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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 4 1 ( 2 0 1 6 ) 1 3 4 2 6 e1 3 4 3 5

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Energy and economic analyses of models


developed for sustainable hydrogen production
from biogas-based electricity and sewage sludge
a,*

lu a, Sinan Demir b, Emrah Ozahi


Aysegul Abusog
a

Department of Mechanical Engineering, University of Gaziantep, 27310, Gaziantep, Turkey


West Virginia University, Mechanical and Aerospace Engineering Department, Morgantown, WV, 26506-6106,
USA

article info

abstract

Article history:

Five models were developed for the use of biogas-based electricity and sewage sludge

Received 8 March 2016

obtained from a municipal wastewater treatment plant for hydrogen production. These

Accepted 10 May 2016

models included alkaline, PEM, high temperature water electrolysis, alkaline hydrogen

Available online 6 June 2016

sulfide electrolysis and dark fermentation biohydrogen production processes. Energy and
economic analyses were performed on the models by applying thermodynamic procedures

Keywords:

and the results were compared. The daily hydrogen production rates of the models were

Hydrogen production

calculated as 594, 625.4, 868.6, 10.8 and 56.74 kg for models 1, 2, 3, 4 and 5, respectively. The

Electrolysis

electricity costs of the models were calculated as 3.60, 3.43, 2.47, 1.16 and 6.7 $/kg-H2, for

Biohydrogen

models 1, 2, 3, 4 and 5, respectively. In terms of the hydrogen production rate, the high

Wastewater treatment plant

temperature electrolysis process was found to be superior to the other models, followed by

Biogas

the PEM electrolysis process, whereas, in terms of the hydrogen production cost, hydrogen
sulfide electrolysis was found to be superior to the other models. This paper aimed to
determine the most appropriate model for a wastewater treatment plant among the
considered models in terms of both hydrogen production and hydrogen production cost.
2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Introduction
Hydrogen is an energy carrier and it is proposed as an alternative energy source at present and in the future. Several
hydrogen production processes exist, including steam
methane reforming, partial oxidation of methane, autothermal reforming of methane, coal gasification, biomass
pyrolysis and gasification, electrolysis, the sulfureiodine
cycle, photo-synthetic/photo-biological water splitting, and
direct photocatalytic water splitting [1]. Each technology is at a
different stage of development, and each offers unique opportunities, benefits and challenges [2]. As of today, most

produced hydrogen (80e85%) is obtained by the steam


reforming and gasification processes [3]. Although these
preferred hydrogen production methods are considered more
economical compared to the others, they are non-sustainable
and not eco-friendly. In the long run, hydrogen should preferably be produced from renewable sources such as the
electrolysis of water with renewable electricity or by means of
biological hydrogen production [4].
The main task of a wastewater treatment plant (WWTP) is
to treat wastewater to an extent that it can be discharged into
a natural water body after minimizing the harmful impact on
natural water quality. The wastewater treatment process

* Corresponding author. Tel.: 90 342 3172567; fax: 90 342 3601104.

E-mail address: ozahi@gantep.edu.tr (E. Ozahi).


http://dx.doi.org/10.1016/j.ijhydene.2016.05.105
0360-3199/ 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

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 4 1 ( 2 0 1 6 ) 1 3 4 2 6 e1 3 4 3 5

requires large amounts of energy. However, wastewater


sludge can be used as a renewable energy source. As a result of
the anaerobic digestion process, sludge is degraded to produce
biogas which consists of 60e70% CH4, 30e35% CO2, 1e2% H2S,
and 0.3e3% N2 with various minor impurities, notably NH3
and halides. This biogas can be used to produce heat and
electricity onsite [5]. Electricity produced by the cogeneration
facilities of a WWTP can be used as work input to the installed
water electrolysis unit for hydrogen production. This
hydrogen production method, in which biogas is used as a
renewable energy source, can be considered as an eco-friendly
or green process. The importance of electricity obtained from
renewable energy sources is increased for the production of
hydrogen [6].
In the electrolysis process, electricity is used to decompose
water into its elemental components: hydrogen and oxygen.
Electrolysis is often seen as the preferred method of hydrogen
production, as it is the only process which does not rely on
fossil fuels. It also provides high product purity, and is feasible
for both small and large scale hydrogen production. Many
different types of electrolysis cells have been proposed and
constructed such as alkaline, PEM and high temperature
steam electrolysis processes [7]. Another option is biohydrogen production from bio-renewables. Biohydrogen is a
renewable biofuel produced from bio-renewable feedstocks by
chemical, thermochemical, biological, biochemical, and biophotolytic methods. Processes for biological hydrogen production mostly operate at ambient temperature and pressure,
and are expected to be less energy intensive than thermochemical hydrogen production methods. These processes can
use a variety of feed stocks as carbon sources, such as organic
waste materials, which facilitate waste recycling. Since activated sludge waste obtained from municipal WWTPs contains
high levels of organic matter, it can be used as a carbon source
and is considered a potential substrate for hydrogen production. Direct and indirect bio-photolysis, photo-fermentation,
dark fermentation and integrated dark and photofermentation can be given as some examples of biohydrogen
production processes [8e10].
Numerous studies have been undertaken to conduct
water electrolysis and biohydrogen production [11e17].
However, only a few of these studies have been directly
related to biogas-based hydrogen production and biohydrogen production from sewage sludge. Coskun et al. [6]
performed an energy analysis of hydrogen production with
biogas-based electricity. In their study, a facility generating
its own electricity from biogas obtained from a WWTP was
considered for investigation. The hydrogen production process conducted using biogas-based electricity was examined
by three methods of electrolysis and PEM electrolyzing system was found as having higher overall system efficiencies of
the other two electrolyzing systems. Pandu and Joseph [18]
reviewed biohydrogen production processes and stated that
the major biological processes discussed for hydrogen production were bio-photolysis of water by algae, dark fermentation, photo-fermentation of organic materials and
sequential dark and photo-fermentation processes. Genc [19]
reviewed biohydrogen production from wastewater sludge
and emphasized the importance of sludge pretreatment due
to the low sludge yield of fermentative hydrogen production

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methods. Wang et al. [10] presented a study on biohydrogen


production from wastewater sludge by Clostridium bifermentans. This work examined the anaerobic digestion of wastewater sludge using a Clostridium strain isolated from the
sludge as the inoculum.
Despite the existence of numerous studies on hydrogen
production from renewable energy sources, hydrogen production from biogas-based electricity and sewage sludge are
very limited in the open literature, to the best of our knowledge. In this study, five different hydrogen production models
were developed based on the outputs of an actual municipal
WWTP. These five models include alkaline, PEM, high temperature water electrolysis, hydrogen sulfur alkaline electrolysis and dark fermentation hydrogen production
processes. The energy relations and economic analyses of the
models were performed using the data provided from the
plant management and previously published works [5,20] of
the authors. The significance of the models presented in this
paper is that they can be used to predict the hydrogen production potential of any municipal wastewater treatment
plant since these plants have more or less similar processes
and outputs such as biogas, sewage sludge, electricity, etc.

Model descriptions
The GASKI WWTP is a municipal wastewater treatment plant
located in the city of Gaziantep, Turkey, and the flow schematic of the facility is given in Fig. 1. The plant treats nearly
222,000 m3/day of domestic wastewater using primary, secondary (biological) and tertiary (anaerobic sludge digestion)
treatments. The daily biogas production is nearly 15,200 m3, as
a result of the sludge stabilization process which takes place
in the anaerobic digesters of the plant. 61% (9275 m3/day) of
the total biogas produced in the anaerobic digestion system is
used as a fuel for the installed gas engine powered cogeneration facility on the campus of the WWTP. The remaining
part (5925 m3/day) is reserved in the biogas storage tank. The
electricity production of the cogeneration plant is 1000 kWh.
The digested sludge is sent to the de-watering unit of the
WWTP to increase the dry matter content to 22%. The mass
flow rate of the digested sludge is reduced to 2.48 kg/s as it
exists the de-watering stage. In this study, five models were
developed for the use of actual WWTP outputs (biogas, electricity and sewage sludge) for hydrogen production. The
models are described in detail below.
In model 1 (see Fig. 2), an alkaline electrolysis process was
considered for hydrogen production. In this model, the work
output of the biogas engine powered cogeneration plant,
1000 kWh, is used as the work input to the electrolysis process. Water is heated before entering the electrolysis stage.
For the process of heating water, there are two different options at the plant. The first involves the use of a very small
amount of reserved biogas (about 0.001 kg/s) in a boiler (see
Fig. 1a); the second option is to use the waste heat of the
exhaust gas from the cogeneration plant by means of an
exhaust gas heat exchanger (see Fig. 1b). The mass flow rate of
the water entering the electrolysis process is taken as 0.062 kg/
s. The temperature and pressure of preheated water by the
boiler are 80  C and 1 bar, respectively.

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Fig. 1 e Flow schematic of GASKI WWTP.

Fig. 2 e Hydrogen production model 1 with an alkaline electrolysis process using a (a) biogas boiler or, (b) exhaust gas heat
exchanger.

In model 2 (see Fig. 3), a PEM electrolysis process was


considered. In this model, work input to the electrolysis process and biogas consumed through the boiler to preheat the
water are the same as in model 1. As mentioned above,
exhaust gas from the cogeneration unit can be used if available. In this model, the mass flow rate of the water entering
the electrolysis process is taken as 0.065 kg/s. The temperature and pressure of the water preheated by the boiler are
80  C and 1 bar, respectively.
In model 3 (see Fig. 4), a high temperature electrolysis
process was considered for hydrogen production. In this
model, the work demand of the electrolysis system is also
provided by the cogeneration system. A small amount of the
reserved biogas (0.025 kg/s) from the WWTP can be used to
produce high temperature steam in the boiler. The mass flow

rate of the water entering the electrolysis process is taken as


0.09 kg/s. The temperature and pressure of the steam produced in the boiler are 800  C and 5 bar, respectively.
In model 4 (see Fig. 5), a hydrogen sulfide (H2S) electrolysis
process (H2S / H2 1/2S2) was developed for hydrogen production. The biogas produced by anaerobic digestion of the
sludge is mostly methane (up to 60%); the remaining part is
mostly acidic gases, primarily carbon dioxide, and hydrogen
sulfide. When biogas is directly burned as a fuel, engines tend
to wear out quickly. To prevent this, the H2S in the biogas is
eliminated in a desulfurization unit (DeSOx) before the combustion process. Although its presence in the biogas may
cause considerable system and environmental problems, the
energy demand for the electrolysis process of H2S is lower (by
about 3.25 times) than that of water. In model 4, biogas

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Fig. 3 e Hydrogen production model 2 with a PEM electrolysis process using a (a) biogas boiler or, (b) exhaust gas heat
exchanger.

produced by the anaerobic digestion of sludge in the WWTP is


first passed through a hydrogen sulfide separator and the H2S
content is collected. H2S-free biogas enters the cogeneration
unit at the same mass flow rate, and 1000 kWh of electricity is
produced. The mass flow rate of H2S entering the electrolysis
process is 0.0021 kg/s, which can be found theoretically by
taking the H2S content of the biogas. In this model, due to the
small amount of H2S collected, the work demand of the electrolysis process is small (5.83 kWh for the GASKI WWTP).
In model 5 (see Fig. 6), a fermentative hydrogen production
(biohydrogen) model was considered. In this process, sewage
sludge is used directly for hydrogen production under
fermentative conditions (C6H12O6 6H2O / 12H2 6CO2). In
contrast to anaerobic methane digestion in which the

intermediate product (hydrogen) is converted to methane, the


final product of the dark fermentation process is hydrogen. An
important distinction from anaerobic methane digestion is
that, in hydrogen fermentation, only hydrogen-producing
microorganisms are active. Thus, in this system, there is no
biogas production. The electricity and heat requirements of
the dark fermentation process can be met by the sludge
incineration plant. Digested sludge after the dark fermentation process enters the incineration plant and a sludge drying
process takes place as the first step. Then, the dried sludge is
incinerated in a fluidized bed incineration system. Exhaust
gas is obtained at 850  C, which then enters a gas turbine for
electricity production (1500 kWh). Also, the necessary heat
required for the sludge in the dark fermentation process can

Fig. 4 e Hydrogen production model 3 with a high temperature electrolysis process.

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Fig. 5 e Hydrogen production model 4 with an alkaline electrolysis process of the H2S.

be provided by the sludge incineration plant. The mass flow


rate of the sludge in the GASKI WWTP before the fermentation
processes is 12.06 kg/s. Since hydrogen produced through dark
fermentation is only 60% by volume, it must be purified using
a gas separator.

Energy and economic analyses


The minimum work needed for 1 kg of hydrogen production
by the water and hydrogen sulfide electrolysis processes can
be calculated by the following equations:
wrev;elect

DGelect;H2 O
kJ=kg
MH2

(1)

wrev;elect

DGelect;H2 S
kJ=kg
MH2

(2)

Where DGelect;H2 O and DGelect;H2 S are the Gibbs free energy (kJ/
kmol) of water and hydrogen sulfide, respectively, and MH2 is
the molar mass of hydrogen (kg/kmol). Thus, the actual work
demand can be calculated as:
wact;elect

wrev;elect
kj=kg
hth

(3)

The thermal efficiency of the electrolysis unit can be


calculated as:
hth

DH
EDH

DG Losses Ecell

Fig. 6 e Hydrogen production model 5 with a dark fermentation process.

(4)

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where DH is the enthalpy change of the water decomposition


reaction as energy input. EDH is the equilibrium voltage and
Ecell is the cell voltage which is always between 1.8 and 2.0 V at
a current density of 1000e300 Am2 for industrial water
electrolysis [21]. For alkaline and PEM electrolysis, Eq. (4) can
be rewritten in a simple form as:

In this study, we considered an actual municipal WWTP and


elaborated five hydrogen production models. Hydrogen production rates and hydrogen production costs were calculated
using thermodynamic calculations and a simple economic
analysis procedure.
For model 1, water is heated up to 80  C; the value of the
Gibbs free energy of water at this temperature is 228,378 kJ/
kmol. The heat requirements of the water heating process
were calculated to be 14.25 kW. The daily hydrogen produced
by model 1 was calculated as 594 kg and the actual electricity
cost of hydrogen production was found to be 3.60 $/kg-H2.
Using Eq. (5), the thermal efficiency of the electrolysis process
for model 1 was found to be 78%. The thermodynamic data

and the results of the energy analyses for model 1, according


to the nomenclature provided in Fig. 2, are given in Table 1.
For model 2, the heat requirements of the heating process
of water were calculated to be 15.0 kW. Using Eq. (5), the
thermal efficiency of the electrolysis process for model 2 was
found to be 82%. The daily hydrogen produced by model 2 was
calculated as 625.4 kg and the actual electricity cost of
hydrogen production was found to be 3.43 $/kg-H2. The thermodynamic data and the results of the energy analyses for
model 2, according to the nomenclature provided in Fig. 3, are
given in Table 2.
For model 3, the value of the Gibbs free energy of steam is
18,519 kJ/kmol at 800  C. The heat requirements of the boiling
process for steam production were calculated to be 363 kW.
The daily hydrogen produced by model 3 was calculated as
868.6 kg and the actual electricity cost of hydrogen was found
to be 2.47 $/kg-H2. Using Eq. (4), the thermal efficiency of the
electrolysis process for model 3 was found to be 94%. The
thermodynamic data and the results of the energy for model 3,
according to the nomenclature provided in Fig. 4 are given in
Table 3.
For model 4, the value of the Gibbs free energy of hydrogen
sulfide is 73,289 kJ/kmol at 25  C, while the Gibbs free energy of
water is 237,180 kJ/kmol at the same temperature. As stated
previously, the energy demand for the electrolysis process of
H2S is lower (by about 3.25 times) than that of water at the
same temperature. The biogas produced by the WWTP includes nearly 1% H2S and, assuming that all of the hydrogen
sulfide is collected by the separator, the mass flow rate of H2S
for the electrolysis process was found to be 7.63 kg/h. The
daily hydrogen quantity produced by model 4 was calculated
as 10.8 kg and the actual electricity cost of hydrogen production was found to be 1.16 $/kg-H2. If the proportion of
hydrogen sulfide in the biogas was greater than in of the
present case, it would be possible to produce 1901.5 kg/day of
hydrogen with a work input of 1000 kWh to the electrolysis
process. The thermodynamic data and the results of the

Table 1 e Thermodynamic data and results of the energy


analyses of model 1 with respect to the points indicated
in Fig. 2.

Table 2 e Thermodynamic data and results of the energy


analyses of model 2 with respect to the indicated points
in Fig. 3.

State no

State No

hth

1:48
Ecell

(5)

According to the price of electricity, the unit cost of


hydrogen can be calculated with the following equation:
CostH2 Celectricity  Wdemand

(6)

where Celectricity is the unit cost of electricity produced by the


cogeneration unit of the WWTP and is taken as 0.0893 $/kWh
[20]. Wdemand is the electricity work needed for hydrogen
production using these models in kWh/kg H2. The total cost
of an electrolyzer unit consists of capital costs (55%), electricity costs (35%) and operating and maintenance costs
(10%) [22].

Results and discussion

1
2
3
4
5
6
7
8

Fluid

Values

Biogas inlet
Work
Water
Pure water
Heated water
Biogas (with boiler)
Heat (with EGHE)
Hydrogen (g)
Oxygen (g)

0.129 (kg/s)
1000 kWh
0.062 (kg/s) @25  C and 1 bar
0.062 (kg/s) @25  C and 1 bar
0.062 (kg/s) @80  C and 1 bar
0.001 (kg/s) (Fig. 1 (a))
14.25 kW (Fig. 1 (b))
594 kg/day
4762.8 kg/day

Type of electrolysis: Alkaline.


Efficiency of electrolysis: 78%.
Minimum power consumption of electrolysis: 113,282.7 kJ/kg
(31.47 kWh/kg H2).
Actual power consumption of electrolysis: 145,234.23 kJ/kg
(40.34 kWh/kg H2).
Cost of electricity: 0.0893 $/kWh.
Minimum electricity cost of hydrogen: 2.81 $/kg H2.
Actual electricity cost of hydrogen: 3.60 $/kg H2.

1
2
3
4
5
6
7
8

Fluid

Values

Biogas inlet
Work
Water
Pure water
Heated water
Biogas (with boiler)
Heat (with EGHE)
Hydrogen gas
Oxygen gas

0.129 (kg/s)
1000 kWh
0.065 (kg/s) @25  C and 1 bar
0.065 (kg/s) @25  C and 1 bar
0.065 (kg/s) @80  C and 1 bar
0.0011 (kg/s) (Fig. 2 (a))
15.0 kW (Fig. 2 (b))
625.4 kg/day
5003.2 kg/day

Type of electrolysis: PEM.


Efficiency of electrolysis: 82%.
Minimum power consumption of electrolysis: 113,282.7 kJ/kg
(31.47 kWh/kg H2).
Actual power consumption of electrolysis: 138,149.6 kJ/kg
(38.37 kWh/kg H2).
Cost of electricity: 0.0893 $/kWh.
Minimum electricity cost of hydrogen: 2.81 $/kg H2.
Actual electricity cost of hydrogen: 3.43 $/kg H2.

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Table 3 e Thermodynamic data and results of the energy


and analyses of model 3 with respect to the indicated
points in Fig. 4.

Table 5 e Thermodynamic data and results of the energy


analyses of model 5 with respect to the indicated points
in Fig. 6.

State No

State No

1
2
3
4
5
6
7
8

Fluid

Values

Biogas inlet
Work
Water
Pure water
Steam
Biogas (with boiler)
Heat (with EGHE)
Hydrogen gas
Oxygen gas

0.129 (kg/s)
1000 kWh
0.09 (kg/s) @25  C and 1 bar
0.09 (kg/s) @25  C and 1 bar
0.09 (kg/s) @800  C and 5 bar
0.025 (kg/s)
363 kW
868.6 kg/day
6948.8 kg/day

Type of electrolysis: High temperature electrolysis.


Efficiency of electrolysis: 94%.
Minimum power consumption of electrolysis: 93,511.4 kJ/kg
(25.98 kWh/kg H2).
Actual power consumption of electrolysis: 99,480.2 kJ/kg
(27.63 kWh/kg H2).
Cost of electricity: 0.0893 $/kWh.
Minimum electricity cost of hydrogen: 2.32 $/kg H2.
Actual electricity cost of hydrogen: 2.47 $/kg H2.

Table 4 e Thermodynamic data and results of the energy


analyses of model 4 with respect to the indicated points
in Fig. 5.
State No
1
2
3
4
5
6

Fluid

Values

Biogas inlet
Biogas
H2S
Work
Hydrogen gas
Sulfur gas

0.212 (kg/s)
0.129 (kg/s)
0.0021 (kg/s)
5.83 kWh
10.8 kg/day
170.6 kg/day

Type of electrolysis: Alkaline.


Efficiency of electrolysis: 78%.
Minimum power consumption of electrolysis: 36,353.7 kJ/kg
(10.1 kWh/kg H2).
Actual power consumption of electrolysis: 46,607.3 kJ/kg
(12.95 kWh/kg H2).
Cost of electricity: 0.0893 $/kWh.
Minimum electricity cost of hydrogen: 0.90 $/kg H2.
Actual electricity cost of hydrogen: 1.16 $/kg H2.

energy analyses for model 4, according to the nomenclature


provided in Fig. 5 are given in Table 4.
Wang et al. [10] demonstrated that the hydrogen yield of
the original sewage sludge can be up to 0.9 mmol-H2/g-DS (dry
solid content). The sludge content of the GASKI WWTP is
2170.8 kg-DS/h. According to this value, daily hydrogen production was found to be 56.74 kg with a 100% purity. This
hydrogen production rate is 10 times lower than the hydrogen
production rate of the water electrolysis process. This phenomenon is one of the most important drawbacks for the
commercialization of fermentative hydrogen production. The
thermodynamic data and the results of the energy analyses
for model 5, according to the nomenclature provided in Fig. 6,
are given in Table 5.
Applying a pre-treatment process such as freezing, sterilization or thawing before the dark fermentation process
remarkably increases the hydrogen production rate up to

1
2
3
4
5
6
7
8
9

Property

Value

Sludge
Sludge
Hydrogen gas
Hydrogen gas
Carbon dioxide gas
Sludge
Heated water
Water
Work

12.06 (kg/s) @25  C


12.06 (kg/s) @36  C
94.56 kg/day @ 60% purity
56.74 kg/day @ 100% purity
37.82 kg/day
12.05 kg/s @36  C
2.1 kg/s@ 88  C and
2.1 kg/s@ 25  C
176.4 kWh

Type of hydrogen production: Dark fermentation (Without pretreatment).


Actual power consumption of electrolysis: 268,920 kJ/kg
(74.7 kWh/kg H2).
Cost of electricity: 0.0893 $/kWh.
Electricity cost of hydrogen: 6.7 $/kg H2.

1.5e2.1 mmol-H2/g based on the chemical oxygen demand


(COD) [10]. A pre-treatment process not only releases insoluble organic matter into the water to increase the efficiency of
fermentation, but also inactivates methanogenic bacteria in
the substrate to reduce their consumption of hydrogen. If we
assume that a pre-treatment process is applied to the sludge,
since the COD value of the sludge for the GASKI WWTP is
65.28 g-COD/l, hydrogen production would be increased to
171.4 kg/day with 100% purity and the actual electricity cost of
hydrogen production would be 2.2 $/kg-H2. Although pretreatment processes increase the hydrogen production rate,
they are not so economical in terms of commercial practice.
Most studies related to pre-treatment applications performed
so far have been done only at the laboratory scale; the application of these methods for huge amounts of sewage sludge in
practice requires a considerable amount of energy. For
instance, for the sterilization pre-treatment process, sludge
should be heated up to 121  C. This means heating the sludge,
which has a mass flow rate of 12.06 kg/s from 25  C to 121  C,
requiring nearly 3500 kW of thermal energy. In the near
future, with further developments in technology, pretreatment processes may be applicable at high capacities.
Fermentation reactors may be designed in accordance with
the high thermal energy requirements of sludge. However, at
the current time, this area requires more attention and more
study to overcome this limitation.
The hydrogen production rate is most strongly affected by
the electrolysis temperature of the water electrolysis process.
Fig. 7 shows how the daily hydrogen production rate changes
with respect to the operation temperature of the electrolysis
process for models 1, 2 and 3. According to Fig. 7, it can be seen
that as the operation temperature of the electrolysis process
increases, the hydrogen production rate increases.
In Fig. 8, the hydrogen production rate of the models
developed for the GASKI WWTP are compared to each other.
As can be seen, model 3 had the highest hydrogen production
rate compared to the other four models. Among the five
models, model 4 had the lowest hydrogen production rate.
The electricity produced by the biogas powered cogeneration
system of the WWTP was totally consumed by the electrolysis

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620

H2 (kg/day)

610

600

590

580

570
275

310

345

380

415

450

T (K)

Fig. 8 e Comparison of hydrogen production rates of the


models developed for the GASKI WWTP.

(a)
650

H2 (kg/day)

640

630

620

610

600
275

310

345

T (K)

380

415

450

(b)
850

H2 (kg/day)

815

780

745

710

675
700

800

900

1000

1100

1200

1300

T (K)

appropriate option for municipal WWTPs for two important


reasons: (1) After the wastewater treatment process, the
sludge is considered to be a by-product of the treatment facility and it must be eliminated. Using model 5, this elimination process is replaced by a dark fermentation process for
hydrogen production. This means that the sludge can be used
for another valuable production system, i.e. hydrogen production. (2) Energy can be stored as hydrogen in the fermentation process. Since wastewater contains 10 times more
energy potential than is needed to treat it [23], the surplus
energy produced can be stored by this method in the plant.
Fig. 9 shows the comparison of the actual electricity consumption of the hydrogen production models. Model 5 had the
highest electricity consumption rate for 1 kg of hydrogen
production because of the low hydrogen production rate of the
dark fermentation process, whereas model 4 had the lowest
electricity consumption rate due to the low hydrogen production rate.
According to the economic analysis based on the electricity
costs of the models, model 4 had the lowest hydrogen production cost (see Table 6 and Fig. 10). This was due to the low
hydrogen production rate of the model as a result of the low
amount of hydrogen sulfide in the biogas. Model 5 incurred
the highest cost rate of all the models, due to the high investment and operation and maintenance costs of the dark
fermentation process. However, considering the remarkable
economic and environmental advantages of the high

(c)
Fig. 7 e Daily hydrogen production rate with respect to the
electrolysis operation temperature for (a) model 1 (b) model
2 (c) model 3.

processes for hydrogen production in the first three models.


For model 4, only a small amount of electricity produced by
the cogeneration system was consumed due to the inadequate
amount of H2S in the biogas produced by the anaerobic
digestion system, as previously mentioned.
Although its greatest disadvantage is the low hydrogen
production rate from sewage sludge, the performance of a
dark fermentation process can be improved by a pretreatment unit. Thus, model 5 can be seen as the most

Fig. 9 e Comparison of electricity consumption rates of the


models developed for the GASKI WWTP.

13434

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 4 1 ( 2 0 1 6 ) 1 3 4 2 6 e1 3 4 3 5

Table 6 e Economic analysis of the considered hydrogen production models.


Hydrogen
production model

Model 1
Model 2
Model 3
Model 4
Model 5

H2 production
rate

H2 electricity cost

Capital investment
cost

Operating and
maintenance cost

Total H2 cost

kg/year

$/kg H2

$/year

$/kg H2

$/year

$/kg H2

$/year

$/kg H2

$/year

207,900
218,890
304,010
3600
18,913.3

3.60
3.43
2.47
1.16
6.7

748,440
750,792.7
750,792.7
4176
126,719.1

5.66
5.39
0.96
1.82
6.87

1,120,680
1,123,635.3
277,852
6552
129,936.6

1.03
0.98
0.75
0.33
2.06

203,940
204,297.3
217,150
1188
38,981

10.29
9.8
4.18
3.31
15.63

2,037,420
2,042,973.3
1,210,249
11,916
295,614.9

 According to the energy and economic analyses of these


models, model 3 can be seen as the most appropriate one.
In this model, as well as in the other electrolysis models,
cogeneration waste heat (exhaust) can be used if available
as a second option to heat water. Model 5 is a biological
hydrogen production process that requires a dark
fermentation reactor. The commercial limitations of the
biological hydrogen production process are a result of the
low hydrogen yield of this model. The application of a pretreatment process on the sludge could increase the
hydrogen yield.

Fig. 10 e Comparison of hydrogen production costs of the


models developed for the GASKI WWTP.

temperature electrolysis process, model 3 can be considered


as the most appropriate model for municipal WWTPs in terms
of both the hydrogen production rate and the hydrogen production cost. In Fig. 10, a comparison of the hydrogen production costs for the models is presented.

Conclusion
In this study, five hydrogen production models were developed, and energy and economic analyses were performed
considering the actual operation data from an existing
municipal WWTP. The following conclusions can be drawn
based on the analyses and results:
 The daily hydrogen production rates of the models were
calculated as 594,625.4, 868.6, 10.8 and 56.74 kg, for models
1, 2, 3, 4 and 5, respectively. Of the models considered in this
study, model 3 had the highest hydrogen production rate,
whereas model 4 had the lowest hydrogen production rate
due to the inadequate H2S level present in the biogas produced from the anaerobic digestion process in the WWTP.
 The electricity costs of the models were calculated as 3.60,
3.43, 2.47, 1.16 and 6.7 $/kg-H2, for models 1, 2, 3, 4 and 5,
respectively. According to these results, model 5 had the
highest electricity costs while model 4 has the lowest
electricity costs due to the lower Gibbs free energy of H2S as
compared to water at the same temperature.
 The total hydrogen production costs (capital, operating and
maintenance, electricity) of the models were 10.29, 9.8, 4.18,
3.31 and 15.63 $/kg-H2, for models 1, 2, 3, 4 and 5,
respectively.

Acknowledgments
The authors acknowledge the support provided by the Scientific Research Projects Unit at the University of Gaziantep.

Nomenclature
wrev;elect
wact;elect
DG
MH2
DH
E
Celectricity
W

reversible electricity work, kj/kg


actual electricity work, kj/kg
gibbs free energy, kj/kmol
molar mass of hydrogen, kg/kmol
enthalpy change, kj/kg
voltage, V
unit cost of electricity, $/kWh
work, kW

Abbreviations
PEM
proton exchange membrane
WWTP wastewater treatment plant
Greek letters
h
energy efficiency

references

[1] Simpsona AP, Lutzb AE. Exergy analysis of hydrogen


production via steam methane reforming. Int J Hydrogen
Energy 2007;32(18):4811e20.
[2] http://www.iea.org/papers/2006/hydrogen.pdf.
[3] Konieczny A, Mondal K, Wiltowski T, Dydo P. Catalyst
development for thermocatalytic decomposition of methane
to hydrogen. Int J Hydrogen Energy 2008;33(1):264e72.
[4] de Vrije T, Claassen PAM. Dark hydrogen fermentations. In:
Reith JH, Wijffels RH, Barten H, editors. Bio-methane & bio-

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 4 1 ( 2 0 1 6 ) 1 3 4 2 6 e1 3 4 3 5

[5]

[6]

[7]
[8]

[9]
[10]

[11]

[12]
[13]

hydrogen. Netherlands: NL Agency for Energy and


Environment; 2003. p. 103e23.
Abusoglu A, Demir S, Kanoglu M. Thermoeconomic
assessment of a sustainable municipal wastewater
treatment system. Renew Energy 2012;48:424e35.
Coskun C, Akyuz E, Oktay Z, Dincer I. Energy analysis of
hydrogen production using biogas-based electricity. Int J
Hydrogen Energy 2011;36:11418e24.
http://www1.eere.energy.gov/hydrogenandfuelcells/tech_
validation/pdfs/fcm02r0.pdf.
Manish S, Banerjee R. Comparison of biohydrogen
production processes. Int J Hydrogen Energy
2008;33(1):279e86.
Demirbas A. Biohydrogen for future engine fuel demands.
London: Springer; 2009.
Wang CC, Chang CW, Chu CP, Lee DJ, Chang BV, Liao CS.
Producing hydrogen from wastewater sludge by Clostridium
bifermentants. J Biotechnol 2003;102:83e92.
Kreuter W, Hoffman H. Electrolysis: the important energy
transformer in a world of sustainable energy. Int J Hydrogen
Energy 1998;23(8):661e6.
Ganley JC. High temperature and pressure alkaline
electrolysis. Int J Hydrogen Energy 2009;34(9):3604e11.
Shen M, Bennett N, Ding Y, Scott K. A concise model for
evaluating water electrolysis. Int J Hydrogen Energy
2011;36(22):14335e41.

13435

[14] Dincer I. Green methods for hydrogen production. Int J


Hydrogen Energy 2012;37:1954e71.
[15] Kapdan IK, Kargi F. Bio-hydrogen production from waste
materials. Enzyme Microb Technol 2006;38:569e82.
[16] Show KY, Lee DY, Tay JH, Lin CY, Chang JS. Biohydrogen
production: current perspectives and the way forward. Int J
Hydrogen Energy 2012;37(20):15616e31.
[17] Chang PL, Hsu CW, Lin CY, Hsiung CM. Constructing a new
business model for fermentative hydrogen production from
wastewater treatment. Int J Hydrogen Energy
2011;36:13914e21.
[18] Pandu K, Joseph S. Comparisons and limitations of
biohydrogen production processes: a review. Int J Adv Eng
Technol 2012;2:342e56.
[19] Genc N. Biohydrogen production from waste sludge. J Eng
Nat Sci 2010;28:235e48.
[20] Abusoglu A, Demir S, Kanoglu M. Thermoeconomic analysis
of a biogas engine powered cogeneration system. J Therm Sci
Technol 2013;33:9e21.
[21] Zeng K, Zhang D. Recent progress in alkaline water
electrolysis for hydrogen production and applications. Prog
Energy Combust Sci 2010;36:307e26.
[22] Ivy J. Summary of electrolytic hydrogen production.
Milestone completion report. National Renewable Energy
Laboratory; September 2004. NREL/MP-560e36734.
[23] http://www.werf.org/.