UNIVERSIDADE FEDERAL DO RIO GRANDE DO SUL

DEPARTAMENTO DE ENGENHARIA QUÍMICA

TRABALHO DE CONCLUSÃO DE CURSO

Combustão Parcial dos Gases Residuais do Ânodo de uma Célula a

Combustível PEM (Proton Exchange Membrane Fuel Cell)

Elena Cândida dos Santos

00125300

Jörg Nitzsche (TU Bergakademie Freiberg)

Orientador

Oscar Perez Lopes

Professor Co-orientador

Trabalho apresentado como requisito à conclusão da

Disciplina Trabalho de Conclusão em Engenharia
Química do Departamento de Engenharia Química
da Universidade Federal do Rio Grande do Sul.

Porto Alegre
2008/2
 FEDERAL UNIVERSITY OF DO RIO GRANDE DO SUL
DEPARTMENT OF CHEMICAL ENGINEERING
DIPLOMA THESIS

Catalytic Partial Combustion of Anode Off-Gas from a PEMFC

(Proton Exchange Membrane Fuel Cell)

Elena Cândida dos Santos

00125300

Jörg Nitzsche (TU Bergakademie Freiberg)

Supervisor

Oscar Perez Lopes

Co-supervisor

Work presented as a prerequisite to the conclusion of

The Chemical Engineering Diploma Thesis Project
from Chemical Engineering Department of the
Federal University of Rio Grande do Sul.

Porto Alegre
2008/2
 ACKNOWLEDGMENTS

To Prof. Dr. Oscar Perez Lopez for guidance, suggestions and attention.

I would like to cordially thank the TU-Bergakademie Freiberg, represented by Prof. Dr.-
Ing. D. Trimis, for having accepted me and having provided financial and material
resources for this Diploma Thesis. In special to:

Dipl-Ing. Jörg Nitzsche, my supervisor, for lessons, guidance, friendship,
encouragement and especially the confidence placed in me during the entire
period of development of work.

Dipl-Ing. Björn Fischer for having passed his experience, the support and
friendship.

Dipl-Ing. Reinhard Steinbrück to encourage me by following the experimental
tests, and also to have corrected my thesis next to my supervisor.

Stefan Anger to his patience, friendship, lessons and aid to run the simulations in
Aspen.

Manfred Schemmel and Ulrich Herzig for the dedication in the construction of
the reactor, and the sympathy with which they dealt with me in the event of any
repairs.

Marianne Leffler and Frank Gleißner

Special thanks to my mother, Maria Salete dos Santos, for her love, patience and
unconditional support in all the moments. And also to my boyfriend, Ralf Laternser, for
his understanding, advices and lengthy conversations

To everyone who contributed directly or indirectly in this work

i
TABLE OF CONTENTS
ABSTRACT...............................................................................................................................iv

LIST OF TABLES .................................................................................................................... v

LIST OF FIGURES ................................................................................................................. vi

LIST OF VARIABLE ............................................................................................................. vii

LIST OF VARIABLE INDEX .............................................................................................. viii

INTRODUCTION..................................................................................................................... 1

I BIBLIOGRAFIC REVIEW .............................................................................................. 3

1. History of the Fuel Cells...................................................................................................... 3

2. Types of Fuel Cells ............................................................................................................ 3
3. Fuel processing and power generation................................................................................. 4
3.1. Inhouse 4000................................................................................................................. 4
3.2. Feedstock...................................................................................................................... 5
3.3. Desulphurization........................................................................................................... 6
3.4. Multifuel Burner........................................................................................................... 6
3.5. Steam reforming........................................................................................................... 6
3.6. Gas Clean-up................................................................................................................ 7
3.6.1. Water Gas Shift Reaction.................................................................................. 7
3.6.2. Preferential Oxidation of CO in excess of hydrogen......................................... 8
3.7. Fuel Cell Stack ............................................................................................................ 9
3.7.1. PEMFC (Proton Exchange Membrane Fuel Cell.............................................. 9

II FUEL CELL STACK SIMULATOR PROJECT ........................................................ 10

1. Objective definitions.......................................................................................................... 10
2. Presentation of the parameters to be known...................................................................... 10
3. Inhouse processes Mass Balances ..................................................................................... 10
4. Simulator Stack Mass and Energy Balance....................................................................... 12
4.1. Adiabatic Combustion Temperature .......................................................................... 15
5. Choosing appropriate catalyst............................................................................................ 16
5.1. Preparation for catalytic preliminary testing ............................................................. 16
5.2. Catalytic testing ......................................................................................................... 17

ii
 5.2.1. FC-HC35B Catalyst ........................................................................................ 18
5.2.2. FCCB-2 Catalyst ............................................................................................. 20

III STACK SIMULATOR DESIGN................................................................................... 23

1. Reactor............................................................................................................................... 24
2. Insulation............................................................................................................................ 24
3. Cooling System ................................................................................................................. 26

IV RESULTS AND DISCUSSION...................................................................................... 30

1. Tests Procedures................................................................................................................ 31
2. Evaluation of different Gas Natural Loads........................................................................ 31
2.1. Adiabatic Combustion Temperature using Hess’s Law............................................. 34
2.2. Analysis of Stack Simulator Anode Off-Gas using Aspen......................................... 35
3. Evaluation of different Gas Natural Loads with alumina Spheres bed.............................. 37
4. Extrapolations results......................................................................................................... 38

V CONCLUSIONS............................................................................................................... 40

VI DIRECTIONS FOR FUTURE WORK......................................................................... 41

REFERENCES....................................................................................................................... 42

APPENDIX A1........................................................................................................................ 44
Calculus sequence of mass balances……………………........................................................ 44
APPENDIX A2........................................................................................................................ 52
Empirical formulas to get the Anode Off-Gas physical Properties ........................................ 52
APPENDIX B1........................................................................................................................ 53
Obtained results of the experiments with FC-RC35B catalyst on the catalyst bed................. 53
APPENDIX B2........................................................................................................................ 56
Obtained results of the experiments with spheres in the catalyst bed.......................................56

iii
 ABSTRACT
In view of the major changes taking place in the power system infrastructure, the trend
is to actively engage distributed generation technology (DGT) to meet the increasing demand
for energy services and quality. One of the most feasible and attractive DGT is the fuel cell
technology, since the fuel cell-based DGT system produces almost zero emission and
provides a high efficiency and modularity of its output. Distributed generation technology
involves the use of small generators as Inhouse 4000, a fuel cell mini block heat and power
plant for stationary energy supply (4 kW electrical power).
In this context the objective of this work was to project, build a Stack Simulator and
analyse its behaviour front some parameters as load of natural gas, composition of inlet
reformate and temperature of the reaction. Therefore a partial catalytic combustion with air
was used to generate artificial Anode Off-Gas with reformate as the feed. Concerning gas
flow and composition, the Stack Simulator will behave similar to a Fuel Cell Stack, not
producing electrical energy, but with the same conversion of fuel, and resulting in the same
heat value (LHV) given to the multifuel burner. Therefore the Stack Simulator enables to test
and tune the fuel processor under realistic operational conditions without risk of damaging the
Fuel Cell Stack.

iv
LIST OF TABLES
Table 1: Fuel cell characteristics (adapted from Penner, 1995) ...…......……………………. 4
Table 2: Fuel cell requirements (adapted from Penner, 1995) ...……………………………. 4
Table 3: Composition of the Natural Gas from the North Sea ..…………………………… 11
Table 4: Mass Balances in Inhouse System………………………………………………… 11
Table 5: Low Heat Value and Lambdas of the Simulator Stack …..………………………. 13
Table 6: Air input to convert 27% of the inlet stream……………………………………… 14
Table 7: Stack Simulator Outlet Gas Composition (Anode Off-Gas) ……………………... 14
Table 8: Adiabatic Combustion Temperature of Stack Simulator Anode Off-Gas…….…... 16
Table 9: Synthetic Reformate gas Inlet Composition………………………………………. 17
Table 10: Comparison of the relevant parameters of both catalysts ……………………….. 22
Table 11: Insulation project parameters and its thickness value …...……………………… 25
Table 12: Theoretical Stack Simulator inlet stream………………………………………… 26
Table 13: Stack Simulator Anode off-gas Outlet composition obtained from the catalytic tests
……………………………………………………………………………………………… 27
Table 14: Inhouse Reformate inlet composition…………………………………………… 32
Table 15: Comparison between the temperatures inside the reactor and the adiabatic
temperatures obtained from Hess’s Law …………………………………………...……… 35
Table 16: Anode Off-Gas Composition Simulation using RGIBBS……………...………... 36

v
LIST OF FIGURES
Figure 1: Flow sheet of Inhouse System process………..…………………………………… 5
Figure 2: LHV vs Lambda …………………………………………………………………. 13
Figure 3: Sketch of the preliminary tests plant……………………..………………………. 18
Figure 4: Detailed sketch of the testing section…………………..……………………...…. 18
Figure 5: Picture of FC-HC35B catalyst……………………………………………………. 18
Figure 6: Experiment with FC-HC35BC-B catalyst - Gas outlet composition front of
different lambdas…………………………………………………………………………… 19
Figure 7: Experiment with FC-HC35BC-B catalyst - LHV and Temperature of the product
front different Lambdas…………………………………………………………………….. 19
Figure 8: Picture of FCCB-2 catalyst………………………………………………………. 20
Figure 9: Experiment with FCC-B catalyst - Gas outlet composition front of different
lambdas………………………………………………………………………..……………. 21
Figure 10: Experiment with FCC-B catalyst - LHV and Temperature of the product front
different Lambdas…………………………………………………………………………... 21
Figure 11: Sketch of Stack Simulator ……………………………………………………… 23
Figure 12: Reactor Insulation sketch…………………………………………………….… 24
Figue13: Picture of Insulation……………………………………………………………… 25
Figure 14: Tubular Heat Exchanger………………………………………………………… 27
Figure 15: Picture of Stack Simulator………………………………………………….…… 30
Figure 16: Picture of the electric heating blanket ………………………………………...... 31
Figure 17: Off-gas Outlet composition and Temperatures depending on the amount of air
fed…………………………………………………………………………………………... 33
Figure 18: Comparison of temperature and LHV between the both cases ………………… 37
Figure 19: Extrapolation of the LHV and Temperature to a lambda 0,27. ………………... 38
Figure 20: Extrapolation of LHV and Temperatures to a natural gas flow of 20 L/min….... 39

vi
LIST OF VARIABLE
V Volume (L)
A Area (m2)
v& Flow (L/min)
y Volumetric fraction (%)
X conversion
∆H Enthalpy (kJ/mol)
Q& Energy outlet (kW)
LHV Low Heat Value (MJ/m3)
λ Lambda
ρ Density (g/L)
cp Heat capacity (kJ/m3K)
υ Molar Volume of the Ideal Gas (L/mol)
M Molar weight (kg/kmol)
µ Viscosity (kg/m.s)

h fg Water evaporation enthalpy (kJ/kg)

T Temperature (°C)
SV Space Velocity (h-1)
N Total number of moles (mol)
n Number of moles (mol)
p Partial pressure (bar)
P Absolute pressure (bar)
x Molar fraction (%)
D Diameter (m)
H Height (m)
L Length (m)
e Thickness (m)
k Conduction heat transfer coefficient (W/mK)
h Convection heat transfer coefficient (W/m2K)
U Overall heat transfer coefficient (W/m2K))
Pr Prandtl
Nu Nusselt

vii
LIST OF VARIABLE INDEX
i Component
Sum Total
IN Inlet
OUT Outlet
D Dry base
Dep Depleted Air
Max Maximum
Cond Condensed
OffGas Anode Off-Gas
RR Rich Reaction
R Reforming
SR Water Gas Shift Reaction
PO Preferential Oxidation
FC Fuel Cell Stack
SS Stack Simulator
CT Catalyst Testing
f Formation
R Reaction
0 Reference
HC Hydrogen Combustion
MC Methane Combustion
Ex Extra
Cool Cooling
ad Adiabatic
cat Catalyst
G Gas
W Water
s specific

viii
INTRODUCTION

Currently, there is great interest in researching electric power generation systems more
efficient and less polluting, from renewable and non-renewable sources.
The first conference that addressed the harm and some solutions to the problem of
environmental pollution caused by the excessive burning of fossil fuels, occurred in the mid-
70s, in Stockholm (VILAS, 2003). Increasing the efficiency of procedures, aiming to reduce
the fuel consumption, was one of the solutions presented at that time. Currently, renewable
energy sources, involved in the development of more efficient processes, have proven a more
concrete alternative to reduce impacts caused by the burning of fossil fuel. This proposal was
presented during the meeting RIO92, held in Rio de Janeiro in 1992. In another meeting, held
in Kyoto in 1997, it was proposed that 10% of the energy consumed by humanity would have
to be from renewable sources (VILAS, 2003). Several countries supported this goal, including
Germany and Brazil.
Regarding this, the fuel cells are becoming an interesting and promising alternative in
the solution of environmental problems caused by the generation of electricity. One major
advantage of using fuel cells, when compared to conventional thermoelectric systems, is its
high efficiency. The fact that a process is more efficient than another means for the same
amount of generated electricity, the fuel consumption is lower. Consequently the quantity of
pollutants that are released into the atmosphere, as CO2, CO, NOx, SOx, oil and particles,
may be reduced.
Among the benefits of the use of fuel cells, what stands out is the fact these generate
virtually no air pollution or noise, and they are compact and easy to maintain. They also
provide high-quality energy and high confidence. The use of the fuel cells contributes to the
deployment of distributed generation systems of electric power, which advantages are the
absence of losses in transmission, the insensitivity to the weather and the consequent
reliability, lower environmental impact, quick and easy installation.
On the other hand, one of the central issues is the degradation of the fuel cell. The
degradation can be divided into a reversible and an irreversible degradation. Reversible
degradation means a degradation of the cell voltage resulting of bad operating conditions
(temperature, humidity, mass flow of reactants, pressure), inefficient or inhomogeneous fluid
allocation and others. Irreversible degradation means a degradation of the cell voltage

1
resulting of an alteration of the components of the fuel cell. This includes an alteration and
loss of catalysts, carbon corrosion and a disintegration of the membrane caused by radicals.
Fuel cells that nowadays are commercially sold use natural gas as fuel, such as the unit
Inhouse System. The environment benefit of the use of natural gas, compared to other heavier
fraction of fossil fuels, is a lower emission of carbon dioxide per amount of energy generate.
(RIFKIN, 2003).
The unit Inhouse System is composed of various equipments that have the purpose of
producing hydrogen, remove the excess CO content, generate electric and thermal energy
efficiently, and furthermore, reuse the anode off-gas from the fuel cell, which still contains
methane and not converted hydrogen, as an energy source to the start up the plant, since the
production of hydrogen consist in a highly endothermic reaction.
Therefore, in the context, where the fuel cell is extremely sensitive and expensive,
moreover its anode off-gas should be sent to a burner for the plant to have a stable and
energetic integrated behaviour, the development of a Stack Simulator is very important for
setting important parameters.
Stack Simulator was positioned in place of the Fuel Cell. This is a combustion reactor
that was designed to comport reactions such as partial combustion of hydrogen and
combustion of methane. In these combustions, off-gas (Stack Simulator Anode Off-Gas) will
be produced, which contains the same calorific value (LHV) than the anode off-gas from the
Fuel Cell would produce and following would give to the burner.

2
I BIBLIOGRAPHIC REVIEW

1. History of the Fuel Cells

The fuel cell is an electrochemical device that directly converts the chemical energy of a
reaction in electrical and thermal power (CHOUDHURY et al., 2002). According to
TICIANELLI & GONZALEZ (1998) the main difference between the fuel cell and other
electrochemical systems is that in the fuel cell reagents in gaseous form are fed continuously.
The concept of the fuel cells has existed for over 150 years and his paternity is attributed
to William Grove. He got the idea during his experiments with electrolysis of water, when he
imagined how the reverse process would be, which means, to react hydrogen with oxygen to
generate electricity. The term “fuel cell” came in 1889, created by Ludwig Mond and Charles
Langer. (WENDT et al., 2000; VILAS, 2003).
The first functional fuel cell was built by engineer Francis Bacon in 1932. The cell used
an alkaline electrolyte and operated at a temperature of 200°C under pressure. In the 50's,
Broers and Ketelaar carried out experiments with molten carbonate fuel cells. Later Broers
developed at NASA the first cell with polymer membrane, but the results were not
satisfactory. Soon after, the alkaline cells were developed for space applications. (WENDT et
al., 2000; VILAS, 2003).
In the 60s, the membrane fuel cells arise, from the development of the polymeric
electrolyte membranes (PEMFC) (HIRSCHENHOFER, J.H., et al,1998). By offering greater
density of power, this type of cell boosted the vehicular applications.

2. Types of Fuel Cells

Currently, there are at least six different fuel cell types in varying stages of
development. Four of these are receiving the most development attention. In general,
electrolyte and operating temperature differentiates the various types. Listed in order of
increasing operating temperature, the four fuel cell technologies currently being developed
are:
• Proton exchange membrane fuel cell (PEMFC)—175°F (80°C)
• Phosphoric acid fuel cell (PAFC)—400°C (200°C)
• Molten carbonate fuel cell (MCFC)—1250°F (650°C)
• Solid oxide fuel cell (SOFC)—1800°F (1000°C)

3
 The following tables give a summary of the characteristics and fuel requirements of
these fuel cell types.
Table 1: Fuel cell characteristics (adapted from Penner, 1995)

Table 2: Fuel cell requirements (adapted from Penner, 1995)

3. Fuel processing and power generation

3.1. Inhouse 4000
The Inhouse 4000 is a fuel cell mini block heat and power plant for stationary power
supply (4kW electrical power), that has been developed since 2003 not only by TU-
Bergakademie Freiberg, but also by a great team of other universities and partner companies.
The main application might be in apartment buildings, commercial enterprises, office
buildings, hotels, public buildings, research facilities and demonstrators, etc.

4
 The overall process by which H2 is extracted from a hydrocarbon fuel source is called
fuel processing. It is in fact a multi-stage process where a number of chemical and physical
events can be combined in different ways to yield optimum performance. However, because
PEMFC electrodes can tolerate only very low concentrations of CO, it is imperative that fuel
processors used in such applications also minimize the production of CO in addition to
maximizing the generation of H2. The stage where H2 is first extracted from the hydrocarbon
fuel is referred to as fuel reforming. Subsequent conditioning of the hydrogen rich stream for
use in the fuel cell is referred to as CO clean-up. After, the gas stream rich in H2 and with a
concentration of 10 ppm of CO, called reformate would enter in the anode of the Fuel Cell
Stack, producing an Anode Off-Gas still containing methane and hydrogen that result a
certain LHV given to the multifuel burner. Finally, multifuel burner is used, where the anode
off-gas and also some amount of natural gas are burned to improve the overall thermal
integration of the overall process (and therefore the overall efficiency) by utilizing heat from
the combustion of excess hydrogen to increase the energy efficiency of the system.
For a better understanding, the following flow sheet illustrated in Figure 1, shows the
whole process of the Inhouse System.

Figure 1: Flow sheet of Inhouse System process

3.2. Feedstock
Today, nearly all hydrogen production is based on fossil raw materials. Worldwide, 48%
of hydrogen is produced from natural gas, 30% from oil (mostly consumed in refineries), 18%
from coal, and the remaining (4%) via water electrolysis. The production of hydrogen from
natural gas is an integral part of the strategy to introduce hydrogen into the transportation and

5
utility energy sectors, by reducing the cost of conventional and developing innovative
hydrogen production processes that rely on cheap fossil feed stocks.

3.3. Desulphurization
A preliminary desulphurization process is necessary in the reforming of natural gas.
Sulphur containing compounds are poisons for many downstream catalysts especially for the
PEMFC anode. They are also poisons for any base metal oxide catalysts present in the fuel
processor. Consequently, it is necessary to decrease the sulphur levels to less than 10 ppb (<
0.01 ppm) to maximize durability.

3.4. Multifuel Burner

Natural gas, reformate or the spent anode gases from the Fuel Cell Stack are burnt in a
multifuel burner to produce energy oxidizing the hydrocarbons or small amount of H2 and
CH4 that are present in reformate gases or on the anode gases. In the multifuel burner, fuel
and oxygen react in a flame combustion. The burner is thermally integrated with the steam
reformer. In this way, most of the heat generated in the multifuel burner is used internally in
the fuel processor system, with a minimum of the heat being wasted.

3.5. Steam reforming

Natural gas and liquid water enter the evaporator section at the top and flow to the
center inside a helical tube. The gas and water are heated by the hot flue gas from the gas
burner. The natural gas/steam mixture then enters the reactor consisting of an inner and outer
tube filled with catalyst material.
At the catalyst bed the first reaction to take place is called Reich Reaction and refers to
the conversion of light hydrocarbons (methane, propane, butane…) with water vapour in just
methane.
Cm H 2 n + d H 2O 
→ l CO2 + k CH 4
2m − n d (Equation I.3.1)
d= l= k = m−l
2 2

Soon after, the Steam reforming reaction occurs itself.

CH 4 + H 2O → CO + 3H 2 (Equation I.3.2)

CH 4 + 2 H 2O → CO2 + 6 H 2 (Equation I.3.3)

6
 Processes of this type are normally carried out at temperatures of 750-950°C, pressures
in the range of 0.3-2.5 MPa and low space velocity (GHSV at 3000 to 8000 h-1) owing to
slow kinetics.

3.6. Gas Clean-up / purification

After H2 is extracted from the hydrocarbon fuel in the reforming stage, the conditioning
of the hydrogen rich stream is necessary before it can be used in the PEMFC electrode for
power generation. A problem is the competitive adsorption of hydrogen and carbon monoxide
on the platinum sites. CO is preferentially adsorbed on the Pt electrocatalyst, thus blocking
the access of hydrogen to the surface and resulting in the degradation of the fuel cell
performance. Lowering the CO concentration by decreasing the temperature of the reforming
reactor would inevitably lead to a loss in efficiency, due to lower methane conversion and
lower H2 yield. Therefore, several chemical processes are required for CO removal
immediately following the reforming stage. The goal is to reduce the concentration of CO
below the tolerance limit of the electrode (typically <10 ppm), while minimizing any losses in
efficiency.

3.6.1. Water gas shift reaction

The Water Gas Shift reaction is independent of pressure and is slightly exothermic
therefore exhibits lower equilibrium conversion with increasing temperature. This process
includes the reaction:
CO + H 2O → CO2 + H 2 (Equation I.3.4)

Consequently, lowering the reaction temperature favours higher conversion but requires
more catalyst and results in a larger reactor. These trade-off often lead to a practical limit to
how much CO can be removed from the flow stream. The lowest limit temperature of
operation often depends on the kinetic limitations of the process. Therefore, the reaction is
normally carried out in two stages.
In the high-temperature shift reactor the reactants are fed at 350-450 °C. Thus, CO
clean-up subsystems using the water gas shift reaction operating at considerably lower
temperatures, compared with the methane reforming stage. The thermal energy released in
cooling the reformer outlet stream to achieve water-gas shift temperatures can also be
captured to help further increase the efficiency of the reforming stage. The temperature rise in

7
the reactor depends on the inlet CO concentration. Rapid reaction kinetics promote an initial
rapid approach to equilibrium corresponding to a CO concentration of ca. 2 vol.%. Then, the
reaction mixture is cooled down in a heat-exchanger.
The low-temperature shift reactor operates in a temperature range of 160-250 °C. As the
temperature decreases, less energy is available to overcome the activation energy barrier for
the reaction to proceed. This behaviour makes the reaction rate to slow down, yielding CO
concentrations far from thermodynamic limits, which decreases the CO level from 2 to 0,5
vol. %. Possibilities exist, though, for distorting the thermodynamic equilibrium in favour of
CO removal and H2 generation. These possibilities include devices that physically change the
composition of the gas stream, either by introducing additional reactants (H2O) or selectively
removing the products (CO2 or H2) from the reaction process.
Therefore, the gas at the outlet of two-stage WGS reactor typically contains 45-75 vol.%
H2, 15-25 vol.% CO2, a few vol.% H2O, traces of unconverted fuel and ca. 0,5 vol.% CO.
Thus, WGS reaction can provide a high degree of carbon monoxide conversion but can not
achieve the low level of carbon monoxide to prevent significant degradation of the PEM fuel
cell stack performance.

3.6.2. Preferential oxidation of CO in excess of hydrogen

The outlet concentration of CO from the water gas shift reactor is from 0,1 to 1,0 %
depending on operating conditions. The most effective mechanism for CO removal for fuel
cell quality H2 is preferential oxidation. This process includes the reaction:

CO + 0,5O2 → CO2 (Equation I.3.5)

The reaction is highly exothermic, therefore, it is crucial to remove heat from the reactor
and to keep the temperature near isothermal conditions. The adiabatic temperature rise for a
typical reformate stream exiting a Low Temperature Shift reactor with 5000 ppm CO and
with 2500 ppm added O2 is 45 K (assuming 100% selectivity to CO oxidation). Therefore,
depending on the operating window of the specific catalyst formulation, the catalyst
temperature has to be controlled. This can be accomplished by varying the inlet temperature
to the PROX reactor to account for the temperature rise along the length of the reactor and/or
use of a staged reactor with inter-stage cooling.

8
 In order to achieve levels smaller than 10 ppm of CO needed for PEM fuel cell
application, CO conversions of 90% or more are needed in the PROX unit. Because of the
high ratio between H2 and CO (>>100:1) in the reformate gas, the catalyst needs to be highly
selective. Stoichiometric amounts of O2 are desirable to keep the selectivity toward CO
conversion high. Any O2 remaining after conversion of CO will react with H2 thus decreasing
the effectiveness of the reactor.

3.7. Fuel Cell Stack

The power output of a single PEM Fuel Cell is limited. Therefore, in order to raise the
amount of energy coming from the PEM Fuel Cell, multiple cells are needed. PEM Fuel Cell
stacks are multiple PEM Fuel Cell’s attached in series.

3.7.1. PEMFC (Proton Exchange Membrane Fuel Cell)

The PEM fuel cell uses a solid polymer electrolyte and operates in a temperature range
of 80 to 100 °C with an efficiency around 40% (BALLARD, 2008).This type of cell displays
high-density power and flexibility of operation. Due to the low working temperature the
PEMFC quickly enters the operational state. This technology has several stationary
deployments of small and medium power (up to 250 kW). Its main feature is the use of a solid
polymer membrane as electrolyte, with capacity to transport protons (H+) and to block the
passage of electrons. This process includes the reaction:

H 2 + 0,5O2 → H 2O (Equation I.3.6)

This membrane has filed in its two areas, a thin layer of platinum - the catalyst for
reaction. The reduced thickness of the membrane PEM, allows this type of cell reduced
weight and volume when compared with other types of cells (HIRSCHENHOFER, 1998).
The PEM fuel cells may, apart from hydrogen, be supplied with natural gas, methane,
methanol, ethanol or other fuels rich in hydrogen. Doing so, they need a reformer stage where
the fuel is heated, so that, the extracted hydrogen can be supplied to the cell.

9
II STACK SIMULATOR PROJECT

1. Objective definitions
It is intended to develop a Stack Simulator that will be positioned in place of the Fuel
Cell. This is a combustion reactor that will be designed to comport reactions such as partial
combustion of hydrogen and combustion of methane. In this combustion, off-gas (Stack
Simulator Anode Off-Gas) will be produced, which contains the same calorific value (LHV)
of anode off-gas that the Fuel Cell would produce. This off-gas will be sent to a burner with a
view to promote the energy integration of the Inhouse system and allow it operates stable.
Today, to ensure sufficient energy for the Reforming reaction that follows, there are two
different ways of feeding the burner, feeding natural gas in the start-up and after feeding
reformate, or only feeding natural gas. However, the plant presents a totally different behavior
in each case, moreover, these two alternatives are not ideal, since the plant can not operate
with full-load (20 L / min) as it was designed to operate with the Anode Off-Gas from the
Fuel Cell.
Therefore, feeding the burner with Stack Simulator Anode Off-Gas, it would allow a
stable and energetic integrated behavior of the plant.

2. Presentation of the parameters to be known

Some important parameters must be known to be able to build the Stack Simulator and
to choose its appropriate accessories as air MFC (mass flow control) and heat exchangers.
These parameters are:
• Inlet, outlet flow and its composition
• Outlet LHV
• Adiabatic temperature inside of the reactor
• Amount of air fed.
To know these values, mass and energy balances were used as a main tool.

3. Inhouse processes Mass Balances

The Fuel Cell Stack Simulator project begins primarily with mass balances in every
stage of the Inhouse System. The stages are: Reich-reaction, Steam Reformer, Water Gas
Shift reactor, Preferential Oxidation reactor, and also the Fuel Cell Stack, so that it is later
possible to replace the Fuel Cell Stack by the Fuel Cell Stack Simulator.

10
 The natural gas composition varies by region and locality due to differences in its
source, and processing. In Germany, it comes from the North Sea. In Table 3 is shown the
composition of North Sea natural gas.

Table 3: Composition of the Natural Gas from the North Sea

Natural Gas from the North Sea (Norway, The Netherlands…)

Component CH4 C2H6 C3H8 C4H10 C5H12 CO2 N2 Sum

Vol.-fraction 85,89% 8,85% 2,31% 0,65% 0,12% 1,64% 0,54% 100,00%

The Natural Gas stream is split in the Inhouse system. One part of the gas feeds the
combustion chamber of the reformer, the other, called process gas, is used for the production
of hydrogen. Just the process gas stream is considered on the mass balance. The Stack
Simulator is projected so that the system works with full load, it means, process gas supply of
20 L / min. Therefore, the mass balances begin from this value.
The desulphurization reactions were not considered in the balances calculation due to
the low-sulphur content in the Natural Gas.
For these balances, the stoichiometric coefficients of each reaction were considered,
which was already presented in Chapter I.
The values of the inlet and outlet compositions of each stage are shown in Table 4
below and as it is a sequence of processes, the outlet composition of one is the inlet
composition of another. The equations used and the sequence of calculations are shown in
Appendix A1.
Table 4: Mass Balances in Inhouse System

Mass Balance in Inhouse System

Total flow
Composition
(L/min)
Stages CH4 H2 H2O CO CO2 N2

Reich Gas Equivalent 94,69% 0,0% 0,0% 0,0% 4,84% 0,47% 23,18

Reforming 0,8% 43,5% 41,1% 14,5% 0,0% 0,1% 143,76

Shift reaction 0,8% 57,0% 27,6% 1,0% 13,5% 0,1% 143,76

Preferential Oxidation 0,7% 52,1% 28,1% 0,0% 13,7% 5,4% 151,87

Fuel Cell Stack 1,2% 21,4% 46,0% 0,0% 22,5% 8,9% 92,55

11
 4. Simulator Stack Mass and Energy Balance:
Only the partial oxidation of hydrogen and oxidation of methane, shown in the
Equations II.4.1 and II.4.2 respectively, were considered on mass and energy balance of the
Stack simulator owing to the fact that these are the main reactions.

H 2 + 0,5O2 → H 2O (Equation II.4.1)

CH 4 + 2O2 → CO2 + 2 H 2O (Equation II.4.2)

To be able to proceed with the mass balance, first, the concept of LHV is introduced.
Burning a fuel normally produces water. If the produced water is considered to be in the
liquid phase, then higher heating value (HHV) is applied. If the produced water is in the
gaseous phase, then lower heating value (LHV) is used. The difference is related to the latent
heat of vaporization of water. As the anode off-gas that is produced in the Stack Simulator is
purely on gaseous phase, the concept of LHV was applied.
As the main goal of this work is to produce an off-gas, which the composition offers the
same LHV of the Fuel Cell anode off-gas, the LHV from the Fuel Cell was necessary to be
calculated. It was made multiplying the enthalpy of reaction from the hydrogen combustion
by the remain hydrogen composition that did not react in the Fuel Cell. Therefore the LHV
from the Fuel Cell was 5, 06 MJ/m3.
Due to discover the theoretical conversion of the reactants on the Stack Simulator that
would produce the same LHV recently calculated for the Fuel Cell, it was necessary to build a
graphic that showed a trend line between lambda λ which is the ratio of the oxygen
consumption and its demand, as shown in the Equation II.4.3 and the values of LHV,
calculated by the Equation II.4.4, for the Stack Simulator considering only the combustion
reactions as mentioned above.
v&OSS2 ,cons
λ= (Equation II.4.3)
v&OSS2 , Dem

LHV = ∆H R0 , HC * y HSS2 , D + ∆H R0 , MC * yCH

SS
4 ,D (Equation II.4.4)

Therefore, Table 5 was build to generate a graphic that is shown in Figure 2.

12
 Table 5: Low Heat Value and Lambdas of the Stack Simulator

H2 utilization rate CH4 utilization rate LHV (MJ/m3) λ

0,0% 0,0% 8,16 0,00

25,0% 25,0% 5,20 0,25

50,0% 50,0% 3,01 0,50

75,0% 75,0% 1,33 0,75

100,0% 100,0% 0,00 1,00

9
8
7
LHV (mJ/m )
3

6
5
4
3
2
1
0
0,00 0,20 0,40 0,60 0,80 1,00 1,20
Lambda

Figure 2: LHV vs Lambda

So, putting the value of LHV from the fuel cell (5,06 MJ/m3) in the equation that is
obtained from the graphic, it comes to a lambda of 0,27.
This lambda is approximately the same as the conversion rate that must be obtained
within the catalytic combustion on the Stack Simulator due to give to the burner the same heat
value that the Anode Off-Gas from the Fuel Cell would offer, so it can be used to calculate
the theoretical composition of the Stack Simulator Anode Off-Gas within the inlet gas
composition that was already shown from the Preferential Oxidation in Table 5.
To ensure that conversion of gases, the amount of oxygen that must be fed to the reactor
is a very important factor, which also depends on lambda (0,27) and the amount of process
gas fed in the beginning of the process (20 L/min). Thus in the Table 6 below is shown the
necessary values for the calculation of the amount of inlet air.
The whole calculation sequence is shown in the Appendix A1.

13
 Table 6: Air input to convert 27% of the inlet stream

Oxygen demand 41,74 L/min

Consumed Hydrogen 21,36 L/min

Consumed Methane 0,30 L/min

Consumed Oxygen 11,27 L/min

Air input 53,67 L/min

In possession of the conversion of the inlet gases and the amount of air input, was
finally possible to calculate the theoretical outlet gas composition (Stack Simulator Anode
Off-Gas). Therefore the theoretical outlet gas composition is shown in Table 7. The whole
calculation sequence is shown in the Appendix A1.

Table 7: Stack Simulator Outlet Gas Composition (Anode Off-Gas)

Stack Simulator Anode Off-Gas Outlet Stream

CH4 H2 H2O CO CO2 N2 Sum

L/min 0,80 57,74 64,56 0,00 21,15 50,62 194,86

Vol.- % (wet) 0,41% 29,63% 33,13% 0,00% 10,85% 25,98% 100,00%

Vol.- % (dry) 0,61% 44,31% 0,00% 0,00% 16,23% 38,85% 100,00%

It is necessary then to know the amount of total heat released by the combustion
reactions so that it is possible after estimating the amount of water needed for cooling down
the system.
Total Energy outlet is calculated with the following relations:
Energy outlet of Hydrogen Combustion is calculated by the Equation II.4.5:

∆H R0 , HC * X HSS2 * v&HPO2 * ρ H 2
Q& HC = (Equation II.4.5)
M H2

Energy outlet of Methane Combustion is calculated by the equation II.4.6:

& ∆H R0 , MC * X CH
SS
* v&CH
PO
* ρ CH 4
QMC = 4 4
(Equation II.4.6)
M CH 4

14
 Thus the Total Energy outlet is consequently calculated by the sum of Equation II.4.5
and Equation II.4.6 resulting in a value of 4,01kW.
Total cooling water demand is an important value to know, since the reactions on the
Stack Simulator are extremely exothermic, and its outlet stream should be reused as a fuel to
the burner on the beginning of the Inhouse process. To be able to calculate its amount by the
equation II.4.7, the thermodynamic water properties were necessary to be found on literature
(SPRINGER-VERLAG, 2006).

Cooling water demand is calculated by the Equation II.4.7:

Q& Sum ,C
v&CoolH 2O = (Equation II.4.7)
ρ Steam * Cp H O * ∆T
2

Delta Cooling Water temperature ∆T = 40 K

Maximum of condensable water is calculated by the Equation II.4.8

v&Cond , Max = v& HPO2O * ρ CoolH 2O (Equation II.4.8)

Extra Cooling Load water is calculated by the Equation II.4.9:

Q& Ex = v&Cond , H 2O * ρ CoolH 2O * h fg (Equation II.4.9)

Extra cooling water demand water is calculated by the Equation II.4.10:

Q& Ex
v& Ex , H 2O = (Equation II.4.10)
ρ Steam * Cp H 2O * ∆T

Consequently the total cooling water demand is calculated by the sum of Equation II.4.7
and Equation II.4.10 resulting in a value of 2,35 L/min

4.1 Adiabatic Combustion Temperature

The temperature that results from a combustion process that occurs adiabatically with no
work or changes in kinetic or potential energy involved is commonly referred to as the
(constant pressure) adiabatic combustion temperature. Because of the assumptions of no work
and no changes in kinetic or potential energy, this is the maximum temperature that can be
achieved for the given reactants because any heat transfer or work from the reacting

15
substances and any incomplete combustion would tend to lower the temperature of the
products.
This is a crucial concept by the limitations of design. The maximum allowed system
temperature is 1000°C, because the catalyst deactivates above this temperature. The adiabatic
Combustion temperature of the Stack Simulator is calculated by the Equation II.4.11 and its
value is shown on table 8.
Q&
Tad = T0 + SS
Sum
(Equation II.4.11)
v& Sum ,Off − Gas ⋅ Cp

Table 8: Adiabatic Combustion Temperature of Stack Simulator Anode Off-Gas

Adiabatic Combustion Temperature Anode off-gas (Air)

To 273 K
Q 4,01 kW
V 194,86 L/min
Cp 1,8 kJ/m3K
T 959,72 K
T 686,72 °C

As the adiabatic combustion temperature calculated was lower than the limit, it was
possible to say that reactions can take place in only one reactor. If the adiabatic combustion
temperature was higher than 1000 ° C, reactions should occur in more than one reactor and
after each one it would be necessary to introduce a cooler. That would increase system
complexity and costs.

5. Choosing appropriate catalyst

5.1 Preparation for catalytic preliminary testing
The preliminary experiments were carried out in a tubular reactor. It consists of a
tubular module with a volume of 20 mL. A synthetic reformate gas was fed on the module
pretending the exact outlet gas composition of the preferential oxidation reactor, which were
only methane, carbon dioxide, hydrogen and steam. The steam is fed to consider that the gas
comes humid into the Stack Simulator.
As the maximum catalytic space velocity front each reagent was known, the lower

value (30000 h-1) was used pretending to be closer to the reality. Also with the fixed

volume of the module, the gas inlet stream could be calculated by the equation II.5.1.

16
 v&0
SV = (Equation II.5.1)
Vcat

Thus, the input flow of air is calculated based on the oxygen demand to convert 27% of
methane and hydrogen, following their stoichiometric ratio of combustion and also
considering 21% of oxygen in the composition of air.

Due to calculate the composition of the synthetic gas, its properties as density and molar
weight had to be sought from the literature (SPRINGER-VERLAG, 2006). The Inlet Gas
Composition and condition are calculated and showed in Appendix A1.

Steam is also added to the reactor, and its inlet flow is calculated and shown in
Appendix A1, considering that the gases released from the preferential oxidation reactor are
wet. For this reason, it is assumed that the steam is saturated at a temperature of 70°C and its
correspondent saturated pressure which is the same as the partial pressure is 0,32 bar .

Consequently, the synthetic gas inlet composition could be calculated, and therefore it is
shown in Table 9.
Table 9: Synthetic Reformate gas Inlet Composition
Inlet Stream
CH4 H2 H2O CO2 Air sum
v0 (L/min) 0,10 7,24 0,003 1,91 4,91 14,16
Vol % 0,71% 51,11% 0,02% 13,48% 34,68% 100,00%
n (mol/h) 0,27 19,36 8,98 5,12 11,29 45,03
X mol 0,01 0,43 0,27 0,11 0,25 1,07
Pi (bar) 0,01 0,52 0,32 0,14 0,30 1,20

5.2. Catalytic testing

Both catalysts that were tested are provided from Süd Chemie Industrie.
The only parameter that was changed during the experiments was the flow of air, so
within was possible to evaluate the behaviour of the reactions front of different lambdas (λ).
The tests were carried out in a cylinder reactor, in just one module, which is 20 mL
volume. Before the reactor, took place an evaporator and also a super heater, which had the
task to vaporize the water, with the objective not to cool down and not dampen the catalyst in
the testing section as steam was also fed to represent the humidity of the gases. The products
of the reaction were sent to a flare, to ensure that they are burned before being released into
the atmosphere. Also from the reactor were removed small samples and sent to the gas
analyzer. In Figure 3 is shown a diagram of the preliminary testing plant.

17
 Super Testing
Evaporator Section Flare
Heater ( 20 mL)

Gas
Analyser

Figure 3: Sketch of the preliminary tests plant

Only the reactor (testing area) was detailed in Figure 4 aiming to show how was its
inner and exactly the places where the temperatures were measured.

Thermocouple
Thermocouple

Figure 4: Detailed sketch of the testing section

5.2.1. FC-HC35B Catalyst

The FC-HC35B catalyst is composed of a noble metal and supported by cerium and
aluminum oxide. It has a cylindrical shape and has dimensions 3x3mm. It is stable and
reactive up to 1000°C. This catalyst reacts in ambient temperature, for this was not necessary
to pre heat the plant. In the Figure 5 below is shown a picture of this catalyst

Figure 5: Picture of FC-HC35B catalyst

18
 The results of this experiment are shown in the next two figures, which were tested and
evaluated different composition of the gases output front of each Lambda, their correspondent
LHV and also the temperature of the reaction measured at the end of the fixed bed.

FC-HC35B
Gas Outlet
80% Reaction with steam 4,0%
70% 3,5%

CH4, CO Composition
H2, CO2 Composition

60% 3,0%
H2
50% CO2 2,5%
40% CH4 2,0%
CO
30% 1,5%
20% 1,0%
10% 0,5%
0% 0,0%
0,09 0,13 0,16 0,21 0,24 0,27 0,28 0,30 0,33
Lambda

Figure 6: Gas outlet composition front of different lambdas

FC-HC35B
9,0 Reaction with steam 900
8,5 800
8,0 700
Temperature (°C)

7,5
600
LHV (MJ/m3)

7,0
500
6,5
400
6,0
300
5,5
LHV 200
5,0
4,5 Temp 100
4,0 0
0,09 0,13 0,16 0,21 0,24 0,27 0,28 0,30 0,33
Lambda

Figure 7: Experiment with FC-HC35BC-B catalyst - LHV and Temperature of the product
front different Lambdas

As one can see in the graph of Figure 6, there was production of CO, this could be
explained by the non-complete combustion of methane or also may have taken place a reverse
shift reaction, which is an acceptable explanation, since this reaction is very easy to forward
front a vast range of catalysts and high temperatures as is the case. It also can be seen that
there was methane formation by the reaction of methanation, this reaction can occur because

19
of CO content that have been produced, and also because of the temperature conditions were
favourable.
Also in the graph of Figure 7 it can be observed that during the course of the reactions,
increasing the lambda, the values of LHV decrease. These values reached almost the same
goal-value which is approximately 5 MJ/m3. However, according to the theoretical results,
this value should have already been achieved with a lambda equal to 0,27. Nevertheless, this
result was not obtained as unwanted reactions, mentioned before, took place.

5.2.2. FCCB-2 Catalyst

The FCCB-2 catalyst is composed of manganese dioxide and copper oxide supported by
aluminum oxide. It has a triple holes shape and has dimensions of 5x5 mm. It is stable and
reactive up to 700°C.
This catalyst does not react in ambient temperature. So, it was necessary to pre-heat the
plant until at least 250°C, what is a disadvantage comparing to the FC-HC35B catalyst.
Because in this case, the stack simulator should need ignition plugs to be installed.
In the Figure 8 below is shown a picture of this catalyst.

Figure 8: Picture of FCCB-2 catalyst

The results of this experiment are shown in the next two figures, which were tested and
evaluated exactly the same parameters as the experiments carried with FC-HC35B catalyst.

20
 FCCB-2
80% Gas Outlet 4,0%
Rection with Steam
70% 3,5%

CH4, CO Composition
H2, CO2 Composition
60% 3,0%
H2
50% CO2 2,5%
40% CH4 2,0%
CO
30% 1,5%
20% 1,0%

10% 0,5%
0% 0,0%
0,09 0,13 0,16 0,21 0,24 0,27 0,28 0,30 0,33
Lambda

Figure 9: Experiment with FCC-B catalyst - Gas outlet composition front of different lambdas

In this case, the methanation is even stronger as is possible to observe in Figure 9, what
justifies the lower content of carbon monoxide. Although this is an advantage, the amount of
methane resulting from methanation minus its consumption by the combustion is even greater
than the amount fed. Resulting in a higher LHV as one can see in the graphic of the Figure 10.

FCCB-2
Reaction with steam
9,0 900
8,5 800
8,0 700
Temperature (°C)

7,5 600
LHV (MJ/m3)

7,0
500
6,5
400
6,0
5,5 300
5,0 LHV 200
4,5 Temp 100
4,0 0
0,09 0,13 0,16 0,21 0,24 0,27 0,28 0,30 0,33
Lambda

Figure 10: Experiment with FCC-B catalyst -LHV and Temperature of the product front
different Lambdas

To decide which of these two catalysts would be more appropriate, a table comparing
some important parameters was built. These parameters are evaluated in the Table 10.

21
 Table 10: Comparison of the relevant parameters of both catalysts
Comparison

Parameter FC-HC35B FCCB-2

Ignition Temperature + -
Temperature of deactivation + -
Space Velocity 0 0
LHV + -
CO content - +

How can be we conclude from the Table 10, the catalyst FC-HC35B has a larger
number of positive characteristics, which are the ignition temperature, established by the
reaction has begun with the ambient temperature, the temperature of deactivation, which is the
temperature which the reaction can reach without disabling the catalyst is relatively higher
than using the catalyst FCCB-2, LHV, the heat capacity would be provided to the burner has a
value closer to the LHV of Anode Off-Gas from the fuel cell. Therefore the chosen catalyst
was FC-HC35B.
These preliminary tests served to the catalyst choice and also had an important role to
get an idea of how the Stack Simulator would behave. Although this plant has served as an
example, no one can guarantee that these results will have repetitiveness.

22
III STACK SIMULATOR DESIGN

The Stack Simulator consists in a combustion reactor which will use a partial catalytic
combustion of reformate to produce an off-gas with a LHV around 5 MJ/m³. For the design of
the Stack Simulator, the dimensions of the reactor and the thickness of the insulation must be
aware. Beyond the verification of both heat exchangers performance was desired.
A sketch of the Stack Simulator is shown in Figure 11, where one can better see a
detailed configuration of the reactor, insulation and both heat exchangers that should be
design in this chapter.
Reformate Air

Mixer Chamber

Flame trap

Ø56

Heat
Exchanger 1

Condensate
Separator

Figure 11: Sketch of Stack Simulator

23
 1. Reactor
With the knowledge of the compositions of reformate, the amount of inlet steam, the
amount of air and the maximum space velocity of the catalyst, was possible to calculate the
necessary volume of the reactor. The calculation of the volume of the reactor, which is shown
on Equation III.1.1, was made from the opposite way of calculating flow rates in catalytic
test, as the catalyst is the same.
v&0
SV = (Equation III.1.1)
V SS
Also, the cylinder volume is given by the equation III.1.2:
2
D
V =π H (Equation III.1.2)
4
With these equations, it was possible to calculate the height of the reactor, since the
diameter was already known, because it was decided before to use a stainless steel cylinder
which we already had in stock. To calculate its height, was used a safety factor of
approximately 25%. Therefore, the height of the reactor is 12 cm.

2. Insulation
It was necessary to calculate the thickness of the insulation to ensure a low temperature
on the outer surface of the reactor due to safety reasons. To obtain this value, it was
considered that the heat forwarded by convection from the hollow cylinder to the environment
is the same of the heat forwarded by heat conduction inside of this tube. Moreover the
material of the insulation is alumina silicate fibre.
For a better understanding the insulation sketch is shown in the figure 12.

ri ri - ro

Ta
Air

Tw,o

Figure 12: Reactor Insulation sketch

24
 The thickness was calculated by the Equation III.2.1 using iteration since the inner
radius is dependent variable in both side of the equation.

ro  κ 
ri
= exp (Tw,i − Tw,o ) (Equation III.2.1)
 h2 ro (Tw,o − Ta ) 

The Table 11 shows the variables considered to the above calculation and also the value
of the thickness of the insulation.

Table 11: Insulation project parameters and its thickness value

Thicknes of the insulation

K 0,11 W/mK
Di 5,6 cm
h2 10 W / m2K
Tw,i 700 °C
Tw,o 50 °C
Ta 20 °C
ro 12 cm

A picture of the material to illustrate the shape that was obtained from the insulation
after being assembled is shown in Figure 13.

Figure 13: Picture of Insulation

25
 3. Cooling system
The anode off-gas flow that comes out from the reactor is cooled in two different heat
exchangers. Both heat exchangers were already in our possession. The second is a plate
exchanger, identical to those used after each stage of the Inhouse system. However, this does
not permit to exceed an input temperature of 350°C, so it was necessary an intermediate heat
exchanger. The first heat exchanger has a cylindrical shape and it is made of stainless steel. It
consists of two concentric cylinders that looks like a double-tube format. The tasks therefore
were to calculate the amount of heat exchanged and check if it would be able to achieve a
temperature under than 350°C from the inlet gas temperature.
To check if the use of the plate heat exchanger could be possible, it was necessary to
know in advance the anode off-gas stream that would come out of the reactor, and its physical
properties.
The amount of the off-gas flow was obtained from the catalytic preliminary tests carried
out before. As the gas analyzer did not show the amount of water produced, first was applied
a carbon balance (Equation III.3.1) to discover the dry gases stream. Soon after, an oxygen
balance (Equation III.3.2) was applied to find out the steam flow. So, adding up both values,
the total volumetric flow of the anode off gas was obtained.

Carbon Balance:
v&IN , D * ( yCO2 , IN + yCH 4 , IN ) = v&Out , D * ( yCO2 ,Out + yCH 4,Out + yCO ,Out ) (Equation III.3.1)

Oxygen Balance:
2 * 0,21* v& Air , IN + v&H 2O , IN + 2 * v&CO2 , IN = v&Out , D * ( 2 * yO2 + 2 * yCO2 + yCO ) + v&H 2O (Equation III.3.2)

In the Table 12 and Table 13 are shown the theoretical inlet stream and the composition
of the anode off-gas as well its total volumetric flow.

Table 12: Theoretical Stack Simulator inlet stream

Inlet

CH4 H2 CO2 CO H2O Air sum

v0 (L/min) 1,10 79,63 20,99 0,00 0,03 53,67 155,42

Vol % 0,71% 51,23% 13,51% 0,00% 0,02% 34,53% 100,00%

26
Table 13: Stack Simulator Anode off-gas Outlet composition obtained from the catalytic tests

Outlet

CH4 H2 CO2 H2O CO O2 N2 sum

v (L/min) 1,12 71,15 22,27 24,23 2,97 0,30 27,59 149,78

Vol % 0,75% 47,50% 14,87% 16,28% 1,98% 0,20% 18,42% 100,00%

To calculate the amount of heat exchanged, it was necessary to calculate the overall heat
transfer coefficient. The overall heat transfer coefficient, U, is the reciprocal of the overall
thermal resistance across a heat exchanger. It was used to determine the total heat transferred
between the two streams in the heat exchanger by the Equation III.3.3:
Q& = UA∆T (Equation III.3.3)

But for that, first the convective heat transfer coefficients from the gas that flows inside
of the tube and also from the water that flows outside of the tube was calculated using some
empirical formulas adapted to our case.
The tubular heat exchanger is illustrated by Figure 14. The off-gas flows inside of the
inner tube, between a solid cylinder and the wall. As one can see in the following sketch, in
the area where the off-gas flows, fins also of stainless steel are placed due to increase the
amount of heat transferred. Outside water in ambient temperature flows in counter –current.

Figure 14: Tubular Heat Exchanger

The convection heat transfer coefficient depends of the Reynolds number and the
Prandtl number, what means, that this coefficient depends of the flow regime and also the of
the gas properties.
To get the physical properties of the Anode off-gas is not trivial work. It was necessary
again to use empirical formulas, which are found in Appendix A2. For its use, the only

27
condition was that the properties would not be easy changeable with temperature. As the fluid
is gas at ambient temperature, this condition was met.
Hence, knowing all the properties, it was possible to calculate the Prandtl number and
the Reynolds number for the off-gas side.
For this case, where the heat is transferred from the in to outside, the Nusselt number
has the shape as of the Equation III.3.4:
1
 0, 5 3   1
 1 
3 3
 d     d  3  d − di  3  
NuG =  3,66 + 1,2 i   + 1,6151 + 0,14 i   Re Pr o    (Equation III.3.4)
   o   
d  d
 o   l  
     
 

As the Nusselt number also is given by the Equation III.3.5:

hG d h
Nu = (Equation III.3.5)
k

The convection heat transfer coefficient from the off-gas side could be obtained
equalling the Equations III.3.4 and III.3.1.5. Its value was doubled considering the fins that
are placed between the wall and the solid cylinder inside of the tube, increase highly the heat
transfer. Therefore hG is 264,61 W/m2K.
Now, for the water side of the tube, the procedures were similar, except that in this case
the heat will only be exchange to inside direction.
The water properties are easily found, with these and the velocity known from the total
cooling water demand, was possible to calculate the Prandtl number and the Reynolds
number.
The Nusselt number has the shape as the Equation III.3.6:
1
 − 0 ,8 3   − 
1 1 
3 3
 d     d  2 d − di  3  
Nu w =  3,66 + 1,2 i   + 1,6151 + 0,14 i   Re Pr o   (Equation III.3.6)
   do     d o   l   
      
 

As the Nusselt number is also given by the equation III.3.5, The convection heat transfer
coefficient from the water side could be obtained equalling the equations III.3.5 and III.3.16.
Its value corresponds hw equal to 352,68 W/m2K.
So then the overall heat transfer coefficient is calculated by the equation III.3.7:

28
 1
U= (Equation III.3.7)
1 e 1
+ +
hG k hW

Being e and k the inner thickness of the tubular heat exchanger and the conductivity
coefficient of the stainless steel, respectively.
Already in possession of the overall heat transfer coefficient, it was still necessary to
calculate the temperature of the gas output to obtain after the total amount of heat transferred.
To check the outlet temperature, was needful to use numerical iteration with equations
III.3.8 and III.3.9:
Q& = UA(TG − TW ) (Equation III.3.8)

Q&
T2G = T1G − (Equation III.3.9)
cpv&ρ

It was found a gas output temperature of 170,8°C. As the limit of the plate heat
exchanger is 350°C, the heat exchange plate could be safety installed after the tubular heat
exchanger.
Finally, the amount of heat transferred in the tubular heat exchanger is 3,1 kW. It is still
remaining 1 kW of heat that can easily be removed by the plate exchangers.

29
IV RESULTS AND DISCUSSION

The Stack Simulator is composed primarily of a fixed mixing chamber, so that air and
gases from the reforming could enter homogeneously in the catalyst bed. Soon after, it
follows a flame trap, it consists of a plurality of closely spaced and rigid fixed alumina plate
which together act as a barrier for flame while nevertheless allowing the passage of gas. It is
positioned between the mixer chamber and the reactor, whit that, flame can not propagate
back to the mixing chamber. The reactor consists of a tube made of stainless steel with a 56
mm and 120mm of diameter and length respectively. Its total volume is full filled with the
catalyst previously chosen. The flame trap and the reactor are covered with a 120mm alumina
silicate fibre mat insulation. After, follows the both heat exchangers and the condensate
separator, as shown in Figure 15.

Figure 15: Picture of Stack Simulator

30
 1. Tests procedures
The burner of the Inhouse System is fed with natural gas, and rapidly the temperatures
of the whole system starts to increase. The steady state is achieved in more or less 1,5 hours.
The reformate gas is fed in the Stack Simulator after had coming through the
Preferential Oxidation condensate separator. Afterwards, the electric heating blanket is turned
on until the catalyst bed reaches a temperature of approximately 100°C. On account of
previously erroneous conclusion, a pre-heating of the e reactor is so necessary for that the
partial oxidation reaction occurs, since this condenser mentioned above is not efficient
enough to condense and separate the saturated condensate (in large part, water) found in
previous reactions. A picture of the electric heating blanket is showed in the Figure 16.

Figure 16: Picture of the electric heating blanket

Immediately after, air is fed to the reactor.

Its products, called Stack Simulator Anode Off-Gas, are directed to a flare to ensure the
burning of gas fuel outdoors and in a safe place. A little part is given to the analytical
continuous gas analyzer, which measure H2, CH4, CO, CO2 and O2 contents.

2. Evaluation of different gas natural loads

The reactor is loaded with 253g of catalyst FC-HC35B what corresponds to the total
volume of the reactor. The stack simulator was projected to work on the full load of the plant,
it means 20 L/min of natural gas. But for limitation of the size of the compartment in the
burner that burns natural gas, only a range of 7 until 11 L/min could be tested.

31
 In the following results, the natural gas load, temperature and air flow, are considered.
The air flow was calculated based on the lambda, which is the ratio between oxygen demand
and consumed oxygen.
Several tests were prepared expecting that the only reactions which would take place
were the partial combustion of hydrogen and methane. However as the reactor has been
designed so that it could work with the desired flow of 20 L/min natural gas, unwanted
reactions, as methanation and reverse water shift reaction, occurred in the bottom of the
reactor where the temperature is relatively lower. Anyway, the experiments with a flow of
natural gas from 7 to 11 L/min were carried out. The inlet reformate gas composition is
shown in Table 14.
Table 14: Inhouse Reformate inlet composition

CH4 H2 CO CO2 Sum

1,5% 75,7% 6,2% 16,6% 100,0%

From the Table 14, what draws attention is the relatively high inlet composition of CO
due to the preferential oxidation reactor was not working properly. Therefore in all
experiments had to be taken into account the entry of CO, what was not expected. As the CO
content was calculated as absent on mass and energy balances.
At least five reactions took place on these experiments. The observed reactions were
following:
Partial hydrogen Combustion:
H 2 + 0,5O2 → H 2O (Equation IV.2.1)
Methane Combustion:
CH 4 + 2O2 → CO2 + 2 H 2O (Equation IV.2.2)
Carbon Monoxide Combustion:
CO + 0,5O2 → CO2 (Equation IV.2.3)
Methanation:
CO + 3H 2 ↔ CH 4 + H 2O (Equation IV.2.4)
Reverse Water Gas Shift reaction:
CO2 + H 2 ↔ CO + H 2O (Equation IV.2.5)
Becoming this, an extremely complex system, dependent not only on the inlet
composition condition and type of catalyst, but also to the temperature and size of the reactor.

32
 In the Figure 15, graphics of the outlet composition of the experiments carried out with
7 L/min and 10 L/min of natural gas are illustrated, owed to show that independent of full
load or not, the system behaves pretty similar. And also, in the Appendix B1 is possible to
observe the tables that generated these graphics below and all the outlet composition with
other loads of natural gas inclusively some more secondary details.

60% 7 L/min Natural Gas 14% 60% 10 L/min Natural Gas 14%

"Anode Off-Gas" CH4, CO2, CO

"Anode Off-Gas" CH4, CO2, CO

"Anode Off-Gas" H2 Composition

58% 12% 12%
58%
"Anode Off-Gas" H2

10% 10%

Composition
Composition
56% 56%
Composition

8% 8%
54% 54%
6% 6%
52% 52%
4% 4%

50% 50%
2% 2%

48% 0% 48% 0%
0,07 0,08 0,09 0,10 0,11 0,12 0,13 0,07 0,08 0,09 0,10 0,11 0,12 0,13
Lambda Lambda
H2 CH4 CO CO2 H2 CH4 CO CO2

1000 7 L/min Natural Gas 1000 10 L/min Natural Gas

800 800
Temperature (°C)

Temperature (°C)

600 600

400 400

200 200

0 0
0,07 0,08 0,09 0,10 0,11 0,12 0,13 0,07 0,08 0,09 0,10 0,11 0,12 0,13
Lambda Lambda

Temp Reactor Temp Products Temp Reactor Temp Products

Figure 17: Off-gas Outlet composition and Temperatures depending on the amount of air fed

As one can see in the Figure 17, the increasing CO content with increasing temperature
is mainly because of reverse water–gas shift reaction which enhanced by increased reaction
temperature. Nevertheless, a more prominent contradiction could be observed. The
temperature reached a value higher than the adiabatic temperature previously calculated. As it
is something physically impossible, the only plausible conclusion is that we were having hot
spots in the first part of the reactor. Hence the temperature inside the reactor became the
limitation of the experiments, explaining therefore why it has been fed a low flow of air,
reaching lower values of lambda than the desired (0,27).

33
 According to this unexpected result, was decided then to calculate the adiabatic
combustion temperature with another model, but in this time, using the real inlet and outlet
composition of the reactor. For that, Hess’s Law was chosen due to the complex multiple
reactions system.

2.1. Adiabatic combustion Temperature using Hess’s Law

Hess’s Law states that energy changes are state functions. The amount of energy
depends only on the states of the reactants and the state of the products, but not on the
intermediate steps. Energy (enthalpy) changes in chemical reactions are the same, regardless
whether the reactions occur in one or several steps. The total energy change in a chemical
reaction is the sum of the energy changes in its many steps leading to the overall reaction.
Hess’s Law is given by the Equation IV.2.1:
i i

∑ ni , IN ∆H 0f ,i (Tref ) = ∑ ni ,OUT hs ,i (T )
0 0
(Equation IV.2.1)

Assuming the specific enthalpy as a first order function, depending only on the
temperature, the Equation IV.2.2 is obtained:
hs ,i (T ) = aiTad + bi (Equation IV.2.2)

Consequently, the adiabatic combustion temperature assumes the shape as the Equation
IV.2.3:
i i

∑ ni , IN ∆h 0f ,i (Tref ) − ∑ bi ni ,OUT
0 0
Tad = i
(Equation IV.2.3)
∑a n
0
i i ,OUT

The adiabatic combustion temperatures for each case are shown in Table 15 as well the
temperatures obtained from inside the reactor.

34
 Table 15: Comparison between the temperatures inside the reactor and the adiabatic
temperatures obtained from Hess’s Law
NG 7 L/min NG 8 L/min NG 9 L/min NG 10 L/min NG 11 L/min

Lambda Ad T (°C) T R (°C) Ad T (°C) T R (°C) Ad T (°C) T R (°C) Ad T (°C) T R (°C) Ad T (°C) T R (°C)

0,07 585,2 558,6 571,7 604,1 551,1 606,8 549,0 613,5 544,3 613,7

0,08 618,9 627,9 581,2 638,8 569,4 638,8 563,7 645,8 551,7 644,0

0,09 621,5 654,6 600,1 661,0 592,7 664,4 573,8 672,4 557,3 670,7

0,10 651,1 682,5 613,0 685,2 603,1 691,2 585,2 697,3 570,8 695,9

0,11 664,2 719,4 629,6 714,2 618,8 722,0 610,6 726,5 584,9 724,1

0,12 687,7 760,9 675,7 753,3 640,5 759,7 628,9 762,1 607,7 753,2

0,13 726,6 811,0 701,3 803,0 662,0 803,4 651,1 804,7 633,6 784,2

As is possible to observe, the adiabatic combustion temperatures are anyway lower than
what were obtained on the experiments. The values are similar comparing with those which
were already been calculated, showing that the previously model is also a good assumption
for our case.

2.2. Analysis of Stack Simulator Anode off-Gas using Aspen

The outlet compositions and the adiabatic combustion temperature inside the reactor
were simulated by using the RGIBBS reactor modules in Aspen, a market-leading process
modelling tool for conceptual design of chemical processes, in order to compare the
composition of the Stack Simulator Anode Off-Gas with the equilibrium, since the reverse
water shift reaction and methanation follow the Gibbs equilibrium. The Gibbs reactor works
by finding the equilibrium state with the lowest Gibbs free energy without any specific
catalyst. It appears to be akin to finding all the possible equilibrium reactions and allowing
them all to equilibrate. This model could be used since was necessary just to know reaction
stoichiometry and the inlet composition. Analyses just were made with the extremes
conditions as is shown in Table 16.

35
 Table 16: Anode Off-Gas Composition Simulation using RGIBBS
Aspen Results Experimental

Lambda Lambda

0,07 0,13 0,07 0,13

CH4 5,9% 0,5% 4,8% 1,0%

H2 58,1% 53,7% 57,6% 54,2%

Natural Gas
CO 11,6% 13,9% 9,4% 11,5%
7 L/min
CO2 9,6% 7,7% 11,1% 9,3%

Ad T (°C) 625,7 709,7 585,2 726,6

CH4 5,4% 1,6% 4,8% 1,0%

H2 57,8% 55,3% 57,6% 54,2%

Natural Gas
CO 11,7% 13,2% 9,4% 11,5%
11 L/min
CO2 9,5% 8,3% 11,1% 9,3%

Ad T (°C) 628,8 671,3 544,3 633,6

The outlet composition given by RGIBBS was similar comparing with the outlet from
the experiments, except the carbon monoxide and dioxide content. This difference might be
related to the fact that the simulator does not consider the existence of the catalyst, which is
mostly selective to methane and hydrogen conversion.
The adiabatic combustion temperature was in the same behaviour of prior models.
Therewith, definitely, the high temperatures obtained on the experiments were owed to hot
spots on the reactor. Due to minimize this undesirable effect, alumina spheres were added to
the mixer chamber on a mood to increase the homogeneity of the input gas with air.
After this parameter was changed, some more tests were tried to be running. But, the
temperature inside of the mixer chamber increased rapidly, meaning that the gases were
having reaction with alumina spheres before of the catalyst bed. Because of that, it was
necessary to change the material of the tube that fed the reformate gas to the mixing chamber
from plastic to steel, due to security.
The reaction with alumina spheres is not a normal effect, one of the reasons should be
that the alumina spheres might be not 100% pure, and contain some minimal percentage of
any oxidant material, which is enough to start a combustion. Another reason could be that the
reformate reacts with air homogeneously, what is less acceptable.

36
 In order to take advantage of this phenomenon and also to try to reduce the undesirable
reactions, reverse water gas shift reaction and methanation, the reactor fixed bed was full
filled with the same alumina spheres and just a layer of more or last 5 cm of catalyst
corresponding to 100 g was loaded upper alumina spheres surface.

3. Evaluation of different gas natural loads with alumina spheres in the fixed bed.
The manner how the experiments were carried out was the same as before, apart of the
alumina spheres in the reactor fixed bed.
To evaluate if these experiments are significant front the first case with the fixed bed
full filled with catalyst, a graphic, shown in the Figure 18, was build to compare the LHV
given by each case, as this is the main goal of the work, and the maximum temperatures
reached, since this is the limitation as mentioned before.
Moreover, the load of 7 L/min natural gas was chosen to make this comparison and to
represent the performance of the whole experiments since the behaviour of the plant is quite
similar and constant, as could be observed in the Figure 17.

7L/min Natural Gas

10,0 900

9,0
800 Temperature (°C)

8,0
LHV (MJ/m3)

700
7,0
600
6,0

500
5,0

4,0 400
0,07 0,08 0,09 0,10 0,11 0,12 0,13
Lambda

LHV Full catalyst loading LHV 5 cm catalyst + Al2O3-spheres

Temp Full catalyst loading Temp 5cm catalyst + Al2O3-spheres

Figure 18: Comparison of temperature and LHV between the both cases

Comparing the values of temperature and LHV obtained in the Figure 18 above, one can
conclude that the experiments with the alumina spheres inside of the fixed bed is highly
relevant. Which had shown to have better results, as lower temperature inside the reactor and
a LHV closer to 5 MJ/m3. This means that the effect of unwanted reactions was slightly
reduced and also that this is an alternative to move the equilibrium of the reaction in favour of

37
the combustions. Besides, this result could be seen as an advantage, thus the catalyst is made
from a noble metal and its cost is around €1000 per liter, resulting in a potential economy.

4. Extrapolations results
Since the experiments with the alumina spheres inside the reactor fixed bed showed to
have a behaviour closer to the desired, extrapolations with results of these experiments were
made trying to assess the performance of the system, if it could have been used the necessary
amount of air to reach the value of lambda equal to 0,27. What is shown in Figure 19.
If the trend continues the same, which is very likely, since the system reproduces results
whether working with partial or full load, it can be concluded from the extrapolations that
already with a lambda of 0,21, the goal of a LHV equal to 5 MJ/m3 could be achieved.
However, the temperature inside the reactor would exceed the limit of deactivation
temperature from the catalyst FC-HC35B. To choose another catalyst, which operates at
temperatures above to 1000°C would be an alternative. Or, as the gases and air are reacting
with the alumina spheres, another option would be simply to remove the 5 cm catalyst layer
that still tied the fixed bed.

7L/min Natural Gas

10,0 1600

9,0 1400
Temperature (°C)

8,0 1200
LHV (MJ/m3)

7,0 1000

6,0 800

5,0 600

4,0 400
0,07 0,09 0,11 0,13 0,15 0,17 0,19 0,21 0,23 0,25 0,27

Lambda

LHV 5 cm catalyst + Al2O3-spheres Temp 5cm catalyst + Al2O3-spheres

Figure 19: Extrapolation of the LHV and Temperature to a lambda 0,27.

The amount of the air supplied to the reformer that should be 20 L/min for the system to
work with full load would be another parameter possible to be evaluated by the

38
extrapolations. For that, in Figure 20, it is only extrapolated the results given by the lambdas
0,07 and 0,11, which are just intermediate values but can well represent the others.

9,00
5 cm catalyst + Al2O3-Spheres 900

8,50
850

8,00
800

7,50

Temperature (°C)
750
LHV (MJ/m3)

7,00
700
6,50

650
6,00

Lambda = 0,07 600

5,50
Lambda = 0,11
lambda = 0,07
5,00 550
lambda = 0,11

4,50 500
0 2 4 6 8 10 12 14 16 18 20 22
Natural Gas (L/min)

Figure 20: Extrapolation of LHV and Temperatures to a natural gas flow of 20 L/min

Extrapolating the results to a natural gas flow of 20 L/min, one can see that there is a
trend. The LHV decreases while the temperature rises. In this graphic, it can be observed that
already with a lambda of 0,07, if the plant could be operated with 20 L/min of natural gas, the
LHV would be much smaller value, in the magnitude of 7 MJ/m3, and with a lambda of 0,11
it would already correspond to a value in the magnitude 6 MJ/m3. What can me assessed as a
positive result.
This graphic also confirms the results obtained in Figure 19, as with this trend, a lambda
of 0,21 could already be enough to reach the desired value of LHV, nevertheless the
temperature is still a restriction.

39
V CONCLUSIONS

The Stack Simulator, consisted by an insulated reactor and two heat exchangers,
showed up to be an excellent equipment to test the whole plant, no more the reformer module
stand-alone.
From the experimental tests could be concluded:

The reactor had a regular performance since it was designed to receive a bigger
amount of gas flow. Moreover it could operate in safe conditions, without leaks,
and its surface after the insulation was not warmer than 50°C. Therewith it could
be concluded that the Stack Simulator was well design.

A pre-heating of the e reactor until at least 100°C was so necessary, since the
condenser was not efficient enough to condense and separate the saturated water
from the inlet reformate.

It was necessary to do some adjustments, as change the material of the tube that
feed the reformate gas to the mixing chamber from plastic to steel, due to
security since once was reached high temperatures.

Both heat exchangers worked perfectly.

It could be observed that somehow the reformate gas reacted with the alumina
spheres inside of the mixing chamber. Thus the catalyst has been replaced by
these. Resulting in a presumable economy.

The results of the experiment with alumina spheres inside of the reactor fixed
bed showed up to have a better performance, because it could be possible to
minimise the effects of the unwanted reactions and also to move the equilibrium
in favour of the combustion.

It was not possible to reach the desired LHV of 5,06 MJ/m3 since the
temperatures inside of the reactor were too high.

The reformate gas that was fed in the Stack Simulator had a CO content higher
than expected owing to the preferential oxidation reactor was not working
properly, therefore a high content of CO was obtained also on the Stack
Simulator Anode Off-Gas.

Undesirable reactions, as methanation and reverse shift reaction took place on
the bottom of the reactor, due to the low temperatures in this extent.

40
VI DIRECTIONS FOR FUTURE WORK

It is important to emphasize that there are still some improvements to make both in the
Stack Simulator, in the reformate inlet stream such as in the Inhouse system.
Some advices are given:

Test the Stack Simulator separately from the other equipments, feeding synthetic
gases from the bottles, as was done in preliminary test, so without CO content
due to evaluate the effect of the reaction with the alumina spheres.

Automating the process with micro-controls using files taken from the Inhouse
system and also from the Stack Simulator in according to have safe reactions
with air in high temperatures.

The preferential oxidation reactor needs too be operated properly within the CO
content on the reformate meets the requirement of being less than 10ppm.

It is necessary to define the right composition of the anode off-gas, after that
split the stream as the gases are quite diluted in nitrogen, so finally it can be fed
to the burner. Therefore is possible to operate the plant as a whole, enhancing the
overall efficiency of the Inhouse system.

41
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CERBE, G. Grundlagen der Gastechnik: vollständige neu arbeitete auflagen. 7th ed. Wien.
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CHOUDHURY, S. R.; DESHMUKH, M. B.; RENGASWAMY, R. A two- dimensional

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HAYES, R.E., KOLACZKOWSKI, S.T. Introduction to Catalytic Combustion. 1st Ed.

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TICIANELLI, E. A; GONZALEZ, E. R. Eletroquímica; EDUSP, 1ª Edição, 1998.

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43
 Appendix A1:
CALCULUS SEQUENCE OF MASS BALANCES

1. Reich – Reaction Mass Balance:

Process Gas inlet stream: v& PG = 20 L/min

Cm H 2 n + d H 2O 
→ l CO2 + k CH 4
2m − n d
d= l= k = m−l
2 2

Water Demand to convert hydrocarbons in methane and carbon dioxide is calculated by

the equation 1.1:

v& H 2O , Sum , IN = ( 1 v& PG * y C2 H 6 ) + (v& PG * y C3 H 8 ) + ( 3 v& PG * y C4 H10 ) + (2v& PG * y C5 H12 ) (1.1)

2 2

Methane production is calculated by the equation 1.2:

v&CH 4 , Sum ,OUT = ( 7 v& PG * y C2 H 6 ) + ( 5 v& PG * y C3 H 8 ) + (13 v& PG * y C4 H10 ) + (4v& PG * y C5 H12 ) (1.2)
2 2 4

Carbon Dioxide production is calculated by the equation 1.3:

v&CO2 Sum ,OUT = ( 1 v& PG * y C2 H 6 ) + ( 1 v& PG * y C3 H 8 ) + ( 1 v& PG * y C4 H10 ) + (v& PG * y C5 H12 ) (1.3)
4 2 3

Outlet Gas Composition is calculated by the following group of equations numbered

from 1.4 to 1.7:
CH4:
RR
v&CH
RR
v&CH = y CH 4 * v& PG + v&CH 4 Sum ,OUT RR
y CH = 4
RR
(1.4)
4 4
v& Sum ,OUT
CO2:
RR
v&CO
RR
v&CO = y CO2 * v& PG + v&CH 4 Sum ,OUT RR
y CO = 2
RR
(1.5)
2 2
v& Sum ,OUT
N2:
v& NRR2
v& NRR2 = y N 2 * v& PG y NRR2 = RR
(1.6)
v& Sum ,OUT

Total flow:

RR
v& Sum & RR & RR & RR
,OUT = vCH 4 + vCO2 + v N 2 (1.7)
 2. Steam Reforming Mass Balance:

CH 4 + H 2O → CO + 3H 2

R
Methane conversion, X CH 4 , in the reformer is 95%
The Steam-Carbon Ratio used in the project is: S / C = 4. It is an important parameter
affecting the performance of the reformer. The Inhouse reformer is operated with a high S/C
ratio of 4.0 to 4.5. This S/C ratio is maintained to prevent carbon deposition on the catalyst,
shift conversion of carbon monoxide and reduce carburisation damage to the tube material.

Outlet Gas Composition is calculated by the following group of equations numbered

from 2.1 to 2.6:
CH4:
R
v& R RR
= v&CH * (1 − X CH 4 ) R v&CH R
R
y CH 4 (2.1)
CH 4 4 y CH = 4
y CH 4 ,D
=
4 R
v& Sum ,OUT (1 − y HR 2O )
H2O:
R v& HR 2O
v& HR 2O = v& PG * S / C − v&CH
R
* yCH 4 * X CH
R y H 2O = R
4 4 v& Sum ,OUT (2.2)
CO:
R R
v&CO y CO (2.3)
R
v&CO RR
= v&CH * yCH 4 R
y CO = R
yCO ,D =
4 R
v& Sum ,OUT (1 − y HR 2O )
H2 :
v& HR 2 y HR 2
v& HR 2 = v&CH
RR
* yCH 4 * 3 y HR 2 = y R
H 2 ,D = (2.4)
4 R
v& Sum ,OUT (1 − y HR 2 O )
N2:

v& NR2 = v& NRR2 (2.5)

Total flow:
R R
v& Sum,OUT = v&CH 4
+ v& HR 2O + v&CO
R
+ v& HR 2 + v& NR2 (2.6)

3. Water Gas Shift Reaction (Part 1 CO Removal) Mass Balance:

CO + H 2O → CO2 + H 2

SR
Based on the fact that the CO residue after Shift reaction, y CO , should be no more than
SR
1% of CO, the conversion to CO, X CO , must be 93%
 The CO Conversion is calculated by the equation 3.1:

SR
R
yCO − 1%
X CO = R
y CO (3.1)
Outlet Gas Composition is calculated by the following group of equations numbered
from 3.2 to 3.8:
CH4:
SR
v&CH SR
y CH
SR
v&CH R
= v&CH SR
y CH = 4 SR
y CH = 4 (3.2)
4 ,D
4 4 4
v& SR
Sum,OUT (1 − y HSR2O )
CO2:
SR R SR SR
yCO = yCO − yCO y CO
(3.3)
SR
v&CO SR
= yCO * v& Sum
SR
,OUT
2
SR
y CO 2 ,D
= 2
2 2
(1 − y HSR2O )
CO:
SR
yCO (3.4)
SR
v&CO SR
= yCO * v& Sum
SR
,OUT
SR
y CO ,D =
(1 − y HSR2O )
H2O:

y HSR2O = y HR 2O − yCO
R
(3.5)
v& HSR2O = y HSR2O * v&Sum
SR
,OUT
2

H2:
y HSR2 = y HR 2 + yCO
SR
y HSR2
v& HSR2 = y HRS2 * v& Sum
SR
,OUT
2 y HSR2 , D = (3.6)
(1 − y HSR2 O )
N2:

v& NSR2 = v& NR2 (3.7)

Total flow:
SR
v& Sum & SR & SR & SR & SR & SR & SR
,OUT = vCH 4 + vCO2 + v H 2 O + vCO + v H 2 + v N 2
(3.8)

4. Preferential Oxidation (Part 2 CO Removal) Mass Balance:

CO + 0,5O2 → CO2

Based on 1% of CO residue after the shift reaction, the excess air rate must be 3. In this
case, all the CO content is converted.

Oxygen Demand to convert all CO in CO2 is calculated by the equation 4.1:

v&OPO2 , Dem = yCO

SR
* v& Sum
SR
,OUT * 0,5
(4.1)
 Oxygen input is calculated by the equation 4.2:

v&OPO2 , IN = v&OPO2 , Dem *3 (4.2)

Air input is calculated by the equation 4.3:

v&O2 , IN
PO
v& Air , IN = (4.3)
0,21

Nitrogen input is calculated by the equation 4.4:

v& NPO2 , IN = v& Air

PO
, IN * 0,79
(4.4)

Outlet Gas Composition is calculated by the following group of equations numbered

from 4.5 to 4.11:
CH4:
PO
v&CH PO
y CH
PO
v&CH SR
= v&CH PO
y CH = 4 PO
yCH = 4 (4.5)
4 ,D
4 4 4
v& PO
Sum ,OUT (1 − y HPO2O )
H2:
v& HPO2 y HPO2
v& HPO2 = v& HSR2 − (v&OPO2 , IN − v&OPO2 , Dem ) * 2 y HPO2 = y HPO2 , D = (4.6)
v& PO
Sum ,OUT (1 − y HPO2O )
H2O:

v& HPO2O
v& PO
H 2O = v& SR
H 2O + (v& PO
O2 , IN − v& PO
O2 , Dem )*2 y PO
H 2O = PO
(4.7)
v& Sum ,OUT
CO2:
PO PO
v&CO y CO
PO
v&CO SR
= v&CO SR
+ v&CO PO
y CO = 2 PO
y CO = 2 (4.8)
2 ,D
2 2 2 PO
v& Sum ,OUT (1 − y HPO2O )
CO:
v& PO
CO =0 (4.9)
N2:
v& NPO2 y NPO2
v& NPO2 = v& NSR2 + v& NPO2 , IN y NPO2 = y NPO2 , D = (4.10)
v& PO
Sum,OUT (1 − y HPO2O )

Total flow:
PO
v& Sum & PO & PO & PO & PO & PO & PO
,OUT = vCH 4 + vCO2 + v H 2 O + vCO + v H 2 + v N 2
(4.11)

5. Fuel Cell Stack Mass Balance:

The only reaction that takes place on the fuel cell stack is the partial oxidation of
hydrogen, which produces only water.

H 2 + 0,5O2 → H 2O
 The excess air that is blown through the cathode is not only to maintain the
electrochemical reaction at the cathode but also to cool the stack and to remove the water
produced by the electrochemical reaction as well. Therefore, the excess air rate use in the
project is 2,5 and consequently the hydrogen conversion, X HFC , is 75%
2

Oxygen Demand to meet the partial combustion is calculated by the equation 5.1:

v&OFC2 , Dem = X HFC2 * v& HPO2 * 0,5 (5.1)

Oxygen input is calculated by the equation 5.2:

v&OFC2 , IN = v&OFC2 , Dem * 2,5 (5.2)

Air input is calculated by the equation 5.3:

v&OFC2 , IN
FC
v& Air , IN = (5.3)
0,21

Nitrogen input is calculated by the equation 5.4:

v& NFC2 , IN = v& Air

FC
, IN *0,79 (5.4)

Outlet Gas Composition (Fuel Cell Anode Off-Gas) is calculated by the following group
of equations numbered from 5.5 to 5.11:
CH4:
FC
v&CH FC
y CH
FC
v&CH PO
= v&CH FC
y CH = 4 FC
yCH = 4 (5.5)
4 ,D
4 4 4
v& FC
Sum,Off − Gas (1 − y HFC2O )
H2 :
v& HFC2 y HFC2
v& FC
= v& PO
− (v& PO
*X FC
) y FC
= y HFC2 , D = (5.6)
H2 H2 H2 H2 H2
v& FC
Sum,Off − Gas (1 − y HFC2O )
H2O:
v& HFC2O
v& HFC2O = v& HPO2O y HFC2O = FC
(5.7)
v& Sum ,Off −Gas
CO2:
FC FC
v&CO y CO
FC
v&CO PO
= v&CO FC
y CO = 2 FC
y CO = 2 (5.8)
2 ,D
2 2 2 FC
v& Sum ,Off − Gas (1 − y HFC2O )

CO:
v& FC
CO =0 (5.9)
 N2:
v& NFC2 y NFC2
v& NFC2 = v& NPO2 y NFC2 = y NFC2 , D = (5.10)
FC
v& Sum ,Off − Gas (1 − y HFC2O )

Total flow:
FC
v&Sum & FC & FC & FC & FC & FC & FC
,Off −Gas = vCH 4 + vCO2 + vH 2O + vCO + vH 2 + vN 2
(5.11)

6. Stack Simulator Mass Balance

6.1. Amount of Air Input
Oxygen Demand to meet the partial combustion is calculated by the equation 6.1:

v&OSS2 , Dem = v& HPO2 * 0,5 + v&CH

PO
*2 (6.1)
4

Oxygen Consumed is calculated by the equation 6.2:

v&OSS2 , Cons = v&OSS2 , Dem *λ (6.2)

Hydrogen Consumed is calculated by the equation 6.3:

v&OSS2 , Cons −v&CH
SS
, *2
v& HSS2 , Cons = 4 Cons
(6.3)
0,5

Methane Consumed is calculated by the equation 6.4:

v&OSS2 , Cons −v& HSS2 , Cons *0,5
SS
v&CH , = (6.4)
4 Cons 2

Air Input is calculated by the equation 6.5:

v&OSS2 , Cons
SS
v& Air , IN = (6.5)
0,21

Nitrogen Input is calculated by the equation 6.6:

v& NSS2 = v& Air
SS
, IN *0,79 (6.6)

Water Production is calculated by the equation 6.7:

v& HSS2O ,Pr od = v& HSS2 ,Cons + v&CH
SS
4 ,Cons
*2 (6.7)
 6.2. Outlet Gas Composition
Outlet Gas Composition (Stack Simulator Anode Off-Gas) is calculated by the
following group of equations numbered from 6.8 to 6.14:
CH4:
SS
v&CH SS
y CH
SS
v&CH PO
= v&CH SS
− v&CH y SS
= 4 SS
yCH = 4 (6.8)
4 ,Cons 4 ,D
4 4 CH 4
v& SS
Sum,Off − Gas (1 − y HSS2O )
H2 :
v& HSS2 y HSS2
v& HSS2 = v& HPO2 − v& HSS2 ,Cons y HSS2 = y HSS2 , D = (6.9)
v& SS
Sum,Off − Gas (1 − y HSS2O )
H2O:
v& HSS2O
v& HSS2O = v& HPO2O + v& HSS2O ,Pr od y HSS2O = SS
(6.10)
v& Sum ,Off −Gas

CO2:
SS SS
v&CO y CO
SS
v&CO PO
= v&CO SS
+ v&CH SS
y CO = 2 SS
y CO = 2 (6.11)
4 ,Cons 2 ,D
2 2 2 SS
v& Sum ,Off − Gas (1 − y HSS2O )

CO:
v& SS
CO =0 (6.12)

N2:
v& NSS2 y NSS2
v& SS
= v& PO
+ v& SS
N 2 , IN y SS
= y SS
N2 ,D = (6.13)
N2 N2 N2 SS
v& Sum ,Off − Gas (1 − y HSS2O )

Total flow:
SS
v& Sum & SS & SS & SS & SS & SS & SS
,Off −Gas = vCH 4 + vCO2 + v H 2O + vCO + v H 2 + v N 2
(6.14)

7. Preparation for catalytic preliminary testing

7.1. Inlet Gas Composition and Condition:
Inlet Composition is calculated by the following group of equations numbered from 7.1
to 7.3:
CH4:
ρ CH
CT
v&CH 4
PO
= y CH 4 ,D
* v&0 CT
nCH 4 = v&CH 4
* 4
xCH 4 = nCH 4 * N pCH 4 = xCH 4 * P (7.1)
M CH 4
 H2:
ρH
v& HCT2 = y HPO2 , D * v&0 n H 2 = v& HCT2 * 2
x H 2 = nH 2 * N pH4 = xH 2 * P (7.2)
M H2

CO2:
ρ CO
CT
v&CO 2
PO
= y CO2 ,D
* v&0 CT
nCO2 = v&CO 2
* 2
xCO2 = nCO2 * N pCO2 = xCO2 * P (7.3)
M CO2

7.2. Water demand:

Water demand is calculated by the equation 7.6

PH 2O , Sat = p H 2O (7.4)

p H 2O (nCH 4 + n H 2 + nCO2 ) * x H 2O
x H 2O = n H 2O = (7.5)
P 1 − x H 2O

n H 2O * M H 2O
v& HCT2O = (7.6)
ρH O2
 Appendix A2:
EMPIRICAL FORMULAS TO GET THE ANODE OFF-GAS PHYSICAL PROTPERTIES

1. Off-Gas Viscosity
The viscosity of the anode off-gas was approximated by the Equation 1.1 and 1.2 below:
n
yi µ i
µG = ∑ n
(1.1)
i =1
∑y φ
j =1
j ij

2
 1 1

2 
1 +  µi   M j  4


  µ j   M i  
φij =   (1.2)
1
  Mi  2

81 + M 
  j 

2. Off-Gas Density
The density of the anode off-gas was approximated by the equation 2.1 below:
n
ρ G = ∑ yi ρ i (2.1)
i =1

3. Off-Gas conduction heat transfer coefficient

The conduction heat transfer coefficient of the anode off-gas was approximated by the
equation 3.1 below:
 
 
1 n 1 
k G = ∑ yi k i + n (3.1)
2  i =1 yi 
 ∑i =1 ki

 

4. Off-Gas specific heat capacity

The specific heat capacity of the anode off-gas was approximated by the equation 4.1
below:
n
cpG = ∑ yi cpi (4.1)
i =1
 Appendix B1:
OBTAINED RESULTS OF THE EXPERIMENTS WITH CATALYST ON THE
CATALYST BED
Natural Gas 7L/min
"Anode Off-Gas" Composition
Air (L/min) CH4 H2 CO CO
6 6,4% 57,1% 8,2% 11,8%
7 5,4% 56,1% 8,6% 11,4%
8 3,9% 55,9% 9,6% 10,8%
9 3,1% 55,0% 9,8% 10,6%
10 2,0% 54,4% 10,4% 10,2%
11 1,4% 53,6% 10,8% 9,8%
12 0,9% 52,3% 11,0% 9,6%
6 5,9% 58,1% 11,6% 9,6%
12 0,5% 53,7% 13,9% 7,7%

Air (L/min) TR average (°C) TP average (°C) Adiabatic T (°C) LHV (MJ/m3)
6 558,61 455,77 585,2 9,50
7 627,91 550,66 618,9 9,08
8 654,60 559,25 621,5 8,63
9 682,53 572,02 651,1 8,27
10 719,42 587,72 664,2 7,91
11 760,90 603,50 687,7 7,63
12 811,03 619,46 726,6 7,36
6 625,7
12 709,7
* Aspen Results

Natural Gas 8L/min

"Anode Off-Gas" Composition
Air (L/min) CH4 H2 CO CO2
7 6,1% 57,1% 8,8% 11,3%
8 4,9% 56,7% 9,5% 10,8%
9 3,6% 56,1% 9,9% 10,5%
10 2,8% 55,6% 10,4% 10,1%
11 2,0% 55,1% 10,8% 9,9%
12 1,3% 54,2% 11,1% 9,5%
13 0,8% 53,3% 11,5% 9,2%

Air (L/min) TR average (°C) TP average (°C) Adiabatic T (°C) LHV (MJ/m3)
7 604,11 527,02 571,7 9,44
8 638,79 556,85 581,2 9,07
9 661,01 571,98 600,1 8,61
10 685,15 582,85 613,0 8,30
11 714,15 596,01 629,6 8,03
12 753,32 608,95 675,7 7,72
13 803,05 626,90 701,3 7,49
Natural Gas 9L/min
"Anode Off-Gas" Composition
Air (L/min) CH4 H2 CO CO2
8 5,3% 57,5% 9,4% 11,0%
9 4,3% 57,0% 9,7% 10,7%
10 3,7% 56,2% 10,1% 10,4%
11 2,6% 55,7% 10,5% 10,1%
12 1,9% 55,2% 10,8% 9,9%
13 1,3% 54,4% 11,1% 9,6%
14 0,9% 53,5% 11,5% 9,2%

Air (L/min) TR average (°C) TP average (°C) Adiabatic T (°C) LHV (MJ/m3)
8 606,81 518,42 551,1 9,28
9 638,83 560,57 569,4 8,92
10 664,43 570,20 592,7 8,65
11 691,24 579,83 603,1 8,28
12 721,97 591,81 618,8 8,00
13 759,70 603,71 640,5 7,74
14 803,40 618,49 662,0 7,53

Natural Gas 10L/min

"Anode Off-Gas" Composition
Air (L/min) CH4 H2 CO CO2
9 4,3% 57,2% 9,7% 11,2%
10 3,9% 56,9% 10,0% 10,6%
11 3,1% 56,4% 10,4% 10,2%
12 2,3% 56,0% 10,8% 10,0%
13 1,8% 55,2% 10,9% 9,8%
14 1,2% 54,5% 11,2% 9,6%
15 0,8% 53,6% 11,5% 9,3%

Air (L/min) TR average (°C) TP average (°C) Adiabatic T (°C) LHV (MJ/m3)
9 613,46 507,35 549,0 8,94
10 645,77 561,58 563,7 8,80
11 672,45 577,71 573,8 8,50
12 697,31 588,44 585,2 8,22
13 726,48 599,63 610,6 7,96
14 762,08 610,04 628,9 7,74
15 804,67 627,39 651,1 7,54
Natural Gas 11L/min
"Anode Off-Gas" Composition
Air (L/min) CH4 H2 CO CO2
10 4,8% 57,6% 9,4% 11,1%
11 3,7% 57,4% 10,2% 10,5%
12 3,0% 56,9% 10,6% 10,2%
13 2,3% 56,3% 11,0% 9,9%
14 1,7% 55,7% 11,3% 9,6%
15 1,3% 55,0% 11,4% 9,4%
16 1,0% 54,2% 11,5% 9,3%
10 5,4% 57,8% 11,7% 9,5%
16 1,6% 55,3% 13,2% 8,3%

Air (L/min) TR average (°C) TP average (°C) Adiabatic T (°C) LHV (MJ/m3)
10 613,73 533,11 544,34 9,12
11 644,04 574,21 551,74 8,82
12 670,67 586,87 557,29 8,54
13 695,93 597,85 570,85 8,29
14 724,09 608,36 584,88 8,05
15 753,15 618,19 607,69 7,85
16 784,19 628,20 633,59 7,66
10 628,79
16 671,32
* Aspen Results
 Appendix B2:
OBTAINED RESULTS OF THE EXPERIMENTS WITH SPHERES IN THE CATALYST
BED
Natural Gas 7L/min
"Anode Off-Gas" Composition
Air (L/min) CH4 H2 CO CO2
6 4,1% 58,1% 7,0% 13,0%
7 3,9% 55,3% 8,4% 11,5%
8 3,1% 54,3% 9,3% 10,8%
9 2,3% 53,4% 9,8% 10,3%
10 1,5% 52,3% 10,5% 9,7%
11 1,0% 51,4% 10,9% 9,3%
12 0,6% 50,2% 11,3% 8,9%
6 6,8% 57,5% 10,9% 9,8%
12 0,9% 53,8% 13,3% 8,0%

Air (L/min) TR average (°C) TP average (°C) Adiabatic T (°C) LHV (MJ/m3)
6 522,07 429,43 595,53 8,61
7 591,29 459,93 642,59 8,41
8 635,39 482,62 659,63 8,13
9 666,85 497,68 680,81 7,83
10 701,13 515,60 701,42 7,51
11 742,42 534,77 726,01 7,27
12 788,70 554,77 756,04 7,07
6 617,83
12 687,08
* Aspen Results

Natural Gas 8L/min

"Anode Off-Gas" Composition
Air (L/min) CH4 H2 CO CO2
7 4,0% 57,2% 7,6% 12,6%
8 3,6% 55,4% 8,7% 11,5%
9 3,0% 54,1% 9,7% 10,7%
10 2,2% 53,3% 10,3% 10,2%
11 1,5% 52,5% 10,8% 9,7%
12 1,1% 51,6% 11,2% 9,4%
13 0,7% 50,3% 11,4% 9,1%

Air (L/min) TR average (°C) TP average (°C) Adiabatic T (°C) LHV (MJ/m3)
7 541,98 392,90 602,83 8,57
8 600,40 467,19 630,74 8,35
9 647,79 491,62 650,69 8,14
10 676,82 508,94 664,63 7,83
11 701,38 526,48 681,92 7,57
12 726,49 542,95 705,31 7,37
13 740,90 560,53 743,09 7,13
Natural Gas 9L/min
"Anode Off-Gas" Composition
Air (L/min) CH4 H2 CO CO2
8 3,2% 57,6% 7,7% 12,6%
9 3,0% 55,8% 8,7% 11,7%
10 2,5% 54,4% 9,6% 10,8%
11 2,0% 53,5% 10,2% 10,3%
12 1,5% 52,6% 10,7% 9,9%
13 1,0% 51,6% 11,1% 9,4%
14 0,7% 50,5% 11,6% 9,0%

Air (L/min) TR average (°C) TP average (°C) Adiabatic T (°C) LHV (MJ/m3)
8 545,84 331,06 590,40 8,33
9 593,18 462,82 621,75 8,19
10 638,18 495,72 642,55 7,98
11 665,68 521,38 659,40 7,77
12 697,04 535,96 677,24 7,54
13 733,55 554,11 699,09 7,34
14 768,15 575,14 723,81 7,17

Natural Gas 10L/min

"Anode Off-Gas" Composition
Air (L/min) CH4 H2 CO CO2
9 3,0% 57,2% 8,1% 12,4%
10 2,6% 56,0% 8,8% 11,7%
11 2,3% 54,6% 9,6% 10,9%
12 1,9% 53,7% 10,2% 10,4%
13 1,4% 52,7% 10,7% 9,9%
14 1,0% 51,7% 11,2% 9,4%
15 0,7% 50,7% 11,6% 8,9%

Air (L/min) TR average (°C) TP average (°C) Adiabatic T (°C) LHV (MJ/m3)
9 548,67 491,28 590,43 8,27
10 598,89 500,42 611,61 8,08
11 635,74 519,59 634,63 7,92
12 668,88 532,91 650,76 7,74
13 699,71 548,49 669,10 7,53
14 727,46 563,48 689,48 7,35
15 763,84 589,27 709,53 7,20
Natural Gas 11L/min
"Anode Off-Gas" Composition
Air (L/min) CH4 H2 CO CO2
10 3,1% 60,7% 8,3% 12,4%
11 2,8% 59,2% 9,3% 11,4%
12 2,4% 58,1% 10,1% 10,7%
13 1,9% 57,1% 10,8% 10,1%
14 1,5% 56,3% 11,4% 9,6%
15 1,1% 55,4% 11,8% 9,2%
16 0,8% 54,3% 12,2% 8,8%
10 6,4% 57,4% 11,1% 9,7%
16 2,3% 55,2% 12,6% 8,6%

Air (L/min) TR average (°C) TP average (°C) Adiabatic T (°C) LHV (MJ/m3)
10 571,36 479,65 505,22 8,70
11 615,76 515,03 526,34 8,57
12 651,48 537,51 539,61 8,39
13 679,66 552,11 555,49 8,22
14 705,72 569,43 568,58 8,04
15 737,34 585,48 587,29 7,87
16 767,79 604,70 610,55 7,70
10 620,39
16 657,09
* Aspen Results