processes

Article
Dynamic Modeling and Control of an Integrated
Reformer-Membrane-Fuel Cell System
Pravin P. S., Ravindra D. Gudi * and Sharad Bhartiya *
Department of Chemical Engineering, Indian Institute of Technology Bombay, Mumbai 400076, India;
[email protected]
* Correspondence: [email protected] (R.D.G.); [email protected] (S.B.);
Tel.: +91-(22)-2576-7231 (R.D.G.); +91-(22)-2576-7225 (S.B.)




Received: 30 July 2018; Accepted: 11 September 2018; Published: 17 September 2018


Abstract: Owing to the pollution free nature, higher efficiency and noise free operation, fuel cells
have been identified as ideal energy sources for the future. To avoid direct storage of hydrogen
due to safety considerations, storing hydrocarbon fuel such as methane and suitably reforming
in situ for hydrogen production offers merit for further investigation. Separating the resulting
hydrogen in the reformate using membrane separation can directly feed pure gas to the anode
side of fuel cell for power generation. Despite the numerous works reported in literature on the
dynamic and steady state modeling and analysis of reformers, membrane separation units and fuel
cell systems, there has been limited work on an analysis of the integrated system consisting of all the
three components. This study focuses on the mathematical modeling and analysis of the integrated
reformer, membrane, fuel cell system from first principles in a dynamic framework. A multi loop
control strategy is developed and implemented on the mathematical model of the integrated system
in which appropriate controllers based on the system dynamics are designed to examine and study
the overall closed loop performance to achieve rapidly fluctuating target power demand and rejection
of reformer feed and fuel cell coolant temperature disturbances.

Keywords: auto thermal reformer; palladium membrane hydrogen separation; polymer electrolyte
membrane fuel cell (PEMFC); multi-loop control

1. Introduction
The main focus of emergent hydrogen economy for the last few decades has been on the use of
hydrogen fuel cells for stationary and portable applications. Almost all practical fuel cells available in
the current market use hydrogen or hydrogen-rich hydrocarbons as the fuel [1]. While designing a fuel
cell system, the primary challenge of a systems engineer is to make sure that the desired quantity of
fuel is delivered at the appropriate time. In the case of fuel cells driven by hydrogen, the prevailing
method to deliver hydrogen entails storing of the fuel in appropriately designed high pressure tanks
that can withstand high pressures of the order of 350 to 700 bars [1]. Large volume vessels are generally
needed for hydrogen storage because of its low volumetric energy density [1]. For automotive
applications, while this demanding requirement of large volume might have a lesser impact on heavy
duty vehicles, it can be a crucial issue for light duty vehicles. A key issue for portable applications
is the non-availability of hydrogen fueling infrastructure for refueling purposes. Furthermore,
hydrogen when exposed to air can easily catch fire and can lead to explosion thereby underlining
the high risk of direct hydrogen storage. The need to avoid direct storage of hydrogen triggered the
development of integrated fuel processing system that converts hydrogen rich hydrocarbons directly
to a hydrogen fuel stream. It is well known that hydrogen production by reforming natural gas is an
economically viable alternative since infrastructure for natural gas supply already exists.

Processes 2018, 6, 169; doi:10.3390/pr6090169 www.mdpi.com/journal/processes

Processes 2018, 6, 169 2 of 25

In the current work, an auto thermal reformer that incorporates both endothermic steam reforming
and exothermic partial oxidation is used. Hence, the hydrocarbon fuel viz. natural gas reacts with
oxygen from air and steam over a catalyst in a fixed bed reactor at suitable operating conditions to
obtain appropriate hydrogen yield along with other gases such as CO, CO2 , O2 , unconverted CH4 , H2 O
(steam) and the inert N2 [2]. The advantage of auto thermal reforming over steam reforming include
self-sustained reaction by using the heat generated by the combustion reaction for the prevalent
endothermic reactions. Among the methods for separation of gases at the reformer exit, dense
palladium membrane has been employed in the current work for separation of H2 from mixture of
other gases [3]. Palladium membranes have the advantage of high hydrogen permeability as well as
fast hydrogen absorption and transport kinetics. Another advantage is its excellent thermal stability
at an operating temperature range of 300–850 ◦ C [4]. These behaviors are important from a rapid
dynamic response viewpoint when used in an integrated system. Finally, a low temperature polymer
electrolyte membrane fuel cell (PEMFC) is used for electrical power generation that occurs in response
to the electrochemical reaction of hydrogen and air as source of oxygen.
To overcome the deficiencies of direct hydrogen storage, this work explores the potential of an
integrated natural gas reformer fuel cell system with membrane-based gas separation/purification
using the dynamic models for each. The frequency of start/stop cycles as well as the weight and size
of the integrated system are a few of the vital factors to be considered while designing the power
supply system [5]. While significant works have been carried out on the dynamic behavior of the
individual subsystems viz. reformer, membrane and fuel cell, only a handful of them have directed
their research on integration of these subunits [5,6]. The integration of the downstream fuel cell system
with the upstream fuel processing system poses several challenges from a dynamics and control
viewpoint. Firstly, the response time of a fuel cell is at least an order of magnitude faster than the
fuel processing system (auto thermal reformer). Also, the variation in power demands, depending on
the duty cycle of the electrical load in the application, needs to be adhered by the fuel cell and this
should trigger appropriate decisions at the reformer level. Secondly, due to slow reformer dynamics,
lead-like behavior in control mechanisms could be anticipated. Also, the integrated system needs to
accommodate line-pack associated aspects for hydrogen. Hence, in this work, we focus on examining
the feasibility of the integrated reformer fuel cell system with a membrane separation unit for power
applications. Use of hydrocarbon fuels with solid oxide fuel cell via internal reforming have been
reported [7,8]. In Ref [9], syngas has been used with molten carbonate fuel cell for power generation.
Hydrocarbon as the primary source of hydrogen in PEMFC is challenging since PEMFC cannot tolerate
impurities. The authors in Ref [6] discuss a detailed design and control framework of a bio-ethanol
steam reformer integrated with PEMFC using Aspen HYSYS simulation software. Protection of the
fuel cell stack due to hydrogen/oxygen starvation, higher system efficiency (i.e., maximum ethanol
to hydrogen conversion) were a few of the objectives considered by the authors while designing the
controllers. The authors in Ref [5] investigated and compared high temperature and low temperature
PEMFCs with different fuel processors using glycerol as the fuel. Ref [10] examined the dynamic
electrochemical model of a PEMFC along with a methanol reformer and a power conditioning unit.
This latter work used a simplified transfer function-based fuel cell model and did not discuss the
possibility of integration of the units. Out of the very few works on the integrated reformer fuel cell
system reported in the literature, Ref [11,12] explored the dynamic system interaction using liquid
methanol as the fuel. However the authors did not consider separation of the hydrogen gas exiting
from the reformer output.
The main contribution of this paper is exploring the integrated reformer membrane fuel cell system
for dynamic performance under realistic scenarios. An appropriate control structure is designed based
on four single loop controllers for overall system operation. The integrated system is evaluated for
tracking the target power profile for a representative power application as well as disturbance rejection.
The results show the potential of the integrated system for power generation applications and highlight
the need for auxiliary power supply during cold startup of the reformer.
Processes 2018, 6, 169 3 of 25

The rest of the paper is organized as follows. A brief description of the fuel processing, fuel
purification, power generation subsystems as well as the overall integrated system along with its
mathematical modeling are discussed in the next Section. In Section 3, we present three case studies:
the first being an open loop simulation for start-up of the integrated reformer membrane fuel cell
system. Subsequently, the relative gain array analysis is presented to choose the input-output pairings
for carrying out control relevant studies. The second case study involves the integrated system
used for a generic power application with suitably designed controllers and the final case study
evaluates disturbance rejection by considering uncertainty in both the inlet CH4 feed concentration
to the reformer as well as coolant temperature in fuel cell. This is followed by simulation results and
discussions. Conclusions are presented in Section 4.

2. System Description
To understand the behavior of the integrated reformer membrane fuel cell system as a whole,
detailed dynamic modeling of the individual subsystems is necessary. This will help identify possible
challenges for achieving smooth, demand-driven production and delay-free delivery of hydrogen
fuel [6]. The basic block diagram showing the integrated system is depicted in Figure 1. The input to
the auto thermal reformer consists of appropriate proportion of methane, air and steam thoroughly
mixed and preheated to reforming temperatures during start of the reaction. Once the reactions are
initiated, the preheater can be removed from the loop as the heat liberated by the exothermic reactions
can be further used by the endothermic reactions. The reforming reaction of methane with air and
steam results in products such as H2 , CO and CO2 along with some unreacted CH4 , O2 , N2 and steam.
Two heat exchangers, one at the reformer exit and other at the fuel cell anode inlet side, are used
to maintain the gas temperatures at their target values and is assumed to be under perfect control.
The gas mixture exiting the reformer is then separated to obtain pure hydrogen by using the palladium
membrane based separation unit. The pure hydrogen gas separated from the gas mixtures is then
fed to the control valve 2 inlet through a check valve or non-return valve (NRV). The hydrogen is
then used by the fuel cell to generate power. Four controllers, one to regulate hydrogen flow at the
fuel cell anode inlet side, second to regulate methane flow at the reformer inlet side, third to regulate
the coolant flow at the PEMFC coolant circulation side and fourth to regulate the ratio of air to H2
in PEMFC are implemented to achieve effective operation of the integrated system. The three major
components namely, fuel processing subsystem, fuel purification subsystem and power generation
subsystem are discussed in detail in the subsequent sections.

Figure 1. Block diagram showing the integrated reformer membrane fuel cell system. (NRV: non-return
valve ; PEM: polymer electrolyte membrane)
Processes 2018, 6, 169 4 of 25

2.1. Fuel Processing Subsystem: Auto Thermal Reformer

An auto thermal reformer employing methane as the fuel is chosen as the fuel processing
subsystem in the current study. The upstream part of the reactor is dominated by the highly exothermic
oxidation reaction whereas endothermic steam reforming reactions dominates the downstream part.
A feed stream consisting of steam to carbon molar ratio of 1:1 and oxygen to carbon molar ratio
of 0.45:1 is considered. Many reactions such as steam reforming, water gas shift, total combustion,
partial oxidation, partial combustion, dry reforming, boudouard reaction and decomposition reaction
are likely to occur in an auto thermal reformer [2]. Among this possible set of reactions, only the
dominant reactions with significant rates are considered in this study in order to reduce the complexity
of the mathematical model. Reactions in Equations (1) and (2) represents the steam reforming
reactions while Equations (3) and (4) represents the water gas shift and total combustion reactions
respectively [2].

CH4 + H2 O ↔ CO + 3H2 (1)

CH4 + 2H2 O ↔ CO2 + 4H2 (2)
CO + H2 O ↔ CO2 + H2 (3)
CH4 + 2O2 ↔ CO2 + 2H2 O (4)

Mathematical Model of Auto Thermal Reformer

Auto thermal reforming has been widely studied and experimental validation has been reported
in the literature [2,13–15]. The authors in [13] performed a steady state analysis of hydrogen production
from methane using an auto thermal reformer with a dual catalyst bed configuration, but did not
discuss the dynamic behavior of the system. Extensive experiments were conducted on an in-house
developed auto thermal reformer by the authors in [14] and the experimental results were used to
validate the mathematical model developed. Ref [15] analyzed the steady state modeling aspects of
a miniaturized methanol reformer for fuel cell powered mobile applications but did not study the
dynamic behavior of the system. In this work, a one-dimensional dynamic model of the auto thermal
reformer is selected [2]. Energy and mass balances are applied both in gas and solid phases to obtain
the mathematical model of the reformer. The reformer consists of a cylindrical reactor of 0.2 m in
length and with Nickel as the catalyst having a density of 1870 kg/m3 . Both the gas feed as well as
catalyst temperature is maintained at a value of 542 ◦ C. The reformer operating pressure is chosen
to be 1.5 atm with a Gas Hourly Space Velocity (GHSV) of 3071 h−1 implying a residence time of
1.17 s and a gas mass flow velocity of 0.15 kg/m2 s. The schematic showing the flow diagram of the
modeled region in an auto thermal reformer is shown in Figure 2. The auto thermal reformer model
involves seven main species (CH4 , O2 , CO, CO2 , H2 , H2 O) including one inert component (N2 from
air). For more particulars on the operating conditions, kinetic parameters, constants, kinetic reaction
model and gas properties examined in the model, the reader is referred to Ref [2].

Figure 2. Flow diagram of modeled region in an auto thermal reformer.

While modeling the reformer subsystem, it is assumed that the gas behavior is ideal and the
reforming operation is adiabatic in nature. Thermal dispersion in the axial direction is modeled and
Processes 2018, 6, 169 5 of 25

negligible radial gradients are assumed. Temperature gradient in the catalyst particles is also ignored
assuming the particle size and bed porosity to be uniform.
Mass balance for each species in the gas phase is given by:
∂Ci ∂(uCi ) ∂2 C
eb + + k g,i av (Ci − Ci,s ) = eb Dz 2i (5)
∂t ∂z ∂z
i = CH4 , O2 , CO, CO2 , H2 , H2 O, N2

Mass balance for the solid phase is given by:

k g,i av (Ci − Ci,s ) = (1 − eb )ρcat ri (6)

The first term on the left hand side of Equation (5) represents the mass accumulation term of each
component while the second term indicates convective diffusion. Mass transfer from gas to solid is
represented by the third term and is evaluated using Equation (6). The term on the right hand side of
Equation (5) gives the axial dispersion of components.
Energy balance on the gas phase is given by:
2
∂Tg ∂Tg f ∂ Tg
eb ρ f C pg + uρ f C pg = h f av ( Ts − Tg ) + λz 2 (7)
∂t ∂z ∂z
The first term on the left hand side of Equation (7) represents the heat accumulation term while
the second term indicates convective heat transfer. The first term on the right hand side represents the
heat transfer from gas to solid and the second term indicates the conductive heat transfer.
Energy balance on the solid phase is given by:

∂Ts
ρbed C p,bed + h f av ( Ts − Tg ) =
∂t
ρcat (1 − eb ) ∑ −∆Hrxn,j η j R j (8)

The term on the right hand side of Equation (8) involves the heat of reaction term multiplied by
the catalyst density and packed bed porosity.
The pressure drop across the reformer bed is given by Ergun equation and can be expressed as:
∂Pg
= − K D u − KV u 2 (9)
∂z
Boundary Conditions are as follows:
At the reformer inlet z = 0
Ci = Ci,o ; Tg = Tg,o ; Ts = Ts,o ; Pg = Pg,o (10)
At the reformer exit z = L
∂Ci ∂Tg ∂Ts
= 0; = 0; =0 (11)
∂z ∂z ∂z
Initial conditions are as follows:
Ci = Ci,o ; Tg = Tg,o ; Ts = Ts,o (12)

The reformer model equations Equations (5)–(12) provide a dynamic description of the
concentration of six species taking part in the reforming reaction along with the temperature of
the gas and solid phase.

2.2. Fuel Purification Subsystem: Palladium Based Membrane Separation

Efficient operation of a low temperature PEMFC inevitably demands purified hydrogen gas at the
anode inlet. The efficiency and lifetime of the fuel cell strongly depends on the rate of poisoning of the
Processes 2018, 6, 169 6 of 25

catalyst due to the presence of impurities in the feed. Palladium alloy-based membrane separation is
reported to be an attractive method for the purification of hydrogen gas from mixture of other gases [16].
Another alternative method for hydrogen gas purification is the pressure swing adsorption (PSA) that
works according to the species molecular characteristics and affinity for an adsorbent material [17,18].
However due to size constraints, this method may not be suitable for portable applications and hence
not considered for this particular study. The authors in [19] has developed a mathematical model of the
palladium-based membrane separation for hydrogen gas separation and has experimentally validated
the model. Irrespective of whether the separation is required for portable or stationary applications,
palladium-based membrane separation can be efficiently exploited for the gas purification process.
Palladium membrane has the added advantage of having low permeability for other gases compared
to hydrogen gas which effectively qualifies it for gas separation/purification [3,4].

Mathematical Model of Palladium Membrane Separation

According to Sievert’s law [16], permeation of gas occurs through the palladium membrane based
on the difference in partial pressures of hydrogen at both sides of the membrane. The molar flow rate
of hydrogen permeating through the palladium membrane according to Sievert’s law is given by [16]
!
Amem n n
M H2 ,perm = (1 − θmem ) Pe [CH − CH 2 ,m
]( RTgr )n (13)
Lmem 2

Variable θmem stands for the membrane poisoning caused by the adsorption of CO on the
membrane surface which can partially prevent or obstruct the hydrogen permeation and (1 − θmem )
denotes the fraction of membrane actually available for the hydrogen gas separation. The membrane
permeability Pe is a function of temperature which can be represented by the Arrhenius law as
!
− Ea
Pe = Peo exp (14)
RTgr

where Peo , Ea , R and Tgr represents permeability pre-exponential factor, activation energy for
hydrogen permeability, gas constant and gas temperature at the exit of heat exchanger 1 respectively.
More hydrogen crossover can be facilitated than the predicted behavior by the Sievert’s law due to
the presence of defects in the membrane layers. However, due to this, other gas species can also pass
across the membrane allowing the overall flux to be the sum of hydrogen flux given by Sievert’s law
and the flux of other gases through the defects. This aspect has not been pursued in the present work.

2.3. Power Generation Subsystem: PEMFC

Hydrogen gas exiting from the fuel processing subsystem after undergoing necessary purification
is fed to the anode side of the PEMFC to generate electricity. Using a blower, air from the atmosphere
is fed to the cathode side of the PEMFC. In this study, hydrogen is considered to be the limiting
reagent while air is considered as the excess reagent. Although the stoichiometric ratio of the inlet
molar flow rate of hydrogen to oxygen is 2, the molar flow rate of air is chosen to be always 5 times
greater than the molar flow rate of hydrogen fed to the fuel cell. This is achieved by employing a
ratio controller that senses the flow rate of hydrogen and adjusts the control valve 4 position to allow
requisite flow of air to enter the fuel cell cathode. As soon as the reactants are directed to the active
catalyst sites through the fuel cell electrodes, electrochemical reactions initiate and load current is
generated. The electrochemical reactions that occur in a PEMFC are shown in Table 1. A single cell
has an open circuit voltage of around 1 V and under load, it drops down to 0.6 to 0.7 V. Real world
applications demand electricity of the order of several tens or hundreds of volts. To achieve these
high voltage values, individual fuel cells are stacked in series so that the aggregate voltage fits any
Processes 2018, 6, 169 7 of 25

specified voltage requirement. To maintain acceptable conductivity, the polymer membrane requires
to be hydrated with water. For achieving this, the fuel cell must operate at temperatures below 90 ◦ C.

Table 1. Electrochemical reactions in PEMFC (PEMFC: polymer electrolyte membrane fuel cell)

Electrode Reactions
Anode H2 ↔ 2H + + 2e−
Cathode 1
2 O2 + 2H + + 2e− ↔ H2 O
Overall H2 + 12 O2 ↔ H2 O

Mathematical Model of PEMFC

Numerous studies in fuel cell dynamics have been reported in the literature [5,20,21]. The study of
the dynamic operation of a fuel cell is crucial for both portable and stationary applications, where power
demand varies, and the fuel cell does not generally operate at the designed optimal steady-state [20].
Considerable amount of work using fuel cell system dynamics have been reported in which authors in
Ref [5] studied the case of a high temperature PEMFC with and without a water gas shift reactor used
for carbon monoxide removal. In Ref [21], the dynamics of the fuel cell using an air compressor as
source for oxygen/air has been studied by assuming direct storage of hydrogen. The model equations
for PEMFC considered in this paper involves an along the channel model adopted from Ref [20].
The schematic showing the flow diagram of the modeled region in a PEMFC is shown in Figure 3 [22].
The mathematical model includes set of ordinary differential equations comprising of consumption
equations for each species (H2 at the anode and air at the cathode), balance of water and temperature of
gas at both the anode and cathode side as well as the coolant temperature. The temperature variation
of the polymer membrane consists of a partial differential equation while the Nernst equation, which
is an algebraic equation, describes the voltage obtained from the PEMFC.
For more details on the amount of water molecules transported by each proton, membrane
conductivity, various assumptions and parameter values used in the model, the reader is referred
to the references [20,23]. Apart from the energy balance equation, all the remaining equations are
considered to be at quasi steady state.

Figure 3. Flow diagram of modeled region in a PEMFC (PEMFC: polymer electrolyte membrane fuel
cell) [22].
Processes 2018, 6, 169 8 of 25

Equations for consumption of a single phase species i along the channel length is given by

dMi ( x )
= −hNi ( x ) (15)
dx
i = H2 , O2 , N2

where,

I (x) I (x)
NH2 ( x ) = NO2 ( x ) = NN2 ( x ) = 0 (16)
2F 4F
Balance of water in liquid form is influenced by the effect of evaporation and condensation which
is given by

l (x) v (x)
( )
dMw,k k c hd Mw,k
= N
Pk − Pwsat ( Tk ) (17)
dx RTk ( x ) ∑i k Mi,k
k = a, c

It is significant to note that Equation (17) is used only when liquid water exists at the anode or
cathode and/or partial pressure of water in vapour form exceeds its saturation pressure.
At the anode side, equation for water vapor balance is given by

v (x)
dMw,a l (x)
dMw,a hα( x )
=− − I (x) (18)
dx dx F
The first term on the right hand side of Equation (18) represents the evaporation/condensation rate
of liquid water while the second term indicates the net amount of water migrated across the membrane.
At the cathode side, equation for water vapor balance is given by

v (x)
dMw,c l (x)
dMw,c hα( x ) h
=− + I (x) + I (x) (19)
dx dx F 2F
The electrochemical reaction at the cathode side of the fuel cell generates some amount of
water vapor and is represented by the last term of Equation (19). Appropriate heat removal and
humidification are essential for the membrane to be suitably hydrated and conductive which in
turn lowers the ohmic losses in the cell. The humidification of membrane is characterised by
the term alpha (α) given by Equation (20) which denotes the ratio of water molecules per proton.
Equations (18) and (19) contain the term α which indicates the net amount of water migrated across the
polymer membrane. Equation (21) indicates the effect of humidity or water content on the conductivity
of the membrane. Reduction in membrane humidity can in turn reduce the membrane conductivity
and can further cause a reduction in the cell voltage (see Equation (31)). The ratio of water molecules
per proton, α, is expressed as

F dcw k p F dpw
α = nd − D − cw (20)
I ( x ) dy µ I ( x ) dy

The expression for conductivity of the membrane is given as

! !
Mm,dry 1 1
σm = 0.00514 cw,a − 0.00326 exp − (21)
ρm,dry 303 Ts
Processes 2018, 6, 169 9 of 25

The expressions for cw,a and cw,c are given by

ρm,dry
cw,k = (0.043 + 17.8ak − 39.8a2k + 36.0a3k ) for ak ≤ 1 (22)
Mm,dry

ρm,dry
cw,k = [(14 + 1.4( ak − 1))] for ak > 1 (23)
Mm,dry
k = a, c

The activities of water in the anode and cathode are defined as,
!
v
Mw,a
xw,a P P
a a = sat = v +M sat
(24)
Pw,a Mw,a H2 Pw,a

!
v
Mw,c
xw,c P P
ac = sat = v sat
(25)
Pw,c Mw,c + MO2 + M N2 Pw,c

The equation for the variation in anode and cathode gas temperatures are given by

dTk ( x ) Ug A g T f c ( x ) − Tk ( x )
= , k = a, c (26)
dx ∑i C p,i Mi ( x )

The variation in temperature of coolant circulated is expressed as


dTcool ( x ) Uw Acool T f c ( x ) − Tcool ( x )
= (27)
dx C p,w Mcool

The spatial and time dependency of solid temperature is determined by the energy balance
equation given by

∂T f c ∂2 T f c Ug A g
ρs C p,s = ks 2
+ ( Ta + Tc − 2T f c )
∂t ∂x f
!
Uw Acool e ∆H
+ ( Tcool − T f c ) − + Vcell I ( x ) (28)
f f 2F

∆Hvap ( T f c )
!
l (x)
dMw,a l (x)
dMw,c
+ +
f dx dx

The first term on the right hand side of Equation (28) represents the heat transfer by conduction,
second term indicates the heat transfer to the fuel and oxidant flows, third term gives the heat transfer
to the coolant channels, fourth term represents the heat generation by the reactions and the last term
indicates the heat of evaporation/condensation.
The boundary conditions given by Equation (29) indicates the heat energy lost to the surroundings
from both the edges of the membrane by convection.

∂T f c
ks | x=0 = Uc ( T f c − Tin f )
∂x (29)
∂T f c
ks | = −Uc ( T f c − Tin f )
∂x x=l
The cell voltage attained from the PEMFC given by the Nernst equation is expressed as
Processes 2018, 6, 169 10 of 25

I ( x )tm
Vcell = Voc − η ( x ) − (30)
σm ( x )

The overall output voltage obtained from the PEMFC considering the losses is given by

PH2 PO0.52
! !
RT f c RT f c I (x)
Vcell = Voco + ln − ln
ne F PH2 O F io PO2 ( x )
I ( x )tm
− (31)
σm ( x )

The third term of Equation (31) represents the activation over potential and last term represents
the ohmic over potential. Concentration over potential is not taken into account in this particular
mathematical model.

2.4. Integrated Reformer Membrane Fuel Cell System

The integrated system essentially comprises of a combination of the three subsystems viz.
reformer, membrane and fuel cell to form a single unit. Present work discusses the detailed
mathematical modeling and control studies of the integrated system with a multi-loop control strategy
along with a few case studies. As can be noticed from Figure 1, control valve 1 is installed at the inlet
side of the reformer to facilitate flow of stored hydrocarbon fuel to the reactor. A blower is installed
ahead of the control valve 1 in order to maintain the feed side upstream pressure greater than the
downstream pressure. The molar flow rate of gas species through the control valve 1 is given by [24].
s
94.8Fp Cv1 Pin Y f 1 X1 WCH4
MCH4 = (32)
3600WCH4 Tin Z

where f 1 ∈ [0, 1], Y and Z represents the control valve 1 opening, expansion and compressibility factors
respectively. X1 is the ratio of pressure drop across the control valve 1 to the absolute inlet pressure
given by

Pin − Pg
X1 = (33)
Pin

The velocity u of gas species entering the reformer is a function of the molar flow rate according
to the equation given by

MCH4 WCH4
u= (34)
ρCH4 A1

Furthermore as seen from Figure 1, control valve 2 is installed at the anode inlet side of the
PEMFC to facilitate flow of hydrogen gas to the anode side.

dCH2 ,m
V = M H2 ,perm − M H2 ( x = 0) (35)
dt

where, M H2 ( x = 0) is given by [24]

s
94.8Fp Cv2 Pm Y f 2 X2 WH2
M H2 ( x = 0) = (36)
3600WH2 Tgr Z

where, pressure in the line pack Pm is calculated based on the ideal gas law given by
Pm = CH2 ,m RTgr (37)
Processes 2018, 6, 169 11 of 25

X2 is the ratio of pressure drop across the control valve 2 to the absolute inlet pressure given by

Pm − Pa
X2 = (38)
Pm

Pressure drop across the lines are neglected in this study.

A dynamic mathematical model for the variation in molar concentration of hydrogen in the
line pack before the control valve 2 is obtained by applying simple mass balance as can be seen in
Equation (35). The change in moles of hydrogen in the line pack is given by CH2 ,m . M H2 ,perm represents
the molar flow rate of hydrogen permeating through the membrane and M H2 ( x = 0) depicts the molar
flow rate of hydrogen to the PEMFC anode inlet through control valve 2. The reformer is considered
cylindrical in shape with a volume of 5.65 × 10−4 m3 . The palladium membrane considered is having a
volume of 6.4 × 10−7 m3 . The volume occupied by the fuel cell stack containing 375 cells is calculated
to be 0.01547 m3 . The line pack connecting pipe is considered to have a volume of 2.5 × 10−4 m3 .
Considering all these volumes, the total volume comes to around 0.016 m3 . Assuming the total volume
occupied by all the other ancillary components like the control valves, heat exchangers, mixers etc.
to be around 0.02 m3 , then the total volume of the integrated power system would be approximately
equal to 0.036 m3 .
The third loop involves control valve 3 which facilitates the circulation of coolant to and from the
fuel cell in order to maintain the average solid temperature of the PEMFC at a pre-defined acceptable
value. The spatial and time dependence of solid temperature of the PEMFC is given by a partial
differential equation already discussed in Equation (28). Fourth loop involves a ratio controller that
manipulates the control valve 4 position based on the hydrogen flow rate, in order to feed appropriate
amount of air to the fuel cell cathode through an air blower.

2.5. Numerical Solution of the Integrated System

In the case of an auto thermal reformer, the mathematical model consists of set of partial
differential equations for species concentrations and temperatures (Equations (5)–(12)). Considering
seven gas species concentrations along with gas and solid temperatures, the resulting set of partial
differential equations are converted to a set of nine ordinary differential equations using method of
lines that discretize the spatial derivatives by finite differencing. In the case of palladium membrane,
the molar flow rate of hydrogen permeating through the membrane is expressed by an algebraic
equation (Equation (13)) while the change in molar concentration of H2 in the line pack is given
by an ordinary differential equation (Equation (35)). The mathematical model for PEMFC involves
mass balances given by a set of ordinary differential equations (Equations (15)–(27), energy balance
described by a partial differential equation (Equation (28)) and the output voltage given by an algebraic
equation (Equation (31)). The partial differential equation is converted to set of ordinary differential
equations using method of lines. Since the mass balance equations in PEMFC consist of quasi steady
state equations, but involve time dependent quantities, they are solved separately along the space
after time simulation of the partial differential equations over short time interval of 0.1 s. The reformer
length is divided into a uniform grid of 100 intervals while the PEMFC flow channel is divided into a
uniform grid of 400 intervals.
Using the ode15s differential equation solver available in MATLAB environment 2014b,
the resulting sets of equations are solved simultaneously to study the dynamic and steady state
behavior of the integrated system.

2.6. Controllability Analysis and Choice of Pairing

The ability to maintain the process outputs within specified bounds by appropriately adjusting the
manipulated variables characterizes the controllability of a process [25]. To perform the controllability
analysis of the integrated system, the dynamic model of the system is considered with three inputs:
molar flow rate of CH4 to the reformer inlet through control valve 1 (u1 ), molar flow rate of H2 to the
Processes 2018, 6, 169 12 of 25

fuel cell anode through control valve 2 (u2 ) and molar flow rate of coolant to the fuel cell through
control valve 3 (u3 ). The molar concentration of H2 in the line pack (or H2 pressure in the line pack
assuming ideal gas law) (y1 ), power demanded by the fuel cell output load (y2 ) and average solid
temperature of the fuel cell (y3 ) are selected as outputs. Relative gain array (RGA) is used to select the
input-output pairings and to study their interactions [25].

Remark 1. Since the dynamics of PEMFC are significantly faster than the reformer dynamics, it takes
considerable amount of time for the fuel processing subsystem during cold start to produce hydrogen to run the
fuel cell thereby making the overall system dynamics much slower [12]. Hence, to ensure acceptable performance
of the output electrical load powered by the integrated system, backup power sources like batteries or super
capacitors that have a much faster response time is desirable. The choice of such relevant ancillary power sources
and their impact on the overall system dynamics will be a subject matter of a future paper.

Remark 2. In the designed system, although a small amount of hydrogen inventory still needs to be maintained
in the line pack to meet transients, the hydrogen stored is in gaseous form and is in relatively small amounts.
This is a safer storage option in contrast with the case where liquid / gaseous hydrogen is directly stored in large
volumes and high pressure composite vessels for vehicular fuel cell applications.

3. Case Studies: Dynamic Analysis and Control of the Integrated System

3.1. Case Study 1: Open Loop Simulation for Start-up of Integrated Reformer-Membrane-Fuel Cell System
Without incorporating controllers into the loop, an open loop start-up simulation is carried out
first to analyze the dynamic nature of the integrated reformer membrane fuel cell system. The flow
rate of input fuel species to the reformer is determined by the percentage opening of the control valve 1
which is maintained at a fixed position of 50% throughout the simulation. As already discussed in the
case of auto thermal reformer, a steam to carbon molar ratio of 1:1 and oxygen to carbon molar ratio of
0.45:1 is considered for the simulation studies. This ensures maximum methane conversion thereby
increasing the hydrogen yield at the reformer output. It can also be seen that the percentage conversion
of methane is around 99.58% revealing that the hydrocarbon fuel is almost completely converted into
useful energy. During start-up of the plant, it is assumed that the gas pipeline connecting the NRV
to the control valve 2 is already filled with some amount of hydrogen so as to maintain a line pack
pressure of 1 atm. It is also assumed that the fuel cell anode and cathode sides are completely purged
with inert gas making the initial concentration of gas species present to be ideally zero. The steady
state molar concentration profiles of the species in the reformer after a time period of 2000 s are shown
in Figure 4a where the molar concentration of hydrogen increases along the reformer length as the
reaction progresses and settles to a value of 21.5 mol/m3 . The change in molar concentration of water
along the reformer length at steady state can also be seen in Figure 4a. It can be inferred that the molar
concentration of water starts decreasing near the inlet due to the consumption of water in the steam
reforming and water gas shift reactions. However, at the reformer exit, water is seen to be slightly
increasing. In the water gas shift reaction, CO reacts with steam to produce CO2 and H2 . When larger
quantities of H2 and CO2 are available, the equilibrium shifts in favour of the reverse reaction resulting
in an increase in quantity of water along the reformer length (see Figure 4a). It is assumed that the
inlet gas feed temperature to the reformer as well as the initial catalyst temperature is maintained at a
value of 815 K during the start and throughout the simulation. Because of the relatively low operating
pressure of 1.5 atm and a gas hourly space velocity (GHSV) of 0.15 kg/m2 s, the oxidation reaction is
considerably slower than the endothermic steam reforming reactions. Due to this, the gas and catalyst
temperatures decrease during the initial part of the reformer as shown in Figure 4b. Once the reactions
picks up, the temperature of both gas as well as catalyst increases sharply. The gas temperature profile
is found to be nearly same as the catalyst temperature profile, because of the effective transport of heat
from the catalyst to the gas during the operation.
Processes 2018, 6, 169 13 of 25

(a) (b)
Molar conc. of species (mol/m 3 ) 25 1100

CH 4
20

Temperature (K)
O 1000 T gas
2

15 CO T catalyst
2
H2 900
10 CO
N2
5 800
H2 O

0 700
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Relative reformer length (-) Relative reformer length (-)
Exit molar conc. of species (mol/m 3 )

(c) (d)
25 1100

CH 4
20

Temperature (K)
O2 T gas
1000
15 CO2 T catalyst
H2
10 CO 900
N2
5
H2 O

0 800
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000

Time (s) (e) Time (s)

1.6
Line pack pressure (atm)

1.5

1.4

1.3
Control valve 2 opens at 362 s
1.2

1.1 Non-return valve opens at 341 s

1
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Time (s)

Figure 4. (a) Steady state profile for molar concentration of species; (b) Steady state profile for gas
and catalyst temperatures; (c) Dynamic profile for molar concentration of species at reformer exit;
(d) Dynamic profile for gas and catalyst temperatures at reformer exit; (e) Pressure in the line pack.

The dynamic profiles of the exit molar concentration of each species taking part in the reforming
reactions are illustrated in Figure 4c. It can be noticed from the profile that the molar concentrations of
the species settle to their steady state values in approximately 600 s. The exit molar concentration of
H2 and CO increase while that for all the other species decrease with time as they are consumed in
the reforming reactions. N2 , which is an inert component does not take part in any of the reactions
and thus exhibits a constant profile. As the exothermic reactions dominates the endothermic reactions,
the gas temperature and catalyst temperature profiles at the reformer exit are found to be increasing
with time as seen in Figure 4d and settle at a value of approximately 1090 K.
As already discussed, before the plant start-up, some amount of hydrogen is assumed to be
present between the pipeline connecting NRV to the control valve 2 to maintain a pressure of 1 atm.
The NRV after the membrane separation unit (see Figure 1) restricts the flow of hydrogen further
from the reformer exit through the membrane to the control valve 2 inlet until the upstream pressure
(membrane permeate side) exceeds the downstream pressure (line pack pressure maintained at 1
atm initially). As can be seen from Figure 4e, the NRV remains closed till a time period of 341 s,
after which it opens to allow flow of hydrogen to build up the line pack pressure beyond 1 atm.
As can be seen from Figure 4e, the plant is designed in such a manner that as the line pack pressure
increases and becomes 1.1 times greater than the downstream pressure (1 atm), the control valve 2 is
opened to 50% (at 362 s as seen from Figure 4e). The initially closed control valve 2 allows the molar
concentration of H2 in the line pack to build up (in turn causing a build up in the line pack pressure)
as shown in Figure 5a. In response to the sudden opening of the control valve 2, the profiles for line
pack pressure and molar concentration of H2 in the line pack starts increasing as can be seen from
Figures 4e and 5a respectively.
Processes 2018, 6, 169 14 of 25

(a) ×10 -5 (b)

through Pd membrane (mol/s)

22 1.5
the line pack (mol/m 3 )

Molar flowrate of H2
Molar conc. of H2 in

21
1

20
Control valve 2 opens at 362 s Control valve 2 opens at 362 s
0.5
19
Non-return valve opens at 341 s Non-return valve opens at 341 s

18 0
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Time (s) Time (s)

control valve 2 to fuel cell (mol/s)

(c) ×10 -5 (d)

Molar flowrate of H2 through

Control valve 2 opening (%)

100 1.5

80
1
60

40
0.5

20 Control valve 2 opens at 362 s Control valve 2 opens at 362 s

0 0
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Time (s) Time (s)
(e) (f)

Average solid temperature (K)

100 340

80
330
Power (W)

60
320
40
310 Control valve 2 opens at 362 s
20 Control valve 2 opens at 362 s

0 300
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Time (s)
Time (s)

Figure 5. (a) Molar concentration of H2 in the line pack; (b) Molar flow rate of H2 through Pd membrane;
(c) Percentage opening of the control valve 2; (d) Molar flow rate of H2 through control valve 2 to fuel
cell; (e) Power generated by a single fuel cell; (f) Average solid temperature of fuel cell.

According to the Sievert’s law given by Equation (13), the molar flow rate of hydrogen permeating
through the palladium membrane represented by M H2 ,perm increases as soon as the NRV opens at 341 s
(see Figure 5b). At 362 s, when control valve 2 opens, a small disturbance is expected in the molar
flow rate of hydrogen as can be understood from Sievert’s law given by Equation (13). In response to
opening of the control valve to 50% at 362 s (see Figure 5c), pressurized H2 from the line pack starts
flowing through the control valve 2 to the fuel cell anode, the molar flow rate of which can be seen
from Figure 5d. As the molar flow rate of H2 to the fuel cell anode increases in response to opening
of the control valve 2, the electrochemical reactions commence, which in turn increases the power
generated by the fuel cell as shown in Figure 5e. From the start up simulation, it can be observed
that the dynamics of reformer-membrane-fuel cell is sluggish. This is because of lack of availability
of H2 for 362 s, when the control valve 2 opens to 50% once the line pack pressure exceeds 1.1 times
the downstream fuel cell pressure. However, as can be seen from Figure 5b,d, the flow rate from the
membrane to the line pack limits the flow rate of H2 to the fuel cell. Thus, the fuel cell dynamics are
slower due to the limitation of the hydrogen produced by the reformer. The dynamics associated
with shut-down of the integrated system has not been studied in the current work. The mathematical
modeling of the ancillary components like heaters, mixers etc. are not taken into account for this
particular study for simplification. Due to the dominating exothermic reactions occurring in the auto
thermal reformer, there is always a possibility for cogeneration which can enhance the overall efficiency
of the plant. The heat extracted by the coolant from the PEM fuel cell can also be used for heat transfer
to the fuel. This will be a subject matter for our future work. The average solid temperature of the
fuel cell increases and settles to a value of approximately 330 K as can be seen from Figure 5f, which is
based on a constant coolant circulation flow rate of 0.055 mol/s.

Relative Gain Array (RGA) Analysis

The controlled variables chosen in this particular study are the molar concentration of H2 in
the line pack (or H2 pressure in the line pack assuming ideal gas law) (y1 ), power demanded by the
output electrical load (y2 ) and average solid temperature of the fuel cell (y3 ) . For achieving satisfactory
operation of the integrated reformer membrane fuel cell assembly, the available manipulated variables
Processes 2018, 6, 169 15 of 25

selected are the molar flow rate of CH4 to the reformer inlet through control valve 1 (u1 ), molar flow
rate of H2 to the fuel cell anode through control valve 2 (u2 ) and molar flow rate of coolant to the
fuel cell through control valve 3 (u3 ). For designing appropriate single input single output (SISO)
controllers to form a multi-loop control strategy, suitable input-output pairings need to be decided for
which the RGA analysis is carried out. By performing step changes in the manipulated variables and
observing the changes in output variables of the integrated system, steady state model of the system in
deviation form is obtained as,
    
∆y1 1.75 0.35 0 ∆u1
∆y2  = 0.225 1 0.13  ∆u2  (39)
    
∆y3 0.789 1.764 −0.45 ∆u3

Given the steady state gain matrix K of the system, the steady-state RGA matrix for the selected
inputs and outputs can be obtained by Equation (40).
 
1.0638 −0.0638 0
( RGA)y1 ,y2 ,y3 ,u1 ,u2 ,u3 = K ⊗ (K −1 )T = −0.0317 0.7047 0.3270 (40)
 
−0.0321 0.3591 0.6730

It can be noticed that the RGA for diagonal pairings (u1 − y1 ) , (u2 − y2 ) and (u3 − y3 ) are 1.0638,
0.7047 and 0.6730 respectively which is closer to 1 indicating stronger interaction. This pairing seems
appropriate from a process point of view because the molar flow rate of CH4 to the reformer inlet
through control valve 1 (u1 ) has a direct effect on the amount of H2 produced at the reformer output
which in-turn has an effect on the molar concentration of H2 in the line pack (or H2 pressure in the
line pack assuming ideal gas law) (y1 ). Similarly, the molar flow rate of H2 to fuel cell anode through
control valve 2 (u2 ) has a direct effect on the power demanded by the output electrical load (y2 ).
Also, the molar flow rate of coolant circulated through the fuel cell (u3 ) has a direct effect on the
average solid temperature of fuel cell (y3 ). As can be seen from the steady-state RGA matrix, the
RGA for off-diagonal pairings are negative and/or are far way from 1 indicating lesser interaction.
A process flow diagram with selected input-output pairings and with appropriate control loops is
shown in Figure 6.

Figure 6. Process flow diagram with control loops for the integrated system.
Processes 2018, 6, 169 16 of 25

3.2. Case Study 2: Integrated System Delivering Target Power Demand

For validating the capability of employing the integrated system for a realistic application,
an electrical load of about 27 kW is considered, which corresponds to a light motor vehicle [26],
powered by an integrated reformer membrane fuel cell system. Taking into account the transmission
and DC/AC converter losses, the maximum power requested is assumed to be 30 kW. In this particular
case study, the PEM fuel cell modeled can generate a maximum current density of 1.5319 A/cm2 at a
cell voltage of 0.53 V based on the model parameters used. As the electrode area per cell is assumed to
be 100 cm2 , a single fuel cell can generate a maximum power of approximately 0.08 kW. In order for
the fuel cell to generate a power of 30 kW, a fuel cell stack consisting around 375 such individual cells
connected in series is necessary. Modeling a fuel cell stack containing these many cells is beyond the
scope of this paper. For the purpose of simulating the fuel cell stack, it is assumed here that each cell in
the stack behaves identically. Thus, the overall stack voltage will be given by the sum of 375 individual
cell voltages given by Equation (31). The average molar flow rate of hydrogen for the fuel cell system
is 1.3 × 10−5 mol/s or 4.68 × 10−2 mol/h. This corresponds to a methane flow rate of 15.12 mol/h.
Assuming that methane is stored at 200 atm pressure and a temperature of 298 K and using ideal gas
law, the corresponding volume of methane is 1.8 litres. The output electrical load power demand is
assumed to exhibit slower dynamics for the first 65 s and extremely faster dynamics during rest of the
time. In this case study, controller 1 tries to regulate the molar concentration of H2 in the line pack to
21.315 mol/m3 irrespective of variation in the power requested by the fuel cell. This is achieved by
manipulating the control valve 1 position thereby varying the molar flow rate of fuel to the reformer
inlet. In other words, controller 1 controls the hydrogen pressure in the line pack by manipulating the
methane flow rate to the reformer inlet. Line pack pressure is calculated from the molar concentration
of hydrogen present in the line pack using the ideal gas law as given by Equation (37). Inlet pressure
at the anode and cathode sides are fixed at 1 atm. Line pack pressure control ensures presence of
sufficient hydrogen always to prevent hydrogen starvation, which can permanently damage the fuel
cell stack. The molar concentration of H2 in the line pack is chosen as the controlled variable keeping
the molar flow rate of fuel from the fuel storage to the reformer inlet through the control valve 1 as the
manipulated variable. In addition to this, controller 2 is designed to take necessary action to supply
requisite amount of H2 to fuel cell anode in order to achieve the desired target power. Output power
demanded by the fuel cell stack is identified as the controlled variable while the molar flow rate of
H2 through the control valve 2 to the fuel cell anode is selected as the manipulated variable. Third
loop involves controller 3 and is designed to maintain a fixed average solid temperature of fuel cell
by manipulating the molar flow rate of coolant circulated. As obvious, average solid temperature is
selected as the controlled variable while molar flow rate of coolant is selected as the corresponding
manipulated variable. Finally, fourth loop involves a ratio controller that regulates the ratio of air to
hydrogen to be fed to the cathode and anode inlets of the fuel cell respectively. The tuning parameters
for the four controllers are listed in Table 2.

Table 2. Design parameters for various control loops.

Loop Controller Kp KI KD Ratio

Pressure controller PID 0.3 0.0001 0.4 -
Power controller P 0.1 - - -
Temperature controller PID −0.1 −0.0001 −0.05
Air to H2 ratio controller Ratio - - - 5

Based on the power demanded by the fuel cell load, the controller 2 manipulates the control valve
2 position as shown in Figure 7a. Opening of the control valve 2 lets an appropriate amount of H2
to flow to the fuel cell anode, the molar flow rate of which can be seen from Figure 7b. Due to the
Processes 2018, 6, 169 17 of 25

feedback mechanism, controller 1 takes necessary action to manipulate the percentage opening of
control valve 1 as shown in Figure 7c.

(a) ×10 -5 (b)

control valve 2 to fuel cell (mol/s)

50 1.6
Control valve 2 opening (%)

Molar flowrate of H2 through

1.5
45
1.4

1.3
40
1.2

35 1.1

1
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Time (s) Time (s)
(c) ×10 -3 (d)

storage to reformer inlet (mol/s)

52 4.6
Control valve 1 opening (%)

Molar flowrate of fuel from

50
4.4
48
4.2
46
4
44

42 3.8

40 3.6
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Time (s) (e) Time (s)
21.52
at reformer output (mol/m 3 )
Molar concentration of H2

21.5

21.48

21.46

21.44

21.42

21.4
0 20 40 60 80 100 120 140 160
Time (s)

Figure 7. (a) Percentage opening of the control valve 2; (b) Molar flow rate of H2 through control valve
2 to fuel cell; (c) Percentage opening of the control valve 1; (d) Molar flow rate of fuel from storage to
reformer inlet; (e) Molar concentration of H2 at reformer output.

Proportionately, the molar flow rate of stored fuel coming as input to the reformer starts varying as
illustrated in Figure 7d. In response to this, the molar concentration of H2 exiting from the reformer also
starts varying as given in Figure 7e. According to Sievert’s law given by Equation (13), in response to
variation in the molar concentration of H2 coming from the reformer, the molar flow rate of H2 flowing
through the Pd membrane starts varying as is obvious from Figure 8a. The controller 1 takes necessary
action to maintain a constant H2 molar concentration in the line pack between NRV and control valve
2 as shown in Figure 8b. As can be seen from the figure, the dashed line indicates the desired target
molar concentration to be maintained while the solid line indicates the actual concentration in the
line pack. As already discussed, the variation in the molar flow rate of H2 to the fuel cell anode
changes the power generated by the fuel cell which can be seen from Figure 8c. The dashed line shows
the desired target power demanded by the electrical load while the solid line indicates the actual
power supplied by the PEMFC. The profile showing the variation in the line pack pressure is given
in Figure 8d. The controller 3 takes care of maintaining the average solid temperature of the fuel cell
at a desirable value irrespective of variations in the power demanded by the fuel cell electric load.
The manipulation of coolant flow rate by varying the control valve 3 position by the controller 3 can be
observed from Figure 8e. The corresponding profile for the average solid temperature of the PEMFC is
shown in Figure 8f. It is observed that the designed controllers with appropriately chosen controller
parameters were able to control the H2 molar concentration in the line pack, fuel cell power demand
and the average solid temperature of fuel cell with relatively short settling times and with negligible
offset. Both slow and fast varying load scenarios have been simulated in the present case study for the
closed loop system for power control and observed that the designed controller could tracks the set
point with a settling time of the order of 0.4 s.
Processes 2018, 6, 169 18 of 25

×10 -5 (a) (b)

21.34
Molar flowrate of H2 through

1.6
Pd membrane (mol/s)

the line pack (mol/m 3 )

Molar conc. of H2 in
21.33
1.4
21.32

1.2 21.31

1 21.3 Desired line pack concentration

Actual line pack concentration
21.29
0.8
21.28
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Time (s) Time (s)
(c) (d)
30 1.915

Line pack pressure (atm)

29
Power (kW)

28 1.91

27
Desired power
Actual power generated by PEMFC
26 1.905
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Time (s) Time (s)
(e) (f)

Average solid temperature (K)

50 349
Control valve 3 opening (%)

40 348.8

30 348.6

20 348.4

Desired average solid temperature

10 348.2

0 348
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Time (s) Time (s)

Figure 8. (a) Molar flow rate of H2 through Pd membrane; (b) Performance of controller 1 maintaining a
fixed molar concentration of H2 in the line pack; (c) Performance of controller 2 tracking the target power
profile; (d) Pressure in the line pack; (e) Percentage opening of the control valve 3; (f) Performance of
controller 3 maintaining a fixed average solid temperature of fuel cell.

3.3. Case Study 3: Disturbance in both the Reformer Inlet CH4 Feed Concentration and Coolant Temperature
The ability of the designed controller to reject the unknown disturbances occurring in the
integrated reformer membrane fuel cell system is analyzed in this case study. In the previous case
study, it was assumed that the inlet CH4 concentration and coolant temperature are fixed and are not
affected by any external disturbances. In this particular case study, disturbance in the form of step
change is introduced in both the inlet CH4 concentration as well as coolant temperature as shown
in Figure 9a,b respectively. The control structure discussed here is also similar to the one discussed
in the previous case study. Controller 1 tries to maintain a fixed molar concentration of H2 in the
line pack by manipulating the flow rate of fuel entering the reformer while controller 2 make sure
that the power demanded by the electrical load is delivered by the fuel cell at the appropriate time.
Controller 3 maintains a fixed average solid temperature in the fuel cell irrespective of changes in the
output power demand as well as variations in the coolant flow rate and temperature. Based on the
power demanded by the fuel cell electrical load, controller 2 manipulates the control valve 2 as seen
from Figure 9c. Based on the opening of control valve 2, the requisite amount of H2 flows to the fuel
cell anode, the molar flow rate of which is shown in Figure 9d. Once the H2 concentration in the line
pack gets disturbed, controller 1 takes necessary action to manipulate the opening of control valve
1 so as to maintain the line pack H2 concentration at a constant value. The change in control valve 1
opening based on the command from the controller 1 can be seen from Figure 9e. Based on the control
valve 1 opening, appropriate amount of stored fuel is supplied as input to the auto thermal reformer,
the molar flow rate of which can be seen in Figure 9f. Because of the presence of impurities in CH4
concentration at the inlet, controller 1 takes additional action so as to compensate for the unknown
disturbance happening at the input side of the plant. As the fuel inlet to the reformer varies, the molar
concentration of H2 at the reformer output also starts varying as shown in Figure 10a. Accordingly,
the molar flow rate of H2 passing through the Pd membrane also starts varying as given in Figure 10b.
The profile showing the desired and the actual molar concentration of H2 in the line pack is shown
in Figure 10c. It can be seen from Figure 10d that the power demanded by the electrical load and
actual power delivered by the fuel cell. Because of the presence of disturbance in the coolant flow rate
Processes 2018, 6, 169 19 of 25

as well as changes in the power demanded, the average solid temperature starts varying from the
required set point value. A significant deviation in the fuel cell power compared to the desired power
at the initial time period (first 5 s) can be observed from Figure 10d. This is due to the disturbance in
the coolant inlet temperature from its nominal value of 340 K to 345 K, as observed from Figure 9b.
This in turn resulted in loss of power, due to which, controller 3 increases the coolant flow rate which
restores the temperature of the fuel cell and consequently the power (see Figure 10d,e). Based on the
command from the controller 3, the average solid temperature sticks to the pre-defined set value as
can be seen from Figure 10f. It is observed that the designed controllers with appropriately chosen
controller parameters were able to control the parameters and track the set point even in the presence
of unexpected disturbances happening in the plant. Due to the presence of disturbances, the deviations
of molar concentration of hydrogen in the line pack as well as the average solid temperature from the
set point is more compared to the scenario when disturbances were absent.

(a) (b)
9.3
at reformer inlet (mol/m 3 )

Coolant temperature (K)

344 Disturbance 2
Disturbance 1
CH4 concentration

9.2
342
9.1
340
9
338
8.9
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Time (s) Time (s)
(c) ×10 -5 (d)
control valve 2 to fuel cell (mol/s)

50 1.6
Molar flowrate of H2 through
Control valve 2 opening (%)

1.5
45
1.4

40 1.3

1.2
35
1.1

30 1
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Time (s) Time (s)
×10 -3 (f)
storage to reformer inlet (mol/s)

(e)
Control valve 1 opening (%)

100
Molar flowrate of fuel from

8
80
6
60

4
40

20 2

0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160

Time (s) Time (s)

Figure 9. (a) Disturbance in the concentration of CH4 at reformer inlet; (b) Disturbance in the coolant
temperature; (c) Percentage opening of the control valve 2; (d) Molar flow rate of H2 through control
valve 2 to fuel cell; (e) Percentage opening of the control valve 1; (f) Molar flow rate of fuel from storage
to reformer inlet.
Processes 2018, 6, 169 20 of 25

(a) ×10 -5 (b)

22 5

through Pd membrane (mol/s)

reformer output (mol/m 3 )

Molar flow rate of H2

Molar conc. of H2 at

21.8
4
21.6
3
21.4
2
21.2

21 1

20.8 0
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Time (s) Time (s)
(c) (d)
21.4
in the line pack (mol/m 3 )

30
Molar conc. of H2

21.35

Power (kW)
28

21.3
26 Desired power
Actual power generated by PEMFC
Desired line pack concentration
21.25
Actual line pack concentration 24

0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160

Time (s) Time (s)
(e) (f)
100
Control valve 3 opening (%)

Average solid temperature (K)

80 349.5 Desired average solid temperature
Actual average solid temperature

60
349

40
348.5
20

0 348
0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120 140 160
Time (s) Time (s)

Figure 10. (a) Molar concentration of H2 at reformer output; (b) Molar flow rate of H2 through Pd
membrane; (c) Performance of controller 1 maintaining a fixed molar concentration of H2 in the line
pack; (d) Performance of controller 2 tracking the target power profile; (e) Percentage opening of
the control valve 3; (f) Performance of controller 3 maintaining a fixed average solid temperature of
fuel cell.

4. Conclusions
A system level mathematical model of an integrated reformer membrane fuel cell system has
been developed in order to assess the feasibility of the integrated system for stationary and portable
power applications. Such an integrated system promotes safety and leverages existing natural gas
infrastructure. The dynamic analysis of the open loop system revealed significant difference in the
dynamics related to the upstream reformer as compared with the fuel cell. This behavior points the
need for an auxiliary power system during startup of the integrated system which is outside the
scope of this work. A multi loop control strategy is implemented on to the integrated system wherein
power demanded by the fuel cell load, molar concentration of H2 in the line pack and average solid
temperature of the fuel cell are chosen as the controlled variables for the two control loops. Relevant
controllers are designed appropriately to control the system which included set point tracking and
disturbance rejection studies. The simulation results show faster settling times with negligible offset
proving the effectiveness of the designed controller.

Author Contributions: All of the authors contributed to publishing this article. The collection of materials and
summarization of this article was done by P.P.S. and the conceptual ideas, methodology and guidance for the
research were provided by R.D.G. and S.B. All the coding and programming works was done by P.P.S.
Funding: This research was funded by the Dept. of Science & Technology, Govt. of India, Grant 13DST057.
Conflicts of Interest: The authors declare no conflict of interest.

Nomenclature
α ratio of water molecules per proton (molecules proton−1 )
∆H heat of reaction (kJ mol−1 )
eb packing bed porosity
ηj effectiveness factor of reaction j
Processes 2018, 6, 169 21 of 25

η over potential (V)

f
λz effective thermal conductivity (W(mK)−1 )
µ water viscosity (g cm−1 s−1 )
ρbed density of the catalyst bed (kg m−3 )
ρcat density of the catalyst pellet (kg m−3 )
ρf density of the fluid (kg m−3 )
ρs density of the solid (kg m−3 )
ρm,dry density of dry membrane of fuel cell (g cm−3 )
σm ionic conductivity of the fuel cell membrane (Ohm−1 cm−1 )
θmem Pd membrane poisoning caused by the adsorption of CO
A heat exchange area per unit length (cm)
A1 area of the fuel flow pipe to the reformer inlet (m2 )
ak activity of water in stream k
av external catalyst surface area per unit volume of catalyst bed (m2 m−3 )
Amem Pd membrane surface area (m2 )
Ci molar concentration of species i in the gas phase (mol m−3 )
Cp molar heat capacity (J(g mol K)−1 )
cw concentration of water in the membrane of fuel cell (mol cm−3 )
CH2 ,m molar concentration of H2 in the line pack (mol m−3 )
Ci,s molar concentration of species i in the solid phase (mol m−3 )
C p,bed specific heat of the catalyst bed (J (kg K)−1 )
C pg specific heat of the fluid (J (kg K)−1 )
Cv1 control valve 1 flow coefficient
Cv2 control valve 2 flow coefficient
cw,k concentration of water at k interface of the membrane of fuel cell (mol cm−3 )
D diffusion coefficient of water in membrane of fuel cell (cm2 s −1 )
d fuel cell channel height (cm)
Dz axial dispersion coefficient (m2 s −1 )
e membrane area per unit length (cm)
Ea activation energy for H2 permeability (J mol−1 )
F Faraday’s constant (C mol−1 )
f cross-section of solid in fuel cell (cm2 )
f1 opening of control valve 1 (%)
f2 opening of control valve 2 (%)
Fp piping geometry factor
h fuel cell channel width (cm)
hf gas to solid heat transfer coefficient (W m−2 s−1 )
I current density (A cm−2 )
io exchange current density (A cm−2 )
k heat conduction coefficient (W (cmK)−1 )
kc condensation rate constant (s−1 )
KD parameter corresponding to the viscous loss term (Pa s m−2 )
KV parameter corresponding to the kinetic loss term (Pa s2 m−3 )
k g,i gas to solid mass transfer coefficient of component i (m s−1 )
Lmem Pd membrane thickness (m)
M molar flow rate (mol s−1 )
Mm,dry equivalent weight of dry membrane of fuel cell (g mol−1 )
n pressure exponent
ne number of electrons taking part in charge reactions
Ni molar flux of species i (mol s−1 cm−2 )
P pressure (atm)
sat
Pw,k vapor pressure of water in kth channel
Pe permeability of Pd membrane (mol (msPan )−1 )
Processes 2018, 6, 169 22 of 25

Pe,o permeability pre-exponential factor (mol (msPan )−1 )

Pin methane fuel storage pressure (atm)
R gas constant (J (mol K)−1 )
ri rate of consumption or formation of species i (mol (kgcat s)−1 )
Rj rate of reaction j (mol (kgcat s)−1 )
t time (s)
Tg reformer gas temperature (K)
tm fuel cell membrane thickness (cm)
Tf c fuel cell solid temperature (K)
Tgr gas temperature at the exit of heat exchanger 1 (K)
Tin f ambient temperature (K)
Tin methane fuel storage temperature (K)
U convective heat transfer coefficient (W cm−2 K−1 )
u superficial gas flow velocity (m s−1 )
V volume of the line pack (m3 )
Vcell cell voltage (V)
Voc open circuit voltage (V)
W molecular weight (kg mol−1 )
X ratio of pressure drop to the absolute inlet pressure
x direction along the fuel cell channel length (cm)
Y expansion factor
Z compressibility factor
z axial dimension (m)

Suffixes

a anode
c cathode
g gas
m line pack
s solid
sat saturation
w water

Appendix A. Data for the Base Case

Parameter Values
CCH4 (mol m−3 ) 9.1705
CO2 (mol m−3 ) 4.1273
CCO2 (mol m−3 ) 0.0001
CH2 O (mol m−3 ) 9.1705
CH2 (mol m−3 ) 0.0001
CCO (mol m−3 ) 0.0001
CN2 (mol m−3 ) 15.5287
Tg (K) 815
Ts (K) 815
CH2 ,m (mol m−3 ) 0.001
M H2 (mol s−1 ) 1.14 × 10−5
MO2 (mol s−1 ) 5.7 × 10−6
l
Mw,a (mol s−1 ) 0
l
Mw,c (mol s−1 ) 0
v (mol s−1 )
Mw,a 9.8555 × 10−6
v (mol s−1 )
Mw,c 4.9278 × 10−6
Ta (K) 353
Tc (K) 353
Tcool (K) 340
T f c (K) 342
Processes 2018, 6, 169 23 of 25

Appendix B. Parameter Values Used for Simulation

Parameter Values
eb 0.4
z (m) 0.2
Dz (m2 s−1 ) 2.91 × 10−4
av (m−1 ) 1200
ρcat (kg m−3 ) 1870
ρbed (kg m−3 ) 1122
C p,bed (J kg−1 K−1 ) 850
∆Hrxn,1 (kJ mol−1 ) 206.2
∆Hrxn,2 (kJ mol−1 ) 164.9
∆Hrxn,3 (kJ mol−1 ) −41.1
∆Hrxn,4 (kJ mol−1 ) −802.7
η1 (K) 0.07
η2 (K) 0.06
η3 (K) 0.7

Parameter Values
η4 (K) 0.05
K D (K) 6.539 times103
θmem 0.2
Amem (m2 ) 0.0064
Lmem (m) 0.0001
R (J mol−1 K−1 ) 8.314
n 0.67
Pe,o (mol m−1 s−1 Pa−n ) 0.4
Ea (J mol−1 ) 8000
x (cm) 10
h (cm) 0.1
d (cm) 0.1
F (C mol−1 ) 96484.69
k c (s−1 ) 100
Pa (atm) 1
Pc (atm) 1
Ug (W cm−2 K−1 ) 0.025
A g (cm) 0.4
Uw (W cm−2 K−1 ) 0.025
Acool (cm) 0.4
C p,w (J g−1 mol−1 K−1 ) 75.38
Mcool (mol s−1 ) 5.5556 × 10−2
ρs (g cm−3 ) 2
C p,s (J g−1 mol−1 K−1 ) 1
k s (W cm−1 K−1 ) 0.005
e (cm) 0.1
Uc (W cm−2 K−1 ) 0.025
Tin f (K) 350
Voc (V) 1.1
tm (cm) 0.01275
ne 2
io (A cm−2 ) 0.01
Fp 0.667
Cv1 0.67
Y 1
WCH4 (kg mol−1 ) 0.016
Z 1
Pin (atm) 2
V (m3 ) 0.00025
Cv2 0.002
WH2 (kg mol−1 ) 0.002

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