Andrzej Kraslawski and Ilkka Turunen (Editors) Proceedings of the 23

rd
European Symposium on
Computer Aided Process Engineering ESCAPE 23, J une 9-12, 2013, Lappeenranta, Finland
2013 Elsevier B.V. All rights reserved. 19
Conceptual design of hydr ogen pr oduction pr ocess
fr om bioethanol r efor ming
Calin-Cristian Cormos,
a
Arpad Imre-Lucaci,
a
Ana-Maria Cormos,
a
Zsolt
Tasnadi-Asztalos,
a
Mihaela Diana Lazar
b
a
Babes Bolyai University, Faculty of Chemistry and Chemical Engineering
11 Arany Janos Street, RO-400028, Cluj - Napoca, Romania
b
National Institute for Research and Development of Isotopic and Molecular
Technologies - INCDTIM, 65-103 Donath Street, RO-400293, Cluj - Napoca, Romania
Abstr act
Hydrogen is considered to be one clean energy carrier for the future. The main
advantage of using hydrogen as energy carrier represents the negligible greenhouse gas
emissions. One of the most encouraging hydrogen production methods is based on
bioethanol. This paper is devoted to the conceptual design of hydrogen production
process using bioethanol reforming at an industrial scale (100000 Nm
3
/h hydrogen
equivalent to 300 MW thermal). The syngas will be then converted into hydrogen by
water gas shift reaction. Two distinct designs were investigated, one without carbon
capture and one with carbon capture. In the design with carbon capture and storage
(CCS), the shifted syngas is treated for removing CO
2
by gas-liquid absorption process.
Considering that bioethanol has a low or negligible fossil carbon footprint, the case with
CCS has a negative CO
2
emissions contributing to decreasing atmospheric CO
2
.
The conceptual designs of bioethanol reforming were modeled and simulated
to produce mass and energy balances for quantification of key plant performance
indicators (e.g. bioethanol consumption, plant energy efficiency, ancillary energy
consumption, specific CO
2
emissions etc.). A particular accent is put on assessment of
reforming unit operation conditions, process integration issues of reforming unit and
syngas conditioning line with carbon capture unit, modeling and simulation of whole
plant, thermal and power integration of various plant sub-systems by pinch analysis.
Benchmark cases based on fossil fuels partial oxidation were also presented.
Keywor ds: Hydrogen; Bioethanol; Reforming process; Carbon Capture and Storage.
1. Intr oduction
Introduction of hydrogen in the energy system as a new energy carrier
complementary to electricity and conventional fuels (e.g. natural gas, oil derived
products, coal etc.) is raising much interest, as this offers significant advantages
including reduction of greenhouse gas emissions at the point of end use, enhancement
of the security of energy supply and improvement of economic competitiveness
(Mueller-Langer et al., 2007). Currently, hydrogen is mostly used in petro-chemical
industry for various processes, e.g. ammonia and methanol synthesis, hydrogenation,
hydrocracking and hydrodesulphurization and it is produced from fossil fuels (mainly
natural gas reforming, coal gasification). The future hydrogen applications in a low-
carbon economy imply for instance power generation using hydrogen-fuelled gas
turbine or transport applications using PEM fuel cells. The issues of environmental
protection, combating climate change by reducing CO
2
emissions, maintaining the
security of energy supply and improving economic competitiveness shape the future
20 C. C. Cormos et al.
energy scene. In this context, developing new hydrogen production routes which use
renewable sources with low or negative CO
2
emissions are of particular importance.
This paper evaluates the hydrogen production options using bioethanol
reforming. Although there are several possibilities of production hydrogen from
bioethanol the one which was used in this work is based on steam reforming (Ni et al.,
2007; Trane et al., 2012). The overall ethanol reforming reaction is follow:

C
2
H
5
OH + 3H
2
O = 2CO
2
+ 6H
2
H =+157 kJ /mole (1)

Apart of the reaction (1), other several reactions take places. The major
components in the syngas are hydrogen, carbon dioxide and carbon monoxide together
with other minor components like methane, ethene, acetaldehyde etc. The carbon
monoxide is then converted with water according to the following reaction:

CO + H
2
O = CO
2
+ H
2
H = -41.02 kJ /mole (2)

The shift conversion has a double purpose: to concentrate the syngas energy in
form of hydrogen and to convert the carbon species in carbon dioxide that can be later
captured. Two distinct plant configurations were evaluated, one without CO
2
capture
and one with CO
2
capture. For both cases, a hydrogen stream of 100000 Nm
3
/h
(equivalent to 300 MW thermal considering hydrogen lower heating value) was
produced. A specific accent is put in the paper on the evaluation of technical
performances (e.g. fuel consumption, energy efficiency, ancillary consumption, heat and
power integration issues etc.) of bioethanol reforming cases with and without CCS.
2. Plant configur ations and main design assumptions
The conceptual layout of hydrogen production based on bioethanol reforming
plant without carbon capture is presented in Figure 1.





















Pr e-heating
Bioethanol + Water
Steam r efor ming
Water Gas Shift
Syngas cooling
Tail gas
Bur ner
Purified hydrogen
Pr essur e Swing
Adsor ption (PSA)
Power
H
2
compr ession
Air Flue gases
Expander Power
Heat r ecover y
& Steam tur bine
Steam flow
Process flow
Figure 1. Layout of hydrogen production by bioethanol reforming without CCS
Conceptual design of hydrogen production process from bioethanol reforming 21
For the design with CCS, the conceptual layout is presented in Figure 2.
























The main plant sub-systems for hydrogen production based on bioethanol
reforming with and without CCS and theirs design assumptions used in the modeling
are presented in Table 1 (Banach et al., 2011, Llera et al., 2012, Cormos, 2009).

Table 1. Main design assumptions
Unit Par ameter s
Bioethanol fed and pre-heating Fuel composition: 25.85 % bioethanol (wt. %)
Bioethanol pre-heating: 500
o
C
Reformer Ni-based catalyst
Pressure: 30 bar
Pressure drop: 1.5 bar
Outlet temperature: 800
o
C
Shift conversion (WGS) Copper-zinc catalyst (low temperature shift)
One adiabatic catalytic bed
Pressure drop: 1 bar
Carbon capture unit (for CCS case) Solvent: Methyl-diethanol-amine (MDEA)
Absorption - desorption cycle
Solvent regeneration: thermal
CO
2
compression and drying Delivery pressure: 120 bar
Compressor efficiency: 85 %
Solvent used for drying: TEG (Tri-ethylene-glycol)
Captured CO
2
quality specification (vol. %): >95 % CO
2
;
<2000 ppm CO; <500 ppm H
2
O; <100 ppmH
2
S
Pressure Swing Adsorption (PSA) Purified hydrogen: >99.95 % (vol.)
Purification yield: 72 %
Tail gas pressure: 1.5 bar (used for reformer burner)
Tail gas expander Tail gas pre-heating before expansion: 230
o
C
Outlet pressure: 1.5
Expander efficiency: 70 %
Steam flow
Process flow
Expander
Car bon captur e
(gas-liquid absor ption)
CO
2
drying
& compression
Pr e-heating
Bioethanol + Water
Steam r efor ming
Water Gas Shift
Syngas cooling
Tail gas
Bur ner
Purified hydrogen
Pr essur e Swing
Adsor ption (PSA)
H
2
compr ession
Air Flue gases
Power
Heat r ecover y
& Steam tur bine
Power
Figure 2. Layout of hydrogen production by bioethanol reforming with CCS
22 C. C. Cormos et al.
Heat recovery steam generation Steam pressure level: 48 bar
Steam turbine isoentropic efficiency: 85 %
Steam wetness ex. steam turbine: max. 10 %
Heat exchangers T
min.
=10
o
C
Pressure drop: 1 % of inlet pressure
3. Results and discussions
Hydrogen production by bioethanol reforming with and without CCS were
simulated with ChemCAD software. The evaluated cases were codified as follow:
Case 1 Hydrogen production based on bioethanol reforming without CCS;
Case 2 Hydrogen production based on bioethanol reforming with CCS.
Bioethanol reforming process was evaluate using thermodynamic calculations
in order to assess the influence of main process parameters e.g. temperature, pressure,
reactant ratio (Hernndez and Kafarov, 2009). Figure 3 presents the influence of
temperature and molar ratio on the bioethanol reforming process. The main influential
parameters are reforming temperature and pressure (800
o
C and 30 bar were considered).














The simulation of the developed models gives the mass and energy balances
for quantification of plant performances. After modeling and simulation, the two cases
were subject of heat and power integration analysis (based on pinch methodology) for
optimization of plant energy efficiency. The hot and cold composite curves for the
investigated cases are presented in Figure 4. As can be noticed from Figure 4, there is a
tight heat integration in both cases which guarantees the overall plant energy efficiency.











4.a. Case 1 (reforming without CCS) 4.b. Case 2 (reforming with CCS)


3 5 7 9 11 13 15 17 19 21 23 25
0
10
20
30
40
50
60
70
80
Temperatura: 800
o
C. Presiunea: 25 bar
raport molar H
2
O:Etanol
c
o
m
p
o
z
i
t
i
a

l
a

e
c
h
i
l
i
b
r
u

r
a
p
o
r
t
a
t

l
a

g
a
z

u
s
c
a
t
,

[
%

m
o
l
.
]


H
2
CH
4
CO
2
CO

300 350 400 450 500 550 600 650 700 750 800
0
10
20
30
40
50
60
70
80
Raport molar H
2
O:Etanol 7. Presiunea: 25 bar
temperatura, [
o
C]
c
o
m
p
o
z
i
t
i
a

l
a

e
c
h
i
l
i
b
r
u

r
a
p
o
r
t
a
t

l
a

g
a
z

u
s
c
a
t
,

[
%

m
o
l
.
]
H
2
CH
4
CO
2
CO

Temperature [
o
C]
Temperature [
o
C]
Molar ratio H
2
O / ethanol 7; Pressure 30 bar
G
a
s

e
q
u
i
l
i
b
r
i
u
m

c
o
m
p
o
s
i
t
i
o
n

[
%

v
o
l
.
]

Molar ratio [water / bioethanol]
G
a
s

e
q
u
i
l
i
b
r
i
u
m

c
o
m
p
o
s
i
t
i
o
n

[
%

v
o
l
.
]

Temperature 800
o
C; Pressure 30 bar
Figure 3. Influence of temperature and molar ratio on gas equilibrium composition
Figure 4. Hot and cold composite curves
Conceptual design of hydrogen production process from bioethanol reforming 23
Table 2 presents the overall technical plant performance indicators for the
hydrogen production designs based on bioethanol steam reforming with and without
carbon capture.
Table 2. Overall plant performance indicators
Main Plant Data Units Case 1 Case 2
Bioethanol flowrate t/h 235.83 235.83
Bioethanol LHV (considered 100 % purity) MJ /kg 28.865
Feedstock thermal energy LHV (A) MW
th
488.92 488.92

Steam turbine output MW
e
7.43 4.48
Expander power output MW
e
8.14 4.02
Gross electric power output (B) MW
e
15.57 8.05

Reformer island power consumption MW
e
0.54 0.54
Carbon capture +CO
2
drying and compression MW
e
0.00 6.64
Hydrogen compression MW
e
3.88 4.06
Power island power consumption MW
e
0.25 0.21
Total ancillary power consumption (C) MW
e
4.67 11.45

Hydrogen output (D) MW
th
300.00 300.00
Net electric power output (E =B C) MW
e
10.90 -3.40
Net hydrogen efficiency (D/A * 100) % 61.35 61.35
Net electrical efficiency (E/A * 100) % 2.22 -0.70
Cumulative energy efficiency % 63.57 60.65
Carbon capture rate % 0.00 80.68
CO
2
specific emissions (hydrogen +power) kg/MWh 374.72 75.80

As can be noticed from Table 2, both cases have the same fuel consumption
providing an overall energy efficiency in the range of 60 % with minor power output
(for Case 1) and deficit (for Case 2). What must be observed it is that the CCS design
has an increased ancillary power consumption with about 145 % compared with the
case without CCS. The main reasons for this significant energy ancillary consumption
are the heat consumption for solvent regeneration (about 0.7 MJ /kg CO
2
) and the power
consumption for captured CO
2
stream compression (in the range of 0.25 kW/kg CO
2
).
The carbon capture rate for Case 2 is above 80 %, the solvent is capturing the
majority of CO
2
(more than 98 %) but the remaining carbon monoxide and methane
cannot be captured reducing the carbon capture capability of the plant. In any case these
two carbon species (CO and CH
4
) have also energy value that is used for covering the
energy deficit of the reforming process (including a part of the hydrogen stream).
Specific CO
2
emissions are significantly reduced down to about 75 kg/MWh. Even the
normal bioethanol reforming case without CCS (Case 1) has significant lower CO
2

emissions compared with fossil fuels-based partial oxidation processes (natural gas
steam reforming or coal gasification) for hydrogen production due to the fact that
feedstock (bioethanol) carbon is coming from atmosphere in the normal photosynthesis.
The case with CCS (Case 2) even more will generate negative CO
2
emissions and by
this will contribute significantly to the reduction of CO
2
concentration from atmosphere.
As a benchmark options for comparison of the two evaluated bioethanol
reforming designs used for hydrogen production, two fossil fuels partial oxidation
options were considered. First option is based on a conventional natural gas steam
reforming process. Second option is based on coal gasification. In both cases the options
with and without carbon capture were considered. The key performance indicators of
fossil fuels (natural gas reforming and coal gasification) for hydrogen production are
presented in Table 3 (based on literature data IEA-GHG, 1996).
24 C. C. Cormos et al.
Table 3. Hydrogen production based on natural gas reforming and coal gasification
Main Plant Data Units Natur al gas
No CCS CCS
Coal
No CCS CCS
Fuel flowrate t/h 27.97 28.41 77.01 90.21
Feedstock thermal energy MW
th
369.72 383.61 553.33 648.05

Hydrogen output MW
th
281.11 281.11 281.38 281.38
Power output MW
e
7.17 15.53 50.03 77.98
Hydrogen efficiency % 76.03 73.28 50.85 43.41
Electrical efficiency % 1.93 4.04 9.04 12.03
Cumulative energy efficiency % 77.96 77.32 59.89 55.44
Carbon capture rate % 0.00 85.00 0.00 97.40
CO
2
specific emissions (hydrogen +power) kg/MWh 267.10 40.45 560.33 5.84

As can be noticed the natural gas cases are more efficient than bioethanol cases
(due to superior energy content of the feedstock) but the coal cases are slightly less
efficient. The most important gain of bioethanol cases is the CO
2
emissions, which are
considered negligible in comparison with fossil fuels cases which emit fossil CO
2
.
4. Conclusions
This paper evaluates the conceptual design of hydrogen production based on
bioethanol reforming process with and without carbon capture. The analysis assess the
influence process factors on reforming processes and estimate the technical parameters
for a hydrogen output of 300 MW
th
. The comparison with fossil fuels-based hydrogen
production (natural gas steam reforming and coal gasification) showed a good overall
plant energy efficiency and much lower CO
2
emissions.
Acknowledgement
This work was supported by a grant of the Romanian National Authority for
Scientific Research, CNCS UEFISCDI, project ID PN-II-PT-PCCA-2011-3.2-0452:
Hydrogen production from hydroxylic compounds resulted as biomass processing
wastes.
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