www.elsevier.com/locate/ijhydene
Can high temperature steamelectrolysis function with geothermal heat?
J. Sigurvinsson
a
, C. Mansilla
a,
, P. Lovera
b
, F. Werkoff
a
a
CEA/DEN/DANS/DM2S CEA/Saclay (Bat. 470), 91191 Gif-sur-Yvette, Cedex, France
b
CEA/DEN/DANS/DPC CEA/Saclay (Bat. 450), 91191 Gif-sur-Yvette, Cedex, France
Available online 10 January 2007
Abstract
It is possible to improve the performance of electrolysis processes by operating at a high temperature. This leads to a reduction in electricity
consumption but requires a part of the energy necessary for the dissociation of water to be in the form of thermal energy.
Iceland produces low cost electricity and very low cost geothermal heat. However, the temperature of geothermal heat is considerably lower
than the temperature required at the electrolysers inlet, making heat exchangers necessary to recuperate part of the heat contained in the gases
at the electrolysers outlet.
A techno-economic optimisation model devoted to a high-temperature electrolysis (HTE) process which includes electrolysers as well as a
high temperature heat exchanger network was created. Concerning the heat exchangers, the unit costs used in the model are based on industrial
data. For the electrolyser cells, the unit cost scaling law and the physical sub-model we used were formulated using analogies with solid oxide
fuel cells.
The method was implemented in a software tool, which performs the optimisation using genetic algorithms.
The rst application of the method is done by taking into account the prices of electricity and geothermal heat in the Icelandic context. It
appears that even with a geothermal temperature as low as 230
C.
Only 3.8 kWh
(e)
/Nm
3
H
2
are needed with a thermal input
of 200
/
k
g
[
H
2
]
Geothermal, Iceland HTR, France
Fig. 1. Cost of vaporising and heating water to the required temperature for
the electrolyser.
nuclear reactors in France. When this price difference, reported
in Table 1, is taken into account, the advantage of producing
hydrogen by HTE in Iceland is evident, as demonstrated in
Fig. 1, only in terms of the cost of vaporising and heating water
to the operating temperature of the electrolyser.
Although only approximately 200
C of thermal input in
the HTE process coupled with a geothermal source is possi-
ble today, this could change. Recent research carried out by
Landsvirkjun on deep drilling in Iceland shows the possibil-
ity of extracting 500.600
C at 15 bar.
This is relatively low and the vaporisation and heating of the
water for the electrolyser therefore needs to be carried out in
several stages.
The water input, which is in liquid state and at ambient tem-
perature (that we will assume to be equal to 20
C),
MT for medium temperature (from 600 to 850
C),
HT for high temperature (above 850
C).
Low temperature LT: T <600
C.
Medium temperature MT: 650
C<T <850
C, nickel-
based heat exchanger capable of 12 MPa at 650
C, cur-
rently under testing.
High temperature HT: T >850
C, further investiga-
tion into what material and which heat exchanger to use for
this temperature level is required.
Tee_O
2
Tin_O
2
T1_HT
T1_MT
Tout_O
2
T2_HT
T2_MT
Tin_H
2
O
O
2
HT
MT
LT
H
2
O
Fig. 3. Diagram of a heat exchanger network for the oxygen branch. Related
to the notation of Fig. 2: T
out_H
2
O
= xT
ee_H
2
+ (1 x)T
ee_O
2
.
At low temperatures stainless steel dominates. Other
steels come next, to be replaced by ceramics at very high
temperatures.
The heat exchanger proposed for the >850
C temperature
level is still being tested and further details will be available
soon. Assuming that plate heat exchangers with primary sur-
faces are used to insure a high level of effectiveness, the over-
all heat transfer coefcient can be derived as explained by
Sigurvinsson [5].
The heat exchanger network for the oxygen branch can there-
fore be shown in a diagram as in Fig. 3.
The same mass ow crosses the three modules. In addition,
it is estimated that the temperature variation between two
J. Sigurvinsson et al. / International Journal of Hydrogen Energy 32 (2007) 11741182 1177
exchangers is negligible. The denition of the exchanger mod-
ules gives us orders of magnitude for these temperatures:
T
1
_HT must be lower than 850
C, and T
1
_MT must be lower
than 600
C.
For the rst exchanger network, the uid in the primary is a
steam-hydrogen mixture. For the second, it is oxygen. Steam
circulates into the secondary of the two exchanger networks.
The integration of the exchangers studied in the HTE sys-
tem imposes bonds between the various ows via the recycling
rate r. Using n
H
2
O
as the total molar water ow through the
two secondary branches of the exchangers, the various molar
ows are:
(1 r) n
H
2
O
of hydrogen in the primary H
2
exchanger,
r n
H
2
O
of water in the primary H
2
exchanger,
(1r)
2
n
H
2
O
of oxygen in the primary O
2
exchanger,
x n
H
2
O
of water in the secondary H
2
exchanger,
(1 x) n
H
2
O
of water to the secondary O
2
exchanger,
where n
H
2
O
is the total molar water ow (mol/s). x is the divi-
sion rate of the principal water ow. It is a number between 0
and 1.
The details of the mass ows in the primary and secondary
of all the exchangers are expressed in [4].
2.2. The electrolyser model
To nd the quantity of thermal and electric energy needed
for water decomposition, the Nernst equation was used and
adjusted for overvoltages. In the chemistry of fuel cells and
electrolysers E is the potential of the cell in (V):
E = E
0
+
RT
2F
ln
_
P
H
2
_
P
O
2
P
H
2
O
P
ref
_
+
_
_
_
R
ohm
R
act
R
con
_
_
_j, (3)
Where E
0
is the thermodynamic potential of steam decompo-
sition at equilibrium (V); R
ohm
the resistance due to ohmic
losses in membrane (m
2
); R
act
the resistance due to reaction
activation (m
2
); R
con
the resistance due to kinetic problems,
caused by inhomogenic concentration of gases in the electrodes
(m
2
); R the universal gas constant (J/mol. K); T the temper-
ature (K); F the Faradays constant (C/mol); P the partial pres-
sure (MPa), P
ref
the pressure of reference =0.1 MPa and j the
current density (A/m
2
).
The rst part of the equation is the Nernst local equation,
which expresses the exact electromotive force of a cell in terms
of the activities of the cells products and reactants. This is only
a function of temperature and pressure. The partial pressures
throughout the electrolyser are not constant. They change with
the position, and the partial pressures of gases will affect the
resulting energy needed for the electrolysis. This is dependent
on how much of the incoming water is electrolysed. The last
terms in the equation represent unwanted losses due to ohmic
losses in membrane, reaction activation and kinetic problems
caused by inhomogenic concentration of gases in the electrodes.
The products Rj, linked to the unwanted losses are usually
called overpotentials.
There are many factors in the overpotential calculations
which are very difcult to evaluate correctly. The evaluation
depends on actual test results for all three types of resistances.
An analytical model was used for the simplications based on
the work of Lovera [6].
The model is validated on results fromexperiments on SOFC.
It is possible that the overpotentials are not exactly the same
for fuel cells and electrolysers but initial results show that they
are very similar.
In this simplied model the overpotentials are linearised,
i.e. assumed to be proportional to the current density. Eq. (3)
therefore becomes
E = E
0
+
RT
2F
_
Ln
_
_
P
O
2
P
ref
_
A + B
in
_
+
RT B
4F
2
q
mol
1
1 e
(RT B/4F
2
q
mol
)/R
s
I, (4)
where is the electrolyte surface (m
2
), I the current intensity
(A),
in
the portion of water electrolysed (input), A = 2.3843;
B =4.7685 the mathematical constants due to the linearisation
of the logarithmic term in the Nernst equation, P
O
2
the partial
pressure of oxygen (supposed to be constant in the model), q
mol
the molar ow rate of hydrogen + steam (mol/s) and R
s
the
total area specic resistance (R
ohm
+ R
act
+ R
con
) (m
2
).
According to [6] the exothermal mode works when the op-
erating cell potential is greater than 1.3V. If the potential is
higher, all of the extra energy will go into heating the gases and
compensating insulation losses. This will allow us to directly
calculate the temperature difference from the electrolysers in-
let to the outlet, using the following simple relation:
(U
electrolyser
U
diss
)I =
mC
p
elec,mix
T
electrolyser
10
3
, (5)
where m is the total mass ow (kg/s), C
p
elec,mix
the specic heat
of the water/hydrogen/oxygen mixture (kJ/kg K), T
electrolyser
the temperature difference from electrolyser inlet to outlet (K),
U
diss
the potential required for dissociation (V) and U
electrolyser
the potential applied to the electrolyser (V).
3. A techno-economic optimisation method applied to
the HTE
3.1. Principles of the techno-economic optimisation
In the following section we will present a method for op-
timising the HTE process including heat exchangers and an
electrolyser from a techno-economic point of view.
The techno-economic approach we selected presupposes a
heat exchanger network, also called a ow sheet. The optimi-
sation procedure consists in minimising an objective function
which takes into account operating as well as investment costs.
In the current context of sustainable development, advanced
systems are being studied. These systems involve either high
pressures, high temperatures, or corrosive products, and some-
times several of these severe conditions. In all of these cases,
1178 J. Sigurvinsson et al. / International Journal of Hydrogen Energy 32 (2007) 11741182
investment costs can increase by one or two orders of magni-
tude when compared to classical alternative systems, leading
to a growing interest in the techno-economic approach.
In a previous study [4], TE optimisations were performed
only for heat exchanger networks (excluding the electrolyser).
In that case the primary heat sources were HTRor Geothermics.
We present an extension of this work of [4] by including an
electrolyser which is coupled with a geothermal source.
The low-temperature heat is very inexpensive froma geother-
mal source. Further on, we do not consider heat exchangers for
pre-heating the cold water entering the boiler.
Another difference fromcoupling with an HTRis that we will
consider the possibility of an electric reheater for increasing
the temperature of the steam at the inlet of the electrolyser.
The heat exchanger networks and the electrolyser are
then optimised by minimising the production cost per kg
of hydrogen. The optimisation was achieved using genetic
algorithms.
3.2. The objective function
The objective function is the function that we want to min-
imise. The objective is to minimise the cost of producing hy-
drogen. CTA is the notation for the total cost (/kg H
2
).
The numerator has two main groups of factors, the rst being
the investment cost for the electrolyser and heat exchangers
and the second, the operating cost of the electrolyser and heat
exchangers.
The investment costs are rstly the capital costs for the heat
exchangers (C
i,exch
) and electrolyser (C
i,elec
). The operating
costs in the numerator are the thermal consumption cost (C
o,th
)
and the electric energy consumption cost (C
o,elec
).
The denominator of the objective function is the hydrogen
production per year (H
t
(kg H
2
/year)). It depends on the cur-
rent intensity, ow rate and recycling ratio in the electrolyser
cell. The objective function is expressed with the following
formula:
CTA =
T
i
+T
e
t =1
__
(C
i,exch
)
t
+ (C
i,elec
)
t
+ (C
o,th
)
t
+ (C
o,elec
)
t
_
(1 + )
t
_
T
i
+T
e
t =1
[H
t
(1 + )
t
]
, (6)
where CTA is the total cost (/kg H
2
)
2
, C
i,exch
the heat ex-
changers investment cost (), C
i,elec
the electrolyser invest-
ment cost (), C
o,th
the thermal consumption operating cost
(), C
o,elec
the electric consumption operating cost (), H
t
the
hydrogen production (kg of H
2
/year), the discount rate, T
e
the number of years in use (years), T
i
the number of years of
investment (years), and t the year considered.
This equation is based upon a similar equation used to calcu-
late the future electricity cost from nuclear reactors [1]. In the
following section we will dene each cost contribution factor
and explain the calculations where necessary.
2
has been chosen, however, it can be replaced by the Icelandic krna
or by any other currency.
3.3. Investment cost of heat exchangers
C
i,exch
is obtained by summing the investment costs of all
the heat exchangers:
C
i,exch
=
N
j=1
C
j
, (7)
with
C
j
= C
j
S
j
, (8)
where N is the number of heat exchangers, C
j
the cost of capital
for the jth exchanger (), C
j
the unit investment cost for the
jth exchanger (/m
2
) and S
j
the heat exchangers surface of
the jth exchanger (m
2
).
C
j
is dened according to the type of exchanger, material
and the operating conditions [4]:
400/m
2
: for the low-temperature exchangers;
800/m
2
: for the medium-temperature exchangers;
4000/m
2
: for the high-temperature exchangers.
3.4. Investment cost, of the electrolyser
The denition of the contribution of the electrolyser
(C
i,elec
) to the total investment cost is obtained by assuming
that:
The cost is proportional to the surface of the electrolyser.
The operation life duration of the electrolyser is expected to
be constant for large ranges of temperatures, voltages and
current densities. It has been estimated to be 5 years.
Based on the target objective for SOFC [7], a 2000 /kW
unit cost for cells with a surface power density of 0.5 W/cm
2
has been retained.
These assumptions take into account improvements expected
at the 2030s horizon, due to the current world research and
development works, related to the SOFC. The investment cost
is then expressed by:
C
i
,
elec
= P
tot,useful
2000
_
0.5
j U
electrolyser
_
(), (9)
where j is the current density in cell (A/cm
2
), U
electrolyser
the
operating voltage of the electrolyser (V), P
tot
,
useful
the electric
power required for the dissociation of water (kW).
Although there are strong uncertainties related to these as-
sumptions and that the nal production cost of hydrogen de-
pends greatly on them, it is reasonable to consider that, in the
J. Sigurvinsson et al. / International Journal of Hydrogen Energy 32 (2007) 11741182 1179
frame of the present preliminary techno-economic study, they
allow to assess the long-term potentiality of the HTE.
3.5. Thermal consumption operating cost
The denition of the contribution of thermal consumption
(C
o,th
) to the total capital operating costs is as follows:
C
o,th
= c
kWh
th
t
e
m
H
2
O
(C
p,H
2
O
T
geothermal
+ C
v,H
2
O
), (10)
where C
o,th
is the thermal consumption operating cost (/year),
c
kWh
th
the unit thermal energy cost (/kWh
th
), t
e
the length of
operation (h/year), m
H
2
O
the mass ow of water (kg/s), C
p,H
2
O
the specic heat of water (kJ/kg K), C
v,H
2
O
the specic latent
heat of water vaporisation (kJ/kg) and T
geothermal
the temper-
ature difference in the geothermal heat exchanger (K) and
T
geothermal
= T
in_H
2
O
T
ext_H
2
O
, (11)
where T
in_H
2
O
is the temperature of steam at the geothermal
heat exchanger outlet (K) and T
ext_H
2
O
the temperature of water
at the geothermal heat exchanger inlet (K).
3.6. Electric consumption cost
The denition of the electric consumptions contribution
(C
o,elec
) to the total operating costs is the sum of the consump-
tion of the electrolyser, the pump and the extra heating.
The cost of the electricity consumption =cost of the kWh
e
pump
, (13)
where EC
pump
is the electric consumption of the pump
(kWh
e
/year),
pump
the mechanical efciency of the pump,
m the mass ow (kg/s), the specic mass (kg/m
3
), P the
pressure losses (Pa) and t
e
the length of operation (h/year).
The pressure losses are proportional to the square of the
ow. They depend on the length of the exchanger, the hydraulic
diameter, the cross section and the density of the uid. This cost
must be taken into account for each branch of the exchanger.
P
i
= 4f
i
L
i
Dh
i
1
2
i
_
m
i
A
i
_
2
, (14)
where P
i
is the pressure loss (Pa), f
i
the friction factor, m
i
the mass ow (kg/s), A
i
the cross section in exchanger i (m
2
),
Dh
i
the hydraulic diameter (m), and L
i
the heat exchanger
length (m).
The friction factor depends on the Reynolds number. The
expression we used is valid for 50 <Re <15000.
Since we assume that there is equal distribution of the uid,
the ow per channel is equal to the ratio of the total ow
per number of channels. Moreover, the total cross section
of the exchanger is equal to the product of the cross section
of a channel per number of channels. Consequently, the
cost of pumping can be calculated using the total size instead
of the size relating to one channel.
3.6.2. The electrolyser
To calculate the total electric consumption we need to mul-
tiply the power dissipated in the electrolyser by the annual
operation duration:
EC
electrolyser
= U
electrolyser
It
e
n 10
3
, (15)
where EC
electrolyser
is the electric consumption of the elec-
trolyser (kWh
e
/year), I the current in each electrolyser cell
(A), t
e
the length of operation (h/year), U
electrolyser
the operat-
ing voltage of each electrolyser cell (V) and n the number of
electrolyser cells.
3.6.3. The electric reheater
The electric consumption of the reheater is evaluated by cal-
culating how much energy is needed to increase the tempera-
ture by a specic amount.
EC
reheater
=
m
H
2
O
C
p,H
2
O
t
e
(T
in_elec
T
out_H
2
O
), (16)
where EC
reheater
is the electric consumption of the reheater
(kWh
e
/year), t
e
the length of operation (h/year), m
H
2
O
the mass
owof water (kg/s), C
p,H
2
O
the specic heat of water (kJ/kg K),
T
out_H
2
O
the temperature at the outlet of the heat exchanger
network and before the reheater (K) and T
in_elec
temperature at
the electrolyser inlet (K).
3.7. Decision variables
There are 14 decision variables. They are the temperatures,
expressed in
C, at the different places of the process except
for T
in_H
2
and T
in_O
2
which are calculated (exothermal mode)
and T
in_H
2
O
which is xed. The temperature of the steam at the
reheaters inlet T
out_H
2
O
is calculated from T
ee_H
2
and T
ee_O
2
(see Fig. 3).
The division rate x of the principal water ow is also a
decision variable.
The values of the decision variables will evolve throughout
the iterations to obtain optimised results. When an optimal point
has been reached, the model has results for each of the decision
variables.
1180 J. Sigurvinsson et al. / International Journal of Hydrogen Energy 32 (2007) 11741182
3.8. Constraints
Several constraints apply to the system. The electrolyser is
operating in exothermal mode so output gases are always hotter
than input ones.
Other physical constraints link the temperatures of each end
of the heat exchangers. The temperatures of the primary ow
are higher than those of the secondary ow throughout each
heat exchanger.
Inlet temperatures are higher than outlet temperatures for the
primary ow, but lower for the secondary ow.
Constraints on heat exchangers efciencies and effective-
nesses are eventually added to obtain meaningful results.
4. The TE optimisation applied to geothermics
4.1. Specication of data for implementing the TE
optimisation model
4.1.1. Economic data
t
e
: length of operation: 7008 hours/year (80% availability),
pump
: mechanical efciency of the pumping: 80%,
: discount rate : 6%
Number of years of construction: 3 years
Distribution of capital expenditures: 10% the rst year, 35%
the second and 55% the third
Number of years of operation: 30 years
Electrolyser operation life duration: 5 years
c
kWh
e
: 0.014/kWh
e
(1.4. 10
5
/Wh
e
)
c
kWh
th
: 0.0014/kWh
th
.
The rst parameters are selected in agreement with [7].
4.1.2. Physical data
These data will not change throughout the optimisation iter-
ations. They have been xed.
T
in_H
2
O
= 503 K or 230
C,
P
tot,useful
=5 kW: useful power requirements for the electrol-
yser,
out
= 0.67: portion of water electrolysed at the outlet,
r = 0.33: recycling ratio,
= 1.39 10
4
m: electrolyte membrane thickness [6],
= 0.985 10
2
m
2
: electrolyte surface for 1 cell [6],
P
H
2
O
=1.510
6
Pa: steam pressure at the electrolysers inlet,
P
O
2
=510
5
Pa: partial pressure of oxygen in the electrolyser
and
U
electrolyser
=1.4 V: cell potential, exothermal operating mode.
The partial pressure of oxygen is not constant throughout
the electrolyser. In our study we do, however, assume constant
pressure at the anode.
4.2. Demonstration results of the HTE optimisation
The results of our optimisation show that two factors domi-
nate the cost of hydrogen production: the electrolysers electric
consumption and the electrolysers investment cost. We found
that the nal cost of producing hydrogen was 1.7/kg H
2
. The
cost breakdown can be found in Table 2.
Table 2
Cost breakdown of the hydrogen production cost
Thermal consumption cost 1.0%
Pumping cost 0.0%
Reheater consumption cost 0.8%
Electrolyser consumption cost 31%
Heat exchangers investment cost 0.1%
Electrolyser investment cost 67%
This value shows that, at least in the Icelandic context, HTE
could compete with alkaline electrolysis [5]. For given electric-
ity price and production capacity, the production cost of hydro-
gen by alkaline electrolysis has been assessed in [58]. In the
Icelandic context, an alkaline electrolysis plant with a capac-
ity of 11.500 tH
2
/year (0.4 kg H
2
/s) can provide hydrogen at
a cost of 1.6/kg.
For a given primary energy source, HTE must be compet-
itive with the alkaline electrolysis fed by electricity produced
by the same primary energy source [8]. HTE will have to reach
an economy in terms of consumption cost. Fig. 4 shows that
about 16 MJ/kg of H
2
are needed for breaking water molecules
in the liquid state (as it is done with the alkaline electrolysis),
while less than 14 MJ/kg of H
2
are needed for breaking water
molecules in the liquid state. Besides in this last case, a part
of the energy can be brought in the form of heat which is less
expensive than electricity. At rst glance, relatively low tem-
perature geothermal sources (#230
C) 680 807
n
cells
71 T
1
_MT (
C) 442 468
m
H2
(kg/s) 4.0 10
5
T
2
_HT (
C) 613 767
m
H2O
(kg/s) 5.5 10
4
T
2
_MT (
C) 324 283
x 0.82 T
ee
(
C) 789 937
(mainly at the level of the electrolyser: its operation life du-
ration, its unit cost and the inuence of temperature on the
latter), the rst optimised results show that if the HTE is
economical one day, then it can also be economical with
a thermal source characterised by a low temperature and a
low cost.
Acknowledgement
We would like to thank Alain Marchal and Andr
Bontemps for their help in dening the heat exchanger fea-
tures, and Michel Dumas and Gilles Arnaud for their help in
implementing genetic algorithms.
1182 J. Sigurvinsson et al. / International Journal of Hydrogen Energy 32 (2007) 11741182
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