Separation and Purification Technology 254 (2021) 117489

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Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

Dissolved methane rejection by forward osmosis membrane to achieve in- T

situ energy recovery from anaerobic effluent
⁎
Tianyu Gao, Hanmin Zhang , Xiaotong Xu, Fenglin Yang
Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, No.2
Linggong Road, Dalian 116024, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Dissolved CH4 (D-CH4) rejection by forward osmosis (FO) membranes requires systematically investigate to
Forward osmosis mitigate anaerobic effluents pollution and energy loss. In this study, effects of membrane materials, orientations
Dissolved methane rejection and alginate fouling on dissolved CH4, H2 and CO2 rejections were evaluated. FO was further connected with
Anaerobic digestion effluent UASB effluent (FO-UASB) to recover D-CH4 for the first time. Results showed that D-CH4 rejections by CTA-ES
Energy recovery
and CTA-NW membranes were above 99.99% in the active layer facing feed solution (AL-FS) and active layer
facing draw solution (AL-DS) orientations. Dissolved H2 rejections (87.5–92.3%) achieved higher than dissolved
CO2 rejections (52.5–73.8%) in AL-FS orientation which was attributed to dissolved gas permeability through
FO. Alginate fouling layer improved dissolved H2 rejection while concentrative internal concentration polar-
ization aggravated dissolved CO2 rejection by fouled CTA-ES membrane in AL-DS orientation. D-CH4 was suc-
cessfully collected by FO-UASB in the synergy effect of FO rejection and liquid-to-gas mass transfer. The max-
imum total CH4 collection rate was 599.0 mg COD/(L d) and 603.4 mg COD/(L d) at 35 °C and 25 °C in the FO-
UASB.

1. Introduction
Anaerobic technology has been widely applied to wastewater
treatment due to biomass energy recovery [1]. However, effluents of
anaerobic bioreactors commonly comprise of 10–25 mg/L of CH4 de-
pending on the partial pressure of CH4 in the process atmosphere [2].
The loss of dissolved CH4 (D-CH4) from anaerobic effluents is a major
problem in terms of following concern: 1. environment: avoiding
emission of a powerful greenhouse gas since CH4 is 21 times more
powerful than that of CO2; 2. safety: eliminating an explosive atmo-
sphere [3]. Recently, various technologies including biological oxida-
tion [4] and aeration [5] have been applied to remove D-CH4 in the
anaerobic effluent [3,6]. Compared to above technologies, hollow fibre
membrane contactors (HFMCs) have overcome the low mass transfer
and methane removal efficiencies [7–11]. Cookney et al. (2016) [12]
demonstrated that D-CH4 removal efficiencies for nonporous and mi-
croporous HFMCs were 92.6% and 98.9%, respectively. However, in-
creasing of operation and maintenance costs are the main drawbacks of
conventional degassing membrane technology [13].
Forward osmosis (FO) is a membrane separation technology in the
field of treating wastewater and desalination. Recently, a novel appli-
cation of FO technology in reducing D-CH4 concentration of anaerobic
effluents was developed. Hou et al., 2017 [14] showed that con-
centration of D-CH4 in the anaerobic forward osmosis membrane
bioreactors (AnOMBRs) (< 2.5 mL CH4/L) was much lower than re-
ported concentration of anaerobic membrane bioreactors (AnMBRs)
effluents [15,16]. The results indicate that D-CH4 is successfully re-
jected by FO membrane since FO membrane pore size (0.25–0.37 nm) is
2–3 orders of magnitude smaller than microfiltration and ultrafiltration
membranes [17]. Our group demonstrated that D-CH4 in the AnOMBRs
was completely rejected by cellulose triacetate with embedded polye-
ster screen support (CTA-ES) and cellulose triacetate with a cast non-
woven support (CTA-NW) FO membranes in the active layer facing feed
solution (AL-FS) and active layer facing draw solution (AL-DS) or-
ientations, which provided a new insight into in-situ D-CH4 recovery
from anaerobic bioreactor effluent [18]. However, mechanisms of D-
CH4 removal by FO membrane are still uncertainty and there is no data
on the effect of FO rejection performance on D-CH4 recovery in the
literature.
In general, FO rejection performance is affected by membrane ma-
terials [19], membrane orientation [20,21], feed solution properties
[22,23] and organic fouling [24]. Liu et al., (2018) [21] showed that
Cs(I) removal efficiency of cellulose triacetate membrane was higher
than thin film composite membrane because of sieving effect.

⁎
Corresponding author at: School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, PR China.
E-mail address: zhhanmin@126.com (H. Zhang).

https://doi.org/10.1016/j.seppur.2020.117489
Received 17 May 2020; Received in revised form 27 July 2020; Accepted 28 July 2020
Available online 07 August 2020
1383-5866/ © 2020 Elsevier B.V. All rights reserved.
T. Gao, et al.
Membrane orientation, including AL-FS and AL-DS was also a sig-
nificant factor for FO membrane performance. Boron rejection was
much lower in the AL-DS orientation induced by severe concentrative
internal concentration polarization (ICP) of boron [25]. Membrane
fouling on the membrane surface cannot be ignored in osmosis mem-
brane filtration progresses, which modify membrane surface char-
acteristics and thereby affect the separation behavior of solutes [26].
Some researchers demonstrated that rejection efficiencies of con-
taminants were enhanced by extra hydraulic resistance of fouling layer
[20,27], while others observed decreased rejections due to cake-en-
hanced concentration polarization [28,29].
The objective of this study is (1) to systematic investigate the effect
of two commercial FO membranes (CTA-ES and CTA-NW membranes),
two membrane orientations (AL-FS and AL-DS) and organic fouling on
the rejection of synthetic dissolved CH4, H2 and CO2 and provide pre-
liminary insights into mechanisms of dissolved gases rejection in FO
processes (2) to examine D-CH4 collection from actual UASB effluent
using a FO system and explore the effects of temperature and water flux
of FO system on the D-CH4 collection rate. Our research for the first
time, proposed a novel strategy for in-situ D-CH4 recovery from anae-
robic effluents.
2. Experimental materials and methods
2.1. Materials
CTA-ES and CTA-NW FO membranes (HTI, USA) were used.
Saturated dissolved gas was synthesized by bubbling deionized water
(Millipore, USA) with 99.9% CH4, CO2 or H2, respectively (Dalian
Junfeng Gas company, China) under sparge rate of 0.8 L/min. The
sealed 2.2 L FS tank was equipped with a magnetic stirrer to enhance
mass transfer rate. The FS tank was maintained at 25 °C and exposed to
CH4, CO2 or H2 rich gas-side conditions (mole fraction of gas phase was
100%). When saturation of dissolved gases were achieved (around
30–40 min), concentration of saturated dissolved gas was around 18.4
mgCH4/L, 1496 mgCO2/L and 1.46 mgH2/L, respectively.
2.2. FO system and dissolved gas rejection tests
The schematic diagram of laboratory-scale FO system was shown in
Fig. S1. The feed solution (FS) and draw solution (DS) was 1.8 L of
saturated dissolved CH4, CO2 or H2 solution and 1.0 L of 1.0 M NaCl
solution, respectively. FS and DS on both sides of the FO membrane
(effective membrane area of 12 cm2) were circulated by two gear
pumps (LongerBT100-2J, China) with a cross-flow rate of 7.4 cm/s
during dissolved gas rejection tests. The water flux (Jw) was determined
by the weight changes of DS tanks recorded by a weighing scale (T-sacle
JSC-QHW, China) at regular time intervals. In the AL-FS orientation, DS
were 1 M, 2 M, 4 M and 5 M, respectively, while DS concentrations in
the AL-DS orientation were 0.5 M, 1 M, 2 M and 2.5 M in order to
compare dissolved gas retention at similar water flux level. The mem-
brane fouling tests were performed before rejection experiment in
which the FS was 200 mg/L alginate. When water flux was stable
(12 h), the fouling CTA-ES membrane was used to the dissolved gas
rejection tests.
In rejection tests, refresh and prefouled membranes were used to
investigate the effect of membrane materials, orientations and mem-
brane fouling on rejection of dissolved gases. The FS was synthetic CH4,
CO2 or H2 saturated solution (seen from Section 2.1) and dissolved gas
rejection tests were conducted for 2 h. Samples from DS tank were
taken for dissolved CH4, CO2 and H2 concentration analyses and the
detailed measurements was shown in Supplementary material. Con-
centration changes of dissolved gas as a function of time were calcu-
lated to determine dissolved gas flux (Jg). Based on the data of Jg, Jw and
Cf,g, rejection ratio of each dissolved gas in FO processes is calculated by
Eq. (2)
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Separation and Purification Technology 254 (2021) 117489
Jg = Ct Vt /(AΔt ) (1)
R = 1 − Jg /(3.6Jw Cf , g ) (2)
where Ct (mg/L) and Vt (L) are dissolved gas concentration and volume
of the DS measured at time Δt (h), Jg (mg/m2 h) is dissolved gas flux. Cf,g
is initial dissolved gas concentration in the FS (mg/L), Jw (μm/s) is the
water flux (1 µm/s is equivalent to 3.6 L/m2 h). R is rejection ratio of
dissolved gases (%).
2.3. FO membrane characterization and prediction of dissolved gas rejection
A pressurized crossflow filtration test unit was used to determine the
pure water permeability coefficient (A), NaCl permeability coefficient
(B) and permeability coefficient of dissolved gases (Bi) of the FO
membrane. The effective membrane area was 38 cm2. The temperature
of feed water was maintained at 25 ± 0.5 °C. The A value was de-
termined by measuring the water flux over a range of applied pressures
(0.3–0.6 MPa). Using a FS containing 18.4 mgCH4/L, 1496 mgCO2/L
and 1.46 mgH2/L. Bi values were determined based on classical solu-
tion-diffusion theory [25].
R = 1/(1 + (Bi/ A (Δp − Δπ )) (3)
where Δp and Δπ are the hydraulic pressure difference and osmotic
pressure difference across the membrane, respectively; where Bi (m/s)
is the dissolved CO2 and H2 permeability of the FO membrane.
By far, solution-diffusion model was successfully applied to predict
inorganic contaminants and trace organic compounds rejections by FO
membranes [22,25]. However, no effort has been made to predict the
FO rejection of dissolved gases by using the solution-diffusion model.
This study evaluated the feasibility of solution-diffusion model in pre-
dicting the rejection of dissolved gases for the first time. We assumed
that ICP of solute do not occur in the AL-FS orientation when dissolved
gases transport through active layer. However, dissolved gases were
retarded in the active layer in the AL-DS orientation which leaded to
concentrative ICP. Hence, the dissolved gases rejection ratios by FO
progress can be calculated by
R = 1 − Bi /(Bi + Jw )(AL − Sorientation) (4)
R = 1 − (Bi exp(Jw / Km, i ))/(Jw + Bi exp (Jw /Km, i ))(AL − DSorientation)
(5)
where Km,i (m/s) is diffusion coefficient in the supporting layer of
dissolved CO2 and H2. According to water permeability (A) and NaCl
permeability (B), the calculated structural parameter (S) of CTA-ES
membrane is 635 μm. Bulk diffusion coefficient of CO2 (DC) and H2
diffusion coefficient (DH) were 2.0 × 10−9 m2/s and 4.5 × 10−9 m2/s
[30], respectively. The calculated diffusion coefficient in the supporting
layer (Km,H = DH/S) of dissolved CO2, dissolved H2 and dissolved CH4
for CTA-ES membrane were 3.45 × 10−6 m/s, 7.20 × 10−6 m/s and
0 m/s, respectively.
2.4. D-CH4 collection by FO-UASB and energy analysis
Based on D-CH4 rejection performance of FO system, the FO system
in the AL-FS orientation was connected to UASB (FO-UASB) to evaluate
the D-CH4 collection potential. The bench-scale UASB (height, 15 cm;
diameter, 12 cm; working volume, 1.2 L) was employed to treat syn-
thetic wastewater at 35 ℃ and 25 ℃ under hydraulic retention time of
12 h. In the synthetic wastewater, glucose, ammonium chloride and
potassium dihydrogen phosphate were main components which were
used as carbon source, nitrogen source and phosphorus source, re-
spectively. The COD value of influent was maintained at around
1000 mg/L, and the COD: N: P ratio was 200:5:1. The reactor was in-
oculated with 0.4 L of anaerobic sludge (volatile solids concentrations is
20.2 g/L) and pH of the bulk liquid was maintained by adding NaHCO3
at 7.0. chemical oxygen demand (COD) in the influent and effluent, D-
T. Gao, et al. Separation and Purification Technology 254 (2021) 117489

CH4 concentrations of UASB effluent and biogas composition (%) in the

headspace of UASB were measured. The analysis methods were iden-
tical to the previous study of Zhang et al., 2019 [18]. According to
COD mass balance of UASB, the COD of 1000 mg/L in influent were
converted to CH4 gas, D-CH4, gained biomass (others) and residual in
the effluent (Eq. S2).
When UASB operation was kept stable, real D-CH4 UASB effluent,
instead of synthetic saturated D-CH4 solution, was added into FS tank
and the flow of UASB effluent was controlled by water flux of FO (Fig.
S2). The system was operated at 35 °C and 25 °C, respectively. The NaCl
was 1 M and the other operation parameters of FO-UASB were identical
to dissolved gas rejection tests. According to D-CH4 mass balance, D-
CH4 UASB effluent might be divided into D-CH4 of DS due to penetra-
tion progress, CH4 in the headspace of FS tank due to gas–liquid transfer
progress and residual D-CH4 in the FS. Clearly, only CH4 in the head-
space of FS tank was recovered by FO-UASB. Therefore, actual D-CH4
collection rate (mg COD/(L d) was calculated by Eq. (6). The energy
calculations were calculated by Eqs. (7)–(9).
RE = (CU − Cf −CD ) Q v / VF (6)

where RE is D-CH4 collection rate mgCOD/(L d)), CU is D-CH4 con-

centration of UASB effluent (mg COD/L), Cf is D-CH4 concentration of
FS tank (mg COD/L), CD is D-CH4 concentration of DS tank (mg COD/
L), VF is working volume of FS tank, Qv(L/d) was feed flow rate of D-
CH4 UASB effluent.
Em=Pm/Qv (7)
3
where Em is energy recovery of FO-UASB (kWh/m ), Pm is power of
methane (kW) and Qv was feed flow rate of D-CH4 UASB effluent (m3/
h).
P = mf v 2/2 + md v 2/2 (8)
E=P/Qv (9)
where P is power of pump (kW), mf is mass of FS (kg), md is mass of DS
(kg), v is water flow rate of FS and DS (m/h) and E is Energy con-
sumption of FO-UASB (kWh/m3)
3. Results and discussion
3.1. Effect of membrane materials and orientation
3.1.1. Dissolved gas flux
Dissolved gas fluxes under different membrane materials and or-
ientations are illustrated in Fig. 1. In the AL-FS orientation, dissolved
CO2 and H2 fluxes of CTA-ES membrane ranged from 9.0 to 12.8 mg/h
m2 and from 2.3 to 2.7 × 10−3 mg/h m2 when NaCl concentration rose
from 1 M to 5 M, respectively. Dissolved CO2 and H2 fluxes of CTA-NW
membrane were 5.9–8.9 mg/h m2 and 1.4–1.9 × 10−3 mg/h m2, re-
spectively. Compared to CTA-NW membrane, higher dissolved CO2 and
H2 fluxes by CTA-ES membrane were obtained which was attributed to
enhancing dissolved CO2 or H2 diffusion of CTA-ES membrane in the
AL-DS orientation induced by difference of water flux (Fig. S3). Ad-
ditionally, Results showed that D-CH4 fluxes were always 0 in all con-
ditions. However, under the same NaCl concentration, dissolved CO2
fluxes for the AL-FS orientation were much lower than that for the AL-
DS orientation for two membranes. This behavior was probably as-
cribed to that concentrative ICP of dissolved CO2 only occurred in the
AL-DS orientation, which greatly increased dissolved CO2 concentration
at the active layer-supporting layer interface.
For both orientations, dissolved gas flux of CTA-ES membrane
mainly followed the order of dissolved CO2 > dissolved
H2 > dissolved CH4, which was consistent with the sequence in per-
meability (Bi) of dissolved CO2, H2 and CH4 (Table S1). The perme-
ability coefficient (Bi) was affected by solute-membrane affinity and
solute dynamic diameter [18,20]. A previous study demonstrated that
Fig. 1. Experimental dissolved gases fluxes of CTA-ES and CTA-NW membrane
in the AL-FS (a) and AL-DS orientation (b). The solid lines were CTA-ES
membrane and the dot lines were CTA-NW membrane.
lower molecular weight of pharmaceuticals has higher permeability due
to size exclusion effect [22]. Dynamic diameter of CH4, CO2 and H2 is,
0.38, 0.33 and 0.289 nm, respectively [31,32]. The CTA-ES FO mem-
brane is composed of an asymmetric CTA and average pore size is
0.37 nm [17]. In terms of the sieving effect, it is more difficult for
dissolved CH4 than dissolved H2 to pass through the CTA FO mem-
brane. However, dissolved CO2 fluxes were significantly higher than
dissolved H2. On one hand, CO2 exhibited a high solubility in the water
compared to H2 under saturated condition [11]. On the other hand, the
forward transport of solutes in the FS was also influenced by reverse
diffusion of DS [33–35]. Hancock et al., 2011 [36] found that an ion
exchange mechanism which allowed the nitrate in the FS to exchange
rapidly with anions from the DS, resulting in a lower nitrate rejection
for FO than RO mode. During permeation progress of dissolved CO2,
main species of dissolved CO2 was H+ and HCO3− in aqueous en-
vironment. H+ and HCO3− in the FS could exchange with Na+ and Cl−
from the DS, which also lead to pH 3 of DS and finally enhance the
dissolved CO2 flux.
3.1.2. Dissolved gas rejection
The rejection ratios of dissolved gas for each FO membrane are
presented in Fig. 2. It was noteworthy that materials and orientations
exerted a direct impact on the rejection of dissolved gas during FO
process. Compared to CTA-ES membrane, lower dissolved CO2 and H2
rejections by CTA-NW membrane were observed. This phenomenon
was attributed to dilution effect. For example, although dissolved CO2
fluxes for CTA-ES membrane and CTA-NW membrane increased 18%
and 10% when NaCl concentration increased from 1 M to 2 M, water
fluxes of the CTA-ES membrane and CTA-NW membrane were en-
hanced by 56% and 37%, respectively (Fig. S3), resulting in the higher

3
T. Gao, et al.
Fig. 2. Experimental and predicted rejections of dissolved gases by CTA-ES and CTA-NW membrane in the AL-FS (a, c) and AL-DS orientations (b, d).
dissolved CO2 rejection ratios for CTA-ES membrane. Likewise, rejec-
tion ratios of dissolved CO2 and H2 for the CTA-ES and CTA-NW
membranes rose initially with the increase in NaCl concentration since
water fluxes increased at a greater rate than dissolved CO2 and H2
fluxes. Rejection ratios of dissolved CH4 were above 99.99% regardless
of membrane materials and orientations difference. For sieving me-
chanism. The larger the size of the solute, the higher is the rejection
which resulted in most of D-CH4 rejection by commercial CTA FO
membrane. In this study, we could not detect dissolved CH4 in the draw
solution which was ascribed to the concentration might be below de-
tection limit probably. The above results demonstrated that CTA-ES
membrane showed a better performance to reject dissolved gas, which
has an important technical implication in the way to in situ reject dis-
solved gas in the AnOMBRs.
In the AL-FS orientation, rejection ratios of dissolved CO2 and H2
increased from 52.5% to 73.8% and from 87.5% to 92.3% for CTA-ES
membrane (Fig. 2a). Compared to AL-FS orientation, AL-DS orientation
exhibited lower rejection of dissolved CO2 and H2 (Fig. 2b). To further
demonstrate the mechanism rejection of dissolved gas, dissolved H2 and
CO2 rejection of CTA-ES membrane was predicted by using Eq. (4) for
the AL-FS orientation and using Eq. (5) for the AL-DS orientation. The
experimental data of dissolved H2 had a good agreement with the
model results (Fig. 2a, b). In the AL-FS orientation, predicted results
revealed that dissolved H2 rejection by CTA-ES membrane ranged from
91.0% to 96.3% when water fluxes of 3.5–9.1 μm/s were achieved
(R2 = 0.855). In the AL-DS orientation, dissolved H2 rejection by CTA-
ES membrane ranged from 86.2% to 87.7% as water fluxes range from
3.6 to 9.8 μm/s (R2 = 0.974), the main difference of predicted results
4
Separation and Purification Technology 254 (2021) 117489
between the two orientations was due to ICP of dissolved H2.
The modeling results of dissolved CO2 also matched well with the
experimentally-obtained rejection ratios when CTA-ES membrane was
operated in the AL-FS and AL-DS orientations (Fig. 2a, b). In the AL-FS
orientation, dissolved CO2 rejection increased with water fluxes in-
creasing (R2 = 0.965). In the AL-DS orientation, dissolved CO2 rejec-
tion increased initially with increasing water flux. However, further
increase in water flux resulted in reduced rejection because of severe
concentrative ICP of dissolved CO2 (R2 = 0.901). Based on model
predictions, the maximum dissolved CO2 rejection by CTA-ES mem-
brane in the AL-DS orientation is only 25.2%, which was much lower
than that of AL-FS orientation. Our results indicated that solution-dif-
fusion model applied in this study can successfully predict the dissolved
CO2 and H2 transport through CTA-ES FO membrane.
3.2. Effect of alginate fouling
3.2.1. Dissolved gases flux
Alginate fouling experiment of CTA-ES membrane was first con-
ducted for 12 h. Then dissolved gas rejection tests were conducted to
examine the effect of alginate fouling. Dissolved gas fluxes of fouled
CTA-ES membrane with different NaCl concentrations are shown in
Fig. 3. D-CH4 fluxes were always 0 in all conditions. Dissolved CO2 and
H2 fluxes were 3.4–5.1 mg/h m2 and 1.0–1.5 × 10−3 mg/h m2 in the
AL-FS orientation and Dissolved CO2 and H2 fluxes were 10.4–32.0 mg/
h m2 and 2.6–3.7 × 10−3 mg/h m2 in the AL-DS orientation, respec-
tively. Membrane fouling causes two opposite effects on the solute
transport in the FO membrane, the enhanced size exclusion effect and
T. Gao, et al.
Fig. 3. Experimental dissolved gases fluxes of fouled CTA-ES membrane in the
AL-FS (a) and AL-DS orientation (b).
concentrative ICP effect in the AL-DS orientation [27,29]. Previous
study showed that alginate fouling inside the membrane support layer
can reduce mass transfer coefficient and thus significantly increase the
boron transport by exacerbating the concentrative ICP effect [20,37].
However, in our study, dissolved H2 fluxes for fouled CTA-ES mem-
brane in the AL-DS orientation were still lower than clean membrane,
which indicated that alginate fouling can change the effective pore size
of the FO membrane and finally exaggerated dissolved H2 permeate.
3.2.2. Dissolved gas rejection
Rejection ratios of fouled CTA-ES membrane are illustrated in Fig. 4.
Dissolved gas ratios for dissolved CH4 were 100% in both orientations.
Alginate fouling had a significant influence on dissolved CO2 and H2
rejection depending on membrane orientations. Rejection ratios of
dissolved H2 were 87.5–96.3% and 77.2–87.1% in the AL-FS and AL-DS
orientations, respectively, which were higher than clean CTA-ES
membrane, suggesting that alginate fouling can effectively restrict the
passage of dissolved H2 and finally enhanced dissolved H2 rejection.
Compared to clean FO membrane, higher dissolved CO2 rejections by
fouled membrane in the AL-FS orientation were observed (Fig. 4a).
However, dissolved CO2 rejections by fouled membrane decreased from
10.9% to 6.2% at the NaCl concentration of 0.5–2.5 M in the AL-DS
orientation (Fig. 4b), which was lower than that of clean FO membrane.
Dissolved CO2 fluxes and water fluxes for fouled CTA-ES membrane
decreased 24.7–32.5% and 35.2–48.2% compared to clean CTA-ES
membrane, respectively. Water fluxes decreased at a greater rate than
dissolved CO2 fluxes induced by concentrative ICP (Fig. 3 and Fig. S4),
causing a decline of dissolved CO2 rejection.
In summary, in the AL-FS and AL-DS orientations, dissolved CH4
5
Separation and Purification Technology 254 (2021) 117489
Fig. 4. Experimental rejections of dissolved gases by fouled CTA-ES membrane
in the AL-FS (a) and AL-DS orientations (b).
rejections of two CTA FO membranes were almost 100% due to CH4
affinity for CTA FO membrane. Dissolved CO2 rejections in the AL-FS
orientation were higher than rejection in the AL-DS orientation since
solute of concentrative ICP effect enhanced dissolved CO2 flux. Alginate
fouling in the membrane surface had an adverse effect on the dissolved
H2 and CO2 rejections. In the both orientations, dissolved H2 rejection
was enhanced by alginate fouling. However, in the AL-DS orientation,
dissolved CO2 rejections by fouled CTA-ES membrane (only 6.2–10.9%)
were lower than clean membrane.
3.3. Methane recovery from FO-UASB
3.3.1. D-CH4 collection by FO-UASB
When FO system was connected with UASB effluent (FO-UASB),
time trace of the distribution between D-CH4 concentration in the FS
and CH4 composition in the headspace of FS tank during first 24 h
operation was first investigated (Fig. S5). Initial CH4 composition in the
headspace of FS tank and D-CH4 concentration of FS (CH4(aq)) was
52.2% and 51.5 mg COD/L, respectively. According to Henry’s law,
theoretical D-CH4 was 46.8 mg COD/L (CH4(eq)) and hence CH4 sa-
turation index (CH4(aq)/CH4(eq)) was then determined to be 1.1 at
35 °C. With operation time increasing, D-CH4 concentration of FS
dropped while CH4 composition in the headspace rose. After 24 h op-
eration, D-CH4 concentration of FS decreased to 2.8 mg COD/L but CH4
composition in the headspace increased to 66.4%. The finial D-CH4
saturation index in the FS was 0.05, which was lower than value of the
AnOMBRs and other anaerobic bioreactors at 35 °C [18,38]. The above
T. Gao, et al.
Fig. 5. D-CH4 concentration in the UASB effluent, feed solution and draw so-
lution of FO at 35 °C and 25 °C (a) and CH4 collection rate of FO-UASB at 35 °C
and 25 °C (b).
results demonstrated that D-CH4 recovery in the FO-UASB was relied on
liquid-to-gas mass transfer in the FS tank.
Table S3 shows the COD of UASB equivalents in the influent, ef-
fluent, CH4 gas, D-CH4 and others. Average D-CH4 concentration of
UASB effluent was 47.8 ± 3.3 mg COD /L 75.0 ± 3.4 mg COD /L
which accounted for 4.7% and 7.5% at 35 °C and 25 °C, respectively.
The increasing in D-CH4 discharge at 25 °C was attributed to an increase
in the solubility of CH4 in the liquid phase with temperature decreasing.
Average D-CH4 concentration of FS was about 2.6 ± 0.4 mg COD /L at
35 °C and 6.5 ± 1.0 mg COD /L at 25 °C, respectively (Fig. 5a). D-CH4
concentration of DS was always 0 due to CTA-ES membrane rejection.
Therefore, D-CH4 UASB effluent was divided into CH4 in the headspace
of FS tank due to gas–liquid transfer progress and residual D-CH4 in the
feed bulk solution. The above results indicated that the calculated D-
CH4 collection efficiency was 94.6 ± 0.9% at 35 °C and 91.3 ± 1.3%
at 25 °C during FO-UASB operation, respectively, which was higher
than the reports of commercial CH4 degassing membrane [7].
From Fig. 5b, D-CH4 collection rate of FO-UASB dropped with water
flux decline at 35 °C and 25 °C due to FO membrane fouling and dilutive
ICP in the AL-FS orientation. Membrane fouling played a key role on
long term performance of the degassing membrane for D-CH4 recovery
[3]. Rongwong et al., 2019 [39] observed that protein-like substances
fouling on the PDMS membrane decreased D-CH4 collection efficiency
after 38 h operation. Compared to membrane fouling behavior of non-
porous PDMS degassing membrane [3], membrane fouling on the CTA-
ES FO membrane is almost reversible because of loose organic fouling
layer. In the Fig. 4, alginate fouling on the FO membrane surface did
6
Separation and Purification Technology 254 (2021) 117489
not affect D-CH4 rejection, which indicated that organic fouling on the
FO membrane cannot affect the D-CH4 removal efficiency. Never-
theless, alginate layer formation on the FO membrane surface ex-
acerbated water flux decline, and consequently decreased D-CH4 col-
lection rate, which indicated that physical cleaning was necessary for
water flux recovery during a long-term operation of FO membrane
system.
3.3.2. Energy analysis
The balance between energy recovery and consumption is pre-
requisite for assessing D-CH4 technologies selection and application.
Several approaches for recovery of D-CH4 in wastewater treatment
processes have been investigated including aeration or degassing
membrane-based recovery. D-CH4 recovery efficiency of various tech-
nologies ranged from 5% to 99.6% (Table S2), but most of these tech-
nologies ignored energy and maintenance costs of post-treatment.
Bandara et al., 2011 [7] showed that the energy requirement of
hollow fibre membrane contactors (HFMCs) was 2 orders of magnitude
greater than energy recovery from D-CH4 for the first time. Recently,
Net energy recovered from the D-CH4 anaerobic effluents can be opti-
mized by operation parameters of HFMCs [40], which solved the pro-
blem of energy deficit.
In this study, Energy recovery from CH4 collection by FO-UASB
included CH4 in the headspace of UASB and D-CH4 UASB effluent.
Average CH4 composition in the UASB headspace was 45.7% and 42.0%
which accounted for 38.8% and 36.8% at 35 °C and 25 °C, respectively
(Fig. S6, Table S3). Methane composition slightly decreased at 25 °C
due to higher methane solubility at lower temperature, which was si-
milar to the results of Wu et al., (2017) [38]. Maximum D-CH4 col-
lection rate of FO was 57.9 mg COD/(L d) and 77.6 mg COD/(L d) at
35 °C and 25 °C, respectively (Fig. 6), which was comparable to
0.012 W and 0.017 W (1 L CH4 is equivalent to 35800 J). Therefore, the
energy recovery by FO was calculated to be 0.16 kWh/m3 at 35 °C and
0.24 kWh/m3 at 25 °C (Eq. (7)). According to the formula (total CH4
collection rate is the sum of CH4 collection rate of UASB and D-CH4
collection rate of FO), maximum total CH4 collection rate was 599.0 mg
COD/(L d) and 603.4 mg COD/(L d) at 35 °C and 25 °C (Fig. 6), which
was comparable to 0.12 W and 0.13 W. The energy recovery (Em) was
then calculated to be 1.62 kWh/m3 at 35 °C and 1.86 kWh/m3 at 25 °C.
Such behaviors indicated that FO-UASB enables to recover energy ef-
fectively from influent COD at mesophilic temperature.
The major energy consumption of FO system was attributed to gear
pump of feed (draw) solution and DS regeneration by nanofiltration.
Energy consumption of gear pump was calculated by Eq. (9). At water
flow rate of 7.4 cm/s, the energy consumption of gear pump was
0.091 kWh/m3 at 35 °C and 0.097 kWh/m3 at 25 °C, which was lower
than the value of energy recovery by FO. In general, energy cost was
also given by DS regeneration when NaCl was used as DS. Mazlan et al.
(2016) [41] showed that energy consumption of DS regeneration by
Fig. 6. CH4 collection rate of FO-UASB at 35 °C and 25 °C.
T. Gao, et al.
nanofiltration (2.29 kWh/m3) accounted for 94.5% of total energy
consumption. However, with the innovation of DS regeneration tech-
nologies, DS may become less energy-intensive. Previous studies
showed that using commercial fertilizer as DS in the FO system can
reduce energy cost because of no need for regeneration [42,43], which
inspired us using commercial fertilizer instead of NaCl in the future to
further reduce energy consumption. When FO membrane is used as the
separation membrane instead of MF or UF membrane in the anaerobic
bioreactors, AnOMBRs would achieve relatively higher D-CH4 collec-
tion than other anaerobic bioreactors with lower energy consumption,
which has significance for energy recovery and mitigation of green-
house gas emission.
4. Conclusions
Novel FO membrane processes were proposed for D-CH4 recovery
from UASB effluent. Results indicated that D-CH4 was almost rejected
by two CTA FO membranes in the both orientations. However, dis-
solved CO2 and H2 rejections were significantly affected by membrane
orientations and materials due to dilution effect and concentrative ICP.
In the both orientations, dissolved H2 rejection was enhanced by algi-
nate fouling CTA-ES membrane. However, in the AL-DS orientation,
dissolved CO2 rejections by fouled CTA-ES membrane (only 6.2–10.9%)
were lower than clean membrane. D-CH4 collection rate of FO-UASB in
long time operation increased under lower temperature and higher FO
water flux. The maximum total CH4 collection rate was 599.0 mg COD/
(L d) and 603.4 mg COD/(L d) at 35 °C and 25 °C in the FO-UASB,
which indicated that FO-UASB has a potential in energy recovery at
mesophilic temperature.
CRediT authorship contribution statement
Tianyu Gao: Conceptualization, Data curation, Formal analysis,
Investigation, Methodology, Visualization, Writing - original draft,
Writing - review & editing, Software. Hanmin Zhang: Funding acqui-
sition, Project administration, Resources, Supervision, Validation,
Writing - review & editing. Xiaotong Xu: Writing - review & editing.
Fenglin Yang: Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgement
This research has been financially supported by the National
Natural Science Foundation of China (No. 51278079).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.seppur.2020.117489.
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