Jordi Moreno1,2,3, Simon Grasman3, Ronny van Engelen4, Kitty Nijmeijer5. 1. Wetsus, European Centre of Excellence for Sustainable Water Technology , Oostergoweg 9 , 8911 MA Leeuwarden , The Netherlands. 2. Membrane Science & Technology , University of Twente , P.O. Box 217, 7500 AE Enschede , The Netherlands. 3. REDstack BV , Pieter Zeemanstraat 6 , 8606 JR Sneek , The Netherlands. 4. Fujifilm Manufacturing Europe BV , Oudenstaart 1 , P.O. Box 90156, 5000 LJ Tilburg , The Netherlands. 5. Membrane Materials and Processes, Department of Chemical Engineering and Chemistry , Eindhoven University of Technology , P.O. Box 513, 5600 MB Eindhoven , The Netherlands.
Abstract
Salinity gradient energy is a sustainable, renewable, and clean energy source. When waters with different salinities are mixed, the change in Gibbs free energy can be harvested as energy and only brackish water remains. Reverse electrodialysis is one of the technologies that can harvest this sustainable energy source. High power densities have been obtained in small lab scale systems, but translation to large industrial scale stacks is essential for commercialization of the technology. Moreover, power density is an important parameter, and efficiency, i.e., the amount of energy harvested compared to the amount of energy available in the feed waters, is critical for commercial processes. In this work, we systematically investigate the influence of stack size and membrane type on power density, thermodynamic efficiency, and energy efficiency. Results show that the residence time is an excellent parameter for comparing differently sized stacks and translating lab scale experimental results to larger pilot stacks. Also, the influence of undesired water permeability and co-ion diffusion (as reflected in permselectivity) is clearly visible when measuring the thermodynamic efficiency. An averaged thermodynamic efficiency of 44.9% is measured using Fujifilm Type 10 anion exchange and cation exchange membranes that have low water permeability and high permselectivity. This value comes close to the thermodynamic maximum of 50%.
Salinity gradient energy is a sustainable, renewable, and clean energy source. When waters with different salinities are mixed, the change in Gibbs free energy can be harvested as energy and only brackish water remains. Reverse electrodialysis is one of the technologies that can harvest this sustainable energy source. High power densities have been obtained in small lab scale systems, but translation to large industrial scale stacks is essential for commercialization of the technology. Moreover, power density is an important parameter, and efficiency, i.e., the amount of energy harvested compared to the amount of energy available in the feed waters, is critical for commercial processes. In this work, we systematically investigate the influence of stack size and membrane type on power density, thermodynamic efficiency, and energy efficiency. Results show that the residence time is an excellent parameter for comparing differently sized stacks and translating lab scale experimental results to larger pilot stacks. Also, the influence of undesired water permeability and co-ion diffusion (as reflected in permselectivity) is clearly visible when measuring the thermodynamic efficiency. An averaged thermodynamic efficiency of 44.9% is measured using Fujifilm Type 10 anion exchange and cation exchange membranes that have low water permeability and high permselectivity. This value comes close to the thermodynamic maximum of 50%.
Salinity gradient energy is a sustainable
and renewable clean energy
source. When waters with different salinities are mixed, the change
in Gibbs free energy can be harvested as salinity gradient energy
and only brackish water remains. The theoretical potential of salinity
gradient energy is huge,[1,2] and the technologies
for harvesting this salinity gradient energy are developing toward
their introduction into the commercial market.[3−6] Reverse electrodialysis (RED)
is one of the technologies that can harvest this sustainable energy
source (Figure ).
A RED stack consists of repeating cells comprised of alternating cation
(CEM) and anion (AEM) exchange membranes. Feed waters, i.e., seawater
and river water, flow alternatingly through the feed compartments
between the membranes. The ion exchange membranes (IEMs) are selective
for cations (CEMs) or anions (AEMs). The salinity gradient over each
ion exchange membrane creates a voltage difference (the Donnan potential),
and this is the driving force for the process. When alternating CEMs
and AEMs are stacked, this voltage difference accumulates. When the
RED stack is connected to an external load, this driving force results
in a flux of ions through the membranes. To allow the ionic flux,
both ends of the pile of membranes are in contact with an electrode
and a redox couple recirculating between the electrodes to transform
the ionic flux into an electrical current. This process in which solutions
with different salinities are mixed in a controlled way can be used
to harvest the change in Gibbs energy as renewable energy to power
an external load.[7]
Figure 1
Principle of a RED stack,
in which a redox couple transforms the
ionic flux into an electrical current.
Principle of a RED stack,
in which a redox couple transforms the
ionic flux into an electrical current.Most research on REDs is performed using small laboratory
stacks
with 0.2 m2 of active membrane area, i.e., a 10 cm ×
10 cm flow compartment and 10 membrane cell pairs. Promising results
have been obtained with such small stacks.[8−10] A first series
of experiments investigating the performance of a scaled-up RED stack
was performed by Veerman et al.[11] using
a stack of 25 cm × 75 cm equipped with 50 cell pairs and an active
membrane area of 18.75 m2. The authors concluded that the
design of the stack, especially the flow direction and the inlet manifolds,
was the key parameter determining the power density output when increasing
the size of the stack. Tedesco et al.[12] used RED technology to harvest energy from brackish water and brine
(in contrast to river and seawater). A RED stack equipped with a 44
cm × 44 cm compartment area, 125 cell pairs, and a total active
membrane area of 48 m2 was investigated. Using natural
sources, i.e., brackish water and brine, a power output of 40 W (0.83
W/m2) was obtained. The authors also observed a constant
performance during a 5 month operation when using natural feed waters
and changing operational conditions. In a follow-up paper,[13] the same system was scaled up from 125 to 500
cell pairs, achieving an active membrane are of 194 m2,
and the authors concluded that the scaling up process did not lead
to any reduction of specific performance indicators. A power density
of 0.84 W/m2 was achieved when using natural sources.Vermaas et al.[14] theoretically investigated
the energy efficiency in a RED using different stack configurations
(flow directions) with single and multiple electrode pairs. An analytical
model was used for this purpose, maximizing the gross energy efficiency
output. The model assumed ideal IEMs and no concentration polarization
effects. Results showed that by optimizing the mixing ratio of seawater
and river water and by using a single-electrode segment, one could
theoretically obtain efficiencies of ≤95%. The limitations
of the model of Vermaas et al. were partially solved in a follow-up
paper,[15] in which IEM imperfections were
included in the model. Co-ion transport, osmotic water transport,
and electro-osmosis were analyzed, and after a careful selection of
the operating conditions and stack parameters, an energy efficiency
of ≤37% could be predicted. Most of the available energy was
dissipated by the internal stack resistance and losses from uncontrolled
mixing of the feed waters due to imperfections in the IEM.Laboratory
scale experiments are easy to perform and give valuable
information about the research phase. Although high power densities
have been obtained in such small lab scale systems, up to a 2.9 W/m2 gross power density,[8−10] the translation to large industrial
scale stacks is essential for commercialization of the technology.
Moreover, power density is an important parameter, and efficiency,
i.e., the amount of energy harvested compared to the amount of energy
available in the feed waters, is critical for commercial processes.
So far, all described experiments were performed under different conditions;
therefore, performances cannot be compared, nor is it possible to
draw conclusions about the effect of stack size on performance and
possible consequences for upscaling. In the work presented here, we
systematically investigate the translation of small lab scale stacks
to larger systems. For that, four stacks with a different active area
per membrane are used: 6 cm × 6 cm, 10 cm × 10 cm, 22 cm
× 22 cm, and 44 cm × 44 cm. Each stack contains 50 cell
pairs, corresponding to total active membrane areas of 0.36, 1.00,
4.84, and 19.36 m2 per stack, respectively. Stacks are
compared in terms of power density and efficiency, and the influence
of membrane type and stack size on performance is discussed.
Materials
and Methods
Stack Configuration
Effect of Stack Size
To investigate
the effect of stack
size, four cross-flow reverse electrodialysis stacks (REDstack BV)
with different dimensions were used. Details about the design of the
stacks can be found elsewhere.[7,8,10] The stacks had dimensions of 6 cm × 6 cm, 10 cm × 10 cm,
22 cm × 22 cm, and 44 cm × 44 cm. Each stack contained 50
cell pairs, corresponding to total active membrane areas of 0.36,
1.00, 4.84, and 19.36 m2 per stack, respectively. Each
single-membrane cell pair consisted of a CEM and an AEM. As a CEM,
a new type of homogeneous profiled membrane was used (T1 CEM P150),
while a reference standard grade homogeneous type I membrane was used
as an AEM. All membranes were separated by 155 μm woven net-spacers
(Deukum GmbH), unless using T1 CEM P150 profiled membranes, which
integrate the membrane and spacer functionality. All membranes in
this research were supplied by Fujifilm Manufacturing Europe BV.
Effect of the Stack Configuration and Membrane Properties
To investigate the effect of membrane type on RED performance,
three cross-flow stacks all with dimensions of 22 cm × 22 cm
(total active area of 4.84 m2) were used. Each stack contained
50 cell pairs but different membrane types. The reference stack was
equipped with a standard grade type I AEM and a multivalent-permeable
T1 CEM. These membranes are commonly used for RED experiments.[16] The second stack was equipped with a standard
grade type I AEM and a new type of profiled homogeneous multivalent-permeable
CEM (T1 CEM P150). The use of a profiled membrane with an integrated
spacer functionality allowed us to operate the stack without net-spacers,
as the integrated profile maintains the intermembrane distance in
the feedwater compartment. In this research, the profiled membrane
was used in only the river water compartment, while the seawater compartment
contained the standard reference AEM (type I AEM). The third stack
was equipped with a type 10 CEM and a type 10 AEM. These membranes
were chosen because of their low water permeability and high permselectivity
compared to those of the other membranes. Also, all these membranes
were supplied by Fujifilm Manufacturing Europe BV.The relevant
properties of all membranes used in this study are summarized in Table .
Table 1
Membrane Types and Characteristicsa
membrane
description
membrane
thickness (μm)
electrical
resistance (Ω cm2)
permselectivity
(%) (0.1–0.5 M NaCl)
water permeability (mL bar–1 h–1 m–2)
type I AEM
reference
115
1.3
91.9
15
type 10 AEM
low water
permeability
125
1.5
94.5
8
T1 CEM P150
multivalent-permeable
profile
115/150b
2.2
92
15
T1 CEM
multivalent-permeable
115
1.7
89.5
15
type 10 CEM
low water permeability
125
2.3
94.7
9
Data provided by the manufacturer
(Fujifilm Manufacturing Europe BV).
Profile height.
Data provided by the manufacturer
(Fujifilm Manufacturing Europe BV).Profile height.Details of the RED stacks are summarized in Table .
Table 2
Specifications of
the three RED stacks
with different configurations
stack 1
stack 2
stack 3
membrane material
type I
AEM/T1 CEM
type I AEM/T1 CEM P150
type
10 AEM/Type 10 CEM
membrane characteristics
reference
profile
low water permeability
membrane surface
flat
profile
flat
intermembrane
distance (μm)
155
150 ± 5
155
compartment support
woven spacer 155 μm
membrane profile RW/woven
spacer 155 μm SW
woven spacer 155 μm
All stacks used titanium electrodes (mesh of 1.7 m2 of
active surface area/m2 of electrode) with a mixed ruthenium/iridium
mixed metal oxide coating as the anode and cathode (Magneto Special
Anodes BV), placed at both sides of the membrane pile. The electrode
rinse solution used to facilitate the redox reactions at the electrodes
consisted of 0.2 M K3Fe(CN)6, 0.2 M K4Fe(CN)6, and 0.25 M NaCl in demineralized water. The electrode
rinse solution was recirculated at selected flow rates along the electrodes
by using a peristaltic pump (Cole-Parmer, Masterflex L/S Digital drive).
At both ends of the membrane pile, next to the electrodes, a double-shielding
cation exchange membrane (type 10) was placed to close the electrolyte
compartments and to prevent leakage of the electrolyte into the feedwater
compartments.
Feed Waters
Artificial seawater
and river water were
used at concentrations of 0.507 M (30 g of NaCl/kg of water) and 0.017
M (1 g of NaCl/kg of water), respectively. These solutions were made
with NaCl (technical grade, ESCO) dissolved in water. The solutions
were kept at 25 ± 0.5 °C with a heater (2000 W standard
immersion heather, IHP). Measurements were performed over 360 s per
flow velocity, at flow velocities of 0.25, 0.50, 1.00, 1.50, and 2.00
cm/s in random order to avoid history effects. This corresponds to
flow rates ranging from 70 to 557 mL/min for the 6 cm × 6 cm
stack, from 116 to 9308 mL/min for the 10 cm × 10 cm stack, from
256 to 2048 mL/min for the 22 cm × 22 cm stack, and from 512
to 4096 mL/min for the 44 cm × 44 cm stack. The artificial solutions
were pumped continuously through the stack by using two peristaltic
pumps (Cole-Parmer, Masterflex L/S Digital drive). The residence time
(seconds) of the feedwaters inside the stack is calculated by dividing
the length of the stack (centimeters) by the flow velocity (centimeters
per second).Two differential pressure transmitters (Vegadif
65, Vega BV) were placed to measure the pressure drop over the seawater
and river water compartments. Data were collected using a data logger
(Symex MultiCon CMC 99 PS3). The pressure drop values used to calculate
the consumed pumping energy were the averaged pressure drop values
per flow velocity during the full duration of the measurement (360
s).Effluent sampling was performed during the experiments to
quantify
the changes in salinity gradient and volume. Sampling was performed
only during the constant current stage. The salinity and conductivity
were measured with a conductivity meter (Cond 3110 + TetraCon 325,
WTW-Xylem), and the sample volume was measured by using a precision
balance (Kern).
Electrochemical Measurements
A chrono-amperometric
series was applied using a potentiostat (Ivium Technologies, The Netherlands).
It involves an initial stage of 60 s without any current for the determination
of the open circuit voltage (OCV), followed by a stage of 300 s measuring
the current at a constant voltage equal to half of the OCV, i.e. at
maximum power density.[17] The gross power
can be calculated as follows:[8,12]where Pgross is
the gross power (watts), V is the voltage (volts),
and I is the current (amperes). The power required
to pump the feed waters is determined from the measured pressure drop
over the stack (hydraulic losses). The pumping power (watts) can be
calculated as[11,18]where Φr and Φs are the flow rates (cubic meters per second) of river and
seawater, respectively, and Δpr and
Δps are the pressure drops (pascals)
over the river and seawater compartments, respectively.The
net power, Pnet (watts), is calculated
as the difference between the gross power, Pgross (watts), and the power consumed for pumping the feed
waters, Ppump (watts):Dividing eqs –3 by the total active
membrane area, Astack (square meters),
we obtain the gross power density, the pumping power density, and
the net power density.
Efficiency Calculations
The gross
energy efficiency
and thermodynamic efficiency calculations are based on exergy,[19] which is the amount of available energy that
can be extracted from a system reaching equilibrium. The most accepted
way of calculating exergy (the energy available to do useful work)
in RED is by calculating the Gibbs free energy of mixing (ΔGmix) (Supporting Information). The gross energy efficiency of a RED stack is defined as the ratio
of extracted useful electrical energy over the total chemical energy
supplied to the stack in the form of the salinity gradient (exergyin). Instead of using the number of moles to calculate the
Gibbs free energy, in this work the molar flow rate (moles per second)
is used. Therefore, the Gibbs free energy of mixing is expressed as
a power (watts), which for efficiency calculations can be combined
with the power produced by the RED stack (Pgross). The gross energy efficiency (ηgross) of a RED
system can then be calculated using the expressionwhere Pgross is
the (maximum) gross power produced (watts) and exergyin is the available chemical energy supplied to the stack per second
(watts).If the pumping power, Ppumping (watts), is subtracted from the gross power, Pgross (watts), then the net energy efficiency of the process
can be calculated using the expressionwhere Pnet is
the net power produced (watts). Moreover, when both outlet concentrations
of a RED stack (i.e., the river and seawater streams exiting the stack)
are not fully mixed, some salinity gradient energy is still available
to be extracted. For this, when the flow rates and outlet concentrations
are known, the thermodynamic efficiency (ηthermodynamic) of a RED stack can be calculated using the following expression:where Pgross is
the gross power (watts) and exergyout (watts) is the unused
exergy exiting the stack per second.The exergy dissipated,
i.e., irreversible loss, in the stack can
be calculated by subtracting the useful work obtained (Pgross) and the unused energy (exergyout) from
the total chemical energy supplied to the stack (exergyin)
Results and Discussion
In this section, the influence
of stack size and membrane type
on power density and energy efficiency is evaluated and discussed.
Influence
of Stack Size on Power Density and Energy Efficiency
The
gross power density and the gross energy efficiency against
the residence time of the feedwater are plotted in panels A and B
of Figure , respectively.
Figure 2
RED performance
indicators for all stack sizes at different flow
velocities (0.25, 0.5, 1.0, 1.5, and 2.0 cm/s): (A) gross power density,
(B) gross energy efficiency, and C) pumping power density vs residence
time and (D) net power density vs net energy efficiency.
RED performance
indicators for all stack sizes at different flow
velocities (0.25, 0.5, 1.0, 1.5, and 2.0 cm/s): (A) gross power density,
(B) gross energy efficiency, and C) pumping power density vs residence
time and (D) net power density vs net energy efficiency.Figure A shows
that stacks with different sizes and different flow velocities, but
equipped with the same membranes and spacers, have an equal gross
power density at equal residence times. The larger stack shows a slightly
higher gross power density at the same residence time compared to
that of the smaller stack. This is due to the fact that the larger
stack needs a higher flow velocity to achieve the same residence time
in the feedwater compartments, and thus concentration polarization
effects are weaker.[20] This higher velocity
comes at the expense of an increased pumping energy (as presented
later in Figure C).
At low residence times (high velocities), only operation of the smaller
stacks is possible as such high flow rates cannot be obtained in the
larger stacks due to limitations of the pumping capacity. Consequently,
the highest gross power density is achieved by the smallest stack
(6 cm × 6 cm) at a residence time of 3 s (flow velocity of 2
cm/s). This is as expected, as at high flow velocities, the salinity
gradient along the flow compartments and thus the voltage difference
(the driving force) over the membranes for ion transport is high and
maintained. At the other extreme, at high residence times (i.e., low
flow velocities), the lowest gross power density is achieved by the
largest stack (44 cm × 44 cm) at a residence time of 176 s (flow
velocity of 0.25 cm/s). The gross energy efficiency, on the other
hand, is highest at high residence times, i.e., for large stacks at
low flow velocities (Figure B). Under fixed conditions, the residence time inside the
stack determines to a large extent the amount of energy that can be
extracted but at the same time also increases the amount of losses
due to irreversible dissipation because of the internal resistance,
concentration polarization, ionic shortcut currents, and osmotic transport.[21]In Figure C, the
consumed pumping power density is plotted versus the residence time.
In general, the pumping power density decreases with an increase in
residence time, i.e., decreasing flow velocity. Higher flow velocities
result in higher friction and increased losses and consequently a
higher pumping power density. Also, the smallest stack requires a
higher pumping power density to pass the water through the compartments
at the same flow velocity compared to that of the larger stacks because
the major contribution to the hydrodynamic losses is located in the
inlet of the stack and not along the feedwater compartment.[8] Therefore, smaller stacks have relatively larger
hydrodynamic losses. However, membrane areas are also smaller in smaller
stacks, and consequently, the impact of stack size on pumping power
density is marginal.Figure D reports
the net power density versus the net energy efficiency. The smaller
stacks have high pumping energy densities at high velocities, and
therefore, the power density is highly affected upon subtraction of
the pumping power density needed to pass the solutions through the
compartments from the gross power density to calculate the net power
density. The large stacks on the other hand have lower pumping energy
densities and are less affected by these losses. Remarkably, the results
described above show that the stack design is highly scalable. Independent
of the size of the stack, all performance indicators overlap, so when
stacks with differents sizes but equal conditions are investigated,
the residence time of the feed waters is a perfect indicator for comparison.[11]
Influence of Stack Size on Energy Efficiency
at an Equal Flow
Velocity
The total chemical energy supplied by the influent
(exergyin) can be split into the power obtained as useful
work (Pgross), the exergy dissipated or
lost in the stack (exergydis), and the unused exergy (exergyout). The relative contribution of each of these terms is presented
in Figure A for all
stack sizes. The percentages mentioned in the bars in Figure A are the gross power, the
exergy dissipated, and the exergy out relative to the total exergy
in. In Figure B, the
gross energy efficiency and the thermodynamic energy efficiency are
plotted for all stack sizes. Stacks are all operated at the same flow
velocity of 1 cm/s corresponding to residence times of 6, 10, 22,
and 44 s for the 6 cm × 6 cm, 10 cm × 10 cm, 22 cm ×
22 cm, and 44 cm × 44 cm stacks, respectively.
Figure 3
(A) Available exergy
in the influent split in gross power, exergy
dissipated, and exergy out and (B) associated gross energy efficiency
(ηgross) and thermodynamic energy efficiency (ηthermodynamic) for all stack sizes at a flow velocity of 1
cm/s.
(A) Available exergy
in the influent split in gross power, exergy
dissipated, and exergy out and (B) associated gross energy efficiency
(ηgross) and thermodynamic energy efficiency (ηthermodynamic) for all stack sizes at a flow velocity of 1
cm/s.Figure shows that
the amount of chemical energy supplied to each stack increases with
an increasing stack size. As the flow velocity is the same for all
stacks and the flow area for the larger stacks is larger than for
the smaller stacks, the amount of chemical energy supplied to the
larger stacks is larger. Moreover, the exergy supplied to the system
is directly proportional to the absolute flow rate (and at an equal
flow velocity to the inflow area) in each stack. The 6 cm × 6
cm stack is the least efficient stack with only 6% gross energy efficiency.
Most of the exergy supplied is not dissipated or obtained but remains
in the effluent as unused exergy. With an increasing stack size, the
gross power or useful energy extracted from the system significantly
increases and also the exergy dissipated increases, both at the expense
of the percentage of unused energy (exergy out), which decreases with
stack size. For the stack with a membrane area of 44 cm × 44
cm and the longest residence time, the gross energy efficiency is
already 24% while the exergy dissipated is 55%, and thus, only 21%
of the exergy supplied at the inlet is still available in the effluent
as unused exergy. This gross energy efficiency increase with an increasing
stack size is clearly visible in Figure .The exergy dissipated includes, for
example, the losses due to
the use of non-ideal membranes that exhibit significant co-ion diffusion
and water permeation. The levels of both co-ion diffusion and water
permeation obviously increase with increasing residence times. The
ratio of Pgross (due to desired controlled
mixing) to dissipated exergy (due to undesired co-ion diffusion and
water permeation) is equal for all stack sizes. This suggests that
the ratio of controlled (to generate useful power) to uncontrolled
(co-ion diffusion and water permeation) mixing is independent of the
residence time and stack size.During the experiments, RED stacks
are operated by applying an
external load maximizing the power output. Under this condition, a
maximum of 50% of the total exergy supplied to the stacks at the influent
can be harvested theoretically.[21−24] Therefore, the maximum thermodynamic efficiency that
a stack can achieve is 50%. When the stack is operating at maximum
power density, the other 50% of the exergy will be dissipated by the
stack internal resistances as irreversible loss. The thermodynamic
efficiency can be increased by increasing the stack load relative
to the stack internal resistance; however, this will reduce the power
density, and therefore, a larger membrane area will be needed to achieve
the same amount of power output.The stacks presented in Figure B show an average
thermodynamic efficiency of 31%.
This thermodynamic efficiency is also the maximum gross energy efficiency
that the stacks can achieve. The thermodynamic efficiency can be increased
by minimizing all irreversible losses in the stacks. This is possible
by using better membranes that are less sensitive to co-ion transport
(i.e., have a higher permselectivity) and undesired water permeation.
Moreover, at longer residence times, the thermodynamic efficiency
can be increased by balancing the internal and external resistance
along the path length of the stack. Although this last aspect is not
investigated in this study, previous work showed that segmented electrodes
with adjustable external resistances indeed allow optimization for
maximal gross energy efficiency leading to a 15% increase in gross
energy efficiency.[23]
Influence of
Stack Configuration and Membrane Type
Continuing on reducing
internal losses and increasing thermodynamic
efficiency, we investigated the influence of membrane type and corresponding
membrane properties (electrical resistance, permselectivity, and water
permeability) and stack configuration (standard flat membranes and
profiled membranes). Three stacks of equal size (22 cm × 22 cm)
but equipped with different ion exchange membranes were used (see Table ). Figure reports the gross power density
(A) and the thermodynamic efficiency (B) versus the flow velocity
for the reference system, the system with profiled membranes instead
of spacers (Profiled), and the systems equipped with membranes with
low water permeabilities (Low water permeability).
Figure 4
(A) Gross power density
and (B) thermodynamic efficiency vs gross
power density for all stack configurations.
(A) Gross power density
and (B) thermodynamic efficiency vs gross
power density for all stack configurations.The gross power density (Figure A) increases with flow rate for all membrane
combinations
investigated. At higher flow rates, there is a better resupply of
feedwater, which keeps the concentration gradient along the length
of the compartments high. Higher flow rates also improve the mixing
and reduce the level of concentration polarization. The highest gross
power density measured is achieved with the stack with profiled cation
exchange membranes because of the lower ohmic resistance of the stack
with profiled membranes. In such a stack, the membrane and the nonconductive
net spacer together are replaced by an ion conductive profiled membrane
integrating the membrane and spacer functionality.[18] As no nonconductive net-spacers are used in such a system,
less non-ion conductive material is used in the stack and therefore
a lower internal stack resistance is obtained.[25] Consequently, the use of profiled membranes improves the
gross power density output.The stack equipped with membranes
with a lower water permeability
and a higher permselectivity (type 10 AEM and CEM) has gross power
densities comparable to those of the stack with profiled CEMs but
power densities significantly higher than the values obtained for
the stack equipped with the reference membranes (type I AEM and T1
CEM). The higher membrane resistance of these low-water permeability
membranes apparently is counterbalanced by the increased voltage difference
over the membranes due to the lower water permeability and higher
permselectivity, especially at low flow rates. Unfortunately, low-water
permeability type 10 profiled membranes are not available, but if
these were to exist, an even stronger increase in gross power energy
output would be expected because of the decrease in stack resistance.In terms of thermodynamic efficiency on the other hand, the behavior
changes drastically (Figure B). The thermodynamic efficiency is rather independent of
the flow velocity, as the thermodynamic efficiency is based on the
chemical energy supplied to the stack (exergy in–exergy out)
(see eq ). The stack
equipped with membranes with a low water permeability has a thermodynamic
efficiency much higher than those of the other two stacks equipped
with standard membranes. This high thermodynamic efficiency is a result
of the improved membrane properties, which reduce the extent of water
permeation and co-ion diffusion. Consequently, the salinity gradient
is not irreversibly lost because of unwanted mixing by co-ion diffusion
and water permeation. With an average thermodynamic efficiency of
44.9%, the stack with the low-water permeability membranes operates
close to the maximum of 50% that can be achieved when operating at
maximum power.The undesired mixing due to water permeation
and co-ion diffusion
is shown in more detail in Figure . In this figure, the change in concentration over
the inlet and outlet of the stack compartments, i.e., river water
(RW) and seawater (SW), under open circuit conditions (Y-axis) is plotted at different flow velocities (X-axis) for all stack configurations (stack size of 22 cm × 22
cm). Under open circuit conditions, there is no desired ion transport
from seawater to river water as there is no current. Therefore, the
change in concentration
over the length of the stack due to desired ion transport is zero.
In that situation, only undesired, uncontrolled water permeation and
co-ion transport occur, resulting in a change in the concentration
in both the seawater and the river water compartment over the length
of the stack, indicated as undesired losses. As such, Figure thus quantifies the net effect
of undesired water permeation and co-ion diffusion and thus the undesired
losses in the three stacks at different flow rates.
Figure 5
Concentration difference
between the inlet and the outlet of both
the river water (RW) and the seawater (SW) compartment under open
circuit conditions vs the flow velocity for all stack configurations
and flow. The stack size is 22 cm × 22 cm.
Concentration difference
between the inlet and the outlet of both
the river water (RW) and the seawater (SW) compartment under open
circuit conditions vs the flow velocity for all stack configurations
and flow. The stack size is 22 cm × 22 cm.In an ideal situation with perfect, 100% selective non-water-permeable
membranes, this change in concentration over the length of the stack
would be zero (no losses). However, when using non-ideal membranes,
the concentrations will change due to water permeation because of
osmosis and co-ion diffusion.[26] When the
change in concentration is due to co-ion diffusion, the change in
concentration will be symmetrical for both compartments, because in
that case only ions will be transported. As such, the decrease in
concentration difference between the inlet and the outlet of one feed
compartment will be exactly equal to the increase in concentration
difference between the inlet and the outlet of the other feed compartment.
On the other hand, when the change in concentration between the inlet
and the outlet is a result of osmotic water permeation, the change
between both compartments is asymmetrical. The reason for this is
that the impact of water transport is higher in the seawater compartment
(due to its higher concentration) than in the river water compartment
(which has a low concentration).From Figure , all
membranes suffer from undesired water permeation and co-ion diffusion
(i.e., undesired losses), as the concentration change under open circuit
conditions is not equal to zero. Obviously, this effect is smaller
when a membrane with a low water permeability and a high ion selectivity
(i.e., low co-ion diffusion) is used. Also, in all cases, an increase
in flow velocity decreases the losses due to the reduced residence
times at higher flow velocities. As for the reference membranes and
the profiled membranes, the change in concentration with flow rate
is nonsymmetrical; losses predominantly stem from undesired water
permeation. For the stack equipped with optimized membranes with low
levels of water permeation and co-ion diffusion, the change in concentration
for both water compartments is much more symmetrical, suggesting that
losses mainly stem from co-ion diffusion.
Outlook
In this
study, the effect of stack size and membrane type on performance
indicators in RED is studied. The influence of stack size on the power
density, energy efficiency, and pumping power density can be directly
related to the residence time of the feedwater in the stack. At equal
residence times, data of all stacks with different sizes overlap.
As such, the residence time is an excellent parameter to compare differently
sized stacks and to translate lab scale experimental results to those
of larger pilot stacks. Also, the influence of water permeability
and permselectivity is clearly visible when measuring the thermodynamic
efficiency. An averaged thermodynamic efficiency of 44.9% is measured
using Fujifilm type 10 AEM and CEM membranes that have low water permeability
and high permselectivity. This value comes close to the thermodynamic
maximum of 50%.
Authors: Mohammad A Alkhadra; Xiao Su; Matthew E Suss; Huanhuan Tian; Eric N Guyes; Amit N Shocron; Kameron M Conforti; J Pedro de Souza; Nayeong Kim; Michele Tedesco; Khoiruddin Khoiruddin; I Gede Wenten; Juan G Santiago; T Alan Hatton; Martin Z Bazant Journal: Chem Rev Date: 2022-07-29 Impact factor: 72.087
Authors: E Mercer; C J Davey; D Azzini; A L Eusebi; R Tierney; L Williams; Y Jiang; A Parker; A Kolios; S Tyrrel; E Cartmell; M Pidou; E J McAdam Journal: J Memb Sci Date: 2019-08-15 Impact factor: 8.742
Authors: Liliana Villafaña-López; Daniel M Reyes-Valadez; Oscar A González-Vargas; Victor A Suárez-Toriello; Jesús S Jaime-Ferrer Journal: Membranes (Basel) Date: 2019-11-04
Authors: Prem P Sharma; Rahul Singh; Syed Abdullah Shah; Cheol Hun Yoo; Albert S Lee; Daejoong Kim; Jeong-Geol Na; Jong Suk Lee Journal: Membranes (Basel) Date: 2022-04-01