i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 5 8 4 1 e1 5 8 4 9

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

Electro-hydrolysis of cheese whey solution for hydrogen gas

production and chemical oxygen demand (COD) removal
using photo-voltaic cells (PVC)

Fikret Kargi*, Sinan Uzunçar

Department of Environmental Engineering, Dokuz Eylul University, 35160 Buca, Izmir, Turkey

article info abstract

Article history: Diluted cheese whey (CW) solution was used for hydrogen gas production by electro-
Received 28 May 2012 hydrolysis using photo-voltaic cells (PVC) as source of electricity. Effects of initial chem-
Received in revised form ical oxygen demand (COD) concentration on the rate and yield of hydrogen gas production
6 August 2012 were investigated using a completely mixed and sealed reactor with aluminum electrodes.
Accepted 9 August 2012 Cumulative hydrogen gas formation (CHF) increased with increasing initial COD concen-
Available online 10 September 2012 tration. The highest cumulative hydrogen gas volume (26472 mL), hydrogen gas production
rate (4553 mL d
1), hydrogen yield (7004 mL H2 g
1 COD), and percent COD removal (21.5%)
Keywords: were obtained with initial COD of 35172 mg L
1. H2 gas formation from water control was
Cheese whey only 5365 mL. pH of the CW solution increased with decreasing conductivities during the
COD removal course of experiments. Gas phase contained more than 99% H2 at the end of experiments.
Electro-hydrolysis The highest energy efficiency (20.4%) was also obtained with the highest COD content.
Hydrogen gas Nearly pure hydrogen gas formation by electro-hydrolysis of cheese whey using PVC
PVC panels panels was proven to be an effective method.
Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction economically feasible due to low rates and yields of H2 gas

Global warming and environmental pollution problems
caused by utilization of fossil fuels stimulated research on
production of alternative clean fuels. Among the other clean
fuel sources hydrogen gas has considerable advantages due to
high energy content (122 kJ g
1) and reduced green house gas
emissions. Moreover, H2 gas is an effective energy carrier and
can be used in fuel cells to generate electricity. However,
hydrogen gas is not readily available in nature and is produced
by costly processes such as electrolysis of water or steam
reforming of hydrocarbons requiring high energy inputs.
Fermentative hydrogen gas production from renewable
resources such as biomass is less energy intensive but is not
production [1,2].
Hydrogen gas production by water electrolysis has been
extensively investigated and reported in literature [3,4]. The
net energy balance for water electrolysis is negative due to
larger energy requirement for electrolysis of water
(4 kWh m
3 H2) as compared to the energy content of
hydrogen gas (3.55 kWh m
3 H2). New approaches were
developed to improve energy balance of H2 gas production by
electrolysis. Photo-electrochemical (PEC) water splitting and
use of proton exchange membranes (PEM) in water electrol-
ysis are new developments [4].
Electro-hydrolysis of organic wastes for nearly pure
hydrogen gas production has been developed as an alternative

* Corresponding author. Tel.: þ90 232 3017109.

E-mail address: fikret.kargi@deu.edu.tr (F. Kargi).
0360-3199/$ e see front matter Copyright ª 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2012.08.025
15842 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 5 8 4 1 e1 5 8 4 9

to water electrolysis [5,6]. Microbial electrolysis cells (MEC) have
also been used for hydrogen gas production from organic wastes
with some energy input [7,8]. Different organic wastes such as
bakers yeast industry wastewater, anaerobic sludge, olive mill
wastewater (OMW) and landfill leachate were used as raw
materials for H2 gas production by electro-hydrolysis [9e12].
Although it is considered as a high strength wastewater
(COD ¼ 50e60 g L
1) of cheese manufacturing processes, cheese
whey (CW) can be used for production of fuels. Ethanol,
methane and H2 gas can be produced by fermentation of cheese
whey due to high carbohydrate content (5e6% w v
1 lactose)
[13e16]. Hydrogen gas production by electro-hydrolysis of
cheese whey is a promising approach among other methods
used for hydrogen gas production. Electro-hydrolysis of cheese
whey for hydrogen gas production using PVC panels as source of
electricity has not been reported in literature. Therefore, the
major objective of this study is to investigate production of
hydrogen gas from cheese whey solution by electro-hydrolysis
using PVC panels and a mechanically mixed-sealed reactor
containing aluminum electrodes. CW control experiments with
no voltage application and water control experiments with
voltage application were also carried out to determine the
extent of hydrogen gas production by bacterial fermentation
and by electrolysis of water, respectively.
2. Materials and methods
Raw cheese whey was obtained from Pinar Company at
Pinarbasi, Izmir, Turkey. Serial dilutions were made from the
raw CW to obtain diluted CW solutions with desired COD
concentrations. The experiments were started by filling the
reactor with diluted CW solutions, closing the head plate
tightly and connecting the PVC to the electrodes through
a voltage regulator and battery. Water control experiments
were performed by applying the same voltage to tap water to
determine hydrogen gas production by electrolysis of water.
CW control experiments with no voltage application were also
performed to determine H2 gas formation by fermentation of
CW solution. Table 1 summarizes characteristics of diluted
CW solutions.
Carbohydrates (mainly lactose) present in CW solution are
fermented by anaerobic bacteria present in CW producing
volatile fatty acids (VFAs), CO2 and H2 (gas). Protons (Hþ)
released from VFAs by dissociation or hydrolysis react with
electrons provided by electrical current to produce H2 gas. In
early periods of operation, some COD removal takes place due
to CO2 release by fermentation. However, no CO2 release or
COD removal occurs during electro-hydrolysis of VFAs for H2
gas production. For this reason, the gas phase contains nearly
pure H2 gas at the end of operations.
Al(III) ions and electrons are released to the solution from
the aluminum anode upon application of electrical power
from PVC.
Anode : Al /AlðIIIÞ þ 3e

0
(1)

2.1. Experimental set up and procedure Volatile fatty acids produced by bacterial fermentation of
lactose present in CW release protons to the medium by
The experimental system consisted of a mechanically mixed dissociation or decomposition.
and sealed plastic (polyvinyl chloride) walled reactor, a PVC
R
COOH/R
COO
þ Hþ (2)
panel (80 cm  120 cm), a voltage regulator and a battery. The
dimensions of the reactor were Do ¼ 21 cm, H ¼ 48 cm with The released protons and electrons react to form H2 gas on
a total volume of 16.8 L. A schematic of the experimental set cathode.
up is presented in our previous publication [11]. Wastewater
volume in the reactor was 13.5 L with a head space of 3.3 L. The Cathode : nHþ þ ne
/n=2H2 ðgÞ (3)
PVC panel was manufactured at the Solar Energy Res. Insti- Some Al(III) ions also react with electrons released from
tute, Ege University, Izmir, Turkey. The panel contained 32 anode to form pure Al0 on cathode surfaces.
cells with a total power supply of 115 W (i.e., 3.6 W for each
AlðIIIÞ þ 3e
/Al
0
cell) providing 18 V with 6 ampere (A) current. A voltage (4)
regulator was used to adjust the voltage to desired level. A
Some Al(III) ions released from anode form Al salts such as
battery was used to store electrical energy during the day and
Al(OH)3 in CW solution.
to provide constant current to the reactor during the night
time. Mechanically mixed and sealed reactor contained
diluted cheese whey, aluminum anode/cathode and a pres- 2.2. Analytical methods
sure gauge. Aluminum electrodes (L ¼ 49.5 cm and
Do ¼ 0.9 cm) were mounted on the head plate of the reactor Samples were removed from the reactor everyday for COD, pH
and were used to conduct electrical current to the CW and oxidationereduction potential (ORP) measurements after
solution. gas analysis. Total sugar (TSG), total volatile fatty acids

Table 1 e Initial characteristics of diluted CW solutions used for H2 gas production by electro-hydrolysis.
Voltage Total Total TVFA pH ORP Conductivity Susp. solids Total solids
(V) COD (mg L
1) sugar (mg L
1) (mg L
1) (mV) (mS/cm) (g L
1) (g L
1)

11.84 20415 15672 1182 5.34 106.7 2.48 1.44 15.24

11.88 25175 20160 1457 5.22 117.8 3.14 2.05 22.16
11.90 31781 24248 1840 5.16 117.6 3.94 2.11 23.90
11.65 35172 26543 2142 5.02 98.2 4.37 2.40 26.50
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 5 8 4 1 e1 5 8 4 9
(TVFA), suspended solids (SS), total solids (TS) were also
measured at the beginning and the end of the experiments.
COD analyses were performed by using the closed reflux
method as described in Standard Methods [17]. pH and oxi-
dationereduction potential (ORP) measurements were done
by using pH and ORP meters with relevant probes (WTW
Scientific, Germany). Conductivities of water and CW were
determined using Hach & Lange conductometer (Model 58258-
00, Germany). Total sugar concentrations were determined by
the acidephenol spectrometric method [18]. TVFA analyses
were carried out by using analytical kits (Spectroquant,
1.01763. 0001, Merck, Darmstadt, Germany) and a PC spec-
trometer (WTW Photolab S12).
Hydrogen gas was collected in the head space of the sealed
reactor and was sampled using gas-tight glass syringes.
Hydrogen gas concentration in the gas phase was measured
by using a gas chromatograph (HP Agilent 6890). The column
was Alltech, Hayesep D 80/100 600  1/800  08500 . Nitrogen gas
was used as carrier with a flow rate of 30 mL min
1 and the
head pressure was 22 psi. The amount of total gas produced
was determined by water displacement method everyday
[19,20]. Total gas measurements were done using sulfuric acid
(2%) and NaCl (10%) containing solution. The cumulative
hydrogen gas production was determined as explained in our
previous publications [19,20].
2.3. Calculation methods
The electrical energy supplied to the system was calculated
using the following equation
Z X
Ee ¼ V Idt ¼ V Ii Dti
where Ee is the electrical energy supplied to the system by the
DC power supply (J); V is the applied voltage (V); Ii is the
average current (A) measured by a multi-meter within a time
period of Dti (h). Electrical energy input was calculated by
determining the area under the curve of current (I ) versus
time (t).
The amount of hydrogen gas was calculated by using the
ideal gas law.
P VH2 ¼ ðm=MÞ R T
where P is the pressure (1 atm); VH2 is the volume of the
cumulative hydrogen gas; m is the mass of the cumulative
hydrogen (g); M is the molar mass of hydrogen (2 g mol
1); R is
the gas constant (0.082 L atm mol
1 K
1), T is the absolute
temperature (K).
The energy content of the produced hydrogen was calcu-
lated using the following equation.
 
EH2 ¼ m 122 kJ g
1
where m is the mass of the cumulative hydrogen produced
within a specified time period.
Energy efficiency of the system was calculated by dividing
the energy content of produced H2 gas (EH2) to electrical energy
input (Ee) as follows
h ¼ EH2 =Ee
15843
The yield of hydrogen gas formation based on COD removal
(mL H2 g
1 COD) was calculated by using the following
equation.
YH2 ¼ VH2 =VðSo
SÞ (9)
where VH2 is the cumulative hydrogen gas volume at the end
of the operation, V is the volume of the cheese whey in the
reactor, So and S are the initial and the final COD contents
(g L
1).
3. Results and discussion
Two sets of electro-hydrolysis experiments were performed.
The first set of experiments consisted of electro-hydrolysis of
diluted CW solutions with different initial COD concentra-
tions (20415e35172 mg L
1) and CW control bottles without DC
voltage application. The second set of experiments was per-
formed with water instead of CW solution (water control) to
determine H2 gas production by water electrolysis using the
same DC voltages. No DC voltage was applied to the CW
control bottles in order to determine hydrogen gas production
and COD removal by bacterial decomposition.
3.1. Hydrogen gas evolution
Fig. 1 depicts time course of variation of cumulative hydrogen
gas formation (CHF) from CW solutions at different initial COD
concentrations (20415e35172 mg L
1) along with H2 gas
production from electrolysis of water (water control) and
bacterial fermentation of CW (CW control). Hydrogen gas
(5)
formations from water and CW controls were lower than the
actual electro-hydrolysis experiments. The lowest initial COD
concentration of 20415 mg L
1 yielded 9237 mL H2 gas within
140 h with the average applied DC voltage of 11.84 V. When
initial COD concentration was increased to 25175 mg L
1,
14283 mL H2 gas was produced within 140 h. Only 48 mL and
51 mL hydrogen gas were produced in the control CW solu-
tions with the same initial CODs within 140 h. Further
increases in initial COD to 31781 and 35172 mg L
1 resulted in
larger cumulative hydrogen gas volumes of 18892 and
(6) 26472 mL within 140 h. Hydrogen gas formations in control
CWs with the same initial CODs (31781 and 35172 mg L
1) were
only 52 and 51 mL, respectively. High initial COD contents (or
high initial sugar contents) yielded high VFA concentrations
by dark fermentation resulting in high volumes of H2 gas
formation as described in reactions (2) and (3). H2 gas evolu-
tions from the control CW experiments were negligible indi-
cating negligible H2 gas formation by anaerobic fermentation
of carbohydrates. CHF by water electrolysis was 5365 mL
within 142 h with the applied average DC voltage of 12.52 V
(7)
which was only 15% of H2 gas produced from CW solution
with a COD content of 35172 mg L
1.
Fig. 2 depicts variation of final CHF and H2 percentage in
the gas phase with the initial COD concentrations. CHF
increased with increased initial COD concentration yielding
the highest CHF of 26472 mL for the initial COD of 35172 mg L
1
due to large amounts of VFA formation at high COD or
(8) carbohydrate contents. Initially the gas phase was mainly
15844 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 5 8 4 1 e1 5 8 4 9

Fig. 1 e Time course of variation of cumulative hydrogen gas formation (CHF) for different initial COD concentrations. No DC
voltage application in CW controls.

composed of H2 and CO2 without methane due to dark
fermentation of carbohydrates producing VFAs and CO2.
However, hydrogen concentration in the gas phase increased
to 98% after two days of operation due to hydrogen gas
formation by reaction (3). Hydrogen percentage in the gas
phase also increased with increases in initial COD concen-
tration and reached the highest level (99.9%) for the initial
COD of 35172.16 mg L
1 at the end of operation due to high
volumes of H2 gas formation at high COD and VFA concen-
trations with no CO2 formation (eqn (3)).
Variation of H2 gas formation rate (HFR, mL d
1) with the
initial COD concentration is depicted in Fig. 3. HFR increased
with increasing COD content as expected due to larger
volumes of H2 gas production at high COD contents within the
same operation period. The initial COD concentration maxi-
mizing cumulative hydrogen gas volume (26472 mL), H2
production rate (4553 mL d
1) and hydrogen percentage (99%)
in the gas phase was 35172 mg L
1.

Fig. 2 e Variation of final (140 h) cumulative hydrogen gas Fig. 3 e Variation of hydrogen gas formation rate with the
volume and H2 gas percentage with the initial COD. initial COD content of CW solution.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 5 8 4 1 e1 5 8 4 9
3.2. COD removals
Fermentation of carbohydrates by dark fermentation bacteria
produced VFAs and CO2 resulting in COD removal from CW
solution. COD removals from diluted CW solutions were
quantified for the electro-hydrolysis and control experiments.
Fig. 4 depicts time course of COD variations for different initial
COD contents. COD concentrations decreased with time for
both the control and the electro-hydrolysis experiments.
Decreases in COD in control CW experiments indicated
bacterial fermentation of carbohydrates to volatile fatty acids
(VFAs) and CO2 in the absence of DC voltage application.
Bacterial fermentation of carbohydrates and therefore COD
removals were completed within 96 h in both the electro-
hydrolysis and control experiments. COD contents of experi-
mental CW solutions decreased from initial levels of 20415,
25175, 31781 and 35172 mg L
1 to final concentrations of 16262,
20410, 25690 and 27613 mg L
1, respectively yielding 20.3%e
21.5% COD removals. The final COD contents of the control
CWs were 17020, 21300, 27210, 30097 mg L
1 yielding 16.7, 15.4,
14.38 and 14.43%% COD removals by bacterial fermentation.
Therefore, most of the COD compounds (carbohydrates) were
Fig. 4 e Time course of variations of COD concentrations for diluted CW solutions.
15845
fermented by anaerobic bacteria releasing CO2 and much
smaller fractions (3.71, 3.53, 4.78 and 7.07%) were decomposed
by voltage application.
Fig. 5 depicts variation of percent COD removal and hydrogen
yields (mL H2 g
1 COD) with the initial COD concentration. The
hydrogen yields were calculated by using eqn (9). Percent COD
removals were low and varied between 19% and 21.5%. The
highest percent COD removal (21.5%) was obtained with the
highest initial COD content. COD removals were mainly realized
by bacterial fermentation of carbohydrates present in CW
solution (i.e., fermentation of lactose to VFAs and CO2).
Hydrogen gas yield (HY) increased with increasing initial COD
content and reached the highest level (7004 mL g
1 COD) at the
highest initial COD concentration (35172 mg L
1).
3.3. Variations in pH and conductivities
pH and conductivity measurements were carried out during the
course of electro-hydrolysis and the control experiments. Figs. 6
and 7 depict time course of variations in pH and conductivities.
Initial conductivity and pH of the raw CW solution was
6.52 mS cm
1 and 4.6, respectively. Due to serial dilutions in
15846 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 5 8 4 1 e1 5 8 4 9
Fig. 5 e Variation of hydrogen gas yield and percent COD
removals with the initial COD concentrations.
experimental CW solutions different initial pH and conductivi-
ties were obtained. pH and the conductivity of the solution are
inversely related. High (Hþ) ion concentration in the CW yielded
lower pH and, higher conductivities after bacterial fermenta-
tion. Conductivities decreased with time due to (Hþ) ion removal
from CW solutions for H2 gas formation with DC voltage
Fig. 6 e Time course of variations of medium pH for the electro-hydrolysis and control experiments with different initial
COD concentrations.
application (eqn (3)) in parallel to increases in pH. In CW control
experiments with no voltage application, the initial pH
decreased from 5.2 to 4.6 due to VFA formation and hydrogen
ion (Hþ) release from VFAs. However, in electro-hydrolysis
experiments, pH increased to 8.69, 9.12, 9.28, 9.36 and the
conductivities decreased to 2.14, 2.49, 2.77 and 2.87 mS cm
1 for
the initial COD concentrations of 20415, 25175, 31781 and
35172 mg L
1, respectively. In the water control experiment, the
conductivity decreased from 0.387 mS cm
1 to 0.18 mS cm
1
within 142 h with an increase in pH from 6.64 to 7.18.
Oxidationereduction potential (ORP) is a measure of elec-
tron density in solution and is inversely related to pH.
Therefore, ORPs decreased during the course of experiments
as a result of increases in pH. ORPs decreased from the initial
levels of 106.7, 117.8, 117.6 and 98.2 mV to final levels of
97.0,

119.6,
121.9 and
139.7 mV for the initial COD concentra-
tions of 20415, 25175, 31781 and 35172 mg L
1, respectively.
Final ORPs at high initial COD concentrations were low due to
removal of large amounts of Hþ ions from solution for H2 gas
formation. ORP in water control decreased from 106.7 mV to

10.2 mV within 142.7 h. Table 2 summarizes initial and final
pH, ORP and conductivities for the electro-hydrolysis and
water control experiments. Medium pH increased, ORP and
conductivities decreased at the end of electro-hydrolysis as
a result of (Hþ) ion removal from the CW solution for H2 gas
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 5 8 4 1 e1 5 8 4 9 15847

Fig. 7 e Time course of variations of conductivities for the electro-hydrolysis and control experiments for different initial
COD concentration.

formation. Changes in pH, ORP and conductivities were low in
water control due to lower levels of H2 gas formation.
3.4. Current intensities and energy efficiencies
Variation of current intensities with time is depicted in Fig. 8
for water control and electro-hydrolysis experiments with
different initial COD contents. Current intensities decreased
with time due to increases in pH (i.e., decreases in (Hþ)
concentrations) and decreases conductivities. High initial
COD contents (high proton release) resulted in higher
current intensities as expected. Considerable reductions in
current intensities were observed at the end of the experi-
ments due to reduced (Hþ) ion concentrations.

Table 2 e Initial and final pH, ORP and conductivity values for the electro-hydrolysis and water control experiments.
Initial COD pH ORP (mV) Conductivity (mS cm
1) Average voltage (V)
(mg L
1)
Initial Final Initial Final Initial Final

20415 5.34 8.69 106.7
97.00 2.48 2.14 11.84

25175 5.22 9.12 117.8
119.6 3.14 2.49 11.88
31781 5.16 9.28 117.6
121.7 3.94 2.77 11.90
35172 5.02 9.36 98.20
139.7 4.37 2.8 11.65
Water 6.64 7.18 106.7
10.2 0.387 0.180 12.52
15848 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 5 8 4 1 e1 5 8 4 9

Total volatile fatty acid concentrations (TVFAs) derived

Fig. 8 e Variation of current intensities with time for the
water control and electro-hydrolysis experiments with
different initial COD contents.
Energy efficiencies for hydrogen gas production for
different initial CODs were calculated using Eqn. (8). Electrical
energy inputs (Ee) were calculated by determining the area
under the curves presented in Fig. 8 (i.e., I versus time for
every initial COD). Energy efficiencies varied with time due to
variations in voltages and current intensities (I, amperes) as
a result of electrode corrosion and changes in the cheese whey
(CW) composition. Fig. 9 depicts variation of energy efficien-
cies with the initial CODs. Energy efficiencies varied between
11.35% and 20.44%. The lowest energy efficiency (11.35%) was
obtained with the lowest initial COD content (20415 mg L
1)
and the highest was with the highest COD (35172 mg L
1). At
low initial CODs H2 gas production was limited by the avail-
able (Hþ) ions yielding low energy efficiencies. As the initial
COD was increased more protons became available for H2 gas
production yielding high energy efficiencies.
from bacterial fermentation of carbohydrates are listed in
Table 3. Final TVFA concentrations in the electro-hydrolysis
experiments varied between 1726 and 2304 mg L
1 depend-
ing on the initial CODs. Final TVFA concentrations in CW
control experiments (no voltage only bacterial fermentation)
were higher and varied between 2180 and 3890 mg L
1. Final
TVFA concentrations increased with increasing COD contents
in parallel to increases in H2 gas formation. At high initial COD
concentrations, carbohydrate fermentations were more
effective yielding higher VFA concentrations. In electro-
hydrolysis experiments TVFA concentrations decreased due
to breakdown of VFAs by applied voltages. The difference in
final TVFA concentrations between the electro-hydrolysis and
control experiments increased with the increase in initial COD
concentrations. For control CW with initial COD of
35172 mg L
1, TVFA concentration increased from the initial
level of 2142e3890 mg L
1 without DC voltage application. For
the electro-hydrolysis experiment with the same initial COD
of 35172 mg L
1, final TVFA concentration was 2304 mg L
1.
Final TVFA in electro-hydrolysis experiment (2304 mg L
1) was
lower than that of the CW control experiment (3890 mg L
1)
and the difference was probably due to partial breakdown of
VFAs by electrical current. Table 3 also summarizes weight
losses from the electrodes due to Al(III) release to the solution
during electro-hydrolysis. Released Al(III) ions can be removed
from the solution by precipitation in form of Al(OH)3 with the
addition of lime (Ca(OH)2) solution followed by filtration.
Hydrogen gas production by electro-hydrolysis of cheese
whey solution is a promising approach for fast and effective
production of nearly pure H2 gas. However, electrode corro-
sion and break-down is one of the problems to be resolved.
More durable and highly conductive electrodes should be used
for longer operations. Aluminum electrodes were used in this
study due to high conductivity of aluminum. However, due to
electrode break-down the experiments were ended after 144 h
Table 3 e Initial and final total sugar and TVFA
concentrations and weight losses of electrodes.
Parameters Initial COD concentration (mg L
1)

Water 20415 25175 31781 35172

T. sugaro (mg L
1) e 15672 20160 24248 26549

T. sugarf (mg L
1) e e 12787 16958 20489 22455
Exp.CW
T. sugarf (mg L
1) e e 13011 17052 20742 22522
Cont.CW
TVFAo (mg L
1) e 1182 1457 1840 2142
TVFAf (mg L
1) e e 1726 2132 2175 2304
Exp.CW
TVFAf (mg L
1) e e 2180 2927 3311 3890
Cont.CW
Initial weight 106.05 106.09 106.26 99.21 105.76
of cathode (g)
Final weight 91.62 102.75 99.81 93.05 99.46
of cathode (g)
Initial weight 106.12 104.37 102.75 106.53 105.85
of anode (g)
Final weight 97.54 92.21 88.33 91.42 88.77
Fig. 9 e Variation of energy efficiencies with the initial COD
of anode (g)
content for electro-hydrolysis experiments.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 7 ( 2 0 1 2 ) 1 5 8 4 1 e1 5 8 4 9
operation. In order to increase the initial VFA content of CW
solution dark fermentation can be realized before electro-
hydrolysis. Simultaneous dark fermentation and electro-
hydrolysis during the first 96 h of operation may have
adverse effects on bacterial activity reducing VFA formation.
Therefore, application of electro-hydrolysis after dark
fermentation of CW carbohydrates may improve hydrogen
gas formation. COD concentrations larger than 35172 mg L
1
should be used to determine the performance of the system at
high initial COD or VFA concentrations.
4. Conclusions
DC current generated by a PVC was supplied to diluted cheese
whey (CW) solution in a mechanically mixed and sealed
reactor for hydrogen gas production. Protons released from
volatile fatty acids (VFAs) formed by fermentation of carbo-
hydrates in CW solution reacted with electrons provided by
electrical current to form hydrogen gas. The effects of initial
COD content on the rate and yield of hydrogen gas formation
were investigated. The highest cumulative hydrogen gas
volume (26472 mL), H2 production rate (4553 mL d
1),
hydrogen yield (7004 mL g
1 COD) and hydrogen percentage
(99%) in the gas phase were obtained at the highest initial COD
concentration (35172 mg L
1). Percent COD removals also
increased with increasing initial COD and reached the highest
level (21.5%) at the highest COD content. Conductivities
decreased as a result of increases in solution pH. The highest
energy efficiency (20.44%) was obtained with the highest COD
content. Use of PVC panels as source of electricity for
hydrogen gas production by electro-hydrolysis of cheese whey
was proven to be an effective method. Further improvements
in H2 gas production may be accomplished by using sequential
fermentation and electro-hydrolysis of high strength CW
solution and operating the system under more intensive
sunlight.
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