Advances 1 in Final Project - Bernay Cifuentes

ADVANCE 1 OF FINAL PROJECT
ADVANCED MATHEMATICS
CHEMICAL ENGINEERING GRADUATE PROGRAMS
Name: Bernay Cifuentes Vanegas

Date: March 14th, 2019
Project: Energy optimization of an integrated system for the production of Fuel-cell grade H 2
from bioethanol
1. Introduction
Hydrogen (H2) is a promising fuel to develop a cleaner energy system because it can be used in
fuel cells (FC) to decarbonizing both mobile and stationary applications [1]. Water, heat, and
electricity are the only products in FC fed with H2. Also, this technology can be integrated with
local renewable resources to improve energy efficiency and security. Particularly in Colombia,
bioethanol, produced from renewable sources, has been proposed as a sustainable source to
produce H2 [2].
The general process for energy production from bioethanol may be divided into three stages, as
shown in Figure 1. (I) In H 2 production from bioethanol, steam reforming of ethanol (SRE)
stands out for having higher H2 yield compared to other alternatives, such as partial oxidation or
oxidative steam reforming [3]. However, SRE is an endothermic reaction, thus, high amount of
energy may require in this stage. Depending on the operating conditions and catalyst, SRE yields
different amounts of H2, carbon monoxide (CO), carbon dioxide (CO 2), and methane (CH4) [4].
Therefore, (II) purification of the H2 stream is required but, as the purification requirements
depends on the end-use of H2. As the presence of CO is highly undesirable in PEM-FC
applications due to its deleterious effect on the cell electrodes, the main objective in this stage is
remove CO. The CO-removal is an exothermic process, so, energy produced in this stage could
be used to supply partially energy requirements in the SRE. Finally, (III) FC represents a great
opportunity to develop and deploy environmentally-friendly devices. In FC only water, heat and
electricity are produced. Therefore, energy produce in FC (i.e., heat and electricity) should at
least compensate the energy consumed in SRE in order to develop an efficient energy system.
1
(I) Hydrogen production (II) Hydrogen purification (III) Power generation

Carrier (Ar) Air Air
H2
Purified Biethanol CO
CO2 Power
Bioethanol Fuel
Pump CH4 H2O
Gas mixer Gas mixer Cell
CO
removal Adsorber
SRE Condenser CO2
CH4
H2O
Post-reforming Fuel-cell grade

H2 stream
Rh0.4Pt0.4/CeO2-SiO2 Au1.0Cu1.0/CeO2
Catalyst Catalyst
Figure 1. Overall process for energy production from bioethanol. The equipment of interest for
energy optimization are highlighted in blue.
2. Objective
The objective of this work is to perform an energy optimization of the process presented in
Figure 1. For this, the SRE will be considered as the only source of energy consumption,
similarly the FC will be considered as only source of energy production. This means that the
energy produced in the H2 purification stage will be not taken in account. This simplification
could lead to inconsistencies in the model, however, it is expected that the optimal obtained from
the simplified process is close with the actual optimum. The simplified objective function is
shown in Eq. 1, where E NET is the total energy produce in the system; E FC is the energy produced
in FC, which depend on H2 produced during SRE ( H 2 , SRE); and E SRE is the required energy to
carry out the SRE, which depend on operational variables such as temperature (T), mass of
catalyst (W) and ethanol concentration in the inlet stream of the reformer ( [ EtOH ]inlet ). Note that
H 2 , SRE depend also on T, W and [ EtOH ]inlet . Thus, T, W and [ EtOH ]inlet are the decision variables.
E NET =E FC ( H 2 , SRE )−E SRE ( T ,W , [ EtOH ] inlet ) ( Eq. 1)

2
H 2 , produced ∈ SRE=f ( T ,W , [ EtOH ]inlet ) (Eq . 2)
The optimization of the Eq. 1 requires the previous approach of the material and energy balances
of the process.
3. Mass balance equations
3.1 Mass balance in the SRE

The main reactions involved in the SRE are presented in Table 1. Thus, H 2, CO, CO2, CH4, H2O
and ethanol are the species to consider in the SRE. The mass balance of each specie in the SRE
are presented in Eqs. 8 to 12.
Table 1. Main chemical reactions involved in H2 production by SRE [5–9].
Reaction Description
C H 3 C H 2 OH+3 H 2 O → 2CO 2 +6 H 2 Ethanol reforming (ER) Eq. (3)
CO+ H2 O ⇌ CO2 +H2 Water gas shift (WGS) Eq. (4)
C H 3 C H 2 OH ⇌ CH 4 +CO+ H 2 Ethanol decomposition (ED) Eq. (5)
C H 4 + H 2 O ⇌ CO+ 3 H 2 Methane reforming (MR) Eq. (6)
C H 3 C H 2 OH +H 2 O ⇌ 2CO+ 4 H 2 Formation of syngas (SYG) Eq. (7)
d N EtOH , SRE
=−3 r ℜ−r ED −r SYG ( Eq .8)
dt
d N H O , SRE
2
=−3r ER−r WGS−r MR−r SYG (Eq . 9)
dt
d N H ,SRE
2
=6 r ER +r WGS +r ED +3 r MR +4 r SYG ( Eq . 10)
dt
3
d N CO , SRE
=−r WGS +r ED +r MR+ 2r SYG (Eq . 11)
dt
d N CO , SRE2
=2r ER +r WGS ( Eq . 12)
dt
d N CH , SRE
4
=r ED −r MR ( Eq .13)
dt
3.2 Mass balance in the FC

In FC the only chemical reaction expected is the water formation (WF, see Eq. 14). Thus, the
mass balances for each specie in the FC are presented in Eqs. 15 to 12. Operational conditions in
the FC will be fixed, according to previous reports. Then, H2 conversion will be established in 0.5
at 80 °C. Therefore, r WF could be ascribed in term of H2 fed into FC (Eq. 19), where N H , inlet are
2
the H2 moles inlet in FC. Similarly, N H , inlet is linked with H2 produced in SRE according to Eq.
2
19, y represents the H2 loss during H2 purification processes. In previous reports, a value of 0.83
was identified for y. Replacing Eq. 10 and Eq. 19 in Eq. 20, a relation between mass flow of
consumed or generated species involved in FC is obtained (Eqs. 22 to 24).
2 H 2+O 2 → 2 H 2 O( Eq .14 )
d NH , Fc
2
=−2 r WF ( Eq . 15)
dt
d N O ,Fc
2
=−r WF (Eq .16)
dt
d N H O , Fc
2
=2 r WF ( Eq . 17)
dt
4
d N H ,inlet
r WF =0.8 2
(Eq . 18)
dt
d N H ,inlet y∗d N H , SRE

2
= 2
( Eq . 19)
dt dt
d N H ,inlet
2
= y∗(6 r ER+ r WGS +r ED+ 3 r MR + 4 r SYG )( Eq. 20)
dt
r WF =0.696( 6 r ER +r WGS+ r ED +3 r MR + 4 r SYG )(Eq . 21)
d NH , Fc
2
=−1.392 ( 6 r ER+ r WGS +r ED+ 3 r MR + 4 r SYG ) ( Eq . 22)
dt
d N O ,Fc
2
=−0.696 ( 6 r ER +r WGS +r ED +3 r MR +4 r SYG ) (Eq . 23)
dt
d N H O , Fc
2
=1.392(6 r ER +r WGS +r ED +3 r MR +4 r SYG )(Eq .24 )
dt
Therefore, all mass balances of species involved in the system (i. e., SRE and FC) could be
expressed in terms of SRE, WGS, ED, SRM and SYG reactions.
4. Energy balances equations
d E SRE n m m
=∑ ∆ Ḣ i−∑ H i ,inlet SRE + ∑ H i ,outlet SRE ( Eq .25)
dt i j j
∑ ∆ Ḣ i=∆ H˙ER +∆ H WGS

˙ + ∆ H˙ED +∆ H˙MR +∆ H ˙SYG ( Eq . 26)
i
H i=N i hi (Eq . 27)
5
m m
d E FC
=∆ H WF −∑ H i ,inlet FC + ∑ H i , outlet FC + W FC (Eq . 28)
˙
dt j j
5. Kinetic model
The kinetic models for the reactions involved in the SRE (Table 1) must be previously
established to solve the mass and energy balances of the system. Kinetics of SRE has been
extensively studied with catalysts such as Ni [10], Cu [5], Rh [11], and Pt [12]. The kinetic
models proposed for the SRE involve the reactions presented in Table 1. The Langmuir-
Hinshelwood (L-H) model is more promising to describe adequately SRE [13]. In previous
reports, Graschinsky et al. [11] proposed a kinetic model based in L-H mechanism for SRE on a
Rh/MgAl2O3/Al2O3 catalyst, which include ER (Eq. 3), WGS (Eq. 4), ED (Eq. 5) and MR (Eq. 6)
reactions. Rossetti et al. [5] revised the kinetic equations reported by [11], identifying and
correcting some imprecisions. Then, Eqs. 29 to 31 present the corrected models for rate
determining steps in ER, WGS, ED, and MR reaction, respectively, which can be consulted in
details in [11] and [5].
CHO∗+ OH∗→CO 2∗+ H 2 + S∗( Eq . 29)
CO∗+OH∗→ CO2∗+ H∗(Eq .30)
CHO∗+ S∗→ CO∗+ H∗( Eq .31)
CH 3∗+OH∗→ CO2∗+ H∗( Eq .32)
Then, L-H models for each reaction are showed in Eq. 33 to 36. To compared with previous
reports [5,11], nomenclature of adsorption constants (capital letters) was remained in this work.
6
r ER=QNF C2T ¿ ¿
r WGS =R HF C 2T ¿ ¿
r ED= X N C 2T ¿ ¿
r MR=Y CF C 2T ¿ ¿
The optimization strategy will consist of adjusting the adsorption constants (Eq. 33 to 36) to
experimental data, solving the mass balance equations (Eq. 8 to 13, and 22 to 24) and finally,
solving the energy balance equations (Eq. 25 and 28).
6. Regression for experimental data
Several polynomial regressions were carried out for experimental data (see Table 2) of the H 2
yield obtained in the SRE. A regression of a quartic order polynomial (see Figure 1) was
identified as more promising for adjusted the experimental data. ANOVA, F-test and T-test were
carried out to evaluate the adjusted of the model. The details of statistic test are presented in the
document attached.
Table 2. H2 yield obtained in SRE on RhPt/CeO2-SiO2 catalyst

T (°C) mol H2/mol EtOH inlet
700 4.751
650 3.376
600 2.510 The ANOVA showed that the model fits properly,
550 0.721
500 0.257 and the hypothesis in t-test and f-test were not
450 0.094
400 0.055
700 4.751
7
rejected, indicating a significant difference between the actual and predicted values is presented
and Coefficients (βi) ≠ 0, respectively.
Finally, the residuals evaluation (see Figure 2) shows that the data does not follow a normal
distribution, a effect of two points should be considered.
Figure 1. Regression for H2 yield obtained in SRE on RhPt/CeO2-SiO2 catalyst
Figure 2. Residuals analysis for quartic regression
8
7. References
[1] N.P. Brandon, Z. Kurban, Clean energy and the hydrogen economy, Philos. Trans. R. Soc.
London A Math. Phys. Eng. Sci. 375 (2017) 1–17.
[2] M. Cobo, D. Pieruccini, R. Abello, L. Ariza, L.F. Córdoba, J. a. Conesa, Steam reforming
of ethanol over bimetallic RhPt/La2O3: Long-term stability under favorable reaction
conditions, Int. J. Hydrogen Energy. 38 (2013) 5580–5593.
[3] W. Cai, F. Wang, E. Zhan, A. Vanveen, C. Mirodatos, W. Shen, Hydrogen production
from ethanol over Ir/CeO2 catalysts: A comparative study of steam reforming, partial
oxidation and oxidative steam reforming, J. Catal. 257 (2008) 96–107.
[4] D. Zanchet, J.B.O. Santos, S. Damyanova, J.M.R. Gallo, J.M. C. Bueno, Toward
Understanding Metal-Catalyzed Ethanol Reforming, ACS Catal. 5 (2015) 3841–3863.
[5] I. Rossetti, M. Compagnoni, M. Torli, Process simulation and optimisation of H2
production from ethanol steam reforming and its use in fuel cells. 1. Thermodynamic and
kinetic analysis, Chem. Eng. J. 281 (2015) 1024–1035.
[6] B. Cifuentes, M.F. Valero, J. a. J. Conesa, M. Cobo, Hydrogen Production by Steam
Reforming of Ethanol on Rh-Pt Catalysts: Influence of CeO2, ZrO2, and La2O3 as
Supports, Catalysts. 5 (2015) 1872–1896.
[7] J.W.C. Liberatori, R.U. Ribeiro, D. Zanchet, F.B. Noronha, J.M.C. Bueno, Steam
reforming of ethanol on supported nickel catalysts, Appl. Catal. A Gen. 327 (2007) 197–
204.
[8] B. Valle, B. Aramburu, A. Remiro, J. Bilbao, A.G. Gayubo, Effect of calcination/reduction
conditions of Ni/La2O3–αAl2O3 catalyst on its activity and stability for hydrogen
production by steam reforming of raw bio-oil/ethanol, Appl. Catal. B Environ. 147 (2014)
402–410.
[9] H. Wang, L. Zhang, M. Yuan, T. Xx, Y. Liu, Steam reforming of ethanol over
Ni/Ce0.7Pr0.3O2 catalyst, J. Rare Earths. 30 (2012) 670–675.
[10] M. Patel, T.K. Jindal, K.K. Pant, Kinetic Study of Steam Reforming of Ethanol on Ni-
Based Ceria–Zirconia Catalyst, Ind. Eng. Chem. Res. 52 (2013) 15763–15771.
[11] C. Graschinsky, M. Laborde, N. Amadeo, A. Le Valant, N. Bion, F. Epron, et al., Ethanol
9
Steam Reforming over Rh(1%) MgAl2O4/Al2O3: A Kinetic Study, Ind. Eng. Chem. Res.
49 (2010) 12383–12389.
[12] A. Yee, S.. Morrison, H. Idriss, The reactions of ethanol over M/CeO2 catalysts, Catal.
Today. 63 (2000) 327–335.
[13] V. Mas, M.L. Bergamini, G. Baronetti, N. Amadeo, M. Laborde, A kinetic study of
ethanol steam reforming using a nickel based catalyst, Top. Catal. 51 (2008) 39–48.
10

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ADVANCE 1 OF FINAL PROJECT

Name: Bernay Cifuentes Vanegas

(I) Hydrogen production (II) Hydrogen purification (III) Power generation

Post-reforming Fuel-cell grade

E NET =E FC ( H 2 , SRE )−E SRE ( T ,W , [ EtOH ] inlet ) ( Eq. 1)

H 2 , produced ∈ SRE=f ( T ,W , [ EtOH ]inlet ) (Eq . 2)

3. Mass balance equations

3.1 Mass balance in the SRE

Table 1. Main chemical reactions involved in H2 production by SRE [5–9].

3.2 Mass balance in the FC

d N H ,inlet y∗d N H , SRE

r WF =0.696( 6 r ER +r WGS+ r ED +3 r MR + 4 r SYG )(Eq . 21)

4. Energy balances equations

∑ ∆ Ḣ i=∆ H˙ER +∆ H WGS

H i=N i hi (Eq . 27)

CHO∗+ OH∗→CO 2∗+ H 2 + S∗( Eq . 29)

CO∗+OH∗→ CO2∗+ H∗(Eq .30)

CHO∗+ S∗→ CO∗+ H∗( Eq .31)

CH 3∗+OH∗→ CO2∗+ H∗( Eq .32)

6. Regression for experimental data

Table 2. H2 yield obtained in SRE on RhPt/CeO2-SiO2 catalyst

Figure 1. Regression for H2 yield obtained in SRE on RhPt/CeO2-SiO2 catalyst

Figure 2. Residuals analysis for quartic regression

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