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www.elsevier.com/locate/ijhydene
Received 24 October 2005; received in revised form 10 March 2006; accepted 14 April 2006
Available online 7 July 2006
Abstract
In this study, a parametric investigation is carried out to estimate the hydrogen energy potential depending on the quantities of H2 S in Black
Sea deep waters. The required data for H2 S in Black Sea deep waters are taken from the literature. For this investigation, the H2 S concentration
and water layer depth are taken into account, and 100% of conversion efciency is assumed. Consequently, it is estimated that total hydrogen
energy potential is approximately 270 million tons produced from 4.587 billion tons of H2 S in Black Sea deep waters. Using this amount of
hydrogen, it will be possible to produce 38.3 million TJ of thermal energy or 8.97 million GWh of electricity energy. Moreover, it is determined
that total hydrogen potential in Black Sea deep waters is almost equal to 808 million tons of gasoline or 766 million tons of NG (natural gas)
or 841 million tons of fuel oil or 851 million tons of natural petroleum. These values show that the hydrogen potential from hydrogen sulphur
in Black Sea deep water will play an important role to supply energy demands of the regional countries. Thus, it can be said that hydrogen
energy reserve in Black Sea is an important candidate for the future hydrogen energy systems.
2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
Keywords: Hydrogen; Hydrogen sulphur; Black Sea deep waters; Renewable energy
1. Introduction
Energy is a key factor in discussions of economic, social
and environmental dimensions of sustainable development [1].
An increase in the energy consumption of a country provides a
positive impact on its economic as well as social development,
and also, the supply and utilization of affordable and clean
fuel is particularly signicant for a clean world since energy
plays a vital role in industrial and technological developments
around the world [2]. Energy requirement of the world has been
increasing due to increasing world population, technological
development, and increased living standards. A different type
of energy is fossil-based energy, which includes generally coal,
petroleum and natural gas (NG), etc. As known, fossil energy
sources are not renewable.
In order to explain and nd out well the requirement of
hydrogen energy and technologies for clean energy supply and
Corresponding author. Tel.: +90 388 2252255; fax: +90 388 2250112.
0360-3199/$ - see front matter 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2006.04.006
These problems are the trouble effects for the world and the
livings, and particularly an alarm for the future of the world.
Therefore, in order to partially decline or completely remove
the problems, a new energy source that is clean and abundantly
found all over the world should be considered for practical
applications. Then, what is the main duty of the energy researchers, scientists and experts? The main duty is to investigate
the effective sustainable clean energy sources and technologies
for a clean world. As a consequence, investigations of alternative clean energy sources and technologies will become important, particularly for future world stability. The most important
property of alternative energy sources is their environmental
compatibility. Why not hydrogen? In line with this characteristic, hydrogen likely will become one of the most attractive
energy carriers in the near future. As known, hydrogen is an
excellent energy carrier and can be produced from any source
by using solar, hydro, biomass, wind, geothermal, and boron
compounds, etc. Moreover, another important source for hydrogen is hydrogen sulphur that is abundantly found in Black
Sea deep waters. The Black Sea is an elliptical basin with an
area of 423, 000 km2 . The average depth is 1263 m suggesting
a total volume of 534, 000 km3 [3]. The Black Sea is unique because 90% of sea water is anaerobic. This anaerobic sea water
contains hydrogen sulphur, produced by sulphur reducing bacteria. The interface between anaerobic and aerobic water lies
at depths of about 140 m along the axis of the Black Sea and
about 250 m along the sides. The content of hydrogen sulphur
increases steadily with depth to a concentration of 8 ml/l sea
water at 1000 m, below which increases slightly to 8.5 ml/l sea
water at 2000 m. Above the bottom, hydrogen sulphur reaches
13.5 ml/l sea water [3]. Therefore, Black Sea hydrogen sulphur
may serve as a future energy system.
Although many studies are carried out on hydrogen sulphur
potential of Black Sea [411], there is limited work on hydrogen
potential of Black Sea deep waters. For example, Petrov [3]
studied on the Black Sea and hydrogen energy. Midilli et al.
[12,13], Baykara et al. [14] and Ture [15] performed some
theoretical studies on hydrogen energy potential of Black Sea
deep waters.
Unlike the above studies, this paper reports an attempt to
parametrically investigate hydrogen energy potential of Black
Sea deep waters based on hydrogen sulphur and to discuss
the importance of hydrogen energy potential for the regional
countries. If hydrogen is produced from Black Sea deep waters,
then the energy requirements of the countries in the Black Sea
coast could be compensated, and hydrogen export to European
countries would be possible.
2. Hydrogen energy potential of Black Sea
It is generally known that the Black Sea is the largest anoxic
basin in the world, and the total sulde pool of the contemporary Black Sea is about 4600 Tg, the main part being located between 500 and 2000 m. The spatial distribution of
the oxicanoxic transition in the sea is characterized by the
presence of two dome-shaped structures located in the eastern
and western central parts of the basin between 90 and 100 m.
118
10
Depth=150m
Initial depth of H2S formation
300
600
900
1200
1500
1800
2100
119
16
Neretin et al. [9]
Dimitrov et al. [18]
14
12
Table 1
H2 S potential in Black Sea water layers [9]
Layer (m)
H2 S (mol/l)
100200
200300
300500
5001000
10001500
15002000
20002200
Total
10
8
H2 S (mol/m2 )
2.0
6.5
28.1
132.1
159.1
150.7
40.7
519.2
a 150200 m.
2
0
21a
66
140
274
339
368
368b
b 15002000 m.
200 400 600 800 1000 1200 1400 1600 1800 2000 2200
Water depth in Black Sea (m)
120
1.6
9
Maximum value
= 1.469x109 tons
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
100-200
Fig. 4. Variation of H2 S potential as a function of depth of water layer in Black Sea [9].
BLACK SEA
ANOXIC BASIN
Anaerobic
zone
Bacterial
decomposition
Anaerobic
bacterial
community
H2S formation
in Black Sea
deep water
Harmful
effects
Health
problems
Renewable
energy
sources
H2S taken
from Black
Sea deep water
Air
pollution
H2S
separation
Sulphur
Hydrogen
Local and
industrial
applications
Heat and
power
generation
Environmental
pollution
Water
pollution
Ecological
problems
Fuel cell
assisted energy
technologies
potential is 1469 million tons according to Fig. 4. These values show that it would be possible to produce hydrogen from
H2 S in the water layers starting from 100 to 2000 m by using
appropriate production technique and technologies.
Considering the above explanations, the relationship between
H2 S and hydrogen can be illustrated as in Fig. 5.
3. Results and discussion
In this paper, a study is conducted to investigate hydrogen
energy potential of Black Sea deep water based on H2 S and
importance for the region. For this purpose, the following steps
are carried out: (i) Hydrogen energy potentials which are synthesized from H2 S quantities in different depths of Black Sea
were determined assuming 100% conversion efciency of H2 S
decomposition reaction. (ii) Hydrogen energy potentials from
H2 S quantities in different layers of Black Sea water were estimated. (iii) Importance of hydrogen potential is discussed for
the regional countries. Taking into consideration these steps,
Figs. 6 and 7 and Table 2 are analyzed and discussed in detail.
Figs. 6(a)(c) present the variations of hydrogen potential as
a function of depth and H2 S potential in Black Sea depending
9E-04
Based on H2S data from Neretin et al.[9]
Based on H2S data from Dimitrov et al.[18]
8E-04
7E-04
6E-04
5E-04
4E-04
3E-04
2E-04
1E-04
0
400
200
(a)
9E-04
0E-01
121
800
600
1200
1000
1600
1400
2000
1800
2200
8E-04
7E-04
6E-04
5E-04
4E-04
3E-04
2E-04
1E-04
0E-01
0E-01 2E-03 4E-03 6E-03 8E-03 1E-02 1E-02 1E-02 2E-02
H2S potential in Black Sea (g H2 /liter sea water)
(b)
6E-04
Based on theH2S data from Dimitrov et al. [18]
Depth range=150-2000 m
5E-04
4E-04
Reaction
:
,
assuming 100% conversion efficiency,
H2S => H2 + 1/2S2
3E-04
2E-04
1E-04
0E-01
0E-01
(c)
2E-03
4E-03
6E-03
8E-03
1E-02
Fig. 6. (a)Variation of hydrogen potential as a function of water depth in Black Sea. (b) Variation of hydrogen potential as a function of H2 S potential in
Black Sea depending on the H2 S data from literature [9]. (c) Variation of hydrogen potential as a function of H2 S potential in Black Sea depending on the
H2 S data from literature [18].
122
90
80
70
Maximum potential
= 86.411 million tons
60
50
40
30
20
10
0
100-200
Fig. 7. Variation of hydrogen potential in Black Sea deep water as a function of water layer of Black Sea [9].
Table 2
Comparison of hydrogen potential with other fuels in practical application, and theoretical electricity generation quantity from the hydrogen potential at
different layers of Black Sea deep water
Depth (m)
100200
200300
300500
5001000
10001500
15002000
20002200
Total
MH2 (tons)
EH2 (TJ)
MGasoline (tons)
MNG (tons)
MCharcoal (tons)
MFuel oil (tons)
MLPG (tons)
MBiodiesel (tons)
MMethanol (tons)
MHazelnut (tons)
Msludge (tons)
Mpetroleum (tons)
EEEa (GWh)
1.3e + 6
0.18e + 6
3.87e + 6
3.67e + 6
6.12e + 6
4.04e + 6
3.75e + 6
4.96e + 6
8.23e + 6
10.6e + 6
10.7e + 6
4.08e + 6
0.04e + 6
4e + 6
0.57e + 6
12e + 6
11.4e + 6
18.9e + 6
12.5e + 6
11.6e + 6
15.3e + 6
25.5e + 6
32.7e + 6
33.1e + 6
12.6e + 6
0.133e + 6
16.65e + 6
2.36e + 6
49.8e + 6
47.2e + 6
78.7e + 6
51.9e + 6
48.3e + 6
63.8e + 6
106e + 6
136e + 6
138e + 6
52.5e + 6
0.554e + 6
77.35e + 6
11e + 6
232e + 6
220e + 6
366e + 6
241e + 6
224e + 6
297e + 6
492e + 6
632e + 6
640e + 6
244e + 6
2.57e + 6
86.41e + 6
12.3e + 6
259e + 6
245e + 6
409e + 6
269e + 6
251e + 6
331e + 6
550e + 6
706e + 6
715e + 6
273e + 6
2.87e + 6
71.76e + 6
10.2e + 6
215e + 6
204e + 6
339e + 6
224e + 6
208e + 6
275e + 6
457e + 6
587e + 6
594e + 6
226e + 6
2.39e + 6
12.35e + 6
1.75e + 6
37e + 6
35.1e + 6
58.4e + 6
38.5e + 6
35.8e + 6
47.4e + 6
78.6e + 6
101e + 6
102e + 6
39e + 6
0.411e + 6
270e + 6
38.3e + 6
808e + 6
766e + 6
1280e + 6
841e + 6
783e + 6
1030e + 6
1720e + 6
2210e + 6
2230e + 6
851e + 6
8.97e + 6
a Electrical
123
hydrogen sulphur potential. This amount of hydrogen is almost equal to 808 million tons of gasoline, 766 million tons
of natural gas, 841 million tons of fuel oil, 851 million tons
of natural petroleum. Consequently, these values show that
the hydrogen potential from hydrogen sulphur in Black Sea
deep water will play an important role to supply energy demands of the regional countries. Thus, it is suggested that
all countries in Black Sea should encourage and invest producing hydrogen energy from Black Sea deep waters.
Accordingly, if hydrogen energy is produced from hydrogen
sulphur in Black Sea deep waters, then the energy demand of
regional countries can be partially compensated, and hydrogen
energy can be transported to the European countries. Therefore,
it is suggested that the regional countries such as Turkey, Bulgaria, Ukraine, Russia, Georgia and Romania should encourage
and invest to activate this hydrogen energy reserve in the scope
of Energy collaboration in Black Sea. As a future work, the
environmental impacts and feasibility of hydrogen production
from the Black Sea deep waters should be investigated.
Acknowledgment
The authors would like to thank the UNIDO-ICHET in
Turkey for their scientic supports.
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