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Design and optimization of a fixed bed reactor for hydrogen production via
bioethanol steam reforming


Maria A. Goula
a
, Olga A. Bereketidou
a,b
, Costas G. Economopoulos
a,c


a
Technological Educational Institute of Western Macedonia, Department of Pollution Control Technologies,
Koila, Kozani, 50100, Greece, e-mail: mgoula@kozani.teikoz.gr

b
University of Western Macedonia, Department of Engineering and Management of Energy Resources,
Kastorias & Fleming Str, Kozani, 50100,Greece, e-mail:olgitsa79@yahoo.com

c
University of Patras, Department of Chemistry, Rio, Patras, Greece, e-mail:costas_2001greek@yahoo.gr



ABSTRACT:

Global climate changes caused by CO
2
emissions are currently debated around the world. Renewable
sources of energy are being sought as alternatives to replace fossil fuels. Hydrogen is theoretically the best
fuel, environmentally friendly and its combustion reaction leads only to the production of water. Bioethanol
has been proven to be effective in the production of hydrogen via steam reforming reaction. In this research
the steam reforming reaction of bioethanol is studied at low temperatures over 15,3 % Ni/La
2
O
3
catalyst. The
reaction and kinetic analysis takes place in a fixed bed reactor in 130 - 250
0
C in atmospheric pressure.
This study lays emphasis on the design and the optimization of the fixed bed reactor, including the total
volume of the reactor, the number and length of the tubes and the degree of ethanol conversion. Finally, it is
represented an approach of the total cost of the reactor, according to the design characteristics and the
materials that can be used for its construction.


KEYWORDS: hydrogen, bioethanol, steam reforming, reactor design



1. INTRODUCTION

Nowadays there is a major interest in electricity production from renewable sources as a consequence of the
environmental standards and the decline of the fossil fuel reserves. Hydrogen using as a feed in fuel cells
has been proposed as a major energy source, as it reduces greenhouse gas emissions. Bioethanol
produced by biomass fermentation could be an important hydrogen supplier as a renewable source [1, 2].In
comparison to other fuels, ethanol presents a series of advantages, since it is easier to store, handle and
transport in a safe way due to its lower toxicity and volatility.
Bioethanol steam reforming is one of the best alternatives to obtain hydrogen. Various catalysts are studied
for the reaction of bioethanol steam reforming: oxides, oxide-supported transition metals and noble metals
[3-13]. They are generally prepared by impregnation of various supports. Ni at its supported form is widely
used as a steam reforming catalyst [9, 12, 14]. This is because of the fact that nickel catalysts are much
cheaper than other metals. In laboratorial and industrial scale the process using supported nickel catalysts
has the disadvantage of an important carbon deposition and metal incorporation. Supported nickel catalysts
on Al
2
O
3
, SiO
2
, La
2
O
3
, ZrO
2
, and CeO
2
are commonly used to obstruct carbon formation. The active phase
and the metal oxide interaction appears as extremely important for the stability. The design of an active,
selective and stable catalytic system for the steam reforming of ethanol is one of the key points. The catalyst
main purpose is to optimize the hydrogen production and to discourage the by-products formation.
Bioethanol steam reforming is a very complex reaction where many reaction pathways are possible [13, 15].
Some of them depend on the catalyst used for the reaction. Kinetic studies for nickel catalysts on various
supports have been performed [2, 15, 16]. The catalytic testing takes place in a fixed bed reactor in
atmospheric pressure in the reaction temperature.
In the present study a design of a fixed bed reactor in industrial scale is accomplished for a specific
hydrogen production by the reforming of bioethanol. For a catalytic system of 15, 3 %Ni/La
2
O
3
at the range of
130 250
0
C the reaction is first order with respect to ethanol. Lanthanum oxide species, which decorate Ni
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particles, react with CO
2
to form La
2
O
2
CO
3
, that reacts with surface carbon and clean the nickel surface of
carbon deposits, resulting in good catalytic stability [1]. The cost evaluation refers to the total investment cost
of the fixed bed reactor and the aim is to analyze the influence of feed composition, the reaction
temperature and the catalytic system for the reforming reaction.


2. PROCESS DESCRIPTION

2.1. Reaction Scheme

The ethanol steam reforming overall reaction

C
2
H
5
OH + 3H
2
O 6H
2
+ 2CO
2

r
0
= 173.1 kJ mol
-1
(1)

C
2
H
5
OH + H
2
O 4H
2
+ 2CO
r
0
= 238.5 kJ mol
-1
(2)

is generally considered as an extremely complicated reaction scheme, involving a number of sequential or
parallel steps between, occurring either in the gas phase or over the catalysts surface, the most commonly
recognized of which are the following [1,3,4,7,12,14] :

C
2
H
5
OH CH
3
CHO + H
2
(3)

C
2
H
5
OH C
2
H
4
+ H
2
O (4)

C
2
H
5
OH CH
4
+ CO + H
2
(5)

C
2
H
5
OH + H
2
O CH
3
CHO + 2H
2
(6)

C
2
H
5
OH + 1/2O
2
CH
3
CHO + H
2
O (7)

C
2
H
5
OH 2C + H
2
O + 2 H
2
(8)

C
2
H
5
OH + 3 O
2
2CO
2
+ 3 H
2
O (9)

CH
3
CHO CO + CH
4
(10)

CH
3
CHO + H
2
O 2CO + 3H
2
(11)

CH
4
+ H
2
O CO + 3H
2
(12)

CH
4
+ CO
2
2CO + 2H
2
(13)

CO + H
2
O CO
2
+ H
2
(14)

CO + 1/2O
2
CO
2
(15)

CO + 3H
2
CH
4
+ H
2
O (16)

CH
4
+ 2O
2
CO
2
+ H
2
O (17)

H
2
+ 1/2O
2
CO
2
(18)


2.2 Catalytic systems

The bio-ethanol steam reforming reaction over Ni, Co, Cu and noble metals has been extensively studied.
The target is to develop an active catalyst that inhibits coke formation and CO production. Although noble
metals are less sensitive in carbon deposition, nickel catalysts are also widely used for this reaction
especially because of their lower prices comparing with other metals. Furthermore, in order to obstruct the
carbon deposition and metal incorporation plentiful substances for activation (catalytic amplifiers) have been
added to improve the performance of supported nickel catalysts. Moreover, supporting materials that are
commonly used in the bioethanol steam reforming reaction are Al
2
O
3
ZrO
2
, SiO
2
, La
2
O
3
TiO
2
CeO
2
, zeolites
or a combination of all these [1-16].
This study is based on the use of 15, 3 % Ni/La
2
O
3
catalyst, produced by the impregnation decomposition
method, which exhibits a high activity for ethanol steam reforming reaction with a conversion of ethanol to
81, 9 %. At the range of 130 250
0
C, the reaction is first order with respect to ethanol and the rate
expression is determined by the equation [15]:

| || |
2
n
r k ethanol H O =
where n is determined. Experimental results have proved that at low temperatures and low concentrations of
water and ethanol, water does not participate in the reforming reaction and the reaction is zero order with
respect to water. Therefore, n = 0 and the rate expression is:

| | r k ethanol =

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The catalytic steam reforming reaction of bioethanol for hydrogen production takes place in a fixed bed
reactor in atmospheric pressure. The reactor with tubes will be designed in industrial scale, taking into
account the data for the laboratorial reactor for a specific flow of hydrogen.

2.3 Reactor design

The products of the reforming reaction of bioethanol at the range of 130 250
0
C, as expected from the
predominant reaction, are methane, carbon monoxide and hydrogen. In laboratorial scale, the ethanol
conversion was kept below 20 % [15].The catalyst apparent density is considered as 1 g/mL and the rate
constant in the absence of water vapor is 19, 1 s
-1
[15].In order to design an industrial multi tubular reactor it
is essential to create a scale up system for the operating conditions and parameters [2].


Table 1
The operating conditions and parameters for the laboratory tubular reactor and industrial scale multi
tubular reactor.

Parameter Definition Bioethanol (lab. Scale) Bioethanol (ind. Scale)

T
in
Inlet temperature, K 403 403

D
p
Catalyst particle diameter, mm 1 4
z Catalyst bed length, m 50*10
-3
3
E
a
Activation Energy of reaction, KJ/mol 1, 87 1, 87
P Total pressure, atm 1 1
W
k
Catalyst weight, Kg 150 *10
-6
50
K Rate constant, s
-1
19, 1 19, 1
D
t
Internal diameter of the tube, cm 0, 3 1

A fixed bed reactor of 3930 tubes will be designed by a pseudo homogenous one dimensional model
for hydrogen production of 1100 Kg/day. The production refers to the demanded quantity of hydrogen for a
gas station in order to supply 100 cars with hydrogen fuel in fuel cells with an efficiency of 66 %[17].
The fixed bed reactor consists of vertical cylindrical tubes full of catalytic particles. The operation is
adiabatic, which is accomplished in industrial reactors and the outlet temperature is lower then the inlet
temperature, as the steam reforming reaction of bioethanol is endothermic. The pressure drop through bed
sections must be calculated, although is not significant compared to the total pressure. The Ergun equation
is commonly used to calculate pressure drop [18].
At 200
0
C the rate constant K is 20, 67 s
-1
[15] according to the following equation:

0
E
RT
k k e

=
where E is the activation energy for the specific catalytic system, 1,87 KJ/mol, T the temperature, 473 K, R
the gas constant, 8,314 J/mol K and Ko is calculated using the rate constant at a specific temperature. The
predominant reaction
2 5 2 4
C H OH H CO CH + +
leads to a volume change of
A
= 2 and the sum moles of ethanol output reactor can be calculated as:
0
1
1
A
A A
A A
x
C C
x

=
+

where C
A0
represents the sum mole of ethanol input reactor and x is the degree of ethanol conversion.
According to the equations of the design of PFR reactors, the total volume of the reactor can be defined as
[19]:
0
0
A
x
A
A
A
dx
V F
r
=


where r
A
is the rate expression for first order kinetics with respect to ethanol and F
A0
is the inlet flow of
ethanol in feed composition, which is related to the flow of hydrogen product and the degree of the
conversion through mass equilibrium.
Considering the tube diameter as 1 cm and the catalyst bed length as 3 m, the total length of the fixed bed
reactor will be 4 m and the internal diameter of the reactor will be 0,12 m, as the reactor is regarded as a
cylindrical vessel. The total number of the tubes is calculated by the following equation:
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, tot in
tube
Q
N
Q
=

where the total flow in the inlet of the reactor results from the feed composition of ethanol and water in the
reaction temperature and the flow in the tubes is calculated by the following equation:
2
0
4
t
tube
D
Q U

=
where U
0
represents the superficial velocity, m/s and D
t
is the tube diameter
The Ergun equation is commonly used to calculate pressure drop through catalyst beds[18]:
( )
2
2
0 0
2 3 3
1 1
150 1, 75
U U P
L dp dp



= +
where P is the pressure drop, atm, L is the total length of the reactor, m, dp is the catalyst particle diameter,
m, is the density of the gas mixture at the outlet of the reactor, g/L, is the mixture viscosity which is
equivalent to the viscosity with the lower density in the outlet temperature, cp and is the bed porosity, given
by the equation:
2
2
1 2
0, 38 0, 073
t
P
t
P
D
D
D
D

(
| |
+ (
|
( \
= +
(
| |
(
|
(
\

The results of the reactor design at reaction temperature of 200
0
C, hydrogen production of 1100Kg/day and
ethanol conversion of 80% are summarised at the following table:



Table 2
Operating conditions and parameters for a fixed bed reactor for hydrogen production of 1100 Kg/day at the
reaction temperature of 200
0
C

Parameter Definition Industrial scale

T
in
Inlet temperature, K 473
T
out
Outlet temperature, K 453
E Activation energy, KJ/mol 1, 87
X
A
Degree of ethanol conversion, % 80
R Gas constant, J/mol K 8,314
P Total pressure, atm 1
K Rate constant, s
-1
20, 76
K
0
Constant, s
-1
33, 4

A
Volume change 2
F
H2
Hydrogen production, mol/day 550.000
F
ETOH,0
Feed ethanol flow, mol/day 687.500
C
A0
Initial ethanol concentration, mol/L 0, 02578
C
A
Total ethanol concentration, mol/L 0, 00198
r
A
Reaction velocity, mol/L s

0,041
V Total reactor volume, L 47, 99
D
t
Tube diameter, cm 1
Z Catalyst bed length, m 3
L Total length of the reactor, m 4
D Reactor diameter, m 0, 12
D
p
Catalyst particle diameter, mm 4
U
0
Superficial velocity, m/s 1
N Number of tubes 3930
Bed porosity 0,3946
P Pressure drop, atm 0,000047
Q
tube
Flow in the tubes, m
3
/s 7, 8 *10
-5

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2.4 Economic evaluation

The objective of this part of the study is to evaluate the cost of the fixed bed reactor for hydrogen
production from bioethanol steam reforming in industrial scale. The investment cost consists mainly of the
total cost of the equipment, the vessel, the tubes and the cost of the catalytic system for the reaction [20].
Other apparatuses possibly included in the process simulation have not taken into account in this cost
analysis.
The cost analysis is based on the production of hydrogen of 550.000 mol/day, resulting in the parameters
that are shown in table 2. The purchase cost of the cylindrical vessel is calculated by the following equation
[21, 22]:

m b a
C f C C = +
where f
m
is a factor for the used material, which plays an important role for the resistance in corrosiveness. In
this study, the material is stainless steel 316 and f
m
= 2, 1.
The factor C
a
is defined as:
0,7936 0,7068
246
a
C D L =
where D is the diameter of the vessel, in and L is the total length of the reactor, in.
The weight of the vessel, lbm, is given by the equation [22]:
( )
2
h h m
W t t D L = +
where t
h
is the thickness of the vessel, in and
m
is the density of the construction material, lbm/in
3

The factor C
b
is defined as:
( ) ( )
2
exp 9,1 0, 2889ln 0, 04576 ln
b
C W W
(
= +


The cost of a tube can be calculated as:
0,99
12,12
tube
C d z =
where d is the tube diameter, ft and z is the bed length, ft.
The total cost of the tubes is estimated as:
tubes tube
C NC =
using the total number of the tubes in the reactor, N.
The total cost of the catalyst can be estimated, taking into account the percentage of the metal in the surface
of the support (15,3 % Ni/La
2
O
3
) and the quantities that are essential for the impregnation method in order to
produce the catalytic system. The results of the economic evaluation of a fixed bed reactor for hydrogen
production of 550.000 mol/day are summarized in table 3.

Table 3
Economic evaluation of a fixed bed reactor of 550.000 mol/day hydrogen production from bioethanol steam
reforming in 15, 3 % Ni/La
2
O
3


Parameter Definition Industrial scale
D Reactor diameter, in 4, 7
L Reactor length, in 157
F
m
Factor for SS 316 2, 1
C
a
Factor, 29776
t
h
Thickness of the vessel, in 0,5
p
m
Density for SS 316, lbm/in
3
0,29
W Weight of the vessel, lb 372
C
b
Factor, 8015
C Cost of the vessel, 46608
D
t
Tube diameter, ft 0,033
Z Catalyst bed length, ft 9, 84
C
tube
Cost of a tube, 4, 08
N Number of tubes 3930
C
tubes
Total cost of tubes, 16035
C
Ni(NO3)2 6H2O
Cost of Ni(NO
3
)
2
6H
2
O 34/250 g
C
La2O3
Cost of La
2
O
3
, /Kg

155
W
k
Weight of catalyst, Kg 50


Catalyst density, Kg/L 1,3
C
catalyst
Total cost of catalyst, 18440
C
total
Total cost, 81083
C
total, 2007
Cost in the year 2007, 85730
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The study emphasizes on the evaluation of the investment cost of the reactor, consisting of the vessel, the
tubes and the catalyst. The production cost is not an issue of this study and generally it can be calculated by
counting the project cost, the operating cost, the raw material cost and the utility cost. An escalation of the
ethanol price during the past is shown in figure 1 [23].




Figure 1: Ethanol market price

3. RESULTS AND DISCUSSION

3.1The influence of the desired hydrogen production and the feed composition

In order to evaluate the change in hydrogen production and feed composition, three different values of
hydrogen production are studied. The first one, 550.000 mol/day, refers to the demanded quantity of
hydrogen for a gas station in order to supply 100 cars with hydrogen fuel in fuel cells with an efficiency of 66
%. The second refers to a unit of hydrogen production that is able to supply a prefecture of 70.000 citizens.
Considering that there is a correlation of a car/3 people, in the prefecture will be approximately 23.000 cars.
Hydrogen will be used to supply these cars in fuel cells and efficiency of 66 %. The heat combustion of
hydrogen is estimated in 33, 3 KW/KgH
2
, resulting in a flow of hydrogen about 15571 *10
3
mol/day [17]. The
third value refers to an industry of hydrogen production by steam reforming of bioethanol, with a production
of 100Kt/year = 135 *10
6
mol/day. The results of the economic evaluation and the design of the three reactors
for the three values of hydrogen production are shown in table 4:

Table 4
Parameters and economic evaluation for the three values of hydrogen production

Parameter Hydrogen (100 cars) Hydrogen (23.000 cars) Hydrogen Industry

F
H2
, mol/day 550.000 15571*10
3
135*10
6
Reactor volume, L 47, 99 1358, 73 11780
Cost of vessel, 46608 132866 286068
Number of tubes 3930 111249 964529
Cost of tubes, 16035 453895 3935278
Weight of catalyst, Kg 50 1766, 35 15314
Catalyst cost, 18440 494712 4281470
Total investment cost, 85730 1161676 9133393

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The results in table 4 show that the reactor volume and the total cost depend on the production of hydrogen.
An increase in the value of hydrogen production results in an increase in the quantity of bioethanol in feed
composition, an increase in the volume of the reactor for the reforming of bioethanol and consequently an
increase in the total investment cost of the fixed bed reactor.

3.2 The influence of the reaction temperature

Considering that the rate expression used in this study refers to low temperatures [15], there is an approach
to evaluate the influence of the temperature variation at the range of 130 180
0
C.For reaction temperature
from 130 180
0
C, with a catalyst of 15,3 % Ni/La
2
O
3
and hydrogen production of 550.000 mol/day, the total
volume of the reactor and the total investment cost variations are shown in figures 2, 3:


React Vol (L)
43
43,5
44
44,5
45
45,5
46
46,5
47
47,5
Temperature (
0
C)
V
o
l

(
L
)
React Vol (lt) 44,41 44,9 45,4 45,91 46,42 46,94
130 140 150 160 170 180

Figure2: The influence of the reaction temperature on the reactor volume


Total Cost
52500
53000
53500
54000
54500
55000
55500
56000
56500
Temperature (
0
C)
T
o
t
a
l

C
o
s
t

(

)
Total Cost 53641 54079 54519 54959 55400 55842
130 140 150 160 170 180

Figure 3: The influence of the reaction temperature on the total cost



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From the above diagrams it can be concluded that an increase in the reaction temperature leads to an
increase in the reactor volume and the total investment cost. Increasing the reaction temperature, there is an
increase in the rate constant, K and the total volumetric supply of ethanol in the feed composition. The
reactor volume is proportional to the supply of ethanol, resulting in an increase in the total volume with a
parallel increase in the reaction temperature, considering that the degree of ethanol conversion is constant.
The higher the reactor volume, the higher and the total cost and increasing the temperature, the total cost of
the reactor also increases.

3.3 The influence of the catalytic system

The rate expression in this study is the same for three different catalytic systems [15]. The whole study is
based on the catalyst 15,3 % Ni/La
2
O
3
, but it is essential to take the two other catalysts into account and
evaluate the influence in the reactor volume and the investment cost for hydrogen production of 550.000
mol/day. The rate of the reaction is for the three nickel catalysts first order with respect to ethanol and the
rate constants are given in the absence of water vapour. For ethanol conversion of 80 % and reaction
temperature of 200
0
C the results of the reactor design and economic analysis are presented in table 5.

Table 5
Reactor design and economic analysis for three different nickel catalysts in the same rate expression in
reaction temperature of 200
0
C and ethanol conversion of 80 %

Parameter 15, 3%Ni/La
2
O
3
16, 1%Ni/Al
2
O
3
20, 6%Ni/Y
2
O
3


K, s
-1
20, 76 4, 93 4, 02
E, KJ/mol 1, 87 16, 88 7, 04
r, mol/L s 0,041 0,00978 0,0079
V, L 47, 99 202, 66 247, 97
C
vessel
, 46608 74330 79994
C
tubes
, 16035 16035 16035
C
catalyst
, 18440 32891 316680
C
total, 2007
, 85730 132397 443315


The data from table 5 show that the total investment cost depends on the catalytic system for the reforming
reaction of bio ethanol. The nickel catalyst supported in Y
2
O
3
is very expensive because of the high cost of
the support and the high percentage of the metal on the supports surface. From the three catalysts, nickel
supported on La
2
O
3
shows great stability and activity in the reaction process and seems to be the best
catalytic system for an industrial reactor in order to achieve the desired selectivity in hydrogen production
and avoid carbon formation. Nickel supported on alumina is frequently used, but it leads to an undesired
coke formation. The selection of the optimum catalyst must include a research of the production method, the
activity and stability in the reaction and the total cost of production in order to use it in great quantities in
industrial scale.

4. CONCLUSIONS

A fixed bed reactor design was developed for the catalytic steam reforming of bioethanol for hydrogen
production. The design was based on a pseudo homogenous model and a scale up system was created
for the comparison of laboratorial and industrial scale. The PFR design equations were used to accomplish
the design of the reactor. The cost analysis put emphasis on the total investment cost of the reactor and
specifically the cost of the vessel, the total cost of the tubes and the cost of the catalytic system. From the
cost analysis it can be concluded that an increase in the production of hydrogen, increases the reactor
volume and the total cost. Fluctuations of the reaction temperature also influence the reactor volume and the
reactor cost. The use of three different supported nickel catalysts for the same rate expression, have a great
effect on the total investment cost, because of the cost of the support and the percentage of the metal on the
surface of the support. As a result, the optimum conditions for the reactor, originate from the parameters that
lead to the minimum cost, a high selectivity to hydrogen and a high activity of the catalyst for the reforming
reaction of bioethanol.



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5. ACKNOWLEDGMENTS

This study was supported by the Ministry of National Education and Religious Affairs, The operational
program for education and initial vocational training (O.P. education), project ARXIMIDIS II, 2.6.1. d, Athens,
Greece

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