ISSN 0040-5795, Theoretical Foundations of Chemical Engineering, 2008, Vol. 42, No. 1, pp. 1–11. © Pleiades Publishing, Ltd.

, 2008.
Original Russian Text © V.A. Kirillov, V.D. Meshcheryakov, V.A. Sobyanin, V.D. Belyaev, Yu.I. Amosov, N.A. Kuzin, A.S. Bobrin, 2008, published in Teoreticheskie Osnovy
Khimicheskoi Tekhnologii, 2008, Vol. 42, No. 1, pp. 3–13.

Bioethanol as a Promising Fuel for Fuel Cell Power Plants

V. A. Kirillov, V. D. Meshcheryakov, V. A. Sobyanin, V. D. Belyaev, Yu. I. Amosov,
N. A. Kuzin, and A. S. Bobrin
Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences,
pr. Akademika Lavrent’eva 5, Novosibirsk, 630090 Russia
e-mail: v.a.kirillov@catalysis. su
Received May 28, 2007

Abstract—The catalytic reaction of steam reforming of bioethanol for the production of a hydrogen-containing
gas in a temperature range from 300 to 700°C is studied. Copper-, nickel-, cobalt-, platinum-, and rhodium-
containing catalysts supported on different substrates, including metal grids, are tested. Comparative analysis
of the methods of bioethanol processing to a hydrogen-enriched gas for feeding high-temperature proton-
exchange polymer electrolyte membrane fuel cells is performed.

DOI: 10.1134/S0040579508010016

Bioethanol is a 12–14 wt % aqueous solution of
ethyl alcohol produced by the biochemical brewing of
food and raw agricultural materials, hydrolysis of plant
materials and woodworking industry wastes, and the
like. Unlike natural gas and petroleum, bioethanol is a
renewable fuel and does not pollute the environment.
One of the efficient ways of using bioethanol as a power
source is its steam reforming to synthesis gas and the
production of electric power from the hydrogen con-
tained in the synthesis gas by electrochemical fuel cells.
The studies dealing with the production of hydrogen
by steam reforming of alcohols, including bioethanol,
gained a much higher importance in the recent time
because of the development of high-temperature pro-
ton-exchange membrane (HT PEM) fuel cells based on
a heat-resistant polybenzimidazole polymer and phos-
phoric acid, which is used as the electrolyte, and the
promising applications of these fuel cells for electric
power generation plants [1]. Some problems associated
with the above, such as the development of new cata-
lysts for the steam reforming of ethanol, analysis of the
application of bioethanol as a source for producing a
hydrogen-containing gas for fuel cells, possible process
flowsheets for electric power plants and the theoretical
estimate of their efficiency, will be considered in the
present paper.
THERMODYNAMICS OF THE REACTION
OF STEAM REFORMING OF ETHANOL
At atmospheric pressure, the factors determining the
equilibrium composition of a mixture in the ethanol
stream reforming are the temperature and the water-to-
alcohol (H2O : C2H5OH) molar ratio. It was shown [2, 3]
that when the H2O : C2H5OH molar ratios are 4 : 1 to 10 : 1
in the temperature interval from 300 to 950°ë, the eth-
anol conversion exceeds 99.9% and the main products
are CO, CO2, CH4, and H2. The concentration of the
other substances, as possible reaction products, do not
exceed 10–3 vol %. At low temperatures, the main
hydrogen-containing product is methane. Considerable
amounts of hydrogen are produced at temperatures
higher than 300°ë and the hydrogen concentration
builds up with increasing temperature. On the whole,
thermodynamic estimates show that the 100% conver-
sion of ethanol is reached at H2O : C2H5OH ratios equal
to 2–4 and temperatures from 700 to 800°ë. In this
case, no carbon is formed and the main reaction prod-
ucts are ç2, CO, and CO2. The concentrations of H2,
CO, CO2, and CH4 in the produced syngas are 65 to 69,
8 to 9, 10 to 15, and 0.5 vol % on dry gas basis, respec-
tively.
The syngas of this composition can be used as a fuel
that provides the decreased emission of nitrogen oxides
in gas turbine plants, internal combustion engines,
power plants using solid oxide fuel cells [4]. However,
the presence of 10 to 15 vol % of CO in the reaction
products makes it impossible to use this syngas for
feeding HT PEM fuel cells. The CO concentration can
be reduced to the required level by its additional steam
reforming. The use of a two-step chemical process con-
sisting of the steam reforming of ethanol:
ë2ç5éç + ç2O 4ç2 + 2ëé (1)
and the steam reforming of CO:
ëé + ç2é ëé2 + ç2, (2)
makes it possible to produce a hydrogen-containing gas
with a CO concentration of about 1%, which can be
used as the fuel for HT PEM fuel cells. From the power
viewpoint, ethanol solutions with higher dilution

1
2 KIRILLOV et al.

YH2, % It follows from the calculations that the hydrogen

(‡) selectivity at a fixed water-to-alcohol ratio rises as the
100
90 5 temperature increases to 500°ë (Fig. 1a). At higher
temperatures, the temperature dependence of the selec-
80 4 tivity is characterized by a maximum, which shifts to
70 lower temperatures as the water-to-alcohol ratio
60 3
increases. The location of the selectivity maximum is a
function of the water-to-alcohol ratio and temperature.
50 The CO concentration on dry gas basis reduces with
40 decreasing temperature and increasing water-to-alco-
2
30 hol ratio (Fig. 1b).
1 It follows from Fig. 1 that, if it is desirable in steam
20
10
reforming to achieve a maximal hydrogen yield and the
almost complete absence of methane in the reaction
0 products, the reaction should be performed in the tem-
CCO, %
(b) perature interval from 600 to 700°C and at ç2é :
20 ë2ç5éç molar ratios equal to 4–8. In this case, how-
1 ever, the CO concentration in the mixture will be about
2 10 to 15 vol %. Consequently, the additional reaction of
15 CO steam reforming will be necessary if this mixture is
3 to be used as the fuel for HT PEM fuel cells. At the
same time, if the solution with an ç2é : ë2ç5éç
10 molar ratio equal to 22 is used, which is characteristic
4 of bioethanol, the concentration of carbon monoxide in
5 the reaction products will be 2 vol %, which makes it
5 possible to directly use this hydrogen-containing gas as
the fuel for HT PEM fuel cells. On the other hand, the
power consumed in the reforming of a mixture with a
0 low alcohol concentration (high water–alcohol ratio) is
200 300 400 500 600 700 800 much higher due to the necessity of vaporizing the
T, °C water. Consequently, the efficiency of the power plant,
which is defined as the ratio of the produced electric
Fig. 1. Dependence of (a) hydrogen selectivity Y H and power to the lowest calorific value of the fuel used for
2
(b) equilibrium concentration of carbon monoxide CCO (on its production, will depend on the degree to which the
dry gas basis) in syngas on the temperature T at the reformer heat produced by the energy conversion is utilized.
inlet at H2O : C2H2OH molar ratios of (1) 4, (2) 6, (3) 8,
(4) 15, and (5) 22.
CATALYSTS FOR THE STEAM
REFORMING OF ETHANOL
degrees in which H2O : C2H5OH ratios equal to 20–22
(12 to 14 vol %) are the systems that can be reformed to According to the literature, the reaction of ethanol
syngas by using additional technological processes or steam reforming was studied using supported cobalt
systems. [5–10], rhodium [8, 11–20], nickel [12, 21–31], nickel–
copper [32–35], and palladium [14, 15, 19, 36] cata-
As hydrogen is the reforming end product, it is rea- lysts. The catalysts, as a rule, provides a complete ethyl
sonable to find the conditions that are thermodynami- alcohol conversion at gas hourly space velocities (mix-
cally most favorable for achieving the maximal selec- ture flow rate per unit catalyst volume) of 5000 to
tivity with respect to hydrogen. The thermodynamic 100000 h–1, temperatures of 500 to 700°C, and H2O :
equilibrium was calculated using reactions (1), (2), and C2H5OH molar ratios equal to 2–14. The rhodium and
the reaction of CO hydrogenation: cobalt catalysts show the highest activity and stability
ëé + 3ç2 ëç4 + ç2é. (3) in the steam reforming reaction while the copper and
nickel catalysts show the lowest. According to the liter-
The calculated data are plotted in Fig. 1. The selec- ature data [21], the increase in the reaction temperature,
tivity y is defined as the ratio of the number of hydrogen H2O : C2H5OH ratio, and contact time leads to
moles produced under equilibrium conditions by the increased hydrogen yields and decreased concentra-
steam reforming of one mole of ethanol to the theoreti- tions of CH4, ëé, and ë2ç4 in the reaction products.
cal maximum number of hydrogen moles based on the
stoichiometric equation: The formation of byproducts such as ë2- and
ë3-hydrocarbons, acetaldehyde, and other oxygen-con-
ë2ç5éç + 3ç2é = 2ëé2 + 6ç2. (4) taining compounds causes the carbonization of the cat-

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 42 No. 1 2008

 BIOETHANOL AS A PROMISING FUEL FOR FUEL CELL POWER PLANTS 3

alyst and a rapid decline of its catalytic activity. As a Sample catalysts

result, the achieved service life of most catalysts, based
on the data reported in the cited papers, does not exceed Sample Catalyst composition S, m2/g
at most 100 h. It is well known, however, that the time
Copper-containing
of stable performance without activity decline for the
catalysts used in practical applications should be at 1-Cu Cu/Ce0.9La0.1Ox/ Al2O3 80
least 1000 h. This makes us look for new more stable 2-Cu Cu/Cr/MgO–Al2O3 112
catalysts for the steam reforming of ethanol.
The present paper deals with the development of an 3-Cu Cu/Cr/ZnO–Al2O3 126
active and stable catalyst that can provide the maximal 4-Cu Cu/Cr/Ni/CeO2–Al2O3 96
yield of hydrogen and the absence of methane, ë2- and
5-Cu Pt/Cu/Ce0.9La0.1Ox/Al2O3 74
ë3-hydrocarbons, and oxygen-containing compounds.
During this study, we prepared and tested about 30 Cu-, Nickel-containing
Ni-, Rh-, Pt-, and Co-containing sample catalysts sup- 1-Ni Ni/α–Al2O3 6
ported on porous and metallic mesh-like substrates
[37]. A brief information about the compositions of the 2-Ni Ni/La2O3–Al2O3 86
catalysts and their specific surface areas S are summa- 3-Ni Ni/La2O3–Al2O3 46
rized in the table.
4-Ni Ni/Cu/Cr/La2O3–Al2O3 68
The catalysts were tested in the reaction of ethanol
steam reforming carried out in an automated continu- Rhodium-containing
ous kinetic reactor with a chromatographic analysis of 1-Rh Rh/Al2O3 126
the feed mixture and reaction products. The tested cat-
alysts were compared with each other using the follow- 2-Rh Rh/ZrO2 68
ing parameters: ethanol conversion, concentrations of 3-Rh Rh/Ce0.9La0.1Ox 38
hydrogen, methane, carbon monoxide, and acetalde- 4-Rh Rh/6% La2O3–Al2O3 52
hyde in the reaction products, as well as the concentra-
tion of carbon on the catalyst surface. The tests were 5-Rh Rh/CeO2–ZrO2 (Ce/Zr = 2) 44
performed at a gas hourly space velocity of 2000 h–1, 6-Rh Rh/Fe2O3 12
which was determined as the ratio of the flow rate of
ethanol and water vapors to the volume of the charged 7-Rh Rh/Mg Ni Al2O4/Al2O3 10
catalysts. The water-to-ethanol molar ratio was equal to 8-Rh Rh/Al2O3–MgO–SiO2 11
4. Sample 0.5 to 1.0 mm-fraction catalysts were diluted
with an equal amount of quartz sand. Before the tests 9-Rh Rh/Al2O3 130
were started, the catalysts were pre-reduced using a Cobalt-containing
mixture of 10 vol % of hydrogen and 90 vol % of nitro- 1-Co Co3O4/MnO2/SiO2/MgO/MCH 18
gen for 2 h at a temperature of 250°ë. The test temper-
ature interval was 300 to 700°C. 2-Co Co3O4/MnO2/SiO2/MgO/CuO/MCH 14
The tests showed that the catalysts in which the cop- 3-Co Co3O4/MnO2/SiO2/MgO /CuO/MCH 9
per is the main active component cause the formation of
4-Co Co3O4/MnO2/CuO/Fe2O3 46
a considerable amount of acetaldehyde and other uni-
dentified byproducts. The activity of these catalysts and 5-Co Co3O4/ZnO 82
the hydrogen selectivity decrease with time. For exam-
ple, the hydrogen concentration in the dry gas after a 4
to 5 h operation dropped to 15–30 vol %. In addition, should be noted that we did not observe any formation
we observed a considerable carbonization of the cata- of acetaldehyde and other byproducts under these con-
lysts. The nickel-containing catalysts were more active ditions.
as compared to the copper ones (hydrogen concentra-
tion in syngas reached 53 to 58 vol %), but they like- The results of the comparative tests of catalysts in
wise showed a considerable carbonization, which led to the reaction of ethanol steam reforming given in the
their fast deactivation. The rhodium and cobalt cata- above table imply that among all tested catalysts, only
lysts were best in selectivity and stability. the 1-Rh, 9-Rh (rhodium-containing), and 1-Co
Figure 2 demonstrates the comparison of prepared (cobalt-containing) catalysts are promising for the
catalysts based on the concentrations of ç2, CO, and application in the steam reforming of bioethanol for the
production of a hydrogen-containing gas.
ëç4 in the reaction products. It is seen that at 600°ë the
rhodium and cobalt catalysts provide the concentra- The next stage of our study was service life tests of
tions of hydrogen in the output syngas at a level of 60 the chosen rhodium and cobalt catalysts. In the tests, we
to 65 vol % at CO and ëç4 concentrations of 6 to 11 studied the stability of the 1-Co and 9-Rh catalysts dur-
and 2.5 to 7 vol % on dry gas basis, respectively. It ing a 1000 h operation. The volume of samples in the

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 42 No. 1 2008

4 KIRILLOV et al.

C, vol % C, vol %
(‡) (‡)
70 80
70 1
60
60
50 50
40 40
30
30 20 2
20 10 3
10
80 (b)
0
70 1
60
C, vol %
(b) 50
14 40
12 1 30
2 20 2
10 10 3
8
0 100 200 300 400 500 600 700 800 900 1000
6 t, h
4
Fig. 3. Results of service life tests for (a) 9-Rh and (b) 1-Co
2 catalysts in the steam reforming of bioethanol (T = 600°C,
gas hourly space velocity = 2000 h–1, ç2é : ë2ç5éç
0 ratio = 4): 1, H2 concentration on dry gas basis; 2, CO;
1-Rh 6-Rh 9-Rh 1-Co 4-Co 3, CO2.
3-Rh 7-Rh 3-Co 5-Co
Sample catalyst
To reduce the concentration of CO to the level
Fig. 2. Comparative data on the concentrations of (a) hydro-
gen, (b) CO and CH4 (1 and 2, respectively) in the reaction acceptable for the use of the hydrogen-containing gas
products for the steam reforming of ethanol with Rh- and in HT PEM fuel cells, the reactor was complemented
Co-containing catalysts (í = 600°ë, gas hourly space with a catalyst bed used for the steam reforming of car-
velocity = 2000 h–1, ç2é : ë2ç5éç ratio = 4). bon monoxide. To this end, we used an NTK (industrial
low-temperature copper–zinc) catalyst, the gas hourly
space velocity was 2000 h–1, and the catalyst bed tem-
bioethanol reforming reactor was 5 cm3. The tempera- perature was maintained at 220 to 260°ë. After the
ture was 700°ë and the gas hourly space velocity was steam reforming of CO, the concentration of carbon
set to 2000 h–1. The concentrations of the products leav- monoxide was decreased to 0.6 to 0.8 vol % and the
ing the bioethanol reforming reactor were determined concentration of methane in the reaction products was
by the chromatographic technique. After service life less than 1 vol % (Fig. 4).
tests, the tested sample catalysts were studied using the
methods of transmission electron microscopy (TEM) The main results of the above tests are summarized
and energy-dispersive X-ray (EDX) microanalysis. The below:
TEM photographic images were obtained using a
JEM-2010 microscope with a point-to-point resolution (1) The concentration of all reaction products
remain almost unchanged with time and there are no
of 0.14 nm and an acceleration voltage of 200 kV. The
acetaldehyde and other byproducts in the reaction prod-
energy-dispersive X-ray microanalysis of the elemental
ucts.
composition of the samples was performed using an
EDAX spectrometer with a Si(Li) detector providing a (2) The TEM and EDX measurements showed that
130-eV energy resolution. after service life tests the 9-Rh catalyst did not show
any traces of carbonization. At the same time, the 1-Co
The results of service life tests for the 9-Rh and catalyst showed slight traces of carbonization in the
1-Co catalysts are illustrated in Fig. 3. The studies form of carbon nanotubes with an outside diameter of
showed that the concentrations of the reaction products at most 20 nm characterized by a coaxial-conical struc-
leaving the reactor remained almost unchanged during ture of graphite-like layers.
a 800 to 1000 h operation. It is seen from the figure that
the hydrogen and CO concentrations were 65 to 70 and The obtained results show that the developed Co and
10 to 15 vol % on dry gas basis, respectively. Rh catalysts can be used in the steam reforming of eth-

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 42 No. 1 2008

 BIOETHANOL AS A PROMISING FUEL FOR FUEL CELL POWER PLANTS 5

anol in order to produce the syngas for fuel cell-based C, vol %

(‡)
power plants. 1.0
0.8
0.6 1
0.4
EXPERIMENTAL STUDIES 0.2 2
OF HIGH-TEMPERATURE PROTON EXCHANGE 0
MEMBRANE FUEL CELLS (b)
1.0 1
Low-temperature proton exchange membrane fuel 0.8
0.6 2
cells, developed by several foreign companies for a 0.4
long time, are regarded as most promising for a wide 0.2
commercial application in electric power plants of dif- 0 100 200 300 400 500 600 700 800 900 1000
ferent scales using hydrogen as the fuel [38, 39]. How- t, h
ever, their wide commercialization is limited by:
(1) Insufficient strength of the polymeric material Fig. 4. Experimental data on the steam reforming of CO
contained in the reaction products of bioethanol reforming
(Nafion) and limited service lives of 2000 to 4000 h. with an NTK (low-temperature) catalyst. The reforming of
(2) Narrow operating temperature range of 60 to reaction products of the steam reforming of bioethanol with
80°C and the necessity of monitoring the moisture con- (a) 9-Rh and (b) 1-Co catalysts (catalyst temperature = 220
to 260°C, gas hourly space velocity = 2000 h–1). Reaction
tent of the membrane. product concentrations: 1, methane; 2, carbon monoxide.
(3) Sensitivity of the fuel cells to different distur-
bances in the operating conditions.
(4) Necessity of operating under conditions at which containing gas causes a 4% decline in the monocell
the CO concentrations in the hydrogen-containing gas voltage at current density of 200 mA/cm2. The voltage
do not exceed 10 ppm, which in the case of using a is restored to the original value when the cell comes
reformate gas requires additional devices for treating back to pure hydrogen. It was also found that the cur-
from carbon monoxide. rent–voltage characteristic remains almost unchanged
when inert gases, such as argon, carbon dioxide, and
The high-temperature fuel cells developed in the water vapors are added to the fuel. In the experiments,
recent time [1] are not subject to the above drawbacks, the density of the electric power generated by the
which can be illustrated by the characteristics of HT
PEM fuel cells achieved to date. These fuel cells are monocell can reaches as high as 120 mW/cm2. Conse-
operated at temperatures of 140 to 180°ë and CO con- quently, the conducted experiments confirmed the
centrations up to 5 vol % and do not need the humidifi-
cation of the air supplied to the cell. Their service life
reaches 18000 h. The low sensitivity of these fuel cells
to the concentration of carbon monoxide considerably
simplifies the design of process flowsheets for produc-
ing the hydrogen-containing gas supplied to the stack
of fuel cells because it does not require the reduction of
the CO concentration to 10 ppm. In addition to the
reduced total cost of the power plant due to the simpler
design of the fuel-processing unit, the use of heat
cogeneration or the use of heat for the production of
useful chemical products makes it possible to increase
the overall efficiency of the plant.
In our study, we conducted the tests of a HT PEM
fuel cell manufactured by PEMEAS, Germany, which
was a monocell electrode assembly with electrode areas
of 50 cm2. The monocell general view is plotted in Fig. 5.
The tests were conducted at temperatures of 140 to
180°ë, hydrogen flow rate of 120 cm3/min, air flow rate
of 200 to 600 cm3/min, and a CO concentration in the
hydrogen-containing gas of 0 to 5 vol %. In the experi-
ments, we studied the effect of temperature and the
effects of the flow rates of gases and their composition
on the monocell current–voltage characteristics.
The results obtained in the experiments are illus-
trated in Figs. 6 and 7, from which it can be seen that Fig. 5. High-temperature proton-exchange membrane fuel
the addition of up to 5 vol % of CO to the hydrogen- monocell.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 42 No. 1 2008

6 KIRILLOV et al.
U, V
0.9
1
2 0.60
3
0.8
1 0.56
0.7
2
0.6
3
0.5
0 50 100 150 200
j, mÄ/cm2
Fig. 6. Current–voltage characteristic of the high-tempera-
ture proton-exchange membrane fuel monocell (T = 160°C,
anode gas (H2 + He + CO + CO2) flow rate of 120 cm3/min,
air flow rate of 350 cm3/min): 1, 100% H2; 2, 90% H2 +
10% He; 3, 90% H2 + 5% CO + 5% CO2.
promise of using HT PEM fuel cells for the power
plants in which the fuel is the hydrogen-containing gas
with a carbon monoxide concentration of up to 5% pro-
duced by the steam reforming of ethanol.
POWER PLANT FLOWSHEETS BASED
ON HT PEM FUEL CELLS
AND BIOETHANOL FUEL
The low concentration of ethanol in bioethanol
causes certain difficulties for its wide application as a
fuel. The limiting concentration of ethanol in its mix-
ture with water at which it can be used as a fuel is equal
to 35 vol % (water-to-alcohol molar ratio = 6). Conse-
quently, the first stage of the processing of bioethanol
should be its distillation. The amount of power con-
sumed in distillation is determined mostly by the heat
expended for the heating of bioethanol to the boiling
point and vaporization, which, depending on the value
of the reflux ratio, can exceed 15% of the calorific value
of the alcohol contained in the bioethanol. The power
efficiency of the power plant will largely depend on the
utilization degree of the byproduct heat released in the
conversion of the fuel energy into electric power.
Therefore, high attention should be paid to the utiliza-
tion of byproduct heat in designing the flowsheet of the
power plant. One of the possible flowsheets of this
power plant is given in Fig. 8. In this flowsheet, bioeth-
anol at environmental temperature is supplied to heat
exchanger HE-5, where it is heated to its boiling point
of 92°ë by the heat supplied by the cathode gases of a
stack of fuel cells (SFC) and then is supplied to a distil-
lation column. The steam providing the heat for the dis-
tillation operation is produced due to the combustion of
a part of SFC anode gases. The azeotrope produced by
the distillation (88.4 mol % of ë2ç5éç) is supplied to
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
U, V
0.62
H2 + 5%CO + 5%CO2
0.58
H2 H2
0.54
0.52
0.50
0 50 100 150 200
t, min
Fig. 7. Effect of the CO concentration on the time variation
of the voltage produced by the monocell (T = 160°C, current
density of 200 mA/cm2, anode gas (H2 + CO + CO2) flow
rate of 120 cm3/min, air flow rate of 350 cm3/min).
evaporator HE-1, where it is evaporated due to the heat
of the gases leaving a reactor for ethanol steam reform-
ing. For this flowsheet, it is suggested to use a heat-cou-
pled reactor consisting of a hydrocarbon steam
reformer and a chamber of fuel deep catalytic oxidation
[40] in which SFC anode gases and alcohol are used as
the fuel. To reduce the concentration of CO to 1 to 2 vol %
(Fig. 1b), which are needed for the optimal perfor-
mance of a stack of HT PEM fuel cells, the flowsheet
should include the steam reforming of CO. The cata-
lytic reforming of CO by steam can be effected as a
two-stage operation in adiabatic reactors using
medium- and low-temperature catalysts for the first and
second stages, respectively, or a one-stage operation in
a heat-exchanger–reactor system with a countercurrent
flow of the reacting mixture and coolant. In the two-
stage flowsheet of CO reforming, the reaction water is
pumped from the reboiler of the distillation column to
evaporators HE-2 and HE-3, where it is evaporated due
to the heat of the syngas leaving the reactor of ethanol
steam reforming and the first-stage CO reformer. In this
case, the syngas is cooled to a temperature of 380°ë
before entering the first-stage CO reformer, which con-
tains a medium-temperature catalyst, and to a tempera-
ture of 200°ë before entering the second-stage CO
reformer, which contains a low-temperature catalyst.
The concentration of CO in the syngas at water–alcohol
molar ratios equal to 4 to 5 is 16 to 18 vol % on dry gas
mixture basis at the inlet of the first-stage reformer and
1.5 to 0.6 vol % at the outlet of the second-stage
reformer.
After leaving the low-temperature CO reformer, the
syngas is cooled from 260 to 160°ë in heat exchanger
HE-4 and supplied to the anode compartment of the
stack of fuel cells. The latter is cooled by the air deliv-
ered by a circulation pump. The air to be supplied to the
Vol. 42 No. 1 2008
 BIOETHANOL AS A PROMISING FUEL FOR FUEL CELL POWER PLANTS 7

Overhead condenser
Steam reforming
reactor HE-1
To air
Oxidation
Reforming
HE-2

Distillation
column
First-stage ëé
Second-stage CO
Air To air

reformer
reformer
Water

Afterburner
HE-3
HE-4
compartment

compartment
Cooling
Cathode

HE-5
Anode

Stack of
fuel cells

Bioethanol

Fig. 8. Power plant flowsheet based on high-temperature polymeric fuel cells and bioethanol as fuel.

cathode compartment by a compressor is preheated in The vapor–liquid phase equilibrium in the calcula-
heat exchanger HE-3 to a temperature of 140°ë due to tions of material and heat balances for the condensers,
the heat of the syngas leaving the low-temperature CO evaporators, and heat exchangers was determined using
reformer. In this case, the syngas is cooled to a temper- the equality of partial fugacities in the vapor and liquid
ature of 160°ë. The cathode gas is mixed with the air phases, which was written as [41]
leaving the SFC cooling ducts and is used for heating
γ i φ i P i ( PF ) i
S S
and evaporating the bioethanol and as the oxidizer in y i = -----------------------------
- xi , (7)
the oxidation chamber of the reactor of steam reform- φ̂ i P
ing and in an afterburner.
where yi and xi are the mole fractions of component i in
The flowsheet given in Fig. 8 was analyzed by cal- the vapor and liquid phases, respectively; γi, the activity
culating the heat and material balances for each of the
apparatuses. It was assumed that thermodynamic equi- coefficient of component i in the liquid phase; φ̂ i and
φ i , the vapor-phase fugacity coefficients of component
S
librium was reached in all apparatuses. The equations
of material and heat balances for chemical reactors can i in the mixture and in the saturated vapor of the pure
be written in general form as P

ki (T ) =
e
∏
v
P j ij , (5) component, respectively; (PF)i = exp ( V iL /RT ) dP , ∫
S
j Pi
the Pointing factor accounting for the correction of the
∑ g J ∆H J – ∑ g j ∆H j
in in out out
= Q, (6) liquid-phase fugacity in the interval between the com-
J J ponent pressure and the vapor pressure in the system.
e As this factor at low pressures of about several atmo-
where ki is the equilibrium constant of reaction i; Pj, spheres is virtually equal to unity, this formula was not
the partial pressure of reactant j; vij, the stoichiometric used in the calculations. Equation (7) was used to cal-
coefficient of reactant j in reaction i; gj and ∆Hj, the culate the boiling point for water–ethyl alcohol mix-
number of moles and enthalpy of reactant j at the reac- tures, phase compositions, and dew points. The fugac-
tor inlet (superscript in) and outlet (out), respectively; ity coefficients were calculated using the Soave–
Q, the external heat source; J, the number of reactants. Redlich–Kwong equation [41]. The activity coeffi-

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 42 No. 1 2008

8 KIRILLOV et al.

cients for the liquid were calculated by the Margules J/mol. The operating voltage across the electrodes of
equation [42]. The saturated vapor pressure was calcu- unit fuel cells was taken to be equal to 0.7 V, the hydro-
lated by the Antoine equation [41]. The thermodynamic gen utilization degree η = 0.9, which resulted in EE =
equilibrium constants for the chemical reactions 0.5.
involved in the process were determined using the liter- The thermal efficiency of the power plant is defined
ature data [41, 42]. as the ratio of the lowest calorific value of the hydrogen
The source of electric power in the flowsheet under supplied to the anode compartment of the stack of fuel
consideration is the electrochemical reaction of hydro- cells to the lowest calorific value of the fuel (bioetha-
gen oxidation by oxygen consisting of two half-reac- nol) consumed for its production. Figure 9 illustrates
tions: the dependence of the electric efficiency of the power
plant on the temperature of the steam reforming of bio-
ç2 2ç+ + 2Â
ethanol at different water-to-alcohol ratios. As the
0.5é2 + 2ç+ + 2Â ç2é water-to-alcohol ratio increases, the hydrogen yield
builds up (Fig. 1). At the same time, this gives rise to
ç2 + 0.5é2 ç2é expenditures of power for the preparation of the reac-
tion mixture. When the water-to-alcohol molar ratio is
A hydrogen molecule is oxidized on the anode, higher than 3, the effect produced by the increase in the
which is accompanied by the formation of 2 electrons. ratio cannot make up for the increased heat expended in
The formed protons join a proton-exchange electrolyte evaporating the additional water amount, which leads
and are transported to the cathode compartment of the to a decrease in the total efficiency of the power plant.
fuel cell, where they accept two electrons from the The temperature dependences of the efficiency at dif-
external circuit and react with oxygen molecules to ferent water-to-alcohol ratios (Fig. 9) are characterized
form water. by the presence of maxima, which account mostly for
The criterion of our analysis was the electric effi- the recovery degree of byproduct heat in the flowsheet.
ciency of the power plant, which was calculated as the The rapid drop of the efficiency at a temperature lower
ratio of the produced electric power to the lowest calo- than 650°ë is attributed to the shift of equilibrium in the
rific value of the fuel consumed for its production. The methanization reaction to the formation of methane.
electric efficiency of the power plant is based on the The maximal electric efficiency that can be achieved in
electric efficiency of the stack of fuel cells and the ther- this flowsheet is 42%.
mal efficiency of the fuel-processing unit. The electric As mentioned above, the direct reforming of bioeth-
efficiency (EE) is the characteristic of the stack of fuel anol at a temperature of 550°ë provides the concentra-
cells that depends on the load: tion of CO in the produced syngas allowing the use of
EE = Uη2F/∆H the latter as the fuel for HT PEM fuel cells. In this case,
the flowsheet of the fuel-processing unit is radically
where U is the operating voltage across the electrodes simplified due to the exclusion of the stage of CO steam
of unit fuel cells, V; η, the utilization degree of hydrogen reforming. One of such technological solutions is the
in the stack of fuel cells; F, Faraday constant, K/g-equi- power plant flowsheet given in Fig. 10, in which the
valent; ∆H, hydrogen heat of combustion at 160°ë, bioethanol at ambient temperature is supplied to the
intertubular space of the condenser, where it is heated
to a temperature of about 90 to 92°C due to the heat
h, %
provided by the products of bioethanol reforming sup-
46 plied to the tubular space of the condenser. The heat
44 transfer with the flow of bioethanol causes the conden-
42 2 sation of most of the water contained in the reforming
40 products. At the condenser outlet, the bioethanol is sep-
38 3 arated into two flows. One of them goes to reforming
and the other is delivered to a distillation column,
36 where ethyl alcohol is separated. The produced alcohol
34 1
is used as the fuel for evaporating the bioethanol and
32 providing heat to the reforming reaction. The bioetha-
30 nol flow intended for reforming is evaporated in heat
28 exchangers HE-1 and HE-2 due to the heat of the gases
leaving the steam reforming reactor and due to the heat
550 600 650 700 750 800 brought by the recycle flow of the cathode gas, respec-
T, °C
tively. The syngas dehumidified in the condenser is
heated in heat exchanger HE-3 to a temperature of
Fig. 9. Dependence of the efficiency of the power plant
(Fig. 8) on the bioethanol reforming temperature at the 160°ë due to the heat of the flue gases leaving the after-
reformer inlet at water–ethanol molar ratios of (1) 4, (2) 6, burner and is delivered to the anode compartment of the
and (3) 8. stack of fuel cells.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 42 No. 1 2008

 BIOETHANOL AS A PROMISING FUEL FOR FUEL CELL POWER PLANTS
Steam reforming
reactor
Oxidation
Reforming
He-1
To air
He-2
To air
Stack
of fuel
cells
compartment
compartment
Cooling
Cathode
Anode
Air
Fig. 10. Power plant flowsheet based on high-temperature proton-exchange membrane fuel cells and the reforming of bioethanol to
syngas accompanied by the production of ethyl alcohol.
To condense the water vapors contained in the
reforming products, the condenser should be fed with
an amount of bioethanol that is seven times the amount
of bioethanol that goes to reforming. As a result of
using the byproduct heat of the power plant for the dis-
tillation of bioethanol, the amount of ethyl alcohol is
about 4.5 times the amount of alcohol reformed to the
syngas. This alcohol can be used for producing electric
power in the flowsheet given in Fig. 8. The integrated
power plant flowsheet in which a part of bioethanol is
directly supplied to reforming, the other part is supplied
to distillation, and the produced alcohol is reformed to
syngas at water-to-alcohol ratios of 4 to 12, which is
followed by the steam reforming of CO, can provide a
higher efficiency of electric power generation due to the
higher recovery degree of low-potential heat as com-
pared to the power plant with a conventional H2O :
C2H5OH ratio of 2.
If the electric efficiency of the power plant flowsheet
given in Fig. 10 is calculated ignoring the produced
marketable alcohol, it will be 33%, which is much
lower than the efficiency of 42% for the power plant
flowsheet shown in Fig. 8. The power plant in which
15% of bioethanol is processed according to the flow-
sheet shown in Fig. 10 and 85% is processed according
to the flowsheet shown in Fig. 8 can be used to increase
the efficiency of electric power production up to 44.6%.
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING
9
Overhead condenser
Ethanol
Distillation
column
Condenser
Water
Water
He-3
Afterburner
Bioethanol
In this case, the concentration of CO in the mixture at
the anode compartment inlet will not exceed 1%.
Consequently, it is shown that bioethanol is a prom-
ising source for producing a hydrogen-containing gas
used as the fuel for fuel cell-based power plants. In the
present paper, several technological solutions that can
help solve this problem in practice are proposed and
discussed:
(1) Two new promising catalysts based on rhodium
and cobalt compounds are proposed for the steam
reforming of bioethanol. The catalysts are tested in
short-term and service life experiments.
(2) The performance of a high-temperature proton-
exchange membrane fuel cell is studied. It is experi-
mentally confirmed that its current–voltage characteris-
tic is not much sensitive to the concentration of carbon
monoxide in the hydrogen-containing gas when the
concentration is below 5 vol %.
(3) Two process flowsheets for producing electric
power with high-temperature proton-exchange mem-
brane fuel cells are developed. Their analysis showed
that when bioethanol is used as the fuel, the total effi-
ciency of the power plant, which was calculated as the
ratio of the produced electric power to the lowest calo-
rific value of the fuel consumed for its production,
would be about 44.6%.
Vol. 42 No. 1 2008
10 KIRILLOV et al.
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