chemical engineering research and design 8 8 ( 2 0 1 0 ) 465475

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Chemical Engineering Research and Design
j our nal homepage: www. el sevi er . com/ l ocat e/ cher d
Simulated moving bed technology applied to coal
gasication
Maria Sudiro

, Manuel Pellizzaro, Fabrizio Bezzo, Alberto Bertucco

Department of Chemical Engineering (DIPIC), University of Padova, via Marzolo 9, 35131 Padova, Italy
a b s t r a c t
An alternative technology to conventional coal gasication is discussed in order to improve the performances of the
existing processes. The concept of simulated moving bed (SMB) is applied to coal gasication: a number of xed-bed
reactors are connected in series and a suitable switching policy is applied so that each xed-bed is cyclically operated
both as a combustion and a gasication reactor.
A possible combustion-gasication scheme is designed and simulated considering both chemical kinetics and
mass-transfer phenomena. Sensitivity studies are carried out on a number of performance parameters: the syngas
production efciency, the H
2
/CO molar ratio, the cold gas efciency, the amount of CO
2
emitted per unit of syngas
produced and the total productivity. The simulated performances of the newly proposed process are compared to
those of conventional gasiers.
2009 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Coal gasication; Simulated moving bed; Syngas; Dynamic modelling; Fixed-bed reactor
1. Introduction
The 20th century was a time of explosive growth in energy
consumption and rapid increase in population worldwide. In
the year 1900 population was 1762 million and in 2001 it was
as high as 6153 million. On the other hand, in 1900 the use of
energy amounted to 911 million tons of oil equivalent (TOE)
and energy sources were mostly coal (55%) and renewables
(42%), whereas, at the beginning of 2000, energy consumption
was about 10,048 million TOE, with coal at 24%, petroleum
at 39%, natural gas at 23%, nuclear 6% and renewables down
to 8% only (Song, 2006). The growth in energy consumption
was followed by a parallel increase in greenhouse gases emis-
sions. About 290 billion tons of carbon have been released
to the atmosphere due to the combustion of fossil fuels and
cement production since 1951, and half of these emissions
have occurred since the mid-1970s (Song, 2006).
At present, a major challenge is that petroleumand natural
gas have beenconsumed so rapidly that, as a consequence of a
market demand coming also from developing countries, their
price has been increasing since the year 2000, with obvious
negative effects on the global economy. On the other hand,

Corresponding author. Tel.: +39 0498275470; fax: +39 0498275461.

E-mail address: maria.sudiro@unipd.it (M. Sudiro).
Received12 November 2008; Receivedinrevisedform24 June 2009; Accepted1 September 2009
coal resources are more abundant, more evenly distributed
throughout the world and projected to last longer.
So far, coal has been consumed to supply energy mostly
by combustion, but it can also be exploited to produce chemi-
cals and fuels, through pyrolysis and gasication processes.
In fact, syngas is a very exible intermediate product that
can be used either as fuel for electricity generation (i.e. IGCC
cycles) or as a raw material for synthetic fuel production (i.e.
FischerTropsch synthesis, methanation).
Coal gasication technology has quite a long history,
although the declining price of the oil barrel after the 1970s,
whichlevelled downto lowvalues for about 20 years, hindered
the research interests in the eld. The recent increase and
uctuations of the oil price have renewed the interest of both
the industrial and scientic community to develop state-of-
the-art and economically sustainable gasication processes.
However, the use of coal determines the release of a huge
amount of CO
2
, that should be captured and sequestrated
with relevant increase of the processing costs. Therefore, for
botheconomic reasons andenvironmental concerns there has
been a great recent effort to propose a cleaner use of coal in
order to reduce the considerable emissions of CO
2
, SO
x
, NO
x
,
0263-8762/$ see front matter 2009 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.cherd.2009.09.001
466 chemical engineering research and design 8 8 ( 2 0 1 0 ) 465475
Nomenclature
Ac specic coal surface area per unit reactor vol-
ume (m
2
/m
3
)
b dimensionless factor in Arrhenius expression
c molar concentration (kmol/m
3
)
c
p
molar specic heat (kJ/kmol K)
D diffusion coefcient (m
2
/s)
D
eq
equivalent diameter (m)
d
p
coal particle diameter (50m)
E thermal power (kW)
E
a
activation energy (kJ/kmol)
H molar enthalpy (kJ/kmol)
h
T
heat thermal coefcient (kW/m
2
K)
h
M
mass-transfer coefcient (m/s)
K equilibrium constant
k reaction rate constant, m/s for heterogeneous
reactions and m
3
/mol s for homogeneous reac-
tions
n molar hold-up (kmol)

N molar ow rate (kmol/s)

M mass ow rate (kg/s)

NC components number
NR reactions number
Nu Nusselt number
NT total molar hold-up (kmol)
P pressure (Pa)
PM molecular weight (kg/kmol)
Pr Prandtl number
Q thermal power (kW)
r
i
reaction i and/or rate for reaction i
R universal gas constant (8.314kJ/kmol K)
Re Reynolds number
S surface area (m
2
)
S
specic
specic surface area of ceramic material
(m
2
/m
3
)
Sc Schmidt number
r reaction rate (kmol/m
3
s)
T temperature (K)
t time (s)
V reactor volume (m
3
)
V
gas
gas phase volume (m
3
)
u gas velocity (m/s)
u weight fraction
x molar fraction in the gas phase (without char)
X conversion
y molar fraction in the uid phase (gas and char)
y

volumetric fraction
Greek symbols
coal emissivity (0.95)
ceramic material void fraction
/k LennardJones parameter (K)
k thermal conductivity (kW/mK)
j viscosity (Pas)
, density (kg/m
3
), char density (2170kg/m
3
)
o LennardJones parameter (collision diameter)
()
o
SB
StefanBoltzmann constant
(5.6710
11
kW/m
2
K
4
)
u stoichiometric coefcients
parameter

k
collision integral for conductivity
Subscripts
0 initial condition
bulk bulk reacting gas
c(s) solid carbon
conv convection
mix gas mixture
rad radiation
WGS watergas shift reaction
particulate matter and hydrocarbons generated by coal-based
processes.
In this work the syngas production from coal is consid-
ered. Our goal is to propose and analyze a high-performance
technology for coal gasication where the expensive use of
pure oxygen is avoided. The use of air instead of oxygen has
the drawbacks of both diluting the syngas and of negatively
impacting the environment in terms of nitrogen oxides (NO
x
).
A possible way to overcome these problems is to envisage a
process where the combustion and gasication sections are
carried out separately: as suggested by Levenspiel (2005), this
can be achieved using either two different reactors, which
may be operated in continuous, or a single one, which per-
forms combustion and gasication at different times (batch
or semibatch operation).
According to the rst approach, a dual uidized bed gasi-
cation process has been proposed (Xu et al., 2006; Murakami
et al., 2007; Kaushal et al., 2007; Sudiro et al., 2008), where air
is used in the combustion phase and the gasication phase
occurs in a spatially separated reactor, so that the heat is
transferred from one section to the other through the circula-
tionof some inert solid. Some modications of this technology
are discussed in the recent literature (Kaushal et al., 2008a,b;
Matsuoka et al., 2008).
The other approachrequires toadopt anumber of xed-bed
reactors connected in series, which are sequentially sub-
jected to combustion and gasication reactions at different
times. When the unit is hot the desired endothermic reactions
take place until the reactor cools down; then, combustion
is switched on by feeding air, and the reactor is heated up
again. Several process congurations can be envisaged in
this respect. One of them is to use xed-beds made up of
some inert and porous ceramic materials acting as a ther-
mal capacity during the combustion phase, and releasing the
accumulated heat in the successive gasication phase, where
coal is fed as a ne powder uidized by steam. Alternately,
suitably granulated coal can be mixed with some inert mate-
rial to constitute the xed-bed, which is operated either as a
combustor or as a gasier, depending on the gaseous stream
it is fed with. In both cases a train of xed-beds is required
to ensure a continuous syngas production. This arrangement
recalls the simulated moving bed (SMB) type of operation, pro-
posed elsewhere for different processes (e.g. Ruthven, 1984;
Bertucco et al., 1995). Accordingly, a solid-uid process is oper-
ated counter-currently without really moving the solid, but
simply using a convenient number of xed-beds in series, and
a suitable switching policy of the feeds among them. A possi-
ble block ow diagram of an SMB-like gasication scheme is
showninFig. 1, where it canbe noticedthat, after a givennum-
ber of switches, one xed-bed is removed from the train and,
simultaneously, one is added to the other train end. Thus, a
counter-current process congurationis achieved. Inaddition,
chemical engineering research and design 8 8 ( 2 0 1 0 ) 465475 467
Fig. 1 Block ow diagram of the gasication process, based on the SMB concept (the solid lines within the blocks
qualitatively indicate the coal concentration proles); when the bed of char has been heated to a preset temperature, the
feed is switched to steam that reacts with char to produce syngas. After consuming the char, the bed is sent to regeneration.
if the quality of the feeds is not changed, a cyclic, or periodi-
cal, steady-state operationcanbe reachedina relatively short
time, where temperature and concentration proles (both in
the bed train and in the outlet gaseous streams) are exactly
reproduced after each period.
The aimof our work is to show, by applying process simula-
tion techniques, that such a system can provide a potentially
attractive alternative technology for coal gasication, and
ensure good performances in terms of syngas production ef-
ciency, H
2
/CO molar ratio of the syngas, and amount of CO
2
emitted per unit syngas produced.
As a rst analysis, we have investigated a process where
the xed-beds are made up of some porous ceramic material,
whichis alternately contactedby the ue gases producedinan
external combustor (in the heating phase) and by steam with
suspended char particles (in the gasication phase; refer to
the next Sectionfor details). This congurationallows to easily
assess the effect of a number of operating variables, such as
the total pressure, the steam to coal ratio and the residual
amount of coal at the reactor outlet.
This combustion-gasication scheme has been developed
by using the general purpose modelling tool gPROMS
TM
(Process Systems Enterprise, 2004) to obtain a dynamic model
of a single xed-bed, which includes mass, energy and
momentum balances. Dynamic simulations and sensitivities
studies have been carried out in order to characterize the sys-
tem behaviour in view of subsequent extensions and possible
practical applications.
2. Process modelling
The SMB process is modelled as described in the following.
First of all, as commonly assumed, the SMB technology is rep-
resented as a xed-bed plug ow reactor (PFR) whose feed is
switched according to the varying conditions. It was decided
to describe the combustion step as if occurring externally in
a burner whose ue gas are then exploited to heat up the
xed-bed reactor. The main reason for this was to increase
the overall computational robustness, and to allowsimulating
a steady-state process cycle without too an excessive calcula-
tion burden. However, we note that, although this assumption
determines a more ideal temperature prole in the reactor
(mainly because local combustion effects are not taken into
account), it does not affect the general representation of the
process operation policy and does not upset the general strat-
egy (i.e. heating up the ceramic bed through a combustion
step). The revised process layout is sketched in Fig. 2. After the
ceramic xed-bed has been heated up to the desired tempera-
ture, the reactor feed is switched to pulverized coal and steam.
The gasication reactions occur thanks to the heat delivered
bythe ceramic bed, whichcools downprogressively. As soonas
the xed-bed temperature has decreased to a threshold level,
Fig. 2 Scheme of the cyclic plant (dotted lines are for the combustion and heating step and continuous lines are for the
gasication step).
468 chemical engineering research and design 8 8 ( 2 0 1 0 ) 465475
the feed is switched back to the hot ue gases, and a newcycle
is started. It is also assumed that, before entering the gasi-
cation step, the pulverized coal undergoes a pyrolysis process,
which allows representing the composition of the gas enter-
ing the reactor according tothe simpliedmethoddescribedin
Lee et al. (1998); suspended coal is taken as char. The owrate,
composition and temperature of the stack gas are obtained
by modelling the combustion step as a CSTR (air to coal ratio
equal to 13.5, on weight basis). If the feed conditions and the
switching times are not varied, after aninitial start-up the sys-
tem behaves as a cyclically steady-state process for both the
heating and the gasication phases.
The following species are included in the model: O
2
, CO,
CO
2
, H
2
, H
2
O, N
2
, CH
4
and char (as graphite C). Their thermo-
physical properties have been evaluated as summarised in
Appendix A at the end of the paper. In some cases (compres-
sion factor Z and viscosity of the gas mixture) calculations by
means of the Multiash
TM
package (incorporated within the
gPROMS
TM
software) were adopted.
2.1. Chemical kinetics
Four heterogeneous and three homogeneous reactions have
been considered in this work (data for heterogeneous reac-
tions and watergas shift reaction are taken from Nagpal et
al., 2005 and data for the other two homogeneous reactions
are taken from Kim et al., 2000).
The combustion of char to CO and CO
2
is represented by:
r
1
: C +
_
1
z
_
O
2
2
_
1
1
z
_
CO+
_
2
z
1
_
CO
2
(1)
where z indicates the relative molar amount of CO versus CO
2
and is calculated through the relationship:
CO
CO
2
= Ac
E,RT
= 2
z 1
2 z
(2)
where A=10
2.5
, E=38kJ/mol at low pressures, and A=10
3.5
;
E=50kJ/mol at high pressures (Laurendeau, 1978).
The char gasicationis modelledinterms of the Boudouard
reaction (r
2
), the steam gasication reaction (r
3
), and the
methane formation reaction (r
4
):
r
2
: C + CO
2
2CO (3)
r
3
: C + H
2
O CO + H
2
(4)
r
4
: C + 2H
2
CH
4
(5)
Note that r
4
is signicantly slower than both r
2
and r
3
, and
less relevant todetermine the overall gasicationperformance
(Nagpal et al., 2005).
The above reactions are all heterogeneous and the expres-
sion of the overall reaction rate r
j
should also consider the
mass transfer between gas phase and char particles. If the
reactions occurs only on the surface of the particles (i.e. the
contribution within the pores is assumed to be negligibly
small, in accordance with Nagpal et al., 2005), r
j
can be dened
as:
r
j
=
Ac c
i.bulk
(1,n
M.i
) +(1,k
j
)
(6)
Table 1 Kinetic parameters for the heterogeneous
reactions (Nagpal et al., 2005).
Reaction k
0
(m/s K
b
) E
a
(kJ/kmol) b
r
1
1.22 85.6310
3
1
r
2
3.419 129.7010
3
1
r
3
208 240.0010
3
1
r
4
2083 230.27410
3
0
where the reaction rate constants k
j
depends on the temper-
ature according to an Arrhenius/power law expression:
k
j
= k
j.0
T
b
c
Eu,RT
(7)
The values of parameters k
j,0
, b and E
a
for reactions r
1
, r
2
,
r
3
and r
4
are listed in Table 1.
In Eq. (6) c
i,bulk
is the reacting gas concentration in the
bulk, which depends on the particle diameter, the volumetric
fraction and the char conversion; h
M,i
is the solid-to-gas mass-
transfer coefcient and Ac is the specic char surface area per
unit reactor volume. The value of h
M,i
is given by (Johansson
et al., 2006):
n
M.i
=
D
i.mix
d
p
(2 +1.1 Sc
1,3
Rc
0.6
M
) (8)
where
Sc
i
=
j
mix
,
mix
D
i.mix
(9)
and (Hobbs et al., 1993)
Rc
M
=

M
out
j
mix
(d
p
,4)
with

M
out
=

N
out
PM
mix
(10)
Symbols j
mix
and ,
mix
represent the mixture viscosity and
density, respectively; D
i,mix
is the diffusion coefcient of the
compound i into the mixture and d
p
is particle diameter.

M
out
is the total mass ow rate at the outlet of the reactor and

N
out
is the total molar ow rate at the outlet of the reactor.
It is assumed that char particles are all spherical (the diam-
eter is 50m in the feed, and decreases along the reactor
length indicated by coordinate z); thus, Ac is calculated as:
Ac =
6
d
p
y

cnur
(11)
where y

cnur
is the char volumetric fraction:
y

cnur
=
n
cnur
(z) PM
cnur
,
cnur
V
scction

(12)
Particles diameter d
p
depends on char conversion accord-
ing to:
_
d
p
d
p.0
_
3
= 1 X
cnur
+constant (13)
In order to ensure convergence stability a minimum value
was imposed to d
p
, so that the constant in Eq. (13) was
assumed equal to 110
4
.
In addition to the four heterogeneous reactions above,
three homogeneous ones were considered, i.e. the watergas
chemical engineering research and design 8 8 ( 2 0 1 0 ) 465475 469
Table 2 Kinetic parameters for the homogeneous
reactions.
Reaction k
0
(m
3
/kmol s) E
a
(kJ/kmol)
r
5
1.3510
9
60.6910
6
r
6
3.0910
14
99.810
3
r
7
8.8310
14
99.810
3
shift (WGS) reaction:
r
5
: CO + H
2
O H
2
+CO
2
(14)
and the combustion reactions of H
2
and CO in the gas phase:
r
6
: H
2
+
1
2
O
2
H
2
O (15)
r
7
: CO+
1
2
O
2
CO
2
(16)
If temperature exceeds 1000

C, the WGS reaction is fast

enough to be considered at equilibrium. Below that tempera-
ture, the reaction rate is modelled according to the following
expression (Corella and Sanz, 2005):
r
5
= k
WCS
_
c
CO
c
H
2
O

c
CO
2
c
H
2
K
WCS
_
(17)
where K
WGS
is the WSG reaction equilibrium constant
(Bustamante et al., 2002):
ln K
WCS
= 4.33 +
4577.8
T
(18)
The gas phase combustion reaction rates are given by:
r
6
= k
6
c
2
H
2

c
O
2
c
CO
(19)
r
7
= k
7
c
CO
c
O
2
(20)
The reaction rate constants of reaction r
5
, r
6
and r
7
are rep-
resented in terms of the Arrhenius expression. The values for
the frequency factor (k
0
) and activation energy (E
a
) are taken
from the literature (Kim et al., 2000) and are summarised in
Table 2.
The species concentrations in the gas phase are calculated
as:
c
i
(z) =
x
i
P
R T(z) Z(z)
(21)
where x
i
(z) is the mole fraction of the specie i in the gas phase,
without considering char, and Z(z) is the gas phase compress-
ibility factor, dened as:
Z(z) =
P V
n(z) R T(z)
(22)
where Z(z) was calculated using the Virial equation of state in
Multiash
TM
.
2.2. Mass, momentum and energy balances
The mass balance for each species i in the CSTR, used for
modelling the combustion phase is expressed as:
n
i
t
=

N
i.in

N
i.out
+V
NR

j=1
v
i.j
r
j
(23)
while the energy balance is written as:
(NT c
p
mix
)
T
t
= E
in
E
out
(24)
where the energy inlet is given as:
E
in
=
NC

i=1

N
i.in
H
i
(25)
and the energy outlet is:
E
out
=
NC

i=1

N
i.out
H
i
(26)
Symbols H
i
and

N
i
represent molar enthalpy andmolar ow
rate for specie i, respectively.
The mass balance for each species i in the PFR used for
modelling the gasication step is expressed as:
[u
i
(z) ,
mix
(z)]
t
=
[u
i
(z) u(z) ,
mix
(z)]
z
+PM
i

NR

j=1
v
i.j
r
j
(27)
The gas phase supercial velocity u(z) is calculated through
a momentumbalance (Eulero equation), under the hypothesis
that pressure is constant along the reactor (i.e. P(z)/z =0):
[,
mix
(z) u(z)]
z
= 0 (28)
Eq. (28) is not modeled as time dependent since the
momentum dynamics are much faster than the other phe-
nomena.
Two energy balances are taken into account, a rst one for
the uid phase, consisting of gas and char:
[c
p.mix
(z) ,
mix
(z) T(z)]
t
=
[,
mix
(z) H(z) u(z)]
z

[Q
rud
(z) +Q
conv
(z)]

ccrumic
(29)
and the second one for the porous solid phase:
,
ccrumic
d[c
p.ccrumic
(z) T
ccrumic
(z)]
dt
=
Q
rud
(z) +Q
conv
(z)
1
ccrumic
(30)
Table 3 Ceramic properties (Frigerio et al., 2007).
Physical properties MLM-200
Raw density (kg/m
3
) (,
ceramic
) 2280
Void fraction () 0.52
Specic surface (m
2
/m
3
) (S
specic
) 655
D
eq
(m) 2.9710
3
470 chemical engineering research and design 8 8 ( 2 0 1 0 ) 465475
Note that thermal equilibriumis assumed betweengas and
char (which is reasonable considering the small size of a char
particle).
In Eq. (31), c
p,ceramic
is the solid specic heat (Frigerio et al.,
2007):
c
p.ccrumic
(z) = B
1
+B
2
T
ccrumic
(z) +B
3
T
2
ccrumic
(z) +B
4
T
3
ccrumic
(z)
(31)
with B
1
=753.76; B
2
=1.298; B
3
=1.510
3
; B
4
=6.510
7
.
Other properties for the ceramic material are summarised
in Table 3.
The radiation term Q
rad
(z) and the convective term Q
conv
(z)
are calculated as:
Q
rud
(z) = S o
SB
(T
4
gus
(z) T
4
ccrumic
(z)) (32)
Q
conv
(z) = S n
T
(z) (T
gus
(z) T
ccrumic
(z)) (33)
where is the coal emissivity, o
SB
the StefanBoltzmann con-
stant, h
T
the heat-transfer coefcient (see also Appendix A)
and S is the total surface of the ceramic packing:
S = S
spcciic
(1 ) V (34)
with S
specic
indicating the packing specic surface area.
3. Simulation results
The PFR model is discretised along the axial direction adopt-
ing 200 grid points, whichwe veried as the minimumnumber
avoiding signicant numerical diffusion issues. The combus-
tor is run in order to provide a ame temperature near the
maximum temperature acceptable for the ceramic packing
(15001600K). Once the xed-bed reactor has been heated
up to 1563K (1290

C), the gasication phase is started. By

adopting a cyclic switching it is possible toensure a steady pro-
duction of syngas with constant quality. The cyclic operation
is simulated by switching the feeds (ue gas during the heat-
ing phase, steam and char during the gasication phase). The
gasication phase ends when the char conversion decreases
below 90%. The reactor volumes are assumed to be 2000m
3
for the combustion chamber and 60m
3
(length: 60m) for the
xed reactor. Geometry and volumes are not optimized and
were chosen in order to provide reasonable operating results.
Table 4 Operating conditions for heating and/or
combustion phase and gasication phase.
Variable Value
Operating pressure 25bar
Steam to char molar ratio 1
Input gas velocity (during heating phase) 2.5m/s
Input gas velocity (during gasication phase) 0.35m/s
Inlet gas feed to combustion phase 300K
Inlet gas feed to gasication phase 950K
a
a
950K is the temperature needed to sustain the gasication reac-
tions.
Table 5 Composition of the feed to the combustor
reactor and composition of the resulting product.
Compound Mass fraction
Input to the combustor
N
2
0.6110
O
2
0.3248
C (solid) 0.0642
Combustor output (stream in input to the heating phase)
N
2
0.6110
O
2
0.1536
CO
2
0.2354
C (solid) 0.0000
Namely, the combustor reactor volume was selected to ensure
the complete conversion of char for the given mass ow rate,
andthe residence time of the gas phase (gas andchar particles)
in the gasication reactor was set to a value typical of a u-
idized bed of this type, according to the literature (in the range
10100s, following Higman and Van Der Burgt, 2003, around
30s, as used by Nagpal et al., 2005).
The operating conditions are summarised in Table 4. In
Table 5 the composition of the feed to the combustor reactor
is reported; also, the output of the combustion phase is here
reported.
Fig. 3 shows the temperature proles inside the reactor as
a function of time: red is for high temperatures and blue for
low temperatures. At the end of the heating phase the reactor
temperature is close to the maximum admitted; on the con-
trary, in the gasication phase the temperature progressively
decreases. For the selected operating conditions, four cycles
are sufcient for the proles to become cyclically steady.
Fig. 3 Temperature proles during the cyclic process (four cycles).
chemical engineering research and design 8 8 ( 2 0 1 0 ) 465475 471
Fig. 4 H
2
and CO molar fractions during a four cyclic
process (it can be seen that during the heating phase no CO
and H
2
are produced because CO
2
is the only combustion
product).
In Fig. 4 the mole fractions of H
2
and CO at the reactor
outlet during four working cycles are plotted. These proles
show that a syngas with a H
2
/CO=0.97 ratio is obtained, and
conrm that after four cycles a process cyclic steady state is
achieved.
Fig. 5 shows the temperature proles along the reactor at
the end of the heating (Fig. 5(a)) and gasication (Fig. 5(b))
phases.
During heating, the temperature inside the reactor
increases up to 1563K and the temperature front starts
Fig. 5 Temperature proles along the reactor at the end of
the heating (a) and gasication (b) phases for only one
cycle, in this case the rst one.
advancing from the inlet towards the outlet (Fig. 5(a)). The
heating phase is stopped when the temperature in the outlet
section reaches 1400K. During the gasication step a num-
ber of endothermic reactions takes place and the temperature
of the reactor decreases creating a cold front moving towards
the outlet. However, when char conversion goes below 90%
the gasication phase is stopped as only the very last end of
the xed-bed would exhibit a sufciently high temperature to
start-up the endothermic reactions (Fig. 5(b)) and that would
make the operation scarcely effective.
3.1. Sensitivity analysis
In order to assess the process behaviour under varying operat-
ing conditions, some sensitivity studies were carried out. The
effects of the following variables was analysed:
- pressure in the gasication phase;
- steam to char molar ratio in the feed;
- char conversion at the end of the gasication phase.
Five performance indexes were dened and estimated
according to simulation results (other possible indexes can be
found in Nikoo and Mahinpey, 2008):
1. Syngas production efciency:
j
syngus
=
n
H
2
+ n
CO
n
C(solid)
(35)
2. H
2
/CO molar ratio:
H
2
CO
=
n
H
2
n
CO
(36)
3. Cold gas efciency:
Cold gas efciency (%)
=
Heating value in product gas (MW)
Heating value in feedstock (MW)
100 (37)
4. Relative CO
2
production:
CO
2
emissions =
m
CO
2
m
H
2
+CO
(38)
5. Total productivity:
Productivity =
m
H
2
+CO
t
totul cyclc
(39)
The above parameters were evaluated after reaching a
cyclic steady-state process behaviour. We have considered
three pressures (10, 25, 60bar), ve steam/char molar ratios
(0.9, 1, 1.1, 1.5, 2) and six values of char conversion at the end
of the gasication phase (0.5, 0.6, 0.7, 0.8, 0.9, 0.99).
First, the char conversion was kept constant (90%, respec-
tively). Some interesting results of the sensitivity studies are
displayed in Figs. 610.
In Fig. 6 the syngas production efciency is reported as
a function of pressure and steam to char molar ratio. It is
clear that pressure has a positive effect on this parameter,
whose value is maximized (0.90) with a steam to char ratio
between 1 and 1.1. The calculated syngas production efcien-
cies are similar to those of a moving bed conventional gasier
472 chemical engineering research and design 8 8 ( 2 0 1 0 ) 465475
Fig. 6 Syngas production efciency as a function of
pressure and steam to char molar ratio.
Fig. 7 H
2
/CO molar ratio as a function of steam to char
molar ratio at pressure P=60bar.
Fig. 8 Cold gas efciency as a function of pressure and
steam to char molar ratio.
(0.80.9, depending on coal used), for a Lurgi dry ash gasier.
Entrained-bed coal gasiers (and uidized bed ones) have dif-
ferent values, for example 0.71 (0.61) for a reactor using lignite
coal, and 1.39 (1.16) with bituminous coal as feed. All of these
data are reported by Higman and Van Der Burgt (2003).
Onthe other hand, it was veried that the effect of pressure
on H
2
/CO molar ratio is nearly negligible; quite obviously, the
Fig. 9 Total productivity as a function of pressure and
steam to char molar ratio.
steam to char molar ratio is more important, as illustrated
in Fig. 7. Calculated values are higher with respect to 0.40.7
of an entrained-coal gasier and to 0.60.7 of a uidized bed
(Higman and Van Der Burgt, 2003), due to the fact that, in our
case, only steam (no oxygen) is fed together with coal to the
gasication reactor.
The proles of cold gas efciency, which is a key parameter
for gasication processes, are presented in Fig. 8. Pressure has
a positive effect on this parameter, which is maximized for
steam to char molar ratio between 1 and 1.1. It is noteworthy
that the process cold gas efciency increases with pressure
and reaches a value around 60% at 60bar, clearly less than
a conventional gasication process using oxygen (8084%) as
reported by Higman and Van Der Burgt (2003). Other sources,
too, report similar cold gas efciency values for conventional
coal gasiers: for example, according to Guo et al. (2007) it is
81.4% for the Shell coal gasication process (SCGP), 77.5% for
the Shell Koppers technology and in the range 7173% for the
GSP gasicationtechnology (by Siemens). Data publishedby Ni
and Williams (1995) indicate a 81.4% efciency for a Shell coal
gasier, and about an 80% one for a Texaco gasier (another
entrained-ow reactor). Similar gures hold for uidized bed
gasiers, as well (Akunuri, 1999). In summary, the cold gas
efciency of the proposed process is considerably lower than
in conventional gasication. This is so because it is assumed
that combustion does not occur inside the reactor, but in an
external burner, and the ceramic packing is heated up by the
Fig. 10 kg of CO
2
per kg of syngas produced as a function
of pressure and steam to char molar ratio.
chemical engineering research and design 8 8 ( 2 0 1 0 ) 465475 473
Fig. 11 Cold gas efciency, productivity and syngas
production efciency as a function of char conversion at the
outlet of the gasication phase.
hot ue gas, whose energy is partly wasted. As a result, with
respect to a dual-bed scheme developed elsewhere (Sudiro et
al., 2008), here a higher ratio between masses of coal fed to the
combustor and to the gasier is needed in order to be able to
heat upthe xed-bed. However, we are quite condent that the
heat integration of the whole process could partly overcome
this problem. In any case, we recall the following advantages:
(i) obtaining a largely nitrogen-free syngas evenif air is used as
oxidant; (ii) avoiding the expensive air separation unit (ASU)
to produce high purity oxygen; and (iii) the need for a signif-
icantly simpler plant (at least, with respect to dual uidized
bed with inert recirculation).
Fig. 9 shows the productivity proles, where the positive
effect of pressure can be observed.
Finally, pressure has a positive effect also in minimizing
the CO
2
emissions (see Fig. 10). The minimum value of this
parameter (1.68) has been calculated at 60bar with a steam
to char molar ratio of 0.9. Calculated values are much larger
than those of both a uidized bed gasifer (Higman and Van
Der Burgt, 2003) and an entrained-bed gasier (Shelton and
Lyons, 1998), due to the high mass ow rate of coal needed
to produce the ue gas. Anyway, a correct comparison should
be made at the same working conditions (i.e. a syngas with
the same H
2
/CO molar ratio), taking into account also the CO
2
produced by the watergas shift section needed to increase
the H
2
/CO value of the syngas from a conventional gasier.
On the base of the results reported above it can be con-
cluded that the steam ow rate fed to the gasier plays the
main role if a syngas with a high H
2
content is sought. A
clear indication was also obtained for the steam/char molar
ratio, whose values should span between 1 and 1.1: under
these conditions both the syngas production efciency and
the coldgas efciency are maximized. Inparticular, the syngas
production efciency displays a maximum (Fig. 6), due to the
opposite effects of char conversion (promoted by more steam)
and of chemical equilibriumof watergas shift (unfavoured by
temperature). In addition, it was conrmed that pressure has
positive effects on all the performance parameters, except for
the H
2
/CO ratio which is unaffected by pressure.
Finally, the effect of changing the char conversion at the
outlet of the gasicationreactor is discussed, assuming for the
operating pressure a value of 25bar and a steamto char molar
ratio of 1. Results are illustratedinFigs. 11 and12; Fig. 11 shows
that cold gas efciency, productivity and syngas production
efciency decrease when the char conversion increases. A
similar behaviour (not reported) holds for the H
2
/CO molar
Fig. 12 CO
2
emissions as a function of char conversion at
the end of gasication phase.
ratio which is weakly affected by char conversion; on the con-
trary, signicantly lower CO
2
emissions can be obtained as a
consequence of a lower char conversion (see Fig. 12).
From the temperature proles inside the reactor at the end
of the gasication phase (data not reported) it was also seen
that the reactor temperature gets lower when decreasing char
conversion, indicating a better exploitation of the thermal
capacity of the ceramic packing. This explains the best per-
formance of the gasication reactor at low char conversion
values.
4. Conclusions
In this work an innovative technology for coal gasication was
developed and simulated by applying the simulated moving
bed concept to coal gasication. Accordingly, each xed-bed
reactor undergoes both the heating and gasication steps
at different times, thus resulting in a cyclically steady pro-
cess. The process was modelled by using a dynamic process
simulator. The model includes mass, energy and momen-
tum balances. It was shown that after four cycles a cyclically
steady-state behaviour is achieved. The simulation model can
be useful to assess new process schemes for coal gasication
and to promote the use of coal in a more efcient way for both
electricity and synfuel production.
Sensitivity studies were carried out with respect to pres-
sure, steam to char molar ratio and char conversion at the
gasication reactor outlet to assess the effect of the most
important operating conditions. Five efciency parameters
were considered for comparison.
The increase of pressure has positive effects on all the
parameters evaluated (an increase of the reactors productiv-
ity, an increase of syngas production efciency and cold gas
efciency as well as a decrease of the CO
2
produced). The
steamto char molar ratio has a positive effect on H
2
/COmolar
ratio and on the total yield. A maximum value for the syn-
gas production efciency and cold gas efciency was found,
corresponding to a minimum of CO
2
emissions.
The cold gas efciency of the process increases with the
operative pressure and reaches a value around 60% at 60bar,
lower thanwithconventional gasiers. However, the energetic
efciency can be improved by heat integration of the whole
process.
Char conversion should be kept low because its increase
is followed by a decrease of syngas production efciency, of
cold gas efciency and of total productivity. Also, in this con-
474 chemical engineering research and design 8 8 ( 2 0 1 0 ) 465475
dition a high H
2
/CO molar ratio and lower CO
2
emissions are
obtained.
With respect to conventional gasication reactors, the pro-
posedprocess has the advantages of producing a nitrogen-free
syngas evenif air is usedas oxidant, andof avoiding the expen-
sive air separation unit (ASU) to supply high purity oxygen.
Also, with respect to dual uidized bed gasication with inert
recirculation, it results in a much simpler plant.
On the other hand, there are some practical concerns that
should be assessed for an actual industrial implementation
to occur. First of all, potential hydrogen residues in reactor
after the gasication phase may determine some safety issues
when air is fed to the reactor during the combustion phase.
Secondly, the use of pulverized coal may clog up the ceramic
packing and cause frequent maintenance interventions to
clean the system (or even replace the packing).
Appendix A.
The correlations used to estimate the gas properties are con-
sidered here.
The thermal conductivity of a pure gas is estimated accord-
ing to the ChapmanEnskog relationship (Bird et al., 2002):
k
i
= 8.32796 10
5

_
T,PM
i
o
2
i

k.i
(A.1)
where

k.i
=
1.16145
T
0.14874
i
+
0.52487
exp(0.773320 T

i
)
+
2.16178
exp(2.43787 T

i
)
(A.2)
T

i
= T
_
k

_
i
(A.3)
The thermal conductivity of a gas mixture is given by (Bird
et al., 2002):
k
mix
=
NC

i=1
x
i
k
i

j
x
i

ij
(A.4)
The binary diffusion coefcient of gas at low and mod-
erate pressures is estimated following the ChapmanEnskog
relationship (Bird et al., 2002):
D
ij
=0.0018583 10
4

T
3
_
1
M
i
+
1
M
j
_

1
P o
2
i.j

D.ij
(A.5)
Table A.1 LennardJones parameters for the species
considered in the model (from the GRI-Mech3-0
Database).
/k (K) o ()
O
2
113 7.433
CO 110 3.590
CO
2
190 3.996
H
2
38 2.915
H
2
O 809.1 2.641
N
2
99.8 3.667
CH
4
154 3.78
C 30.6 3.385
where
o
ij
=
o
i
+o
j
2
(A.6)
The collisionintegral,
D,ij
, is a dimensionless quantity cal-
culated using the following expression:

D.ij
=
1.06036
(T

ij
)
0.15610
+
0.19300
exp(0.47635 T

ij
)
+
1.03587
exp(1.52996 T

ij
)
+
1.76474
exp(3.89411 T

ij
)
(A.7)
with
T

ij
=
_
_
k

_
i

_
k

_
j
T (A.8)
The parameters used in Eqs. (A.1)(A.8) are summarised in
Table A.1.
The following empirical law has been used to calculate the
diffusion of a compound i into a mixture of other compounds
(Bird et al., 2002):
D
i.mix
=
1 u
i

NC
j / = i
u
j
,D
i.j
(A.9)
The molar enthalpy for species i is determined as
(parameters can be found in the GRI-Mech3-0 Database
[http://www.me.berkeley.edu/gri mech/index.html]):
H
i
= RT
_
A
1
+
A
2
T
2
+
A
3
T
2
3
+
A
4
T
3
4
+
A
5
T
4
5
+
A
6
T
_
(A.10)
The molar specic heat for species i is estimated through
correlation (parameters from the GRI-Mech3-0 Database):
c
p
i
= R (A
1
+A
2
T +A
3
T
2
+A
4
T
3
+A
5
T
4
) (A.11)
The molar specic heat for the gas mixture is given by:
c
p
mix
=
NC

i=1
x
i
c
pi
(A.12)
The mass specic heat is given by the ratio between the
molar specic heat for the gas mixture and the mixture molec-
ular weight:
c
p
mix.ucignt
=
c
p
mix
PM
mix
(A.13)
The solid-to-gas heat-transfer coefcient needed to calcu-
late the convective termis obtained as (Johansson et al., 2006):
n
T
=
k
mix
D
cq
(2 +1.1 Pr
1,3
Rc
0.6
) (A.14)
where the dimensionless numbers are dened as follows:
Rc =
,
mix
v D
cq
j
mix
(A.15)
Pr =
c
p
mix.ucignt
j
mix
k
mix
(A.16)
chemical engineering research and design 8 8 ( 2 0 1 0 ) 465475 475
Nu =
n
T
D
cq
k
mix
(A.17)
The gas mixture density is calculated as follows:
,
mix
=
PM
mix
P
R T
(A.18)
References
Akunuri, N., 1999, Modeling the performance, emissions, and
costs of Texaco gasier-based integrated gasication
combined cycle systems, MS Thesis, Department of Chemical
Engineering, North Carolina State University, Raleigh,
available at the website: http://www.lib.ncsu.edu/etd/
public/etd-1143132579932361/etd-title.html.
Bertucco, A., Sanmartin, F. and Storti, G., 1995, Simulated moving
bed technology for continuous, countercurrent solid-uid
supercritical extraction. The Journal of Supercritical Fluids, 8:
138148.
Bird, R.B., Stewart, F. and Lightfoot, E.N., (2002). Transport
Phenomena (2nd ed.). (John Wiley & Sons, Inc, New York, USA).
Bustamante, F., Enick, R.M., Cugini, A., Killmeyer, R., Howard,
B.H., Rothenberg, K.S., Ciocco, M., Morreale, B.,
Chattopadhyay, S. and Shi, S., 2002, Kinetics of the
homogeneous reverse watergas shift reaction at high
temperature, available on website: http://www.netl.doe.gov/
technologies/hydrogen clean fuels/refshelf/papers/hydrogen/
Kinetics%20of%20the%20Homogeneous%20Reverse%20Water-
Gas%20Shift%20Reaction.pdf.
Corella, J. and Sanz, A., 2005, Modeling circulating uidized bed
biomass gasiers. A pseudo-rigorous model for stationary
state. Fuel Processing Technology, 86: 10211053.
Frigerio, S., Mehl, M., Ranzi, E., Schweiger, D. and Schedler, J.,
2007, Improve efciency of thermal regenerators and VOCs
abatement systems: an experimental and modeling study.
Experimental Thermal and Fluid Science, 31: 403
411.
gPROMS Advanced User Guide Rel. 2.3, Process Systems
Enterprise Ltd., London, UK, 2004.
Guo, X., Dai, Z., Gong, X., Chen, X., Liu, H., Wang, F. and Yu, Z.,
2007, Performance of an entrained-ow gasication
technology of pulverized coal in pilot-scale plant. Fuel
Processing Technology, 88: 451459.
Higman, C. and Van Der Burgt, M., (2003). Gasication. (Gulf
Professional Publishing (Elsevier), Burlington (USA)).
Hobbs, M.L., Radulovic, P.T. and Smoot, L.D., 1993, Combustion
and gasication of coals in xed-beds. Progress in Energy
Combustion Science, 19: 505586.
Johansson, R., Thunman, H. and Leckner, B., 2006, A model for
simulation of xed bed combustion, Thesis for the Degree of
Licentiate of Engineering, Department of Energy and
Environment, Chalmers University of Technology, Gteborg,
Sweden.
Kaushal, P., Proll, T. and Hofbauer, H., 2007, Model development
and validation: co-combustion of residual char, gases and
volatile fuels in the fast uidized combustion chamber of a
dual uidized bed biomass gasier. Fuel, 86: 26872695.
Kaushal, P., Proll, T. and Hofbauer, H., 2008, Model for biomass
char combustion in the riser of a dual uidized bed
gasication unit. Part I. Model development and sensitivity
analysis. Fuel Processing Technology, 89: 651659.
Kaushal, P., Proll, T. and Hofbauer, H., 2008, Model for biomass
char combustion in the riser of a dual uidized bed
gasication unit. Part II. Model validation and parameter
variation. Fuel Processing Technology, 89: 660666.
Kim, Y.J., Lee, J.M. and Kim, S.D., 2000, Modeling of coal
gasication in an internally circulating uidized bed reactor
with draught tube. Fuel, 79: 6977.
Laurendeau, N.M., 1978, Heterogeneous kinetics of coal char
gasication and combustion. Progress in Energy Combustion
Science, 4: 221270.
Lee, J.M., Kim, Y.J., Lee, W.J. and Kim, S.D., 1998, Coal-gasication
kinetics derived from pyrolysis in a uidized-bed reactor.
Energy, 23: 475488.
Levenspiel, O., 2005, What will come after petroleum? Industrial
& Engineering Chemistry Research, 44: 50735078.
Matsuoka, K., Kuramoto, K., Murakami, T. and Suzuki, Y., 2008,
Steam gasication of woody biomass in a circulating dual
bubbling uidized bed system. Energy & Fuels, 22: 19801985.
Murakami, T., Xu, G.W., Suda, T., Matsuzawa, Y., Toni, H. and
Fujimari, T., 2007, Some process fundamentals of biomass
gasication in dual uidized bed. Fuel, 86: 244255.
Nagpal, S., Sarkar, T.K. and Sen, P.K., 2005, Simulation of petcoke
gasication in slagging moving bed reactors. Fuel Processing
Technology, 86: 617640.
Ni, Q. and Williams, A., 1995, A simulation on the performance of
an entrained-ow coal gasier. Fuel, 74: 102110.
Nikoo, M.B. and Mahinpey, N., 2008, Simulation of biomass
gasication in uidized bed reactor using ASPEN PLUS.
Biomass & Bioenergy, 32: 12451254.
Ruthven, D.M., (1984). Principles of Adsorption and Adsorption
Processes. (John Wiley & Sons, Inc, Toronto, Canada).
Shelton, W. and Lyons, J., 1998, Process Engineering Division,
Texaco Gasier IGCC Base Cases, Report of Department of
Energy (DOE), number: PED-IGCC-98-001, July.
Song, C., 2006, Global challenges and strategies for control,
conversion and utilization of CO
2
for sustainable development
involving energy, catalysis, adsorption and chemical
processing. Catalysis Today, 115: 232.
Sudiro, M., Bertucco, A., Ruggeri, F. and Fontana, M., 2008,
Improving process performances in coal gasication for
power and synfuel production. Energy & Fuels, 22: 38943901.
Xu, G.W., Murakami, T., Suda, T., Matsuzawa, Y. and Tani, H.,
2006, The superior technical choice for dual uidized bed
gasication. Industrial & Engineering Chemistry Research, 45:
22812286.