PROCESS MODELLING AND

SIMULATION OF ETHANOL
STEAM REFORMING FOR THE
PRODUCTION
By OF HYDROGEN
Nihal Rao (R670217004)
M.Tech, II year, Chemical Engineering (Process
Design)

Under the guidance of

Mr. Kumargaurao D Punase
Assistant Professor - SG
Chemical Engineering Department,
OBJECTI
VES

•Modelling of ethanol steam reforming based on mechanistic kinetic

model using fixed bed tubular reactor

•Simulation of ethanol steam reforming reactor and WGS reactor in

ASPEN PlusTM for hydrogen production

•Integration of ethanol steam reforming process with High Temperature

Polymer Exchange Membrane fuel cell through simulation studies.
 ETHANOL STEAM REFORMING
 The general reaction for ethanol steam reforming is given by-:

Catalysts Supports Side products Mechanism

Ni, Co, Ru, Rh, Pd Al2O3, ZnO, Acetaldehyde, Langamuir-

,Pt, Au CeO2,La2O3, ZrO, Acetone, Ethylene, Hienshelwood-
MgO, Y2O3 methane, carbon- Hougen-Watson,
monoxide, carbon Eley-Rideal and
di-oxide power law
 POLYMER ELECTROLYTE MEMBRANE FUEL
CELL
Parameters LT-PEMFC HT-PEMFC

Temperature range 323-363 [10] 423-473 [7]

(K)
Gas Diffusion Layer

Gas Diffusion Layer

P
Pt - Catalyst

Pt - Catalyst
CO tolerance Very low tolerance High tolerance
H2 E O2 (> 1%) [10] ( 10%) [7]
M Membranes Water based Nafion H3PO4 doped PBI-
membrane membrane
Catalysts Pt- catalyst Pt, Fe, Co catalyst

Flooding loss at High due to Low due to formation

Anode Cathode
cathode formation of two of a single phase
Fig 1. phase
Fig 1. Schematic representation of HT-PEMFC
MODELLING OF ETHANOL STEAM
REFORMING

•  The reactor is based on the assumption of steady state, 1-D

pseudo –homogenous model, isothermal condition.
• The catalyst used is the Ni- Al- LDH which is based on
mechanistic model developed by Mas et al [2].
• The mole balance equation for the tubular packed bed reactor:

where, F=molar flow rate (mol/ hr), z = length of tube (m), n= number
of tubes, A= Area of the tube (m2), = stoichiometry, = rate of reaction
( mol/g.cat hr), = catalyst bulk density (g/m3)
KINETIC MODELS BY MAS FOR NI-AL-LDH
Rate Model Reaction Rate equation

• The Mas et al model

11 Ethanol
Ethanol decomposition
decomposition assumes that there is no
formation of
acetaldehyde and
Ethanol steam reforming
2
2 Ethanol steam reforming ethylene .
• Carbon formation is
Methane steam reforming
considered to be
3
3
Methane
(1)
(1)
steam reforming
negligible.

Methane steam reforming

4
(2)
Methane steam reforming
4 ;
(2)
 KINETIC PARAMETERS BY MAS FOR NI-AL-
LDH
The kinetic parameters by Mas et al [2] has been optimized using NSGA-II by Punase
et al [3] for fixed bed reactor
Parameter Value [3] Unit 6.98E-11 [-]
3.27E+11 [mol/
(min.gcat)]
1.14E-04 [-]
1.39E+10 [mol/
(min.gcat)]
2.21E+03 [mol/ 3.96E-05 [-]
(min.gcat)]
1.26E+09 [mol/min.gcat -197964 [J/mol]
)]
271902 [J/mol]
-91708 [J/mol]
226768 [J/mol]

123279 [J/mol] -124789 [J/mol]

213936 [J/mol]
INTEGRATION OF ETHANOL STEAM REFORMER AND
WATER GAS SHIFT WITH HT-PEMFC
ESR Section HT-PEMFC Section
Fig 2. Integrated
Ethanol system of ethanol
Anode
ESR WGS
steam reforming
Water reformer reactor
PEM reactor and Water-
Cathode Air Gas shift reactor with
HT-PEMFC

Figure 2

• The Ethanol steam reforming is simulated based on R-Plug module of

ASPEN PlusTM and the WGS reactor based on R-Equilibrium module.
• The HTPEMFC section is modeled in MATLAB.
 DATA USED IN THE ETHANOL STEAM REFORMING-
WGS AND HTPEMFC FOR SIMULATION
Properties Values Ref Properties Values Ref

Steam to Ethanol ratio 3-5 Porosity 0.6 [7]

(S/E) Tortuosity 1.5 [8]
Reformer tube length 1 [5]
(m) Anode film thickness, m 2.5E-07 [8]
Reformer tube diameter 0.007 [5]
(m) Cathode film thickness, 1.48 E-07 [8]
Number of tubes of 100 [5] m
reformer Operating temperature 423-473 [8]
Temperature of 823-923 [2]
reformer (K) Operating pressure, 1 [8]
atm
Pressure of reformer, 1 [2]
atm Anode stoichiometry 1.016
Temperature of WGS 553 [1] ratio
reactor (K) Cathode stoichiometry 1.976
Thermodynamic Peng-Robinson [4] ratio
property method Operating current 0-10000 A/m2 [8]
Catalyst bulk density 1990 [2] density
(kg/m3)
Active area, m2 0.025 [8]
 VARIATION OF REACTANT AND PRODUCT ALONG
THE LENGTH OF REACTOR (MODELLING)
400
350
Molar flow rate (mol/hr)

300
250 ethanol
200 water
CO
150
CO2
100
methane
50 hydrogen
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Length (m)

Figure 3
Fig 3. VARIATION OF REACTANTS AND PRODUCTS ALONG THE LENGTH OF
THE REACTOR (MODELLING) AT A TEMPERATURE OF 923 K AND S/E RATIO
4
 VARIATION OF CONVERSION AND YIELD
ALONG THE LENGTH OF REACTOR

100 6
Ethanol Conversion(%)

80 5
4
60

H2 yield
923 K 3 923 K
40 898 K 898 K
2
20 873 K 873 K
823 K 1 823 K
0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Length(m) Length (m)

Figure 4. Figure 5.
Fig 4. Variation of conversion along the Fig 5. Variation of yield along the length
length of reactor at different temperature of reactor at different temperature with
with S/E ratio 4 S/E ratio 4
 VARIATION OF PRESSURE AND YIELD

5 6
5 5
5 4
H2 yield

H2 yield
5 3
S/E 3
4.99 H2 yield 2 S/E 4
4.99 1 S/E 5
4.99 0
1 1.5 2 2.5 3 3.5 4 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Pressure (in Bar) length (m)

Figure 6. Figure 7.
Fig 6.) Variation of yield along the Fig 7.) Variation of yield along the length
pressure at a temperature of 923 K and of the reactor at different S/E ratio at 923
S/E 4 K
 H2 PERCENTAGE WITH AND WITHOUT WGS

90
Fig 8.) H2 percentage with and
80
70 without the WGS at different S/E
60 ratio
50
H2(%)

40 Without WGS
30 With WGS
20
10
0
1 2 3 4
S/E ratio

Figure 8.
 POLARIZATION CURVE AND ANODE LOSS

1.21
1.19 0

1.17 0
Voltage (V)

1.15 0

Anode loss
1.13
0
1.11 Anod
e loss
0
1.09
0

0
Current density (A/m2) 0 2000 4000 6000 8000 10000
Current density(A/m2)

Figure 9. Figure 10.

Fig 9.) polarization curve between Fig 10.) anode loss
current density and voltage at fuel cell
temperature of 473 K
 OHMIC AND CATHODE LOSS

Cathode loss
Ohmic loss

0.1 0.01

0.01
0.08
0.01
0.06 Catho
ohmi 0.01 de
c loss loss
0.04
0
0.02
0

0 0
0 2000 4000 6000 8000 10000 0 2000 4000 6000 8000 10000
Current density(A/m2) Current density (A/m2)

Figure 11 Figure 12
Figure 11.) Ohmic losses Figure 12.) Cathode losses
POLARIZATION CURVE AT VARIOUS FUEL CELL
TEMPERATURE

1.2
Fig13.) Polarization
1.15 curve obtained at
1.1 various fuel cell
Voltage (V)

1.05
temperature.
423 K
448 K
1
473 K
0.95

0.9
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
Current density (A/m2)

Figure 13
CONCLUSION
•The optimum condition obtained for ESR is around 923 K, S/E ratio of 4 and
pressure of 1 atm is required to produce the maximum yield of 5 and further addition
of WGS brings the hydrogen yield of 5.95.
• The HT-PEMFC produces a maximum voltage of around 1.2 V at a current density
of zero and further decreases to 1.09 V at higher current density at a temperature of
473 K.
• This is attributed to low CO production (less than 4%) and high yield of hydrogen.
• The fuel cell temperature affects the performance of the fuel cell. Higher the
temperature higher will be the losses.
PUBLICATIONS from THIS WORK

• Conference
Rao N, Punase KD. Evaluation of various kinetic model using a
commercial Nickel-Based Catalyst. CHEMCON -2018.
• Journal
Punase KD, Rao N, Vijay P. A review on various mechanistic
models of ethanol steam reforming for hydrogen production using
a fixed bed reactor. Chemical Papers.2019;73:1027-1042.
(ISI/JCR IF-0.963)
Rao N, Punase KD, Vijay P and Gupta SK. Simulation of an
integrated system of high temperature-polymer exchange
membrane fuel cell and ethanol steam reformer.
(MS is ready and will be submitted in Fuels & Energy (ACS)journal)
THANK YOU
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