Académique Documents
Professionnel Documents
Culture Documents
pubs.acs.org/est
■ INTRODUCTION
Energy-efficient wastewater treatment is gaining attention for
brane bioreactors (AnMBRs)) can improve effluent quality and
reliability due to the perfect separation of suspended
lowering costs and the carbon footprint. Municipal wastewater solids.3,10,11 For example, membrane separation can lower the
treatment plants (WWTPs) mainly have used the activated effluent concentration of BOD enough (<7 mg BOD/L) to
sludge process for almost a century.1 However, activated sludge make discharge feasible in many settings.11−13
is expensive due to the large operations and maintenance AnMBRs present limitations that need to be addressed
(O&M) costs of aeration and sludge disposal, and it has a large before they can be put into widespread use: The main
carbon footprint.2 To reduce O&M costs and improve challenges are lack of nutrient removal and dissolved methane
sustainability, anaerobic biotechnologies are being considered in the effluent.3,12,13 The focus of this work is on dissolved
as alternatives to activated sludge.3 Furthermore, anaerobic methane. Dissolved methane in the effluent should be avoided
biotechnologies allow the recovery of substrate electron as much as possible because, on the one hand, methane is a
equivalents as valuable products, such as methane, hydrogen, potent greenhouse gas,14 and, on the other hand, the energy
H2O2, or electric power.4−7 These merits already have driven benefit from methane gas recovery is lost.13,15,16 Recent
the growth of anaerobic treatment of high strength organic literature has shown supersaturation of dissolved methane in
wastes and wastewaters (e.g., animal manure, industrial steady-state AnMBR permeate, as well as other anaerobic
wastewater, and primary and waste activated sludge), for processes. For example, Bandara et al.17,18 reported dissolved
which achieving a low effluent concentration of biochemical methane concentrations of 11 to 15 mg CH4/L in upflow
oxygen demand (BOD) is not a constraint, since anaerobic anaerobic sludge blanket reactors, while dissolved methane of
treatment often is used as pretreatment, not for meeting 16 to 26 mg CH4/L (the saturated concentration of dissolved
effluent standards.8,9
In contrast, anaerobic treatment of dilute wastewater, such as Received: November 10, 2014
domestic sewage, is rarely used due to deficiencies in effluent Revised: July 24, 2015
quality and process reliability. However, combining membrane Accepted: August 4, 2015
separation with anaerobic treatment (called anaerobic mem- Published: August 4, 2015
Figure 1. Schematic diagram of the laboratory-scale AnMBR. An ultrafiltration membrane module was immersed in the middle of the AnMBR. pH
and temperature probes and pressure transducers were installed in the AnMBR to continuously monitor pH, temperature, transmembrane pressure,
and the pressure inside the AnMBR. The effluent flow was monitored by weight on a scale. All sensors and the scale were connected to a personal
computer.
by the methanogens (mg CODglucose/L-h), kH is Henry’s law biogas was circulated at a constant flow rate of 0.93 ± 0.06 L/
constant for methane (25.6 mg CH4/L-atm at 25 °C), and PCH4 min from the headspace to a gas diffuser connected to the
is the partial pressure of methane in the AnMBR (atm). bottom of the membrane module (Figure 1). These two
Finally, the dissolved methane concentration at steady state vigorous mixing methods of liquid and gas circulation created
can be expressed as completely mixed conditions in the AnMBR, which allowed us
to focus on the effects of substrate-utilization rate and KLa value
( dS )M + KLa·kH·PCH
αfe − dt 4
in the steady-state AnMBR on dissolved methane concen-
tration; the information on tubing is described in the
CH4,L =
(KLa + θ1 ) (3)
Supporting Information. By avoiding serious membrane
fouling, we eliminated the possibility of adverse effects of
AnMBR System Configuration and Inoculation. A membrane-cleaning chemicals on microbial metabolism in the
bench-scale, cylindrical AnMBR (ID 10.2 cm and H 70.0 cm; AnMBR. The membranes were physically cleaned by permeate
total volume 5.72 L; working volume 4.5 L) was equipped with back pulsing conducted for 30 min (1 min back-pulsing and 1
a submerged ultrafiltration membrane module (ZeeWeed, GE min relaxation in 15 cycles) once every 2 days. The only sludge
Water and Technologies, Canada), as shown in Figure 1. The withdrawn from the AnMBR was for samples to quantify mixed
average pore size and the surface area of the membranes were liquor suspended solids (MLSS) and mixed liquor volatile
0.04 μm and 0.047 m2, respectively; the membrane flux of suspended solids (MLVSS) concentrations (sample volumes 20
ZeeWeed for AnMBRs ranges from 5 to 10 L/m2-h (LMH) mL/week). pH, temperature, transmembrane, and the pressure
with regular membrane cleaning.20 A pH probe (PHE-1411, inside the AnMBR were continuously monitored with the
Omega, Canada) and a compact industrial resistance temper- probes and sensors connected to a personal computer. The pH
Downloaded by WESTERN UNIV on September 1, 2015 | http://pubs.acs.org
standard solution (PN 46975-U, Sigma-Aldrich, Canada) for rates of 0.39 and 0.74 kg COD/m3-d, but it was 88 ± 12 mg
every set of measurements. All samples were acidified with COD/L at 1.1 kg COD/m3-d; the detection limit for glucose
phosphoric acid (PX0996-6, HPLC grade, EM Science, USA) concentration was 24 mg COD/L using the glucose test kit.
and filtrated using a syringe filter (Hydrophilic PTFE Syringe High COD concentration, propionate accumulation, and
Filters, 0.2 μm, Cole-Parmer, Canada) prior to analysis. VFAs significant glucose accumulation in the permeate suggest that
were quantified in triplicate for each measurement. a nutrient deficiency (e.g., phosphorus, which was input at only
The concentrations of COD, MLSS, and MLVSS were 3.8 mg/L) limited glycolysis and fermentation for the higher
measured according to Standard Methods.22 A glucose assay kit COD loading rate.24,25 The phosphorus requirement for
(GAGO20-1KT, Sigma-Aldrich, USA) was used to measure complete COD removal is estimated at 3.4, 6.5, and 10.1
concentrations of glucose in the permeate; the kit’s detection mg/L for the three OLRs, based on the COD to phosphorus
range was 20 to 80 mg glucose/L. ratio of 100 g COD:1 g P.9,24
KLa Determination. We experimentally measured KLa Biomass, Soluble Microbial Products (SMP), and
values for the steady-state AnMBR using eq 423 Membrane Flux. The MLSS and MLVSS concentrations
did not change much for the different loading rates: 2,080 ± 40
⎛ Q gPCH4 ⎞⎛ ⎞ Qv
KLa = ⎜ ⎟⎜⎜
1 ⎟⎟ = to 2,300 ± 110 mg/L for MLSS and 1,850 ± 40 to 1,960 ± 120
⎝ VRT ⎠⎝ CH4,L − CH4,eq ⎠ ⎛ CH ⎞ mg/L for MLVSS. Since no sludge was wasted from the
kHRT ⎜ CH 4,L − 1⎟
⎝ 4,eq ⎠ AnMBR, endogenous decay and/or release of soluble microbial
(4) products (SMP) minimized the increase in biomass solids. In
fact, the AnMBR permeate accumulated significant SMP,
where Qg is the gas production rate (L/h), V is the volume of computed from CODSMPs = CODpermeate − CODglucose −
liquid in the AnMBR (L), Qv (Qg/V) is the volumetric methane
Downloaded by WESTERN UNIV on September 1, 2015 | http://pubs.acs.org
production rate (L CH4 /L of AnMBR-h), R is the ideal gas law organic loading rates of 0.39, 0.74, and 1.1 kg COD/m3-d,
constant (0.0821 L-atm/mol-K), and T is the temperature (K). respectively. Thus, SMP accounted for 14% to 31% of influent
We measured the methane-gas production rate (Qv) and the
COD, a situation consistent with SMP reported by the
concentration of dissolved methane in the effluent (CH4, L) for
literature.26−28 Nutrients deficiency with a high organic loading
each organic loading rate in the AnMBR; dissolved methane
rate can increase SMP accumulation,29 and SMP is one of the
concentration in membrane permeate was almost equal to that
important membrane foulants.29,30 In our case, however, the
in the AnMBR. To improve data accuracy, we calculated CH4,eq
membrane flux was constant at 4.5 ± 0.3 L/m2-h (Figure S2A),
with the pressure inside the AnMBR measured using the
and the transmembrane pressure was stable at 6.7 to 10.9 kPa
pressure transducers. The temperature was stable at 25 ± 2 °C
(Figure S2B), even though the SMP concentration increased
in the AnMBR during all experiments.
with organic loading rate (Figure S2A). Thus, biogas
COD Balances in the AnMBR. A COD balance was
circulation, regular maintenance cleaning using permeate
established at each steady state to track the distribution of
back-pulse, and maintaining a relatively low MLSS concen-
substrate electron equivalents
tration effectively attenuated membrane fouling in the AnMBR.
CODin = CODpermeate + YgrowthΔCOD + Q methane gas/Q L Methane Gas Production Rate, KLa Value, and
Measured and Estimated Dissolved Methane Concen-
+ CODD‐methane (5) trations. The methane-production rate increased proportion-
ally to the organic loading rate, as shown in Figure 2. The
where CODin is the COD concentration in AnMBR feed (mg measured concentration of dissolved methane increased in
COD/L), CODpermeate is the measured COD concentration in parallel but less than proportionally to the organic loading rate,
AnMBR permeate (mg COD/L), Ygrowth is the observed
biomass yield in the AnMBR (0.14 ± 0.005 mg CODbiomass/mg
COD), ΔCOD (COD in − COD permeate ) is the COD
concentration removed in the AnMBR (mg COD/L),
Qmethane gas is the the production rate of methane gas from the
AnMBR in COD equivalents (mg COD/h), QL is the feed flow
rate (L/h), and CODD‑methane is the dissolved methane
concentration in COD equivalents (mg COD/L). Dissolved
methane in the permeate was readily released to the
atmosphere during COD measurement of the permeate
(CODpermeate); thus, CODpermeate did not include CODD-methane.
We experimentally quantified observed biomass yield with
serum bottle tests (see the Supporting Information).
Table 1. COD Balances and Output Fractions of Influent COD at Different Organic Loading Rates in the AnMBR
organic loading rate (kg COD/m3-d)
0.39 0.74 1.1
COD (mg/L) fraction (%) COD (mg/L) fraction (%) COD (mg/L) fraction (%)
influent 335 ± 10 100 654 ± 16 100 1010 ± 120 100
permeate 73 ± 8 22 256 ± 19 39 478 ± 33 47
methane gas 38 ± 8 11 99 ± 18 15 192 ± 32 19
D-methanea 117 ± 4 35 132 ± 23 20 140 ± 21 14
biomass growth 36.7 11 55.7 8.5 74.3 7.3
unknown 70 21 111 17 124 12
a
D-methane: dissolved methane.
methane in the membrane permeate, and methane accumu- (8) Lettinga, G. Anaerobic digestion and wastewater treatment
lation becomes more significant with low-strength wastewater, systems. Antonie van Leeuwenhoek 1995, 67, 3−28.
which normally leads to a low OLR. Thus, success with (9) Speece, R. E. Anaerobic biotechnology for industrial wastewater
AnMBRs demands post-treatment to capture dissolved treatment. Environ. Sci. Technol. 1983, 17, 416A−427A.
(10) Bérubé, P. R.; Hall, E. R.; Sutton, P. M. Parameters governing
methane. The dissolved methane concentration in the
permeate flux in an anaerobic membrane bioreactor treating low-
AnMBR was successfully simulated with the mass balance strength municipal wastewaters: A literature review. Water Environ. Res.
model in eq 3 when the observed substrate-utilization rate was 2006, 78, 887−896.
used for computing the methane-production rate. Future (11) Huang, Z.; Ong, S. L.; Ng, H. Y. Feasibility of submerged
research is needed to elucidate and validate microbial reaction anaerobic membrane bioreactor (SAMBR) for treatment of low-
kinetics that underlie the methane-production rate. This strength wastewater. Water Sci. Technol. 2008, 58, 1925−1931.
information is essential to understand and mitigate super- (12) Kim, J.; Kim, K.; Ye, H.; Lee, E.; Shin, C.; McCarty, P. L.; Bae, J.
saturation of dissolved methane in AnMBRs. Anaerobic fluidized bed membrane bioreactor for waterwater treat-
■
*
ASSOCIATED CONTENT
S Supporting Information
ment. Environ. Sci. Technol. 2011, 45, 576−581.
(13) Yoo, R.; Kim, J.; McCarty, P. L.; Bae, J. Anaerobic treatment of
municipal wastewater with a staged anaerobic fluidized membrane
bioreactor (SAF-MBR) system. Bioresour. Technol. 2012, 120, 133−
The Supporting Information is available free of charge on the 139.
ACS Publications website at DOI: 10.1021/acs.est.5b02560. (14) Contribution of Working Group I to the Fourth Assessment Report
Quantification of dissolved methane concentration; of the Intergovernmental Panel on Climate Change; Solomon, S., Qin, D.,
effects of shaking intensity and incubation time on Manning, Z., Chen, M., Marquis, K. B., Averyt, M. T., Miller, H. L.,
dissolved methane quantification, glucose medium Eds.; Cambridge University Press: Cambridge, United Kingdom and
Downloaded by WESTERN UNIV on September 1, 2015 | http://pubs.acs.org
■ AUTHOR INFORMATION
Corresponding Author
2259−2264.
(17) Bandara, W.M.K.R.T.W.; Satoh, H.; Sasakawa, M.; Nakahara, Y.;
Takahashi, M.; Okabe, S. Removal of residual dissolved methane gas in
an upflow anaerobic sludge blanket reactor treating low-strength
*Phone: 1-519-888-4567 Ext. 31095. Fax: 1-519-888-4349. E- wastewater at low temperature with degassing membrane. Water Res.
mail: hyungsool@uwaterloo.ca. 2011, 45, 3533−3540.
Notes (18) Bandara, W.M.K.R.T.W.; Kindaichi, T.; Satoh, H.; Sasakawa, M.;
The authors declare no competing financial interest. Takahashi, M.; Okabe, S. Anaerobic treatment of municipal wastewater
■ ACKNOWLEDGMENTS
This work was financially supported by Canadian Water
at ambient temperature: Analysis of archaeal community structure and
recovery of dissolved methane. Water Res. 2012, 46, 5756−5764.
(19) Yeo, H.; Lee, H. S. The effect of solids retention time on
dissolved methane concentration in anaerobic membrane bioreactors.
Network (CWN) entitled “Recovering the energy in municipal Environ. Technol. 2013, 34, 2105−2112.
wastewater with membrane-centered processes” (#2011-26- (20) Dagnew, M.; Hong, Y.; Adams, N.; Fonseca, N.; Cumin, J.
845).
■
Zeeweed AnMBR: Advancing anaerobic digestion for industrial
application. WEFTEC 2014, New Orleans, Sep 27-Oct. 1, USA.
REFERENCES (21) Kampbell, D. H.; Vandegrift, S. A. Analysis of dissolved
(1) Alleman, J. E.; Prakasam, T. B. S. Reflections on seven decades of methane, ethane, and ethlyene in ground water by a standard gas
activated sludge history. J. Water. Pollut. Control Fed. 1983, 55, 436− chromathographic technique. J. Chromatogr. Sci. 1998, 36, 253−256.
443. (22) APHA, AWWA, and WEF. Standard methods for the examination
(2) Curtis, T. P. Low-energy wastewater treatment: strategies and of water and wastewater, 18th ed.; American Public Health Association:
technologies. In Environmental Microbiology, 2nd ed.; Mitchell, R., Gu, Washington, DC, 1992.
J. D., Eds.; Wiley-Blackwell: Hoboken, NJ, 2010. (23) Pauss, A.; Andre, G.; Perrier, M.; Guiot, S. R. Liquid-to-gas mass
(3) McCarty, P. L.; Bae, J.; Kim, J. Domestic wastewater treatment as transfer in anaerobic processes: inevitable transfer limitations of
a net energy producer-Can this be achieved? Environ. Sci. Technol. methane and hydrogen in the biomethanation process. Appl. Environ.
2011, 45, 7100−7106. Microbiol. 1990, 56, 1636−1644.
(4) Hatzell, M. C.; Ivanov, I.; Cusick, R. D.; Zhu, X.; Logan, B. E. (24) Alphenaar, P. A.; Sleyster, R.; Reuver, P. D.; Ligthart, G.;
Comparison of hydrogen production and electrical power generation Lettinga, G. Phosphorus requirement in high-rate anaerobic waste-
for energy capture in closed-loop ammonium bicarbonate reverse water treatment. Water Res. 1993, 27, 749−756.
electrodialysis systems. Phys. Chem. Chem. Phys. 2014, 16, 1632−1638. (25) Brice, C.; Sanchez, I.; Tesnière, C.; Blondin, B. Assessing the
(5) Gao, Y.; An, J.; Ryu, H.; Lee, H. S. Microbial fuel cells as Mechanisms Responsible for Differences between Nitrogen Require-
discontinuous portable power sources: syntropic interactions with ments of Saccharomyces cerevisiae Wine Yeasts in Alcoholic
anode-rspiring bacteria. ChemSusChem 2014, 7, 1026−1029. Fermentation. Appl. Environ. Microbiol. 2014, 80, 1330−1339.
(6) Lee, H. S.; Krajmalinik-Brown, R.; Zhang, H.; Rittmann, B. E. An (26) Aquino, S. F.; Stuckey, D. C. Integrated model of the
electron-flow model can predict complex redox reactions in mixed- production of soluble microbial products (SMP) and extracellular
culture fermentative BioH2: Microbial ecology evidence. Biotechnol. polymeric substances (EPS) in anaerobic chemostats during transient
Bioeng. 2009, 104, 687−697. conditions. Biochem. Eng. J. 2008, 38, 138−146.
(7) Rozendal, R. A.; Keller, J.; Rabaey, K. Efficient hydrogen peroxide (27) Aquino, S. F.; Stuckey, D. C. Characterization of soluble
generation from organic matter in a bioelectrochemical system. microbial products (SMP) in effluents from anaerobic reactors. Water
Electrochem. Commun. 2009, 11, 1752−1755. Sci. Technol. 2002, 45, 127−132.