FUE L PR O CE SS I N G TE CH N O LO G Y 89 ( 20 0 8 ) 1 2 0 7 1 2 1 7

a v a i l a b l e a t w w w. s c i e n c e d i r e c t . c o m

w w w. e l s e v i e r. c o m / l o c a t e / f u p r o c

H2 rich syngas by selective CO2 removal from biomass

gasification in a dual fluidized bed system Process
modelling approach

Tobias Prll, Hermann Hofbauer

Vienna University of Technology, Institute of Chemical Engineering, Getreidemarkt 9, 1060 Wien, Austria

AR TIC LE I N FO ABS TR ACT

Article history: A process model of dual fluidized bed gasification is presented based on mass- and energy
Received 15 February 2008 balances. The model further covers the evaluation of thermodynamic equilibrium states.
Received in revised form 14 May 2008 The gasification is investigated for the special case that CaO/CaCO3 is used as bed material
Accepted 19 May 2008 allowing selective transport of CO2 from the gasification reactor to the combustion reactor
by repeated carbonation and calcination. Experimental data are used to determine the
Keywords: model parameters. An empirical approach towards the kinetics of fuel conversion allows
Biomass gasification prediction of process behaviour at varied fuel water content. The selective transport of CO2
Synthesis gas results in high H2 contents in the produced syngas. The lower operating temperatures in the
Hydrogen gasification reactor increase the efficiency of energy conversion. The results are in
Process modelling agreement with experimental data and show the thermodynamic limitations of the
Simulation technology.
2008 Elsevier B.V. All rights reserved.

1. Introduction The use of calcium oxide as a CO2-acceptor inside a

Biomass steam gasification allows the conversion of solid
biomass to medium calorific gas consisting mainly of hydro-
gen, carbon monoxide, methane, carbon dioxide, and water.
The gas may either be used for electricity production (turbines,
engines, fuel cells), or it may be used as renewable resource for
syntheses (liquid hydrocarbon fuels, pure hydrogen, synthetic
natural gas, etc.) [1].
In Austria, a dual fluidized bed (DFB) biomass gasification
technology has been developed and is successfully demon-
strated at the biomass power plant Guessing at a scale of 8 MW
(fuel power) [25]. This conventional system operates with
natural olivine as catalytically active bed material at tempera-
tures of about 850900 C in the gasification reactor. The heat
for the endothermic gasification reactions is transported by
the circulating solids from a second fluidized bed reactor,
where unreacted char is combusted with air (Fig. 1).
fluidized bed gasifier (acceptor gasification process) has been
proposed by Curran et al. [6,7], where the CO2 carrier material
is transported via screw conveyors between gasifier and
regenerator. Bhatia and Perlmutter [8] investigate the reaction
of CO2 with CaO (carbonation) in detail. They report a rapid
drop of the reaction rate after about 60% solids conversion due
to product-layer diffusion limitations. Selective CO2 capture
using CaO has recently become interesting in two areas. The
first application is selective CO2 removal from combustion
exhaust gases in combination with carbon capture and
sequestration technologies. Here, extensive investigations
have been recently carried out [918]. The second field is
sorption-enhanced reforming in order to directly obtain high
H2 contents by selective carbon removal during reforming and
shift reaction [1923]. For the special situation of simultaneous
CO2 removal during steam gasification of biomass a compre-
hensive review has just been presented by Florin and Harris

Corresponding author. Getreidemarkt 9/166, 1060 Vienna, Austria. Tel.: +43 1 58801 15965; fax: +43 1 58801 15999.
E-mail address: tobias.proell@tuwien.ac.at (T. Prll).

0378-3820/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2008.05.020
1208 F U E L PR O CE SS I N G TE CH N O LOG Y 89 ( 20 0 8 ) 1 2 07 1 2 1 7
Fig. 1 Dual fluidized bed steam gasification principle.
[24]. The effects of selective CO2 removal by reaction with CaO
can be exploited in the above-mentioned DFB biomass
gasification process if CaCO3 is used as raw bed material and
the temperatures in gasifier and combustion reactor are
adjusted to appropriate levels [25,26]. In this case, the bed
material serves as a carrier not only for heat, but also for the
selective transport of CO2 from the gasification reactor to the
combustion reactor (Fig. 2).
2. Theoretical and experimental background
In a process according to Fig. 2, the bed material allows
repeated cycles of carbonation and calcination according to
CaO CO2 X CaCO3 :
However, not the whole amount of solids can be effectively
exploited for CO2 transport due to limitations in reactivity.
Grasa and Abanades [27] show for experimental data with up
to 500 reaction cycles that the practical cyclic CO2 carrying
capacity of the bed material rapidly drops with the number of
cycles to reach a final value of only 7.5% of the theoretical
stoichiometrical carrying capacity. The actual value depends
on the surface structure of the material. Abanades and Alvarez
[10] attribute the drop of reactivity to a decreased active
surface area caused by a decreasing number of micro-pores
and an increasing number of larger pores. The residual cyclic
carrying capacity generally determines the specific amount of
circulating sorbent necessary for transport of CO2.
Through simultaneous CO2 capture during the gasification
process the CO-shift reaction
CO H2 O X CO2 H2
will proceed towards H2 and CO2 and also the parallel refor-
ming/gasification reactions are influenced in favour of the
desired product H2 (reforming of hydrocarbons). Furthermore,
the process releases heat in the gasification reactor, that
reduces the need for heat transport by the circulating bed
material. For continuous gas production, CaO and solid fuels
are converted in the reactor at temperatures of 600700 C. The
carbonated bed material is regenerated by endothermic
calcination in the combustion reactor at 800900 C.
CaCO3 X CaO CO2 3
The main fuel in the combustion reactor is unreacted
biomass char transported by the circulating bed material.
Additional gaseous fuel (a part of the synthesis gas produced)
is used to control the temperature of the reactor system.
Table 1 shows measured product gas compositions for DFB
gasification with and without selective CO2 transport if
untreated wood is used as fuel. The hydrocarbon concentra-
tions remain largely unchanged despite the significant
differences in reaction conditions. The CO, CO2, H2, and H2O
concentrations are significantly influenced by selective CO2
removal and the obviously proceeding CO-shift reaction. The
different concentrations of N- and S- species can be explained
by lower N and S content in the pellets (used in the pilot plant)
compared to the wood chips (used in the demo plant). The dry
gas energy content is only a little higher for the case of
selective CO2 transport. Previous experiments on the 100 kW
DFB gasifier showed that the tar content strongly depends on
the gasification temperature [2]. Because of the low gasifica-
tion temperatures required for carbonation, a high amount of
tar could be expected. However, it appears from experimental
findings that CaO is a catalyst for both CO-shift reaction and
hydrocarbon reforming [26]. The catalytic behaviour of CaO
with respect to tar reforming has also been reported by
different authors and reviews on the topic are presented for
instance by Sutton et al. [31] and by Florin and Harris [24].
In the following section, a model of the biomass gasifica-
tion process including selective transport of CO2 is presented.
The model is kept simple and focuses on the aspects that can
be validated by experimental data either from the 8 MW demo
plant or from the 100 kW pilot plant. The procedure of model
1 validation by real plant data is discussed elsewhere [32]. The
model is used in the present study to assess the potential of
the process with respect to H2 yield and fuel conversion
efficiency.
3. Modelling
3.1. Gasification and combustion model
In contact with the hot bed material, the biomass particles
undergo the steps of drying, devolatilization, and heteroge-
neous carbon gasification. The main reactions involved in
gasification processes are summarized e.g. by Reed [33] or
more recently by Kaltschmitt and Hartmann [34]. Different
gasifier models have been presented in the literature. Some
are based on thermodynamic equilibrium [35], some consider-
ing chemical kinetics [3639]. The common task of the models
2
is the prediction of product gas composition. In the case of
dual fluidized bed systems, also the amount and composition
of residual biomass char leaving the gasifier must be consi-
dered in the model. Because of the limited solids residence
time in the gasifier, the degasification step significantly
influences the amount of residual char. It has been assumed
that the steps of drying and devolatilization are completed
first within the gasification reactor releasing the main part of
 FUE L PR O CE SS I N G TE CH N O LO G Y 89 ( 20 0 8 ) 1 2 0 7 1 2 1 7 1209

Fig. 2 Steam gasification with selective transport of CO2.

the product gas compounds. Then, in a next step, hetero-
geneous char gasification reactions determine the degree of
char conversion and, therefore, the degree of total fuel
conversion. For the conditions prevailing in the steam gasifier,
the kinetics of the steam gasification reaction
CS H2 O X CO H2
can be considered to be the fastest carbon gasification reaction
and, thus, the kinetics of Reaction (4) may be applied to
determine the amount of residual char leaving the gasifier
with the circulating bed material towards the combustion
reactor. This turned out to be a suitable approach for
description of the standard DFB gasification process operating
at about 850 C in the gasifier [32]. However, if the gasification
temperature is reduced to allow carbonation of CaO, the
assumption that the devolatilization step is finished inside the
gasifier may be questioned. Complex kinetic approaches for
devolatilization of biomass particles, however, would go
beyond the focus of the present study. Therefore, a relatively
simple empiric approach is followed to describe the net
amount of biomass char leaving the gasifier towards the
combustion reactor.
Experimental data show, that the only elementary reaction
close to equilibrium in the gasifier freeboard is the CO-shift
reaction (2). Therefore, the parameter pEq. is introduced to
express the deviation of the actual product gas composition
from equilibrium of the CO-shift reaction:
2 3
4 j pmi i
pdEq: pi ; T log10 4 i 5: 5
KP T
The equilibrium constant KP(T) can be calculated from
thermodynamic data of the pure substances. The content of
hydrocarbons (CH4, C2-, C3-compounds) in the product gas
strongly depends on the catalytic activity of the involved bed
material and will therefore be prescribed to the values found
by experiments. The contents of H2, H2O, CO, and CO2 in the
product gas can be described by the CO-shift equilibrium and
by the balances for C, H, and O.
In order to formulate the balances, the amount and com-
position of the residual char that leaves the gasifier in solid
state with the circulating bed material must be known.
Neither the amount nor the composition of the char is ac-
cessible by direct measurement. Because the mean solids
residence time in the gasifier is such that the average residual

Table 1 Typical product gas composition ranges for DFB gasification with and without selective CO2 transport (untreated
wood as fuel) All quantities except the water concentration are related to dry gas fraction
Component Unit Conventional process Conventional process Selective CO2 transport
(8 MWth demo plant)a (100 kWth pilot plant)b (100 kWth pilot plant)c

H 2O v-% 3045 3545 5165

CH4 v-% (dry) 1011 912 1014
C 2H 4 v-% (dry) 22.5 2.02.6 12
C3-Fract. v-% (dry) 0.50.7 0.30.6 0.50.8
CO v-% (dry) 2426 1924 48
CO2 v-% (dry) 2022 2025 613
H2 v-% (dry) 3840 3642 6575
H 2S v-ppm (dry) 130170 No data 1137
NH3 v-ppm (dry) 11001700 15002000 840965
Tard g/m3N (dry) 25 48 0.53.5
LHV MJ/m3N (dry) 12.913.6 12.613.3 13.116.5

a) According to Prll et al. [28], wood chips, 860 C; b) according to Pfeifer et al. [29], wood pellets, 850 C; c) according to Pfeifer et al. [29], wood
pellets, 645 C; d) tars detectable by gravimetric methods acc. to Httler et al. [30], i.e. molecular weight higher than toluene.
All quantities except the water concentration are related to dry gas fraction.
1210 F U E L PR O CE SS I N G TE CH N O LOG Y 89 ( 20 0 8 ) 1 2 07 1 2 1 7
fuel is in the transition state between devolatilization and
heterogeneous char gasification, the kinetics of the fuel
conversion, referring to water and ash free fuel,
:
m char;R;in
Xfuel;waf 1  :  
m fuel;G;in  1  wH2 O;fuel  wash;fuel
are roughly described by the empirical formula
1 pEq.,CO2,G N 0 would mean, that the reaction would already
Xfuel;waf 1 
1 kT  sbed;G
where bed,G is the mean residence time of the circulating bed
material in the gasification reactor. Since the energy bound in
the char that goes to the combustion reactor (riser) can be
determined from the energy balance, the empirical factor k(T)
can be determined from experimental data if the composition
of the residual char is known. k(T) can be expected to be
strongly dependent on temperature.
In former studies [35,40] char has been assumed to
consist of pure carbon. Within the present work, literature
values for the H and O contents in biomass char after fast
pyrolysis are applied according to literature [33], what allows
better agreement of mass and energy balances for measured
data.
In the combustion reactor, complete combustion of both
biomass char and additional fuel is assumed. The air ratio R
in the combustion reactor is defined by:
: respect to both model equations and physical property
mFG;R  wO2 ;FG;R kR  1
: :
mA;R  wO2 ;A;R kR
3.2. Selective CO2 transport
The two reactors are linked by the circulating bed material
transporting heat, residual char, and, if carbonates are present
and temperature levels allow conversion, also chemically
bound CO2, which is formally described by variation of the
solid bed material composition, i.e. by the mass fractions of
CaO and CaCO3 respectively. For the prediction of the selective
CO2 transport (1), like for the shift-equilibrium, the current
state of the gas atmosphere with respect to thermodynamic
Fig. 3 Overall structure of the simulation model implemented within IPSEpro.
equilibrium can be formulated according to Eq. (5). If Reaction
(1) progresses towards CaCO3 in the gasifier, the following
inequality must be fulfilled:
" #
6 p T
pdEq:;CO2 ;G log10 CO2
V 0: 9
pCO2 ;PG
7
progress from CaCO3 towards CO2 and CaO. This is not pos-
sible on a macroscopic level as measurements indicate a net
CO2 transport from gasifier to combustion reactor at the same
time.
In analogy to the gasification reactor, the backward
reaction in the combustion reactor requires
" #
pCO2 ;FG
pdEq:;CO2 ;R log10 V 0: 10
pCO2T
3.3. Model implementation and property data sources
The models of the two reaction zones as well as the
surrounding equipment have been implemented in the
equation-oriented steady state simulation software IPSE-
pro. The main advantage of IPSEpro is its flexibility towards
user defined model libraries and its transparency with
8 functions. The graphical representation of the simulation
model used in the present work is shown in Fig. 3. The
model describes gasifier and combustion reactor as sepa-
rate process units. The solid bed material streams are
represented and their composition is determined. The gas
streams may be optionally loaded with dust, char, and tar.
Therefore, mass and energy balances based on measured
data can be reproduced in detail. The streams marked as
optional in Fig. 3 are not considered in the present study.
The reasons for this are that the desired temperatures in
the gasification and combustion reactor can be reached by
proper selection of the solids hold-up and solids circulation
rate.
 FUE L PR O CE SS I N G TE CH N O LO G Y 89 ( 20 0 8 ) 1 2 0 7 1 2 1 7 1211

Energy balances are formulated by using total thermo- The solids circulation rate governs the energy balances of
dynamic enthalpies of the streams including the standard the two fluid bed reactors. In the present study, the circulation
enthalpy of formation: rate is expressed relative to the amount of fuel (water and ash
free) introduced into the gasifier:
h T Dh0f ;298 hT  hT0 : 11 :
m bed;G;in
rcirc :  : 18
In Eq. (11) h(T) can be an enthalpy formulation with m fuel;G;in  1  wH2 O;fuel  wash;fuel
arbitrary offset and T0 means 298.15 K.
Thermodynamic data of ideal gases and inorganic solids The efficiency of the primary energy conversion into energy
used are expressed in terms of the NASA polynomials [41]. The chemically combined in the product gas is called chemical
coefficients for ideal gas data are taken from Burcat and efficiency of gas generation (cold gas efficiency):
McBride [42], while the coefficients for inorganic solids have Pchem;PG
been fitted from data reported by [43]. For liquid water, IAPWS gchem : 19
Pth
IF97 data [44] are used. The total enthalpy of dry organic
mixtures like biomass and biomass char is calculated from The chemical energy in the product gas is defined based on
ultimate analysis and the heating value according to Schuster lower heating value:
et al. [35]: :
Pchem;PG m PG  lhvPG : 20
wC wH wS
Dh0f ;298 lhv  DH0f ;298;CO2  DH0f ;298;H2 Og
MC 2  MH MS The thermal fuel power input is also based on the lower
 DH0f ;298;SO2 : 12 heating value. In the present study, no additional fuel is
entering the system and therefore only the biomass fuel needs
The heating value of the fuel (water and ash free basis) is to be considered:
predicted from ultimate analysis by the Boie formula in kJ kg 1:
:
Pth m fuel;in  lhvfuel;in : 21
lhv 34835  wC 93870  wH  10800  wO 6280  wN
10465  wS : 13

For the temperature dependency of the char enthalpy, the 4. Results and discussion
following correlation by Merrick [45] is used:
The simulation results presented in the following refer to a
" #
R 380 2  1800 medium scale plant with 8 MW fuel power input. The size has
hT      14 been chosen according to current European marked demands
T 1 1
Mwaf exp 380 exp 1800
T
for decentralized CHP solutions and also because reliable data
of the conventional process, without selective CO2 transport,
with the mean atomic mass of the water and ash free organic
are available from the 8 MW Gssing demonstration plant.
mixture
The experimental results of test runs with selective CO2
"  #1 transport at the 100 kW pilot plant have been transformed to
X wi
Mwaf : 15 the demonstration plant scale by maintaining temperatures
i
Mi
and residence times in the reactors and by keeping the steam/
fuel ratio constant in the scale-up calculation.
As mentioned above, the temperature levels in the gasifica-
3.4. Definition of process parameters and efficiencies
tion and combustion reactor are practically controlled by
additional fuel to the combustion reactor and, in the case of
An important parameter for gasifier operation is the steam to
the pilot plant, also by cooling bundles in the gasification zone.
fuel ratio, which means the mass ratio between total H2O
Theoretically, the temperature can also be adjusted by
(fluidization steam + fuel humidity) and fuel (water and ash
adequate control of the fluidized bed hydrodynamics (i.e.
free) into the gasifier:
solids hold-up and circulation rate). A longer mean residence
: : time in the gasifier allows higher fuel conversion in the gasifier
m Fluid m fuel;in  wH2 O;fuel
uSF :  : 16
m fuel;in  1  wH2 O;fuel  wash;fuel and reduces the amount of unreacted fuel to the combustion
reactor. Hence, larger gasifiers and small combustion cham-
A parameter describing the selective transport of CO2 by bers lead to reduced system temperatures while smaller
the bed material is the specific CO2 transport capacity of the gasifiers and larger combustion chambers lead to higher
bed material. In the present work, the transport capacity is system temperatures. It is theoretically possible to design a
formulated in terms of mass CO2 combined per mass of CaO: DFB system for certain fuel properties, where no additional fuel
: or cooling is required to keep the required operating tempera-
m CO2 ;abs
uCO2 =CaO : : : 17 tures in the reactors. Since the present study aims at the
m CaO;in MMCaCO
CaO
m CaCO3 ;in
3
description of the general potential of the technology rather
The actual transport capacity during the experimental runs than on specific plant engineering, the simulation assumes
can be derived from measured data. The simulation presented in that no additional fuel or cooling is available and calculates the
the present study also investigates the sensitivity of the process required hydrodynamic parameters of the system in order to
towards the parameter uCO2 /CaO. reach the prescribed temperatures.
1212 F U E L PR O CE SS I N G TE CH N O LOG Y 89 ( 20 0 8 ) 1 2 07 1 2 1 7

Table 2 Biomass composition (water free basis)

C 51.19 wt.-%
H 6.08 wt.-%
O 41.30 wt.-%
N 0.20 wt.-%
S 0.02 wt.-%
Cl 0.05 wt.-%
Ash 1.16 wt.-%
LHVwf 19.09 MJd kg 1

Because the process performance generally depends on the

properties of the biomass used, the simulation results are
presented depending on the water content of the fuel. The
water free biomass composition summarized in Table 2 is
typical for wood.
The simulation for DFB steam gasification with and without
selective CO2 transport requires two defined reference cases
where the variations start from. These reference cases have
been derived by transformation of experimentally determined
operation states to the defined plant size of 8 MW and the
hydrodynamic situation to reach the required temperatures Fig. 4 Important process parameters vs. fuel water content
without additional fuel or cooling. The most important for conventional DFB steam gasification at an 8 MW fuel
parameters to be kept constant during the variations are power plant.
summarized in Table 3 for both cases (G gasifier, R riser/
combustor). plausible due to the significantly lower operating temperature
The heat losses of the fluidized bed reactors have been and the continuous removal of CO2.
determined at the demonstration plant for the case of
The following presentation of simulation results starts
conventional operation. The values are reduced in the case
with the behaviour of the conventional DFB steam gasifier for
of selective CO2 transport proportional to the temperature
a variation of the fuel water content. Fig. 4 shows the main
gradients between reactor and environment. For the case of operating parameters that are dependent on the fuel water
selective CO2 transport, the main part of the bed material is content for the choice of fixed parameters according to
CaO or CaCO3 respectively (mass fractions expressed for all Table 3. As the steam flow rate is constant, the steam/fuel
Ca-compounds as CaO), while the rest of the bed material still ratio is increasing with increasing water content in the
consists of olivine, which is the standard bed material in the biomass. The energy demand in the gasification zone rises
conventional process. This bed material composition corre- with increasing fuel water content. Therefore, the solids
sponds to the situation in the experiments carried out at the circulation rate increases in order to shift more heat from
100 kW pilot plant [26]. Since the gasification temperatures are the combustion zone to the gasification zone. In the same
not varied, also the kinetic parameter k is kept constant at the
values determined from experimental data. CO-shift equili-
brium prevails in the conditions of the conventional process
(900 C, olivine bed), while the pEq.,CO-shift value that has been
found from experiments in selective CO2 transport conditions
indicates, that the equilibrium is not entirely reached. This is

Table 3 Constant process parameters during the

simulation runs
Parameter Unit Conventional CO2 transport

Pth kW 8000 8000

Qloss,G kW 40 30
Qloss,R kW 160 150
TG C 900 645
TR C 954 900
mFluid,G kg.h 1 500 500
R 1.12 1.12
TFluid,G C 450 450
TA,R C 450 450
wCaO,bed kgCaO kg 1 0.0 0.9
wOliv,bed kg kg 1 1.0 0.1
k(TG) s 1 0.175 0.0228
pEq.,CO-shift 0.0 0.5 Fig. 5 Product gas composition vs. fuel water content for
conventional DFB steam gasification.
 FUE L PR O CE SS I N G TE CH N O LO G Y 89 ( 20 0 8 ) 1 2 0 7 1 2 1 7 1213

time, more fuel is needed in the combustion zone, what

requires lower fuel conversion in the gasifier. This can be
achieved by decreased solids residence times in the gasifier.
As a result of increasing circulation rate and the need for
reduced residence times, the actual solid hold-up in the
gasifier turns out to be almost independent from the fuel
water content. The chemical efficiency of gas generation is
decreasing with increasing fuel water content. This happens
due to different phenomena and can be explained finally by
increasing specific gas flow rates for both flue gas and product
gas containing more energy as sensible heat and latent heat of
water evaporation.
The product gas composition for the conventional case is
presented in Fig. 5. As no significant changes of the CH4
content of the product gas have been found at the demonstra-
tion plant for practical variations of the fuel water content in
the range of 2040 wt.%, this value is kept constant. CO, CO2, H2
and the H2O content change according to the CO-shift
equilibrium what results in a rather steep decrease of the CO
and a slight increase of the H2 content in the dry gas with
increasing fuel water content.
In selective CO2 transport regime, also the influence of the Fig. 7 CO2 transported vs. fuel water content. Parameter:
specific CO2 transport capacity of the bed material is studied. specific CO2 transport by the bed material.
The line where the parameter uCO2/CaO is zero represents a
process without CO2 transport, but operated at the same
gasification and combustion temperatures like in the CO2 in Fig. 7. Higher transport rates are possible at higher fuel
transport case. water contents because of higher solid circulation rates.
The solid circulation rate shown in Fig. 6 is about one order The product gas composition in case of selective CO2
of magnitude lower than for conventional DFB gasification transport is shown in Figs. 811. The water content in the
because of the higher temperature difference between the two product gas is generally higher for higher fuel water contents.
reactors. With increasing specific CO2 transport capacity, the Further, the water content in the product gas is decreased by
circulation rate decreases further because the reaction higher CO2 transport rates at low steam/fuel ratios (low fuel
enthalpy of carbonation and calcination superposes an water content). This effect fades with increasing fuel water
additional energy transport effect from combustion to gasifi- content. CO and CO2 concentrations are coupled together by
cation reactor. The rate of CO2 actually transported is shown the CO-shift reaction and are significantly reduced by the
selective CO2 transport. Compared to the conventional DFB
process, the CO2 content shows a different behaviour with

Fig. 6 Specific bed material circulation rate vs. fuel water

content. Parameter: specific CO2 transport by the bed Fig. 8 Product gas water content vs. fuel water content.
material. Parameter: specific CO2 transport by the bed material.
1214 F U E L PR O CE SS I N G TE CH N O LOG Y 89 ( 20 0 8 ) 1 2 07 1 2 1 7
Fig. 9 Dry product gas CO content vs. fuel water content.
Parameter: specific CO2 transport by the bed material.
respect to the fuel water content. At high steam/fuel ratios, the
CO2 content starts to decrease with increasing fuel water
content when CO2 transport occurs. The points in the graphs
where both CO and CO2 approach zero are of hypothetical
interest since the carbonation equilibrium distance according
to Eq. (9) is close to becoming positive, what indicates that the
prescribed specific transport capacity cannot be practically
reached in these cases. The H2 content rises significantly with
increasing selective CO2 transport and increasing fuel water
content. An upper limit for the practically achievable hydro-
gen concentrations can be localized at about 80 v-% (dry gas).
The values generally agree to the experimental findings
reported in Table 1. However, more data at varied operating
Fig. 10 Dry product gas CO2 content vs. fuel water content.
Parameter: specific CO2 transport by the bed material.
Fig. 11 Dry product gas H2 content vs. fuel water content.
Parameter: specific CO2 transport by the bed material.
parameters need to be determined to validate the simulation
results.
The chemical efficiency of gas generation turns out to be
independent of the specific CO2 transport capacity of the bed
material and is compared to the chemical efficiency of
conventional DFB gasification in Fig. 12. Since the operating
temperatures of the reactors are lower in the case of selective
CO2 transport, the energy transported as sensible heat in the
gas streams is lower and the chemical efficiency is higher than
in the conventional case.
Fig. 12 Chemical efficiency of gas generation vs. fuel water
content comparison between the conventional DFB
concept and operation with selective CO2 transport.
 FUE L PR O CE SS I N G TE CH N O LO G Y 89 ( 20 0 8 ) 1 2 0 7 1 2 1 7 1215

5. Conclusions

A simple process simulation model for the dual fluidized bed

(DFB) gasification process with and without selective CO2
transport by the circulating bed material has been imple-
mented in the equation-oriented steady state simulation
software IPSEpro. The simulations are based on experimen-
tal results from an 8 MW demonstration plant for conven-
tional DFB gasification and from a 100 kW DFB pilot plant
that has been operated in selective CO2 transport mode. The
simulation shows the behaviour of selected process para-
meters during variations of fuel water content and specific
CO2 transport capacity of the bed material. Apart from the
significantly higher H2 content in the product gas, the CO2
transport concept is more efficient in converting primary
fuel energy into product gas because of the lower operating
temperature. The use of CaCO3 as bed material and adjust-
ment of operating temperature in order to allow selective
CO2 transport from gasification to combustion reactor is a
highly promising variation of the conventional DFB technol-
Fig. 13 Important process parameters vs. fuel water content ogy. If pure oxygen is used in combination with flue gas
in case of selective CO2 transport (CO2 transport capacity of recycling in the combustion/calcination reactor (oxy fuel
the bed material: 0.15 kg kg 1CaO). combustion), a relatively pure CO2 stream is provided after
condensation of H2O from the flue gas. Thus, a significant
According to Specht et al. [46], a long-term specific CO2 part of the fuel carbon content can be provided for
transport capacity of about 0.15 kg kg 1CaO can be expected in subsequent compression and sequestration. In the case of
the DFB system for the bed materials that have been tested so biomass fuel, this would result in a net carbon sink process
far. This would mean a long-term cyclic conversion of 19% of and may be an option if a CO2 sequestration infrastructure
the maximum stoichiometrical value and is higher than the establishes in the future.
residual conversion found by Grasa and Abanades [27].
Possible explanations for the higher reactivity in the DFB
system are the continuous addition of new material to Nomenclature
compensate for attrition on the one hand and, on the other h enthalpy J kg 1 K 1
hand, potentially favourable calcination conditions in the DFB h* total enthalpy considering the
system. Fig. 13 shows other process parameters in analogy to enthalpy of formation J kg 1 K 1
Fig. 4 assuming a specific CO2 transport capacity of 0.15 kg k kinetic constant of fuel conversion
kg 1CaO. The steam/fuel ratio has been omitted since it is in the gasifier s 1
identical with Fig. 4. The main differences between conven- KP equilibrium constant for P
tional DFB gasification and the case of selective CO2 transport partial pressures bar i mi
are the lower solids circulation rate and the significantly lhv lower heating value J kg 1
higher mean solids residence time in the gasifier in the latter m mass (of bed material) kg
case. The solids hold-up in the gasifier is again almost m mass flow kg s 1
independent of the fuel water content and only about 0.6 M molar or atomic mass respectively kg mol 1
times the hold-up of the conventional case. p (partial) pressure bar
Summarizing the results, the selective removal of CO2 in p* partial pressure in chemical equilibrium bar
the gasification reactor coupled with the CO-shift reaction peq. logarithmic equilibrium distance
leads, especially at high steam/fuel ratios, to a significant for a specific reaction
increase of the H2 concentration in the product gas. Because of Pchem chemical power of the produced gas
the high temperature difference between gasification and based on LHV W
combustion in the case of selective CO2 transport, the solids Pth fuel power of the entire gas generation
circulation rate must be about one order of magnitude lower unit based on LHV W
than in the conventional DFB process while the mean solids rcirc specific solids circulation rate kg kg 1fuel(wf)
residence time in the gasifier increases by about the same R universal gas constant (R = 8.314 314
factor. The chemical efficiency of the process is not influenced J mol 1 K 1) J mol 1 K 1
by the amount of CO2 actually transported at a certain T temperature K
temperature level. The reason for the observed increase in T0 reference temperature (298.15 K) K
chemical efficiency compared to the conventional process is w mass fraction kg kg 1
the lower operating temperature in the case of selective CO2 X chemical conversion based
removal. on initial quantity
1216 F U E L PR O CE SS I N G TE CH N O LOG Y 89 ( 20 0 8 ) 1 2 07 1 2 1 7

Greek symbols
0
hf,298 specific standard enthalpy
of formation at 298.15 K
0 a dual fluidized bed gasifier. Part II: simulation of solid
Hf,298 molar standard enthalpy
of formation at 298.15 K
uchar,bed fraction of organic fuel that is not
converted in the gasifier
uCO2/CaO specific CO2 transport capacity
of the bed material
uSF total water to fuel (waf) ratio
in the gasifier (steam/fuel ratio)
chem chemical efficiency of gas generation
with gas injection and diffuser, Chem. Eng. Sci. 58 (2003)
41974213.
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circulation rate, pressure loop and stability, Chem. Eng. Sci. 58
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kg kg 1fuel(wf) Am. Chem. Soc., Div. Fuel Chem., Preprints 8 (1964) 128146.
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i stoichiometric factor of compound i
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R combustion reactor (riser)
waf referring to water and ash free fuel fraction
Acknowledgement
The authors gratefully acknowledge the financial support by the
European Commission under the contract AER-Gas (contract
number ENK5-CT-2001-00545) and by the Renewable Energy
Network Austria ReNet (Austrian funds program KNET/KIND).
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