattern with increase in Calcium ion concentration, and Flory-Huggins mechanism governed the extremely high SFR of the alginate gel [31]. The complete reduction of some recalcitrant organic matters can be hardly achieved in aerobic MBR systems while nitrification process could be assessed by these systems. However, for denitrification, some modifications such as modification of the reactor configuration (intermittent aeration and baffled membrane bioreactors), simultaneous nitrification and denitrification (SND) or the addition of an anoxic tank prior to the aeration tank are required [32,33]. In general, the integrated bioreactors, which combine aerobic and anaerobic degradation pathways in a single reactor are cost-effective and efficient. They also have smaller footprints as compared to the sequential anaerobic-aerobic systems [34,35]. An alternative to the conventional MBR, which consists of suspended biomass, involves the combination of the mentioned MBR with a biofilm reactor with attached biomass. If the biodegradation is carried out by suspended and attached biomass, the configuration is called a hybrid biofilm membrane bioreactor. A hybrid growth configuration is achieved when both suspended and biofilm biomass grow simultaneously in the same reactor or when there is external recirculation from the aerated membrane separation [33,36–38]. Moreover, many other researchers use the term hybrid MBR for an MBR combined with any other technologies, such as a granular activated carbon-sponge fluidized bed bioreactor (GACS-FBBR) and a nano-filtration unit [39,40]. Recently, hybrid MBR systems, which include sequential or alternating anoxic-oxic zones, have been applied successfully and been effective for removal of nutrients and organic matters [41–43]. The adjustment of dissolved oxygen (DO) in the integrated anoxic-oxic systems is an important parameter determining the success of removal of pollutants, and the concentration of biomass in the bioreactor has a strong effect on DO value [44–46]. The combination of biofilm support along with the membrane bioreactor has been proposed mainly to improve nutrient removal and reduce membrane fouling. Significantly better TN removal via simultaneous nitrification and denitrification was obtained by providing anoxic condition inside the biofilm [32,47]. The fast-growing heterotrophic biomass, including denitrifiers and PAOs, usually inhabit in the suspended activated sludge, while the slow growing nitrifying biomass preferentially live on biofilms. This feature promotes the optimization of simultaneous nitrogen and phosphorus removal processes [48]. The aim of the present study is to find out the overall performance of nutrients and organic matter removal in the integrated fixed bed membrane bioreactor (FBMBR) and evaluate fouling of membranes for treatment of real paper-recycling wastewater. 2

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Fig. 1. Schematic diagram of the demonstrative FBMBR pilot plant.

2. Materials and methods 2.1. Paper-recycling wastewater The samples of paper-recycling wastewater used in this study were collected from Kahrizak paper mill located approximately 10 km far from Tehran (Tehran province, Iran). The wastewater had COD of 1376–1607 mg/L and suspended solids (SS) of 1132–1321 mg/L. The wastewater also contained ammonia (NH4-N) and TN concentration of 35–134 mg/L and 132–190 mg/L, respectively. The pH of the wastewater was 7.3–7.7. 2.2. FBMBR reactor set-up and experimental process The configuration and operating conditions of FBMBR made of Plexiglas are all shown in Fig. 1 and Table 1. After the acclimation stage (about 20 days), the membrane bioreactor was operated for 48 days without discharging any excess sludge, except for small values (300 ml) for sampling and analyzing. The flux value was maintained constant by frequently adjusting the rotation rate of the Table 1 Operating conditions of the FBMBR. Parameter

Value

HRT (h) pH SRT (d) OLR (kg COD m-3 .d-1) Temperature (°C) MLSS (mg/L)

36 7–7.5 up to 48 0.91–1.1 20–25 4320–7500

3

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suction pump, and water level sensor was applied to maintaining the constant water level in the FBMBR. There was a recirculation pump which worked with recirculation of suspension. A Kubota A4, flat sheet microfiltration membrane made of chlorinated polyethylene (area 0.106 m2, pore size 0.4 μm) was used in the bioreactor. Air was supplied through a diffuser under the flat sheet membrane module. The aeration provides oxygen for the activated sludge, the driving forces for the circulation of the suspension inside the FBMBR and the membrane scouring. In order to monitor the variation of the TMP, the pressure gauge was installed between the effluent peristaltic pump and the membrane module [49]. The fixed biofilm support media used was made of rigid polypropylene (PP), and the high biofilm surface area in the FBMBR was obtained by adding the mentioned biofilm support media. The bottom of FBMBR was packed with granular activated carbon (GAC) media in order to make the biofilm grow, increase removal efficiency of pollutants [50] and prevent activated sludge precipitation in the bottom of the pilot. The performance of the FBMBR on the removal of pollutants was analyzed in terms of several conventional indexes of water and wastewater quality, including COD , NH4+, NO2−, NO3− and TN .

2.3. Analytical methods Effluent samples from the membrane permeate and the supernatant was used for analysis and comparison. According to Standard Methods, the concentrations of COD , SS , NH4+, NO2−, NO3− and TN were analyzed [51]. The pH value was measured with a pH meter (691 pH Meter, Metrohm). The TMP was monitored by a pressure gauge set between the membrane module and the suction pump.

3. Results and discussion 3.1. Organic carbon removal In Fig. 2, the variation in the COD concentration and removal efficiencies during operating time have been shown. It is obvious that the organic matter has been almost totally removed. The COD concentration in the permeate (CODp) was lower than 51 mg/L during the experiments and the overall removal efficiency of CODp remained over 96%, while COD removal in a conventional MBR was 80% [37]. The COD concentration in the supernatant (CODs) was in the range of 32–120 mg/L and removal efficiency of CODs was more than 92% during the operation time in the FBMBR. This high removal of CODp was not only due to biological activation in the FBMBR but also to membrane filtration. It was reported that the total removal efficiency of COD could be maintained over 92% regardless of the SRT in the MBR system. The high and stable COD removal could be achieved by the maintenance of higher TSS concentration in the bioreactor compared with conventional system, and also through the membrane separation of macromolecular COD components [52]. On the other hand, our results are in line with those obtained in a hybrid MBR treating raw domestic wastewater, 94.2% [32]. CODs value was more than CODp during the experimental period, confirming the beneficial influence of dynamic membrane on COD removal and the fact that this COD is the result of biological activity, which is in line with Qu et al. [53]. The high COD reduction shows that the continuous supply of organic matters in the feed is utilized by the microbial population. This is supported by the MLSS growth within continuous operation [54].

Fig. 2. COD concentration and removal efficiency in permeate and supernatant versus time in the FBMBR. 4

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Fig. 3. Performance of the FBMBR: (a) Nitrite and Nitrate and (b) Ammonium and TN removal efficiencies.

3.2. Nitrogen removal The concentrations of ammonium, nitrate, nitrite and TN in FBMBR during the experimental period are shown in Fig. 3. Generally, in order to convert nitrogenous substances to nitrogen gas, an anoxic and oxic environment is needed to make a proper nitrification/denitrification condition. Nitrite is a connecting point between nitrification/denitrification and the product of ammonia oxidation, which could not only be converted to nitrogen gas but also to nitrate via nitrification. Such coordination differs depending on bacterial species and the culture conditions [55]. Fig. 3 (a) indicates the concentration removal of nitrite and nitrate during system operation. It was observed that nitrite removal efficiencies were in the range of 78–97%, which indicates the most nitrite has converted, and nitrification has taken place. In addition, nitrate removal was more than 59%. Fig. 3 (b) demonstrates ammonia and TN removal efficiencies during FBMBR operation. The values of NH4–N removal percentage indicate that the nitrifying bacteria gradually accumulate in the bioreactor. The membrane in the bioreactors promoted complete retention and enrichment of nitrifier population, which eventually led to sufficient nitrification [56,57]. The maximal NH4–N removal percentage and the range of TN removal percentage were 97% and 68–92%, respectively. It was 5

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Fig. 4. TMP and flux profile during operating period.

reported that the removal efficiencies of NH4–N and TN with the conventional membrane bioreactor (CMBR) were 93% and 38%, respectively [37]. Moreover, it was concluded that the value of NH4–N and TN removal in CMBR were, respectively, 32% and 29.5% [58]. Li et al. used airlift MBR for simultaneous nitrification/denitrification and found that the average total nitrogen removals of this configuration were 39.4–63.1% [56]. The High rates of TN removal in this study have been mainly attributed to the simultaneous nitrification/denitrification that takes place in deeper layers of the biofilm component [36]. These conclusions confirm the feasibility, stability and perfect treatment efficiency of the system. On the other hand, generally, removal efficiencies of nitrogenous substances in the permeate were higher compared to the supernatant, indicating the effectiveness of membrane on the removal of nutrients. All these results indicate that the system was stable and feasible and had acceptable nutrient removal efficiencies.

3.3. Membrane performance Since the permeate flow rate was set to a constant value of 12 l m−2.h−1 by means of the suction pump, membrane fouling was controlled through monitoring TMP during more than 48 days of the FBMBR operation (Fig. 4). In order to evaluate the system performance in FBMBR, the rate of change in TMP plays an important role because TMP has a direct relationship with the rate of membrane fouling at a constant permeate flow rate [59,60]. The rate of TMP increase in this study was 2 mbar/day. As it is obvious in Fig. 4, during the initial 6 days of operation, the increase in TMP of the membranes was relatively high (approximately 6.6 mbar/day). This is partly the consequence of the development of biological activities and bioaccumulation of biosolids on the membrane surface. Consequently, the TMP value remained constant for 25 days and then TMP increased and reached 185 mbar after 48 days. During operational period, there was not huge TMP increase, indicating acceptable performance of membrane and resistant against fouling. Many studies have reported that the main foulants for membrane fouling are soluble organic polymers, such as soluble microbial products (SMP) and extracellular polymers (ECPs). Attached biomass, such as biofilm, can adsorb soluble organic polymers from the mixed liquor and consequently decrease their effect on membrane fouling [61–63].

4. Conclusions Biological removal of carbonaceous and nitrogenous materials was investigated in a combined fixed bed and membrane bioreactor during 48 days of the FBMBR operation. The experimental system was capable of simultaneous removal of the carbonaceous and nitrogenous materials. The best COD removal efficiency was 99%. These removal efficiencies were achieved through an HRT of 36 h. Since a high biomass content could be held in the FBMBR reactor, the volume of reactor was minimized. In addition, the performance of the system was successful in mitigating the membrane fouling since the TMP development was only 2 mbar/day which is an important parameter during MBR operation. Application of a biofilm process in an MBR is practically achieved by addition of the fixed support media, which can provide a high surface area for biofilm growth. Higher specific surface areas and higher filling fractions are preferable because they can lead to increase capacities of existing activated sludge systems and also more compact bioreactors. 6

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Acknowledgements This study was financially supported by grant No: 950704 of the Biotechnology Development Council of the Islamic Republic of Iran. References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37] [38] [39] [40] [41]

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