Development of an integrated membrane process for water reclamation

C.H. Lew*, J.Y. Hu*, L.F. Song*, L.Y. Lee*, S.L. Ong*, W.J. Ng* and H. Seah**
*Environmental Science and Engineering Programme, National University of Singapore, 10 Kent Ridge Crescent, Singapore 119260 (E-mail: cvehujy@nus.edu.sg) **Public Utilities Board, 40 Scotts Road, Singapore 228231 Abstract An integrated membrane process (IMP) comprising a membrane bioreactor (MBR) and a reverse osmosis (RO) process was developed for water reclamation. Wastewater was treated by an MBR operated at a sludge retention time (SRT) of 20 days and a hydraulic retention time (HRT) of 5.5 h. The IMP had an overall recovery efciency of 80%. A unique feature of the IMP was the recycling of a fraction of RO concentrate back to the MBR. Experimental results revealed that a portion of the slow- and hard-to-degrade organic constituents in the recycle stream could be degraded by an acclimated biomass leading to an improved MBR treatment efciency. Although recycling concentrated constituents could impose an inhibitory effect on the biomass and suppress their respiratory activities, results obtained suggested that operating MBR (in the novel IMP) at an F/M ratio below 0.03 g TOC/g VSS.day could yield an efuent quality comparable to that achievable without concentrate recycling. It is noted in this study that the novel IMP could achieve an average overall TOC removal efciency of 88.94% and it consistently produced product water usable for high value reuse applications. Keywords Biomass acclimation; integrated membrane process; membrane bioreactor; reverse osmosis; slow- and hard-to-degrade compounds; water reclamation

Water Science & Technology Vol 51 No 67 pp 455463 Q IWA Publishing 2005

Introduction

Economic development and global industrialization over the past decades have inevitably heightened the conict between water demand and water supply. Consequently, water reclamation has increasingly been receiving attention and seriously explored and/or exploited in many parts of the world for augmenting freshwater supplies. In most cases, membrane technology has been employed and that more than one membrane processes are typically used in order to obtain the benets associated with multiple barriers provided by such arrangement and to assure product water with high quality and purity. One such advanced reclamation technology is the coupling of an MBR with a downstream RO process whereby the MBR is used to serve as a pretreatment to the RO process. In this conguration, soluble microbial products (SMP) could potentially be an issue that may impede the performance of the integrated MBR-RO system (i.e. IMP). SMP are dened as the pool of organic compounds that are released into solution from substrate metabolism accompanied by biomass growth, and biomass decay (Duncan and David, 1999). SMP has been said to be inert in nature. It has been shown that the majority of soluble organic matters in efuents from biological treatment processes are actually SMP, and hence its presence could signicantly affect the efuent quality. Similarly, in the treatment of industrial wastewater, the presence of inherent refractory organics can also signicantly affect the quality of the nal treated efuent. In view of this, it could be expected that the major constituents in the efuent of a biotreatment system treating mixed municipal and industrial wastewater would likely contain SMP and wastewater inherent refractory organic compounds.

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One of the potential advantages offered by the MBR is that it could allow the biodegradation of slow- and hard-to-degrade organic compounds. This is because MBR could allow the establishment of specialized microorganisms capable of removing slowly degradable components (Rosenberger et al., 2002). In addition, MBR could facilitate selective growth of specic microorganisms for the degradation of hardly degradable hazardous substances (Yamamoto, 2001). For example, it has been reported that operating MBR at a SRT greater than 20 days could allow the development of slow-growing micro te et al., organisms which in turn results in better removal of refractory organic matters (Co 1997). SMP is noted to be biodegradable over time, although the kinetics of degradation may be much slower than simple substrates. It has been reported that SMP biodegradation occurred in MBRs after an acclimation period (Huang et al., 2000; Shin and Kang, 2003). This observation suggested that one could recycle a fraction of the RO concentrate back to the MBR operated at a long SRT and exploit the MBR for treating slow- and hard-to-degrade organic compounds present in the RO concentrate stream produced from the IMP. That is, carrying out concentrate recycling may facilitate: (i) degradation of any residual easily degradable organic matters present in the recycle stream, and (ii) degradation of a portion of the slow- and hard-to-degrade organic compounds present in both the recycle stream and MBR Mixed Liquor (ML). If these desired aims could be achieved, it will enhance MBR treatment efciency and improve overall performance of the novel IMP. In addition, degradation of a portion of these slow- and hard-to-degrade organic compounds via concentrate recycling (which would otherwise be wasted via the RO bleed line in an IMP without recycling) will result in a less concentrated RO concentrate waste stream. This achievement can also help to reduce the adverse environmental effects due to concentrated waste disposal. A review of literature revealed that an increase in the concentrations of non-reactive compounds in bioreactors at long SRT can lead to microbial inhibition or toxicity (Brindle and Stephenson, 1996). High concentration of SMP in an MBR was reported to be inhibitory to the metabolic activity of the activated sludge (Huang et al., 2000). Similarly, high levels of total dissolved solids (TDS) have been known to produce an osmotic pressure on cells, causing plasmolysis and loss of cell activity. In view of the above, a primary concern in the operation of the novel IMP will be the inhibition and potential intoxication of microorganisms, due to potential elevated concentrations of TDS, SMP and wastewater inherent refractory organic compounds in the MBR ML. Another concern is the deterioration of MBR efuent quality due to the concentrate recycling. These concerns need to be adequately addressed in order for the proposed novel IMP to be technically feasible. In view of this, the objective of this research is to study the operating characteristics of using an IMP to reclaim high quality product water from mixed industrial and domestic wastewater.
Methods

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The schematic diagram of the novel IMP is shown in Figure 1. The MBR was operated with two submerged Kubota at sheet microltration membranes of 0.45 mm pore size. The MBR was operated at a constant HRT of 5.5 h and a SRT of 20 days. The total ML volume in the bioreactor was 16.5 L and 0.825 L of ML was wasted daily in order to maintain a desired SRT. pH in the bioreactor was maintained within a range of 7.0 to 7.5. The ML dissolved oxygen (DO) level was always above 5 mg/L. Membrane ltered efuent was intermittently discharged at a constant ux by a suction pump. Each intermittent suction cycle consisted of an 8 mins suction period followed by a 2 mins non-suction period. The need for a higher suction pressure to maintain a constant permeate ux gave an indirect indication of membrane fouling. In this study, membrane cleaning was

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Figure 1 Schematic ow diagram of the IMP system

initiated once suction pressure exceeded 5.6 psi. The fouling layer formed on the membrane surfaces was removed by washing with a sponge and tap water. Chemical cleaning was carried out once every 34 months by immersing the membranes in sodium hypochlorite solution (0.5 wt.%) for 3 h followed by oxalic acid solution (0.5 wt.%) for another 3 h. A single thin lm GE Osmonics RO membrane element was used for the RO process. As the RO element can only achieve a limited permeate recovery ratio of 1015%, the RO process was operated in a concentrate recirculation mode. This allowed the IMP to achieve an overall recovery efciency of 80%. As bulk of the RO concentrate stream was recycled back to the efuent tank, the TDS and total organic carbon (TOC) concentrations of the RO feed were higher than the MBR efuent. A concentrate ow rate equal to 20% of the wastewater inuent rate was internally recycled back to the MBR, while another concentrate stream of the same ow rate was wasted through a bleed line. Membrane fouling resulted in a higher driving pressure to maintain a constant permeate ux. When a 20 30% increase in the required driving pressure was observed, chemical cleaning was initiated. A chemical solution of EDTA (0.84 wt.%) and sodium tripolyphosphate (2.03 wt.%) were used for organic cleaning while a citric acid solution (2.0 wt.%), with pH adjusted to 4, was used for colloidal and inorganic cleaning. The experimentation period was divided into four phases. Phase 1 represented the seeding and start-up of the MBR for 114 days. The seed sludge and wastewater source for the four phases were collected from a local wastewater treatment plant (WWTP). Phase 2 represented the operation of the MBR alone at a SRT of 20 days for 37 days. Phase 3 represented a transition period of 46 days, whereby the MBR was integrated with the RO process with a concentrate recycle stream. Phase 4 represented the stabilization and operation of the novel IMP at a SRT of 20 days for 147 days. Samples taken from IMP for analyses include the wastewater, ML supernatant, MBR efuent, RO concentrate and RO permeate. TOC tests (TOC Analyzer, Shimadzu) were conducted for all the samples. TDS levels (TDS Meter, Hanna Instruments) were measured for the wastewater, ML, RO concentrate and RO permeate. Ammonia nitrogen, NH3-N, in the wastewater and MBR efuent were both measured using the automated phenate method. Assessment of microbial viability was carried out based on the specic oxygen uptake rate (sOUR). TOC, MLSS, MLVSS and OUR were measured in accordance with Standard Methods (APHA, 2000). Primary settled efuent was collected from the WWTP and the wastewater has a 60% industrial and 40% municipal wastewater composition. The wastewater characteristics are shown in Table 1. As indicated by the standard deviation (SD), the wastewater strength in terms of TOC was highly variable, as compared with the NH3-N and TDS concentrations, which were relatively stable.

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Table 1 Characteristics of mixed municipal and industrial wastewater

Wastewater characteristics Parameters Mean value 6 Standard deviation

TOC, mg/L NH3-N, mg/L TDS, ppm

110.61 ^ 53.19 37.20 ^ 5.49 945 ^ 89

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Results and discussion

To investigate the effects of concentrate recycling on MBR performance, experimental results obtained during Phases 2 and 4 were analyzed and compared. A time period of 2 SRT was given for the stabilization of the MBR during Phase 4, allowing the biomass to be acclimated to the conditions of concentrate recycling. Only experimental data collected after this time period were analyzed. Throughout both phases, nitrication was complete and no NH3-N was detected in the MBR efuent. Table 2 summarizes the mean values and SD of the MBR TOC mass removal rates, ML and efuent characteristics obtained in Phases 2 and 4. Table 3 summarizes the mean values and SD of both the RO concentrate and RO permeate characteristics obtained in Phase 4. The performance of the MBR during Phases 2 and 4 was assessed and compared based on TOC mass removal rate, given by Eqs. (1) and (2). M 2 C ww Qww 2 Ceff Qeff M 4 C ww Qww C R QR 2 Ceff Qeff 1 2

where M2 is the MBR TOC mass removal rate during Phase 2 (g/d), M4 the MBR TOC mass removal rate during Phase 4 (g/d), Cww the wastewater TOC concentration (g/L), Ceff the MBR efuent TOC concentration (g/L), CR the TOC concentration (g/L) of the RO concentrate recycle stream, Qww the wastewater inuent ow rate (L/d), Qeff the MBR efuent ow rate (L/d), and QR the RO concentrate recycle stream ow rate (L/d).
Effect of concentrate recycling on MBR mass removal rate

As shown in Table 2, the average MBR TOC mass removal rate obtained in Phase 4 was higher than that of Phase 2. Similar observation could also be seen from Figure 2 where the proles of TOC mass removal rates during Phases 2 and 4 were plotted over a range of wastewater TOC concentrations. It is noted that the trend line associated with Phase 4 was consistently above that of Phase 2 over the entire range of wastewater concentrations tested. This nding indicated that concentrate recycling resulted in a higher TOC mass
Table 2 Comparison of MBR TOC mass removal rate, ML and efuent characteristics during Phases 2 and 4
Parameters Phase 2 Mean value 6 SD Phase 4

MLSS, g/L MLVSS, g/L sOUR, mgO2/gVSS.hr ML DOC, mg/L ML TDS, ppm MBR efuent TOC, mg/L MBR TOC mass removal rate, g/d

10.12 ^ 0.92 8.20 ^ 0.61 7.86 ^ 0.97 29.75 ^ 2.22 922 ^ 73 14.53 ^ 1.25 5.72 ^ 2.54

12.48 ^ 2.19 10.00 ^ 1.81 6.48 ^ 2.45 30.42 ^ 6.90 1,282 ^ 191 20.47 ^ 3.68 6.44 ^ 2.09

Table 3 RO concentrate and permeate characteristics during Phase 4

Parameters RO concentrate Mean value 6 SD RO permeate

TOC, mg/L TDS, ppm

56.43 ^ 11.53 3,650 ^ 488

0.811 ^ 0.477 140 ^ 35

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removal rate which in turn suggested that in addition to the residual readily degradable organic compounds, a fraction of the slow- and-hard-to-degrade organic compounds present in the recycle stream could be biodegraded in the MBR. The above claim can further be supported by the results presented in Table 2 whereby it could be seen that concentrate recycling did not result in any signicant changes to the ML dissolved organic carbon (DOC) concentration. The higher ML DOC SD was attributed to the highly variable wastewater strength experienced in Phase 4. There was also an observed increase in ML TDS concentration, although it did not reach an inhibitory level. This phenomenon could be attributed to the high TDS concentration present in the recycle stream (Table 3).
Effect of concentrate recycling on MBR biomass concentration

As shown in Table 2, the average MLSS and MLVSS concentrations were higher in Phase 4 than in Phase 2. The higher SD could be attributed to the highly variable wastewater strength experienced during Phase 4. These observations could be better illustrated in Figure 3, which shows the MLVSS concentrations over a range of wastewater TOC concentrations observed in Phases 2 and 4. For both phases, the trend lines obtained indicated a corresponding increase in MLVSS concentration with the wastewater TOC concentration. The increase in biomass concentration with substrate concentration indicated that a higher substrate concentration could support a higher level of growth which in turn suggested that there was insignicant inhibitory effect associated with concentrate recycling. It should be highlighted that the trend line of Phase 4 was consistently above that of Phase 2. This nding could be attributed to the higher growth rate associated with Phase 4 that in turn facilitated a higher mass removal rate during phase 4. These ndings also suggested that the higher TOC mass removal rate was likely attributed to biodegradation. That is, a higher biomass concentration was attainable due to the uptake and assimilation of additional substrates available in the concentrate recycle stream.

Figure 2 Comparison of MBR TOC mass removal rate during Phases 2 and 4 at different wastewater TOC concentrations

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Figure 3 Comparison of MLVSS concentrations during Phases 2 and 4 at different wastewater TOC concentrations
Biodegradation batch tests

To further validate the observation that a fraction of the slow- and hard-to-degrade organic compounds present in the concentrate recycle stream could be degraded by an acclimated biomass, four biodegradability batch tests were conducted. The type of substrate and source of biomass used for each batch test are summarized in Table 4. Residual DOC of each batch test was monitored during a 5 h time period. The four batch tests were operated at F/M ratios of around 0.5 g TOC/g VSS.day. ML from the MBR and WWTP were centrifuged and the resulting supernatant was discarded. The biomass was then washed twice by resuspension with phosphate buffer solution. This preparation procedure allowed compounds adsorbed onto the biomass to be removed. Autoclaving of biomass for batch test B was carried out at 121 8C for 20 mins. After the addition of biomass to their respective substrates in conical asks, the asks were placed on a shaker operated at an rpm of 250. The DO level in the asks was found to be above 4.0 mg/L. Samples were taken intermittently from the four batch tests by withdrawing 10 mL of ML from each ask before passing them through 0.45 mm lter papers. The ltrates were then measured for residual DOC. Figure 4 compares the variations of residual DOC with time for the four batch tests. As shown in Figure 4(a), Batch test D, which used wastewater as the substrate, showed a rapid decrease in DOC during the rst hour, followed by a more gradual decrease. This nding would suggest that bulk of the wastewater could be readily biodegraded. In contrast, Batch test A, which used RO concentrate as the substrate, showed only a relatively small decrease in DOC. The much slower rate of residual DOC decrease observed in Batch test A, as compared with Batch test D, indicated that the bulk of the constituents in the RO concentrate were slow- and hard-to-biodegrade in nature. Figure 4(b) compares the experimental results obtained from Batch tests A and B. The aim of this comparison was to investigate the roles of biomass adsorption and biodegradation. As the biomass used in Batch test B was washed and autoclaved, any decrease in residual DOC would be attributed to bioadsorption of concentrated constituents. It is noted from Figure 4(b) that Batch test B had a smaller decrease in DOC compared with
Table 4 Substrate type and biomass source for Batch tests A, B, C and D
Batch test A B C D

Substrate type Biomass source

RO concentrate MBR

RO concentrate MBR (autoclaved)

RO concentrate WWTP

Wastewater MBR

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Figure 4 Comparisons of the variation of residual DOC with time for Batch tests A, B, C and D

that attained by Batch test A. This nding suggested that the reduction in DOC observed in Batch test A was attributed to both biomass adsorption and biodegradation. In contrast, the reduction in DOC associated with Batch test B was mainly attributed to biomass adsorption. Figure 4(c) compares the experimental results obtained from Batch tests A and C. It is noted from Figures 4(b) and 4(c) that the prole of residual DOC associated with Batch test C was similar to that of Batch test B. This nding suggested that there was minimal or no observable biodegradation occurring in Batch test C, and that biomass adsorption was the main mechanism responsible for the decrease in DOC. Although live biomass was used for both tests, biodegradation only occurred in Batch test A where the biomass had been previously exposed and acclimated to conditions of concentrate recycling. Batch test C, which used non-acclimated biomass, did not show any observable biodegradation. This nding indicated the importance of biomass acclimation to achieve biodegradation of slow- and hard-to-degrade RO concentrate constituents, which is crucial to the success of the novel IMP.
Effect of concentrate recycling on microbial viability and activity

Assessment of microbial viability and activity was carried out based on sOUR measurements. As shown in Table 2, the mean sOUR value obtained from Phase 4 was slightly less than that of Phase 2. The higher SD again could be explained by the highly variable wastewater strength experienced in Phase 4. It is also noted from Figure 5 that sOUR increased with F/M ratio. This nding suggested that the microorganisms could accommodate the increase in substrate loading and the increase in loading led to a corresponding increase in oxygen uptake. The food in all F/M ratios for Phase 4 was calculated based on the weighted concentration of the wastewater and the concentrate recycle stream. It is also noted that the trend line associated with Phase 4 was below that of Phase 2. This nding suggested that Phase 4 experienced a suppression of respiratory activities over the same range of F/M ratios compared with Phase 2. This phenomenon could be attributed to the consequence of concentrate recycling. SMP and wastewater inherent refractory compounds recycled back to the MBR had an inhibitory effect on the microorganisms. However, this inhibition was not severe and the microorganisms remained viable. They accommodated the increase in F/M ratio via a corresponding increase in sOUR (during phase 4).

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Figure 5 Comparison of sOUR during Phases 2 and 4 at different F/M ratios
Effect of concentrate recycling on MBR efuent quality

As shown in Table 2, the average MBR efuent TOC concentration associated with Phase 4 was higher than that of Phase 2. This observation can be better illustrated in Figure 6, which shows the relationship between efuent TOC concentrations and F/M ratios for Phases 2 and 4. It is noted from this gure that the MBR efuent TOC associated with Phase 2 deteriorated slightly as F/M ratio increased. This nding reected the robustness of the MBR in terms of its ability to produce efuent of consistent quality even with varying wastewater strength. However, such a trend was not observed when recycling of a concentrate stream was carried out. The deterioration of the efuent quality was more signicant when F/M ratio was increased. However, it should be pointed out that the increase in F/M ratio during Phase 4 was attributed to both an increase in the wastewater concentration, as well as an increase in the concentration of the recycle stream. Although operating the MBR with a concentrate recycle stream resulted in an overall worsening of the efuent quality, this drawback could be overcome by operating the MBR at a lower F/M ratio. For example, with an F/M below 0.03 g TOC/g VSS.day, the efuent quality associated with Phase 4 was not signicantly different from that obtained from Phase 2 whereby no concentrate recycling was implemented.

Figure 6 Comparisons of MBR efuent TOC trend during Phases 2 and 4 at different F/M ratio

Performance of the novel IMP

The performance of the novel IMP was assessed based on the overall TOC mass removal efciency given by Eq. (3). M IMP C ww Qww 2 Cperm Qperm 2 CR QB 100% Cww Qww 3
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where MIMP is the overall IMP TOC mass removal efciency (%), Cperm the RO permeate TOC concentration (g/L), CR the RO concentrate TOC concentration (g/L), Qperm the RO permeate ow rate (L/d), QB the RO concentrate bleed rate (L/d), and Cww and Qww as previously dened. The mean value and SD of MIMP were found to be 88.94 ^ 3.80%. The RO permeate quality is given in Table 3. Thus, it has been demonstrated that the novel IMP could achieve good TOC mass removal efciency and it is able to produce water of good quality for reuse purposes.
Conclusions

The novel IMP with concentrate recycling could deliver good performance in terms of overall TOC mass removal efciency. A portion of the slow- and hard-to-degrade organic constituents present in the recycle stream could be degraded by an acclimated biomass operating at a SRT of 20 days. The availability of additional substrates in the concentrate recycle stream could support a higher biomass growth that led to a higher biomass concentration. However, the recycled concentrate constituents had an inhibitory effect on the microorganisms, resulting in a slight suppression of respiratory activities. Nonetheless, the inhibition was not severe and the microorganisms remained viable and responded to the increase in F/M ratio by a higher specic oxygen uptake rate. Experimental results suggested that operating the MBR (in the novel IMP) at a F/M ratio below 0.03 g TOC/g VSS.day could yield an efuent quality comparable to that achievable without implementing concentrate recycling. On the whole, the novel IMP had been demonstrated to achieve good overall TOC mass removal efciency and was able to produce water of good quality for reuse purposes.

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