a,*,
Albert Guisasola
Article history:
Received 17 October 2015
Received in revised form
29 July 2016
Accepted 24 September 2016
abstract
A fuel cell sensor was demonstrated as a low cost on-line monitoring tool
for hydrogen producing microbial electrolysis cells (MECs) at lab scale.
Hydrogen produced in the MEC was oxidized at the anode of the fuel cell
generating electricity that could be easily monitored. The total electrical
current obtained was proved to correlate with the hydrogen supplied (r2
0.99) and was equally efficient as other reference analytical
methodologies based on gas chromatography. Signal was repetitive (2.3%
variation coefficient, n = 12) and did not show interferences by the
presence of other compounds like methane and carbon dioxide. The fuel
cell was coupled to single and double chamber MECs validating its
applicability as on-line monitoring portable device for quantifying
hydrogen production. The use of the fuel cell as an on-line hydrogen
sensor offers an alternative to more complex methodologies and offers
the possibility to implement control systems and optimization strategies.
Introduction
In the current oil dependency situation, hydrogen has raised interest
because of being a renewable clean energy vector whose combustion has
no impact on the greenhouse effect. Biohydrogen production technologies
are an interesting alternative to the common steam reforming of fossil
fuels to chemically produce hydrogen, especially when using waste
streams as feedstock. Microbial electrolysis cells (MECs) simultaneously
allow the treatment and valorization of wastewater by producing
hydrogen.
MEC operation relies on the presence of a group of microorganisms
that have the ability to use an external insoluble electrode as final
electron acceptor (known as exoelectrogens or anode respiring bacteria,
ARB). ARB consume organic matter available in wastewater under
anaerobic conditions, donating the last electron involved in their
metabolic pathway to the electrode. The supply of some electrical energy
to overcome thermodynamic limits allows the flow of electrons generated
on the anode to the cathode, where the abiotic
hydrogen production takes place. The interest of this process lies on the
facts that (i) energy requirements to drive this process are much lower
than those required for water electrolysis (ii) wastewater depuration and
valorization are accomplished and (iii) higher hydrogen yields than with
other biohydrogen producing technologies can be reached.
In MEC lab scale studies, analytical methods to monitor the system
performance in terms of hydrogen production may be an issue because of
practical reasons, such as the cost of the equipment, the system location
or the number of replicate reactors to monitor. Operational reasons, such
as too low hydrogen production, can also impede its detection. The use of
a gas chromatograph (GC) is a common practice in lab scale studies when
aiming at hydrogen production monitoring, either by off-line
measurements or by coupling the reactor
with an on-line GC. Both methodologies also require the connection of a
flow-meter to fully quantify the production. Gas production can also be
measured on a GC sparing a flow-meter with a double analysis strategy as
presented by Ambler and Logan. Other analytical techniques described in
the literature for hydrogen detection comprise the use of membrane inlet
mass spectrometry together with a flowmeter system or specific hydrogen
sensors. These techniques are notably expensive and require regular
maintenance. The on-line estimation of biohydrogen production based on
conductivity measurements has also been proposed by Gueguim Kana et
al.. The main advantage of measuring hydrogen production on-line is the
possibility to develop process control techniques that could improve the
system
performance.
As a sensor, a device should present certain characteristics, such as
high sensitivity and selectivity, robustness, small response time, ability to
transduce the sensor signal to electrical signal, operation at room
temperature and low power consumption. Current materials for gas
sensors are semiconductor metal oxides, where the absorption and
desorption of the gas on its surface produces a change on the material
conductivity that can be correlated with the gas concentration. A small
amount of catalytic metal is often added to
improve the selectivity and the sensitivity of the gas sensor. Other
currently used methods to monitor hydrogen in biogas plants are
electrochemical sensors.
A never reported low-cost strategy for on-line hydrogen monitoring
in MEC is presented in this work. A fuel cell is examined to work for
hydrogen production quantification and, therefore, its potential to give a
fast and stable response, a long lifetime and easy calibration and
operation are tested. The possibility of monitoring hydrogen production
with the system proposed in this work is validated coupling it to an MEC in
single chamber and double chamber configuration.
Gas bags with low hydrogen permeability (Ritter, Cali-5- Bond, 100
mL and 500 mL) were used to supply the gas sample to the fuel cell for its
calibration. A Teflon rubber septum permitted the connection with the
needle from the fuel cell. The bags were rinsed three times with nitrogen
gas and emptied with a vacuum pump prior to gas sample introduction.
The gas sample was introduced to the gas bag via a gas tight syringe
(Hamilton Samplelock Syringe, 1 mL and 10 mL). High purity gases
(hydrogen, nitrogen, carbon dioxide and methane, Air Products, Inc.) were
used to prepare the gas samples.
Performance indexes
Voltage response in the fuel cell and MEC was monitored by means
of a 16-bit data acquisition card (Advantech PCI-1716) connected to a
personal computer with a software developed in LabWindows CVI 2013 for
data acquisition. Current intensity (I) in the fuel cell and MEC was
calculated measuring the voltage drop (V) across a resistor (Rext)
according to Ohm's law (Equation (1)).
I = V/Rext
(1)
The electrical charge circulated in the system was calculated as presented
in Equation (2):
Charge(coulombs) =
tf
I (t)dt
(2)
ti
(3)
where nH2 is the moles of hydrogen, calculated with the ideal gas law at
the current temperature, 2 are the moles of electrons available per mole
of hydrogen and F is Faraday's constant (96,485 C/mol-e).
Coulombic recovery for standards was calculated as the percentage
of coulombs measured by the fuel cell (Equation (2)) with respect to the
theoretical coulombs calculated from hydrogen supplied (Equation (3)).
Gas chromatography (Agilent Technologies, 7820-A) was used as
reference method for hydrogen analysis using a thermal conductivity
detector and argon as carrier gas (oven temperature 40 C, HP-mole sieve
column, detector temperature 220 C). Gas quantification was performed
according to the procedure presented by Ambler and Logan, following a
double run methodology. In this methodology, the sample is analyzed in a
first run, then a known volume of nitrogen is added as a reference
compound and the resulting mixture is again analyzed. Mass balances
calculations including the change in sample composition and the volume
added allow the calculation of the initial gas volume as presented by
Equation (4):
(4)
where Vtotal i is the initial total gas volume in the bag, Vadded;N2 is the
known volume of nitrogen added, Vrun 1 is the volume injected in the GC in the
first analysis, and x is the molar fraction of nitrogen in the first analysis or the
second as indicated on the subscript. The output of gas chromatography
analyses is the volumetric fraction (or molar fraction) per compound, thus,
knowing the total initial volume, the initial volume per compound can be
calculated. Acetate concentration was analyzed from 0.22 mm filtered samples
with gas chromatography using a flame ionization detector and helium as carrier
gas (oven temperature 85e130 C, ramp of 3 C min1, 130-220 oC, ramp of 35 C
min-1, nitroterephthalic acid modified PEG capillary column, detector temperature
275 C).
The ability of the fuel cell to work as a sensor was initially tested.
Two fuel cells were used in parallel in the tests performed in this work to
account for the device variability, observing no significant differences. For
each test, the fuel cell was connected to a gas bag containing a known
volume of hydrogen gas. Hydrogen supplied diffused to the anodic
chamber of the fuel cell where it was oxidized. Protons migrated through
the cation exchange membrane whereas the electrons flowed along the
electrical circuit to the cathode producing a voltage signal. In the cathodic
chamber, oxygen was reduced to water. Voltage reached a maximum in
the first minutes of the test and, then, decreased progressively (Fig. 2A).
Current intensity was calculated with Equation (1) using the measured
voltage and then Equation (2) was used to calculate the total electrical
charge. Fig. 2B shows the current intensity obtained with different external
resistances for an identical hydrogen volume supplied. As can be
observed, the system reached higher current intensity for an external
resistance of 12 U, showing less limitation than the external resistances of
100 and 350 U.
increases the probability of human error when sampling the gas, increasing the
standard deviation of the results.
Fig. 4 e Fuel cell sensor calibration for coulombs measured vs. moles of
hydrogen supplied. Error bars indicate standard deviation, which was calculated
based on triplicate tests.
In terms of hydrogen volume, also a lower detection limit for the fuel cell
was of interest. Indeed, 4 mL of hydrogen was found to be the lowest volume
that permitted its quantification at the highest attainable coulombic recovery, i.e.
71%.
A total of 12 consecutive experiments (containing 10 mL of hydrogen
each) were used to assess the repeatability of the fuel cell as an electrochemical
sensor. The fuel cell quantified an average of 71.09 C with a variation coefficient
of 2.3%. Values for the variation coefficient lower than 5% are generally
describing high repeatability.
and therefore no catalytic loss was experienced in the system. Methane and
carbon dioxide are therefore regarded to be inert in the fuel cell.
Carbon dioxide was proven to be inert when fed independently in the fuel
cell. Moreover, mixtures of carbon dioxide with hydrogen were also tested to
investigate about the possible poisoning effects of carbon monoxide, which can
be produced by the reverse water gas shift reaction. Carbon monoxide is
reported to adsorb on the catalyst, decreasing the efficiency of the fuel cell.
Nevertheless, no catalytic loss was observed in the system studied along all the
operational period of this study.
Regarding the lifetime of the device, the system was tested for a period of
four months without seeing any loss in its measuring capacity. A periodical
control analysis and, if necessary, a calibration of the device would be
recommended. An option to avoid catalytic loss by carbon monoxide formation
includes the possibility of trapping carbon dioxide in a sodium hydroxide solution
before the gas mixture arrives to the fuel cell.
Practical implications
The use of a fuel cell at lab scale to monitor hydrogen production is proposed
and evaluated as an alternative to more complex analytical methods, such as
gas chromatography. There are advantages and drawbacks for both systems, but
in the end the possibility of using one or another is highly dependent on the
system to be monitored (configuration, use, location, budget, etc.).
Regarding gas chromatography, the advantages of the system include the
possibility to detect more than one gas compound, not only hydrogen, and the
availability of commercial on-line GC. Nevertheless, the device is notably
expensive (thousands of euros) and it requires the consumption of utility gases.
Also, when it comes to the analysis per se, a double analysis is required in order
to be able to quantify the volume produced (as in Ambler and Logan).
Alternatively the system can be connected to a flow meter to measure total gas
production, increasing the costs.
On the other hand, the fuel cell as a device to monitor the hydrogen
produced represents a completely affordable instrument (less than 50 V in this
case), which can easily be set on-line with the system to monitor and that only
needs a conventional data acquisition system to record voltage. Being selective
for hydrogen, it can be a perfect option in systems where pure hydrogen is
produced, such as double chamber MECs. In a single chamber MEC configuration,
or in other anaerobic systems, only hydrogen produced or its relative
composition can be measured.
The time required to perform the analysis can be quite long when using it
off-line, in the range of few hours, since hydrogen arrives to the reacting
catalytic surface only by diffusion, which can be slow due to the reduced driving
force when the hydrogen concentration decreases. This possible problem could
be minimized by using a fuel cell with higher capacity.
The fact that the fuel cell will consume the product of interest is not an
important drawback at lab scale. More importantly, having a device able to
monitor on-line with high reliability the hydrogen produced also allows the
implementation of control strategies, which can end up improving the whole
performance of the system.
Conclusions
A low cost fuel cell is presented in this work as an alternative,
transportable and robust methodology to quantify hydrogen production in MEC at
lab scale. Tests revealed the high repeatability of the system, showing a high
correlation of the signal with the amount of hydrogen supplied. A strong
correlation was also obtained when comparing the methodology presented here
with gas chromatography as a reference method and no significant differences
were observed at 95% confidence level. In addition, neither interference due to
other biogas compounds nor loss of catalytic activity during all the operational
period were observed. The use of the fuel cell as on-line monitoring device
measuring biohydrogen production in MEC at lab scale was also demonstrated in
single and double chamber configurations.