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Powder Technology 132 (2003) 167 – 183

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Operating concept of circulating fluidized bed gasifier


from the kinetic point of view
Huachung Tsui a, Chung-Hsing Wu b,c,*
a
Research and Development Department, Cotech Engineering Corporation, Fl.1, No. 13, Wu Chuan 1st Road, Wuku Industrial Park,
Hsin Chung, Taipei Hsien, Taiwan, ROC
b
Department and Graduate Institute of Bio-Industrial Mechatronics Engineering, National Taiwan University, Taipei, Taiwan, ROC
c
College of Science and Engineering, National United University, Miaoli, Taiwan, ROC
Received in revised form 10 October 2001; accepted 19 February 2003

Abstract

Circulating fluidized bed gasifiers used in integrated gasification and combined cycle (IGCC) possess unique design and operational
features: high gas velocity, high solid loading, and a large amount of circulating chars. As a consequence, their performance is noticeably
different from the conventional fluidized bed gasifier operating at lower gas velocity. At the same time, limited information has been
published to show how to operate the circulating fluidized bed from the kinetic point of view.
In order to study these aspects, kinetic models are developed using kinetic data from previous literature and two concepts of operating the
circulating fluidized bed gasifier from the kinetic point of view are presented in this paper. The results of the kinetic analysis using Johnson’s
kinetic data of a constant specific gasification rate of char (0.001 1/s) show that all species approach their equilibrium values after travelling a
distance of 2.5 m, which is set as the height of the gasifier. The resident time of the char in the bed is 0.86 s and the required circulation rate of
char and lime are 11.8 and 4.5 kg/s, respectively. In addition to Johnson’s kinetic data, Wen’s kinetic model is also applied in the kinetic
analysis. It shows a way to operate the gasifier in the fast fluidization regime with a superficial velocity between 3.6 and 4.9 m/s and a solid
loading between 50 and 100 kg/m3, these operating conditions are recommended by industrial experience. It points out the necessity to
predict the performance of the gasifier from the kinetic point of view in order to design the optimal geometry and operating methods that will
allow the gasifier to play a successful role in the clean coal technology system such as IGCC, high-performance power system (HIPPS), etc.
D 2003 Elsevier Science B.V. All rights reserved.

Keywords: Circulating fluidized bed; Gasifier; Kinetic model; Solid loading; Circulating chars

1. Introduction solving the transport and storage problem of coal and for
aiming at displacing fuel oil completely, heavily loaded
The world has large coal reserves; in the US, in partic- coal –water slurries (f 70% coal by weight) treated with
ular, they constitute 90% of all known fossil energy resour- additives (f 1% by weight) have been developed. Several
ces in that country. Although natural gas-fired combined demonstration projects have already proven the feasibility of
cycles currently predominate the power generation market, such coal utilization schemes [2]. To cope with the pollution
and interest is increasing in renewable energy sources, coal problems caused by coal combustion, development pro-
will likely maintain its share of the power generation market grams for ‘‘clean coal technologies’’ have been adopted
simply because it has the largest reserves and no alternative worldwide [3]—such as the integrated gasification and
is foreseen to replace it in the foreseeable future [1]. combined cycle (IGCC), the pressurized fluidized bed com-
However, coal usage has been hampered by pollution bustor (PFBC) combined cycle, ‘‘British Coal topping
caused by its transport, storage, and combustion. Partly for cycle’’ in the U.K. [4], the low emission boiler system
(LEBS) and the high-performance power system (HIPPS)
by the U.S. Department of Energy [5], etc. One of the most
* Corresponding author. Department and Graduate Institute of Bio-
Industrial Mechatronics Engineering, National Taiwan University, Taipei,
important chemical processes in the clean coal technologies
Taiwan, ROC. Tel./fax: +886-2-23693159. is coal gasification converting solid coal into gaseous fuel
E-mail address: chwu@ccms.ntu.edu.tw (C.-H. Wu). used to power turbine and subsequently to power generator.

0032-5910/03/$ - see front matter D 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0032-5910(03)00060-3
168 H. Tsui, C.-H. Wu / Powder Technology 132 (2003) 167–183

An advanced gasifier is required in IGCC to accomplish such forced to move towards the wall by centrifugal force and are
work. Conventional gasifiers that operate in either a bubbling collected for recycling, whereas small solid particles are
or entrained mode are not suitable choices because they do carried over by the flue gas. Another advantage of tangential
not provide efficient solid – gas mixing. A novel gasifier injection is that the injected air stays close to the cylinder wall
consisting of a circulating fluidized bed and a cyclone and most of the oxygen in the air can be expected to react with
combustor, shown schematically in Fig. 1, as developed by the char instead of the flue gas that is relative far from the
Foster Wheeler [6], is one of the most promising choices cylinder wall. The energy released in the cyclone combustor
because it provides good contact efficiency between gas and will be carried by the circulating solids to the circulating
solids and reduces the size of gasifier. fluidized bed to provide the required heat for the endothermic
The air enters the circulating bed at velocities high enough chemical reactions of coal gasification.
for the fluidized bed to operate in the ‘‘fast’’ or ‘‘circulating’’ A three-level approach, which involves thermodynamic,
regime. At these velocities, solid entrainment increases sig- kinetic, and hydrodynamic models, was used to analyze the
nificantly, and circulation of solids becomes necessary to operation of the gasifier shown in Fig. 1 [7]. This paper only
preserve a constant solid inventory in the bed. Thus, a cyclone presents the kinetic analysis. The feed rates of materials, the
is introduced to collect solids from the flue gas and recycle generation rate of product gas, and the circulation rate of char
them into the circulating fluidized bed. The cyclone is also used in the kinetic analysis come from the thermodynamic
used as a combustor to supply energy for the endothermic analysis by balancing the mass and energy of the gasifier at
gasification reactions. Therefore, the cyclone is referred to as equilibrium. The kinetic analysis will predict how the
a cyclone combustor. When the flue gas enters the cyclone chemical reactions approach equilibrium in the gas and
combustor tangentially, large solid particles in the flue gas are provides an estimate for the required circulating rate of char.

Fig. 1. Sketch of a novel gasifier consisting of a circulating fluidized bed and a cyclone combustor.
H. Tsui, C.-H. Wu / Powder Technology 132 (2003) 167–183 169

Coal water slurry fuel is used to show its feasibility in this Table 1
Reaction mechanisms and rate expressions of char – steam reaction (source:
coal utilization scheme. Gasification of coal water slurry fuel
Lowry [15])
consists of three steps: evaporation, devolatilization, and the
Source Reaction Rate expression
following char gasification. As the rate of evaporation and
mechanism
devolatiliaztion are fast compared to gasification, the gas-
ification rate of char is considered as the factor that domi- Walker Cf þ H2 OðgÞ K!
1
 K1 ðH2 OÞ
et al. K2 Rate ¼
nates the gasification time of coal water slurry fuel in this H2 ðgÞ þ CðOÞ 1 þ K 1 ðH2 OÞ þ K 2 ðH2 Þ
K3 K3
kinetic analysis [8]. CðOÞ K!
3
COðgÞ
K1 ðH2 OÞ þ Kd ðCO2 Þ
Ergun and Cf þ H2 OðgÞ K!
1
 Rate¼
K2 K1 K2 K5
Menster 1þ ðH2 OÞþ ðH2 Þþ ðCOÞ
2. Problem formulation K3 K3 K4
H2 ðgÞ þ CðOÞ
K3
2.1. Kinetics of coal gasification CðOÞ ! COðgÞ

CðOÞ þ CO K!
4

Numerous experiments have been performed to study the K5

kinetics of coal gasification [9 –12]. Kinetic information has CO2 ðgÞ þ Cf


 
been obtained from either the amount of coal converted or CH2 CCORT
Wen C + H2O(g) ! dx
dt ¼kv CH2 O  ð1  xÞ where:
weight of gaseous products formed during gasification. CO + H2 K
Wide variations exist in the kinetic data reported in the coal Kv = volumetric rate constant;
gasification literature. The variation appears to be caused by K = equilibrium constant
differences in chemical and physical properties of the coal
and the experimental systems used. The chemical properties
1 contains some of the rate expressions and mechanisms
of coal, such as carbon, hydrogen, and oxygen contents,
developed for the char –steam reaction [15]. Carbon mon-
have significant effects on carbon conversion during gas-
oxide and hydrogen are the principal products of a char –
ification. As carbon content increases or as hydrogen and
steam reaction and their concentration may have a retarding
oxygen present in coal decrease, the rank of the coal
effect on the rate.
increases. In general, the reactivity of coal decreases as
The rate of char – steam reaction depends mainly on the
the carbon content increases or the oxygen and hydrogen
temperature and steam pressure. Fig. 2 shows the variation
contents decrease. In other words, lower rank coals are more
of char gasification rates with temperature at 1 atm steam
reactive than higher rank coals [12].
pressure [10]. Although there are wide variations in gas-
The physical properties of coal, such as particle size and
ification rates of different chars, they all increase exponen-
porosity, have significant effects on the kinetics of coal
tially with temperature. The variations in rates are due to
gasification. As the particle size becomes smaller the spe-
difference in chemical and physical properties of the chars.
cific contact area between the coal and the reacting gases
Fig. 3 shows the variation of char gasification rate with
increases, resulting in faster reaction. In general, coal gas-
steam pressure at different temperatures [12]. The rates
ification processes with entrained and fluidized bed reactors
increase with steam pressure but become independent of
use coal with an average size of 75 Am. Processes with fixed
pressure at pressures higher than about 10 atm.
bed reactors use larger size coal with diameter exceeding
300 Am. Porosity of coal is related to the pore volume and
2.2. Desulfurization during coal gasification
surface area present in the coal. It has been found [12] that
reactivity in gasification increases with an increase in pore
In developing coal gasification processes, the removal of
volume and surface area of low and medium rank coals.
the sulfur compounds has been of great concern because of
However, reactivity is not affected by changes in pore
their detrimental effects on air quality and their role in
volume and surface area in high rank coals with carbon
corrosion of equipment. The principal sulfur compound that
content larger than 85%. This is due to the smaller pores
evolves during gasification of coal is H2S with lesser
present in higher rank coals. As pores become smaller, the
portions of COS, CS2. Hot gas desulfurization proceeds in
access of reacting gases to the internal surface of the coal is
two steps when calcium-based sorbent is used. First, the
reduced, i.e. the process is controlled by the rate of diffusion
limestone (mostly CaCO3) is calcined to produce lime
into the coal.
(CaO) and CO2 as shown in Eq. (1). In the second step,
In experimental systems, coal is pyrolyzed to become
lime reacts with H2S to produce a stable sulfide CaS as
char, which undergoes conversion to gas by reaction with
shown in Eq. (2).
steam, carbon dioxide, and hydrogen. The kinetics and
mechanisms of reactions of coal char with steam, carbon
CaCO3ðsÞ ! CaOðsÞ þ CO2 ð1Þ
dioxide, and hydrogen were discussed in the previous liter-
ature [13,14]. In general, Langmuir-type adsorption equa-
tions have been used to represent gasification rates [9]. Table CaOðsÞ þ H2 S ! CaSðsÞ þ H2 O: ð2Þ
170 H. Tsui, C.-H. Wu / Powder Technology 132 (2003) 167–183

between CaO and H2S depends on the concentration of H2S


(C) and the concentration of available CaO (A) as follows:
dN
 ¼ K3 AC; ð3Þ
dt
where K3 is the rate constant of Eq. (2). The concentration of
available lime in the calcined limestone decreases as the
reaction of desulfurization proceeds in two ways: the avail-
able lime reacts with H2S (K3AC) or the surface of the
available lime is covered by CaS layer. The decrease rate of
available lime through the adsorption and desorption of CaS
layer equals the subtraction of the adsorption rate CaS layer
on the exterior of available lime (K1AC) to the desorption
rate of CaS layer on the exterior of inactivated lime (K2B).
Thus, the decrease rate of available lime (  dA/dt) could be
written as follows:
dA
 ¼ K1 AC  K2 B þ K3 AC; ð4Þ
dt
where K1 is the rate constant of adsorption of CaS on the
surface of available lime and K2 is the rate constant of
desorption of CaS on the surface of inactivated lime. Sub-
stituting the expression A from Eq. (3) into Eq. (4) and
rearranging, Eq. (5) is obtained. From Eq. (5), the rate of
decrease of CaO(s) (dN/dt) is obtained as shown in Eq. (6),
Fig. 2. Variation of char gasification rates with temperature (source: where Ke = K1/K2. The decrease rate of CaO(s) (dN/dt) equals
Johnson [10]).
the desulfurization rate because 1 mol of CaO(s) reacts with 1
According to Abel et al. [16], the rate of Eq. (2) is fast, but mol of H2S, as indicated in Eq. (2). The kinetic constants K1,
the rate of Eq. (1) is relatively slow. In addition, CaCO3 is K2, and K3 are determined from experimental results via
chemically inert to H2S. One potential reason for limestone Arrhenius plots [19]. The pre-exponential constants and
not being able to remove H2S effectively is the relatively slow activation energy for the Arrhenius law are described in
calcinations, Eq. (1), that occurs under gasification condi- Table 2. The general Arrhenius expression is given in Eq.
tions. This problem can be solved in the proposed reactor (7). Form Table 2 and Eq. (7), the rate constants K1, K2, and
configuration. A large amount of CaO is recycled in the K3 can be determined. Substituting these rate constants into
gasifier, making the removal of H2S from the gas stream
relatively rapid. According to Schrodt and Hahnn [17], CaS
formed on the exterior of the sorbent prohibits further
reactions of the sorbent with H2S. Thus, CaS appears to form
a diffusion barrier for H2S penetration and this limits the
calcium utilization efficiency. This effect is taken into
account in modeling the process of desulfurization as follows.
A theoretical model for the reaction of CaO with H2S was
developed and experimentally verified by Pell et al. [18].
This model assumes that there is nothing adsorbed on the
surface of CaO at the beginning of reaction of desulfuriza-
tion. As reaction (2) proceeds, the rate slows down, and this
suggests that CaS is adsorbed upon the surface thereby
inactivating the surface. The total amount of lime (CaO) in
the calcined limestone could be categorized into two groups,
according to Pell et al. [18]. One group is the available lime
that can react with H2S to form CaS through reaction (2). The
other group is inactivated lime that cannot react with H2S
due to the adsorption of CaS layer on the surface of lime. The
concentrations of the total amount of lime, available lime,
and inactivated lime in the calcined limestone are specified Fig. 3. Variation of char gasification rates with pressure (source: Quader
as N, A, and B, respectively. The rate of reaction (dN/dt) [12]).
H. Tsui, C.-H. Wu / Powder Technology 132 (2003) 167–183 171

Table 2 (10) is slow compared with the generation of C(o) by


Coefficients of Arrhenius expressions for rate constants (source: Pell et al.
collisions via Eqs. (8) and (9). The kinetic analysis utilizes
[18])
Lindemann’s theory in the way that the gasification process
Constants Preexponential Activation energy
proceeds step by step and the number of C(o) complexes
(Ki) constants ( Pi) (Ei, kcal/gmol K)
reaches a stationary value after each time step. To reach a
K1 8.3 13.1
stationary value of C(o), the number of energized sites C(o)
K2 9.5 28.2
K3 13.1 22.9 desorbed through Eq. (10) should equal the number of the
Ke  1.2  15.1 energized sites C(o) generated through Eqs. (8) and (9) in a
small time interval Dt. Thus, the statement of Lindemenn’s
theory
_ can be written as Eq. (11), where negative values of
Eq. (6), the desulfurization rate (dN/dt) can be obtained if the
N c (atoms/s) represent the number of C(o) complexes
concentration of H2S (C) and the amount of unconverted
desorbed through Eq. (10), and positive values of X and
CaO(s) (N) are known.
Z represent the number of atoms of CO2 and H2 generated
d2 N dN through Eqs. (8) and (9) in the time interval Dt, respec-
þ ðK1 C þ K3 C þ K2 Þ þ K2 K3 CN ¼ 0 ð5Þ tively.
dt 2 dt

Nc Dt decomposition of CðoÞ through Eq: ð10Þ
dN K3 N C
 ¼ ð6Þ þ Z generation of CðoÞ through Eq: ð9Þ
dt 1 þ Ke C
þ ðX Þ Generation of CðoÞ through Eq: ð8Þ ¼ 0: ð11Þ
 
Ei
Ki ¼ Pi exp : ð7Þ A negative sign is added to X in the third term of Eq. (11)
RT
to represent the generation of energized sites C(o) because
2.3. Kinetic model of char gasification the decomposition of CO2 (  X) will implicate the gen-
eration of C(o) through Eq. (8).
The kinetic model of char gasification is derived from the In this reaction system, the total number of oxygen atoms
mechanism of the chemical reactions among the char, water is constant, being either present as energized sites C(o) or
vapor, and CO2. According to Johnson [10] and Ergun [11], contained in the gas species CO, CO2, and H2O. According
the mechanism of the reaction between the char and water to Lindermann’s [20] theory, the number of energized sites
vapor in the presence of CO2 can be written as Eqs. (8) – C(o) reaches a stationary value rapidly, implying that the
(10). They assume that there are many free sites Cf on the oxygen concentration in C(o) complexes will reach a sta-
char, which can adsorb oxygen from the dissociative chem- tionary number. Thus, the number of oxygen atoms con-
isorption of CO2(g) and steam as shown in Eqs. (8) and (9), tained in the gas species (H2O, CO2, CO) will also reach a
respectively. As this happens, the free site is energized and constant value because the total number of oxygen atoms in
becomes an occupied site (C(o)), which in turn is gasified to the chemical system is a constant. The statement indicating
produce CO(g), as shown in Eq. (10). The energized site C(o) a constant number of oxygen atoms in the gas species is
is a chemical complex on the surface of the char which can represented by Eq. (12), where Y is the total number of
be transferred into reaction product CO(g) without receiving atoms of CO generated through either Eq. (8) or Eq. (10)
additional energy. However, the process of desorption of the during the time interval Dt.
chemical complex C(o) (reaction (10)) is slower than Eqs.
(8) and (9), therefore the rate of desorption controls the Z disappearance of oxygen through the generation of H2
reaction rate. ¼ 2X appearance of oxygen through the generation of CO2

CO2ðgÞ þ Cf !k1 þ Y appearance of oxygen through the generation of CO:


kV
 COðgÞ þ CðoÞ ð8Þ
1
ð12Þ
k2
H2 OðgÞ þ Cf ! H2ðgÞ þ CðoÞ ð9Þ _
kV 2 There are four unknowns, N c, X, Y, and Z, in_Eqs. (11)
k3 and (12). Even if the rate of char gasification (N c) can be
CðoÞ ! COðgÞ : ð10Þ obtained from experiments, there are still three unknowns—
X, Y, and Z—in Eqs. (11) and (12). In order to solve the
As Eq. (10) is the rate-controlling step, the gasification problem, another governing equation was applied as fol-
process can be represented as a first-order reaction, i.e. the lows. The equilibrium constants, K1 and K2, of Eqs. (8) and
reaction rate is proportional to the concentration of C(o). (9), respectively, can be written as Eqs. (13) and (14).
According to Lindemann’s theory [20], for a first-order Dividing Eq. (14) by Eq. (13) and simplifying it will result
reaction, the number of energized molecules C(o) will reach to Eq. (15). It is interesting to note that Eq. (15) represents
a stationary value if the conversion of C(o) into CO via Eq. the equilibrium condition for the water – gas shift Eq. (16).
172 H. Tsui, C.-H. Wu / Powder Technology 132 (2003) 167–183

In the next section, the concentration of H2O, H2, CO and velocity are mainly due to the chemical reaction between
CO2 in Eq. (15) are related to X, Y, and Z in the small- char and steam.
compartment scheme. Thus, (Eqs. (11), (12) and (15) are the
governing equations, which can be solved for X, Y, and Z 
Wc ¼ Wc0 þ Nc Dt ð17Þ
when Nc is known and a small-compartment scheme is used
in the next section.
0
WCO ¼ WCO þY ð18Þ
k1 ½CO ½CðoÞ
K1 ¼ ¼ ð13Þ
k1V ½CO2 ½Cf
WH2 ¼ WH0 2 þ Z ð19Þ

k2 ½H2 ½CðoÞ
K2 ¼ ¼ ð14Þ
k2V ½H2 O ½Cf WH2 O ¼ WH0 2 O  Z ð20Þ

K2 ½CO2 ½H2 0
WCO2 ¼ WCO þX ð21Þ
K¼ ¼ ð15Þ 2
K1 ½CO ½H2 O

0 
CO þ H2 O ¼ CO2 þ H2 : ð16Þ WCaO ¼ WCaO þ NH2 S Dt ð22Þ

2.4. One-dimensional control volume analysis 


WH2 S ¼ WH0 2 S þ NH2 S Dt: ð23Þ
A one-dimensional control volume analysis was devel-
oped to determine the extent to which the chemical reactions
of char gasification approach equilibrium in the region from To conduct the one-dimensional control
_ volume analy-
X1 = 0 to X1 = 2.5 m (the gasifier height) as shown in Fig. 1. sis, the five unknowns X, Y, Z, and N H2S appearing in the
The gasification of CWSF is assumed to occur in three above equations should be determined. The first three
consecutive steps: evaporation, combustion, and slow reac- unknowns—X, Y, Z—are obtained using the kinetic model
tion between char and steam. The processes of water developed
_ _ in the previous section. The last two unknowns,
evaporation, coal pyrolysis, and combustion complete at N c and N H2S, are determined by using experimental data in
X1 = 0. This assumption may not fit reality because the the literature [8 – 10]. Eqs. (11)– (13) derived in the pre-
evolution rate of the volatiles, which depends on various vious section can be rearranged to Eqs. (14) and (15),
factors such as particle size, pressure, and heating rate, may respectively. Eq. (24) is obtained by substituting Eqs.
be too slow to assume that coal pyrolysis has been completed (18) –(21) into Eq. (13).
at X1 = 0. A complete pyrolysis model would describe the 0
K2 ðWCO þ X ÞðWH0 2 þ ZÞ
composition and physical state of the char particle and the K¼ ¼ 2
ð24Þ
0
composition and evolution rate of the volatiles at all stages of K1 ðWCO þ Y ÞðWH0 2 O þ ZÞ
pyrolysis. However, the detailed mechanism of the evolution
and combustion of volatiles is not very well understood and 
Z ¼ X  Nc Dt ð25Þ
detailed experimental work is still required. Nevertheless,
this assumption is still a good approximation because in
general the reaction rates of water evaporation, coal pyrol- 
Y ¼ X  Nc Dt: ð26Þ
ysis, and combustion are much faster than that of the
gasification of the char. Based on this assumption, the initial Substituting Eqs. (25) and (26) into Eq. (24), results to Eq.
composition and superficial velocity of the gas mixture can (27), which contains only X.
be obtained from the thermodynamic analysis.
The variation of the composition and the superficial gas
velocity as X1 increases can be determined using Eqs. (17) – aX 2 þ bX þ c ¼ 0 ð27Þ
(23). The variation of the number of mole of species (based
where
on 1 mol of carbon in feed CWSF) as X1 increases can be
calculated from these equations. This information is then
utilized to obtain the composition of the gas mixture (mole a=1K _
fraction) and the superficial gas velocity. The variation in 0
b = KW H 2O
0
KW CO + W 0CO2_+ W0H2 N cDt _ _ _
0 0 0 0
the gas composition and the increase in the superficial gas c = KW H2OWH2O +KW H2O N cDt  KWCO N cDt + K(N cDt)2+ W CO
0
2
0
W CO 2
N CDt.
H. Tsui, C.-H. Wu / Powder Technology 132 (2003) 167–183 173

The solution of Eq. (27) is written as Eq. (28) 2.5. Circulation rate and shrinkage of chars
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
b þ b2  4ac The circulation rate of char is calculated in the following
X ¼ : ð28Þ two steps. First, the cut-off diameter of the cyclone com-
2a
bustor is calculated according to the cyclone geometry and
the Rankine vortex flow condition [21]. Second, the tran-
Substituting the value of X into Eqs. (15) and (16), the
sient mass equations of char particles are developed. A trial
values of Z and Y are obtained._ _ and error method is applied to solve these equations by
The rates of gasification N c and desulfurization N H2S are
varying the initial diameter of char particle and the number
determined from experiments conducted by Wen [9], John-
of circulation of char particle in the gasifier until the
son [10], and Pell et al. [18]. Thus, two sets of kinetic data
diameter of char particle shrinks to the cut-off diameter
were used to indicate the influence of the rate of gasification
and the circulation rate of char is accumulated to the
on the performance of the circulating fluidized bed gasifier:
required amount. In the analysis using Johnson’s kinetic
one set from Johnson [10] as described in Fig. 2 and the
data, the circulation rate of char reaches such amount that
other from Wen [9] as described in Eq. (29). Johnson’s [10]
the chemical reaction of char gasification reach equilibrium
experiments indicate that the rate of the char –steam reaction
at X1 = 2.5 m. In the analysis using Wen’s kinetic model, the
depends mainly upon temperature and steam pressure for a
circulation rate of char reaches such amount that the fluid-
specific kind of char. Fig. 2 contains specific gasification
ized bed has a superficial velocity between 3.6 and 4.9 m/s
rates for different chars in steam at 1 atm. It shows that the
(12 –16 ft/s) and a solid loading density between 50 and 100
gasification rate increases as the temperature increases.
kg/m3, which are recommended for the bed to operate in the
Wen’s [9] experiments indicate that the rate of char gas-
circulating region by industrial experience [22]. The follow-
ification also depends on the concentration of H2O, H2, and
ing assumptions were made in conducting the analysis.
CO. This is shown in his kinetic model, Eq. (29), which
includes the concentrations of these species. In the equation,
1. The char is a spherical solid particle with a constant
KC – H2O is the equilibrium constant of char stream reaction
density.
and Kv is the rate constant for the gasification of coal char in
2. The shrinkage of the char is mainly due to the chemical
the temperature range from 1273 to 1473 K.
reactions between the char and the gas species (steam and
  oxygen), i.e. the effects of attrition and agglomeration on
 CH2 CCO RT the size of the particles have been neglected.
Nc ¼ Kv CH2 O  Wc : ð29Þ
KCH2 O 3. A Rankine vortex [23] is formed in the cyclone
combustor, which is a combination of a central forced
_ vortex and a peripheral vortex.
The rate of desulfurization N H2S is obtained from the
kinetic model of Pell et al. [18], as indicated by Eq. (30). 4. The cut-off diameter of the cyclone combustor can be
The rate constants K3 and equilibrium constant Ke are determined by considering the motion of the particle on a
obtained from experiments [19] of the reaction between imaginary cylindrical surface as described by Ogawa [23]
CaO and H2S from 700 to 1200 K and Barth and Trunz [24].
5. All particles larger than the cut-off diameter are separated
from the product gas and all particles smaller than the
 ¼ K3 WCaO CH2 S :
N ð30Þ cut-off diameter are carried out of the cyclone combustor
H2 S
1 þ Ke CH2 S by the product gas.

The kinetic model of desulfurization described by Eq. (30) 2.5.1. Calculation of cut-off diameter of the cyclone
does not consider the effect of the water concentration on combustor
the rate of desulfurization. The effect of water concentration The separation of the particles and the gas in the cyclone
on the rate of desulfurization is still not well understood. combustor is caused mainly by the centrifugal force
However, water concentration should restrict the extent of imposed on the solid particles. The equation of motion of
desulfurization from the thermochemical_point _ of view. a solid particle in the cyclone combustor in the radial
Substituting the values of X, Y, Z, N c, N H2S into Eqs. direction can be written as Eq. (31)
(17) – (23), the composition of the product gas can be
determined after a time interval Dt or a distance DX1 = UgDt. dUr 1
Mp ¼ Mp Uh2  FD : ð31Þ
The final composition of the product gas at X1 = 2.5 m is dt r
influenced_ by the circulation rate of the char because the
value of N C is related to the circulation rate of the char. The term on the left-hand side is the inertial force. The
Using a computer simulation, the required circulation rate of first term on the right-hand side is the centrifugal force,
the char for the gasification reactions to reach equilibrium at and the second term on the right-hand side is the drag
X1 = 2.5 m was determined. force that is caused by the gas flow in the negative radial
174 H. Tsui, C.-H. Wu / Powder Technology 132 (2003) 167–183

direction. If the centrifugal force is larger then the drag Thus, Eq. (34) can be written as Eq. (35)
force, the solid particle will be accelerated in the radial
direction and be forced to move towards the wall of the  
qp
cyclone combustor. The drag force FD in Eq. (31) can be Vr2 ¼ d2 V 2 : ð35Þ
9l De p h2
written as Eq. (32).
q The velocity Vr2 in Eq. (35) can be obtained by assuming
FD ¼ Cd Ap ðUr  Vr Þ2 : ð32Þ
2 that the inward radial velocity of gas is uniformly distributed
over the imaginary cylindrical surface. Thus,
_ Vr2 is obtained
The expression for the drag coefficient Cd depends on the by dividing the volume flow rate of gas Q by the area of the
type of flow. According to Ogawa [23], the drag coef- imaginary cylinder surface
ficient Cd in Stokes flow can be written as Eq. (33). The
flow is considered as Stokes flow when the Reynolds 
Q
number based on the diameter of the particle Rep is less Vr2 ¼ : ð36Þ
pDe H
than 4

24 Substituting Eq. (36) into Eq. (35) results to Eq. (37), which
Cd ¼ : ð33Þ is the expression for the cut-off diameter
Rep

  !1=2
Substituting Eqs. (32) and (33) into Eq. (31) results to Eq. 
1 9Ql
(34), which is the equation of motion in the radial dpc ¼ : ð37Þ
Vh2 pqp H
direction in Stokes flow.

dUr 1 The cut-off diameter dpc of the cyclone combustor with


Mp ¼ Mp Uh2  3pldp ðUr  Vr Þ: ð34Þ
dt r the geometry indicated in Figs. 1 and 4 is calculated as
follows. The calculation is based on the following specified
The cut-off diameter of the cyclone combustor can be conditions:
determined by considering the motion of the particle on an
imaginary cylindrical surface as described by Ogawa [23] (1) The gasifier operates at 1150 K with a thermal capacity
and Barth and Trunz [24]. The imaginary cylindrical surface of 586 KW and a CWSF containing 30% water by
has a diameter of De and a height of H, as shown in Fig. 4. weight.
The cut-off diameter is the diameter of those particles that (2) The gasifier is fed with rates of CWSF, air, and
can stay on the imaginary surface in a state of mechanical limestone which were determined in the thermody-
balance, i.e. the radial velocity is zero (Ur = 0) and the namic analysis.
centrifugal force equals the drag force. When the particles (3) The product gas reaches chemical equilibrium on the
has diameters larger than the cut-off diameter, the centrifu- surface of the imaginary cylindrical surface.
gal force is larger than the drag force because the centrifugal (4) The feed air to the cyclone combustor is uniformly
force is proportional to the mass of the particle or dp3 but the distributed through 12 pipes of 2.54 cm (1 in.) diameter
drag force is proportional to dp, as indicated by the last term at 298 K.
of Eq. (34). As a result, particles larger than the cut-off (5) The tangential velocity on the imaginary cylindrical
diameter cannot pass through the imaginary cylindrical surface falls in the region of the free vortex of the
surface. For the same reason, when the particles have Rankine vortex.
diameters smaller than the cut-off diameter, the centrifugal (6) The mean density qp and the mean diameter of the char
force is smaller than the drag force. As a result, the particles are assumed to be 1200 kg/m3 and 50 Am, respectively.
smaller than the cut-off diameter pass through the imaginary
cylindrical surface and are carried out of the cyclone Condition (5) has generally been found to be true from
combustor by the flue gas. experimental results [21]. The density and the diameter of
The expression for the cut-off diameter is obtained by the char vary over a wide range depending on the physical
considering the equation of motion of particles that stay on and chemical properties of parent coal and the coal pyrolysis
the imaginary cylindrical surface and in a state of mechan- conditions. Thus, condition (6) is an approximation used to
ical balance under the following conditions: facilitate the calculation.
Based on (1), (2) and (3), the mass flow rate and the
1. Ur2 = 0. volume flow
_ rate of product gas through the imaginary
2. the centrifugal force equals the drag force. surface Q are calculated to be 0.103 kg/s and 0.43 m3/s,
3. the angular velocity of the particle equals that of the gas respectively. The height of the imaginary cylinder H_ is 1.54
(Uh = Vh). m, as indicated in Fig. 4. Substituting the values of Q , l, qp,
H. Tsui, C.-H. Wu / Powder Technology 132 (2003) 167–183 175

Fig. 4. The imaginary cylindrical surface in the cyclone combustor.

and H into Eq. (37), the relation between dpc and Vh2 is is calculated to be Vh = 6.13 m/s based on condition (4). Fig.
written as Eq. (38). 5 shows a sketch of Rankine vortex [25] of a combination of
  a central force vortex and a peripheral free vortex. The
4 1
dpc ¼ 1:816 10 : ð38Þ relation between the tangential velocity Vu and the radius r
Vh2 is given in Eq. (39).

The value of Vh2 can be calculated under conditions (4) and Vh rh ¼ constant: ð39Þ
(5). From the thermodynamic analysis, 0.0435 kg/s of air
was required to be fed into the cyclone combustor. Thus, For the forced vortex, h equals  1 and for the free vortex h
tangential velocity of the air entering the cyclone combustor is found between 0.45 and 0.8 [25]. Based on condition (5),
176 H. Tsui, C.-H. Wu / Powder Technology 132 (2003) 167–183

Fig. 6. Mole ratio of gas species as a function of axial distance along the
gasifier.
Fig. 5. Sketch of the Rankine vortex [25].
As a result, the total mass consumption of a single
particle char in the ith circulation DWi (kg/s) can be written
the tangential velocity Vu2 can be calculated from Eq. (39) as Eq. (41).
with h = 0.5 as follows:  
0:331 0:1
 0:5  0:5 DWi ¼ 1þ þ DWgi ¼ 3:194 104 dp2i1 : ð41Þ
r 9 0:9 0:9
Vh2 ¼ Vh ¼ 6:13 ¼ 9:19 ðm=sÞ:
r2 4
A shrinking particle model is used to estimate the
shrinkage of the char particle after n circulations. The char
From Fig. 1, the values of r and r2 are obtained to be is assumed to have a constant density and to shrink
0.2285 m (9 in.) and 0.1015 m (4 in.), respectively. uniformly when it reacts with either steam or oxygen. The
Finally, the cut-off diameter of the cyclone combustor is diameter of the char dpn after n circulations can be written as
calculated to be 19.7 Am by substituting Vh2 = 9.19 m/s Eq. (42).
into Eq. (38).
! 13
2.5.2. Calculation of the char diameter dpn and circulation 6 X
n
dpn ¼ W0  DWi
rate of char Wn after n circulations pqp i¼1
The shrinkage of a single char in each circulation is due
! 13
to both gasification and combustion. From previous studies 6 p Xn
[26], it has been found that the rate of consumption of char ¼ qp dp30  3:194 104 dp2i1 ð42Þ
pqp 6 i¼1
is the product of its surface area and the rate coefficient Ks
(kg/s m2). The rate coefficient Ks (kg/s m2) for gasification
is estimated from Eq. (40) as follows: Under the assumption that the char particle has a constant
density qp and a uniform diameter dp0 when it enters the
cMp ¼ Ks As ð40Þ

The specific rate of gasification c at 1150 k for a bituminous


char can be obtained as 0.001 (1/s) from Fig. 2 [10]. The
mean density qp and the mean diameter of char dp were
measured as 1200 kg/m3 and 50 Am, respectively. Substitut-
ing these values of c, dp, and qp into Eq. (40). Ks is
calculated to be 2.0 10 5 (kg/s m2). The required resi-
dence time of the char in the gasifier is found to be 0.86 s.
Thus, the mass consumption of a single char particle due to
the gasification in the ith circulation is DWgi = 0.00086Ks
(4pd 2pi  1). The energy balance of this system requires that it
has to burn 0.331 mol of char in the cyclone combustor and
0.1 mol of char in the circulating fluidized bed in order to
sustain 0.9 mol of endothermic steam – coal gasification Fig. 7. Mole ratio of gas species as a function of axial distance along the
process. gasifier.
H. Tsui, C.-H. Wu / Powder Technology 132 (2003) 167–183 177

gasifier, the_ number of char particles fed into the gasifier per
unit time N is obtained by dividing the feeding rate of char
by the mass of a single char particle

 Wf Fc
N¼p : ð43Þ
dp30 qp
6
The circulation rate of char after n circulations can be
written as Eq. (44)
 
Wn ¼ N ðW0 þ ðW0  DW1 Þ þ ðW0  DW1  DW2 Þ
þ ðW0  DW1  DW2  DW3 Þ þ K þ ðW0  DW1
 DW2  DW3  K  DWn ÞÞ
!
 Xn Fig. 9. Composition of product gas species as a function of axial distance
¼ N ðn þ 1ÞW0  ðn  i þ 1ÞDWi along the gasifier.
i¼1

wf Fc
¼p ðn þ 1ÞW0  3:194 (44) by varying the initial diameter of char dp0 and the
dp30 qp number of circulation of char in the gasifier n until the
6 !
Xn system reaches steady or both Eqs. (45) and (46) are
4 2 satisfied.
10 ðn  i þ 1Þdpi1 : ð44Þ
i¼1

Eqs. (42) and (44) are the transient mass equations of char
3. Results and discussion
particles circulating in the fluidized bed and cyclone com-
bustor. The system will reach steady state when the initial
3.1. Johnson’s kinetic data
diameter of char shrinks to become the cut-off diameter of
the cyclone combustor after n circulations
The results of the kinetic analysis using Johnson’s
dpn ¼ dpc ð45Þ kinetic data of a constant specific gasification rate (0.01
1/s) are presented in Figs. 6 – 11. The constant specific
and the circulating rate of chars becomes the amount gasification rate of 0.001 1/s was obtained from Fig. 2 at
required of operating the gasifier simultaneously 1150 K. In the kinetic analysis, the reactor temperature, the
thermal capacity of the gasifier, and the water concentra-
Ẇn ¼ Ẇre : ð46Þ tion of the CWSF, were fixed at 1150 K, 586 KW (2 106
Btu/h) and 30%, respectively. The kinetic models derived
As the system reaches steady state the particle size distri- in previous section were used to predict the required
bution and the circulating rate of char will not vary with circulation rates of char and lime for the chemical reac-
time. A trial-and-error method is used to solve Eqs. (42) and tions to reach equilibrium within the given height of the

Fig. 8. Mole ratio of gas species as a function of axial distance along the
gasifier. Fig. 10. Gas velocity as a function of axial distance along the gasifier.
178 H. Tsui, C.-H. Wu / Powder Technology 132 (2003) 167–183

0.86 s. Figs. 6 – 8 show the approach of the chemical


reactions to equilibrium
_ _ from the curve of the mole ratio of
gas species
_ (X /X eq ) vs. the axial distance along the gasifier,
where X eq is the number of moles of the species in the
gasifier as the char gasification reaches equilibrium. These
figures show
_ _ that all species approach their equilibrium
values (X /X eq = 1) after the gas has traveled a distance of
2.5 m, which was set as the height of the gasifier as
indicated in Fig. 1. Fig. 9 shows the mole fraction of the
species as a function of the axial distance. It shows the
mole fractions of H2 and CO increase and the mole
fractions of H2O and N2 decrease with distance. This
increase in the mole fractions of H2 and CO and decrease
Fig. 11. Solid loading density as a function of axial distance along the of that of H2O are caused by the chemical reaction between
gasifier. the steam and the char. The decrease in the mole fraction of
N2 is mainly due to the generation of gas species of CO and
gasifier. It was found that the required circulation rates of H2 during char gasification. Fig. 9 also shows that the slope
carbon and lime were 11.8 and 4.5 kg/s, respectively, and or the mole fraction of CO2 increases slightly and then
the required residence time of the char in the gasifier was decreases with distance beyond X1 = 0.55 m. This phenom-

Fig. 12. Operating concept of the gasifier with equilibrium feed rates at 1150 K using Johnson’s [10] kinetic data.
H. Tsui, C.-H. Wu / Powder Technology 132 (2003) 167–183 179

enon is caused by the different shift direction of water – gas (47) to shift to the left, which makes the generation rate of
shift reaction H2 to be smaller than that of CO. Figs. 10 and 11 show the
gas velocity and the solid loading density as a function of
CO þ H2 OVCO2 þ H2 : ð47Þ the axial distance, respectively. The gas velocity is
obtained by dividing the volume flow rate of gas by the
Initially, the chemical kinetic makes reaction (47) to shift
cross-sectional area of the gasifier and the solid loading
to the right, this will generate CO2 and make the slope of
density is the ratio of the circulation rate of the solids to
CO2 curve positive. However, beyond X1 = 0.55 m the
the volume flow rate of gas. These figures show that the
chemical kinetic makes reaction (47) to shift to the left,
gas velocity increases and the solid loading density
this will consume CO2 and make the slope of CO2 curve
decreases as the axial distance increases. This phenomenon
negative. The comparison of the slope of CO curve with
is caused by the increase in the volume flow rate of gas as
that of H2 curve in Fig. 9 also shows the same shift
the char gasification reaction
tendency. Initially, the slope of H2 curve is larger than that
gasif ication
of CO curve, but becomes smaller than that of CO curve CðsÞ þ H2 O 
! CO þ H2 ð48Þ
when X1 is beyond 0.55 m. The larger curve slope
represents the larger generation rate of gaseous species proceeds along the axial distance. The char gasification
and vice versa. Thus, the chemical kinetic initially makes reaction consume 1 mol of H2O(g) but generates total two
reaction (47) to shift to the right, which makes the mol of CO and H2.
generation rate of H2 to be larger than that of CO, but All three operating parameters (reactor temperature,
beyond X1 = 0.55 m the chemical kinetic makes reaction thermal capacity, and water concentration in the CWSF)

Fig. 13. Operating concept of the gasifier with equilibrium feeding rates using Wen’s [9] kinetic model.
180 H. Tsui, C.-H. Wu / Powder Technology 132 (2003) 167–183

together with feed rates of materials are shown in Fig. 12.


The recycle ratio, the ratio of the circulation rate of lime to
the feed rates of CWSF, is calculated to be 203. When the
reactor temperature, the composition of the CWSF, and the
thermal capacity of the gasifier are specified, the maximum
volume flow rate in the gasifier is determined, i.e. the
maximum gas velocity in the gasifier is fixed. Industrial
experience indicates that a circulating fluidized bed should
operate at higher gas velocities than those indicated by Fig.
10 for improved performance [20]. In order to obtain higher
gas velocities, the unit should be operated at a higher
temperature and thermal capacity than those indicated in
Fig. 12. Thus, the following section demonstrates a way to
operate the facility at higher gas velocities by increasing the
reactor temperature and the gasifier’s thermal capacity.
Also, Wen’s [9] kinetic model is used in order to show
the effect of a more sophisticated and realistic gasification Fig. 15. The composition of gas as a function of axial distance along the
scheme. gasifier using Wen’s [9] kinetic model.

3.2. Wen’s kinetic model that the gasifier is required to operate at 1450 K with a
thermal capacity of 879 KW (3 106 Btu/h) and circulation
This section demonstrates how to obtain a superficial rates of char and lime of 15 and 4.5 kg/s, respectively, in
velocity between 3.6 and 4.9 m/s (12 – 16 ft/s) and a solid order to reach the specified range of gas velocity and solid
loading density between 50 and 100 kg/m3, which are loading density. The chemical reactions, however, do not
recommended by industrial experience [20]. In this analysis, reach equilibrium at a height of X1 = 2.5 m and only 88% of
Wen’s [9] kinetic model (Eq. (29)) was used to predict the the water is consumed. The emissions of H2S (0.15 lb of
gasification rate of the char in the gasifier. Wen’s kinetic SO2 per million Btu) based on the total conversion of H2S to
model (Eq. (29)) describes the gasification rate of char as a SO2 after combustion were found still to be below the
function of the reactor temperature and the concentration of allowed SO2 emission levels (1.2 lb per million Btu).
the species, steam, CO, and H2. A trial-and-error technique Fig. 13 shows the sketch of the gasifier with the feed
was used to determine the operating parameters and the rates of materials and the operating conditions that are
circulation rates of char and lime so that the superficial gas needed to reach the expected ranges of gas velocity and
velocity and solid loading density fell within the specified solid loading. The recycle ratio, the ratio of the circulation
range. In this method, the water concentration of the CWSF rate of lime to the feed rate of CWSF, is calculated to be
was fixed at 30%, but the other two operating parameters, 163. The equilibrium feed rates were calculated at 1450 K
the reactor temperature and the gasifier’s thermal capacity, for the gasifier’s thermal capacity of 879 KW (3 106 Btu/
were varied. The results of this trial and error method show h) and a CWSF containing 30% of water by weight. Fig. 14

Fig. 14. The consumption of steam as a function of axial distance along the Fig. 16. Gas velocity as a function of axial distance along the gasifier using
gasifier using Wen’s [9] kinetic model. Wen’s [9] kinetic model.
H. Tsui, C.-H. Wu / Powder Technology 132 (2003) 167–183 181

Fig. 19. Circulating rate of char as a function of axial distance along the
gasifier.
Fig. 17. Solid loading density as a function of axial distance along the
gasifier using Wen’s [9] kinetic model. decrease in the gasification rate of the char as the concen-
trations of CO and H2 increase in Wen’s kinetic model.
shows the consumption of steam as a function of axial
distance. It shows that after the gas has traveled a distance of 3.3. Circulation rate and shrinkage of chars
2.5 m, 88% of the steam has been consumed in the gasifier.
From the thermodynamic analysis, it was found that the The transient Eqs. 42 and 44 developed in Section 2.5
consumption of steam should be larger than 99% as the are solved by varying the initial diameter and the number
gasification reaches equilibrium. Thus, this figure indicates of circulation of the chars until the char particle shrinks to
that the gasification reactions have not reached equilibrium be the cut-off diameter and the circulation rate of chars
by the time the product gas reaches the exit at X1 = 2.5 m. equals the required circulation rate of chars. Figs. 18 and
The mole fractions of the gas species as a function of axial 19 show the results obtained by using Johnson’s kinetic
distance are shown in Fig. 15. The superficial gas velocity data at 1150 K. The circulation rate of char is accumulated
and the solid loading density are shown in Figs. 16 and 17, to such amount that the chemical reaction of char gas-
respectively. They show that the superficial gas velocity and ification reach equilibrium at X1 = 2.5 m. The diameter of
solid loading density are within the specified ranges of 3.6 – the char is plotted as a function of the number of circu-
4.9 m/s and 100 –50 kg/m3, respectively. lations in Fig. 18, and the circulation rate of the char is
It is interesting to compare Fig. 16 with Fig. 10. Fig. 16, plotted as a function of the number of circulations in Fig.
which was obtained using Wen’s [9] kinetic model, shows 19. Figs. 18 and 19 show that the circulation rate of char
that the gradient of the superficial gas velocity in the flow will reach a steady value of 11.8 kg/s after 2860 circu-
direction decreases as the axial distance increases. However, lations from the startup if the initial diameter of the char is
Fig. 10, obtained from Johnson’s [10] kinetic model, indi- 80.5 Am. The char particle is expected to shrink from 80.5
cates that the superficial gas velocity increases linearly as Am to the cut-off diameter of the cyclone combustor, 19.7
the axial distance increase. This difference is due to the Am, and be carried out of the cyclone combustor after 2860
circulations.

4. Conclusions and suggestions

The following conclusions have been made:

(1) The char – steam reaction in the gasifier does not reach
equilibrium at low char circulation of 11.8 kg/s and low
temperature of 1150 K. It needs to operate at higher char
circulation rate (15 kg/s) and higher temperature (1450
K) for the char –steam reaction to reach equilibrium. It is
suggested to predict the performance of the gasifier from
the kinetic point of view in order to design the optimal
geometry and operating methods that will allow the
gasifier to play a successful role in the clean coal
Fig. 18. Shrinkage of char as a function of axial distance along the gasifier. technology system such as IGCC, HIPPS, etc.
182 H. Tsui, C.-H. Wu / Powder Technology 132 (2003) 167–183

(2) It shows a concept to operate the gasifier from transient K2 Rate constant of desorption of CaS on the surface
to steady condition after the diameter of char particle of inactivated lime (l/s)
shrinks to equal the cut-off diameter of the cyclone K3 Rate constant of Eq. 2 (E/gmol s)
combustor and the circulation rate of char equals the Ke Equilibrium constant [0.3012 105 exp(7603.2/
required amount simultaneously. Whenever the system T)] (E/mol)
reaches steady condition the particle size distribution K1 Equilibrium constants of Eq. (8)
and the circulation rate of char will not change. K2 Equilibrium constants of Eq. (9)
(3) The use of coal water slurry as fuel has restricting effects K Equilibrium constants of Eq. (16)
on the performance of the gasifier to be used in IGCC kC – H2O Equilibrium constant [exp(17.64– 16810/T)]
because in this way the water feeding rate becomes Ks Surface rate coefficient (kg/s m2)
proportional to the char feeding rate and cannot be varied Kv Rate constant of char gasification[exp(24.3 –
independently. Accordingly, if the gasifier is operated 25,120/T)] (cm3/mol s)
under steady condition in IGCC its thermal capacity n Number of circulations of char
cannot be modified by only varying the water feeding N_ Total unconverted lime
rate without the change of operating temperature. N_ Feed rate of the char (particle/s)
(4) A large amount of circulating lime CaO in the gasifier N_c Rate of char gasification (atom/s)
makes the removal of H2S from the flue gas relatively N H 2S Rate of the reduction of H2S (atom/s)
easy. The emissions of H2S (0.15 lb of SO2 per million Mp Mass of a single particle [6qpdp3/p] (kg)
Btu) based on the total conversion of H2S to SO2 after P
_i Pre-exponential constant
combustion were found still to be below the allowed Q Gas volume flow rate through the imaginary
SO2 emission levels (1.2 lb per million Btu). surface (m3/s)
r Coordinate in the radial direction
List of symbols R Universal gas constant (cal/mol K)
A Concentration of available lime CaO in the Rep Reynolds number [(Ur  Vr)dp/m]
calcined limestone, any units T Temperature (K)
As Surface area of single particle (m2) t Time (s)
Ap Cross-section of char particle (m2) Dt Time interval (s)
B Concentration of inactivated lime CaO covered by Ur Solid particle velocity in the radial direction (m/s)
CaS layers in the calcined limestone, any units Uh Solid particle velocity in the angular direction (m/s)
C Concentration of H2S (gmol/E) Ug Superficial gas velocity (m/s)
Cd Drag coefficient Vr Gas velocity in the radial direction (m/s)
Cf Free site on the surface of char available for Vr2 Gas velocity on the imaginary surface (m/s)
reaction Vh Air tangential entering velocity (m/s)
C(o) Occupied site or activated complex on the surface Vh2 Gas velocity in the angular direction on the
of the char imaginary surface (m/s)
De Diameter of the imaginary cylinder W Number of moles of gas species, char, or lime
dp Diameter of the solid particle (m) (mol) based on 1 mol of carbon in feed CWSF
dpc Cut-off diameter of the cyclone combustor (m) _ (mol)
dpi Diameter of the solid particle after ith circulation W
_c Circulation rate of char (kg/s)
(m) Wf Feeding rate of coal water slurry fuel (kg/s)
d pn Diameter of char particle after n circulations (m) W0 Initial mass of feeding char particle (kg)
dp0 The initial diameter of char (Am) W0 Moles of gas species or lime at the beginning of
Ei Activation energy (Kcal/gmol K) each time interval (mol)
FC Mass fraction of carbon in the CWSF DWgi Gasification of a single char particle in the ith
FD Drag force upon the solid particle in the radial circulation (kg)
direction (N) DWi Total mass reducation of a single char particle in
H Height of the imaginary cylinder (m) the ith circulation (kg)
h Exponential constants of Rankine vortex in Eq. X Converted atoms of in each time interval (mol)
(39) X1 Axial coordinate along the gasifier (m)
k1 Rate constant of Eq. (8) DX1 Traveling distance along the gasifier after a time
k1V Rate constant of Eq. (8) _ interval Dt
k2 Rate constant of Eq. (9) X_ Mole of gas species (mol)
k2V Rate constant of Eq. (9) Xeq Mole of gas species at equilibrium (mole)
k3 Rate constant of Eq. (10) Y Converted atoms of CO in each time interval (mol)
K1 Rate constant of adsorption of CaS on the surface Z Converted atoms of in each time interval (mol)
of available lime (E/gmol s) q Density of flue gas (kg/m3)
H. Tsui, C.-H. Wu / Powder Technology 132 (2003) 167–183 183

qp Density of solid particle (kg/m3) [13] R.J. Dry, I.N. Christensen, C.C. White, Gas – solids contact effi-
ciency in a high-velocity fluidized bed, Powder Technol. 52
m kinetic viscosity of gas
(1987) 243 – 250.
l Viscosity of gas (N s/m2) [14] J.R. Howard, Fluidized Beds Combustion and Applications, Science
c Specific rate of char gasification (l/s) Publish, 1983.
[15] H.H. Lowry, Chemistry of Coal-Utilization—Supplementary Volume,
Wiley, New York, 1963.
References [16] W.T. Abel, F.W. Shultz, P.F. Langdon, Removal of Hydrogen Sul-
fide from Hot Producer Gas by Solid Absorbents, Bureau of Mines,
U.S. Department of the Interior, Morgantown, 1974, Publication RI-
[1] L.A. Ruth, Advanced coal-fired power plants, ASME, J. Energy Re- 7947, 1974.
sour. Technol. 123 (2001) 4 – 9.
[17] J.T. Schrodt, O.J. Hahnn, Hot Fuel Gas Desulfurization, Institute for
[2] E.A.J. Gandolfi, G. Papachristodoulou, O. Trass, Preparation of coal Mining and Minerals Research, University of Kentucky, Lexington,
slurry fuels with the Szego mill, Powder Technol. 40 (1984) 269 – 282. KY, 1976, Publication IMMR/15-PD11-76.
[3] S. De, P.K. Nag, Thermodynamic analysis of a partial gasification [18] M. Pell, R.A. Graff, A.M. Squires, Desulfurization of fuel with cal-
pressured combustion and supercritical steam combined cycle, Proc.
cined dolomite, Chemical Engineering Progress Technical Manual,
Inst. Mech. Eng., A J. Power Energy 214 (2000) 565 – 574. AIChE, New York, NY, 1971.
[4] J.M. Topper, P.J.I. Cross, S.H. Goldthorpe, Clean coal technology for [19] B.J. Overmoe, S.L. Chen, L. Ho, W.R. Seeker, M.P. Heap, D.W.
power and cogeneration, Fuel 73 (7) (1994) 1056 – 1063. Pershing, Boiler simulator studies on sorbent utilization for SO2 con-
[5] L.A. Ruth, The US department of energy’s combustion 2000 Pro-
trol, Proceedings: First Joint Symposium on Dry SO2 and Simulta-
gram: clean efficient electricity from coal, Energy Convers. Manag. neous SO2/NOx Control Technologies, vol. 1, Fundamental Research
38 (10 – 13) (1997) 1249 – 1257. and Process Development, July, 1985, pp. 15-1 – 15-7, EPA-600/9-85-
[6] S.J. Goidich, M. Seshamani, The Foster Wheeler Approach to Cir-
020a (NTIS No. PB85-232353).
culating Fluidized Bed Technology, The Third International Power
[20] K.K. Kou, Principles of Combustion, Wiley-Interscience, New York,
Generation Industries Conference and Exhibition, Orlando, FL, USA, 1986.
1990. [21] D.F. Ciliberti, B.W. Lancaster, Performance of rotary flow cyclones,
[7] H.D. Tsui, Thermodynamic, kinetic, and hydrodynamic analyses of
AIChE 22 (1976) 394 – 398.
the gasification of coal water slurry fuels in a circulating fluidized bed [22] D. Kunii, O. Levenspiel, Fluidization Engineering, Robert E. Krieger
gasifier, PhD Dissertation, Penn State University, 1990. Publishing, New York, 1977.
[8] C. Luo, T. Watanabe, M. Nakamura, S. Uemiya, T. Kojima, Gasifi- [23] A. Ogawa, Separation of Particles from Air and Gases, vols. 1,2, CYC
cation kinetics of coal chars carbonized under rapid and slow heating
Press, 1984.
conditions at elevated temperature, J. Energy Resour. Technol. 123 [24] W. Barth, K. Trunz, Modellversuche mit wasserdurchstromten zyklo-
(2001) 21 – 26. nab-scheidern zur vorausbest timmung der abscheideleistung, Z. An-
[9] C.Y. Wen, E.S. Lee, Coal Conversion Technology, Addison Wesley, gew. Math. Mech. 3 (819) (1950) 255.
Massachusetts, USA, 1979, p. 586.
[25] A.K. Cupta, D.G. Lilley, N. Swirl, Swirl Flows, Energy and Engineer-
[10] J.L. Johnson, Kinetics of Coal Gasification, Wiley, NY, 1979. ing Science Series, ABACUS Press, 1984.
[11] S. Ergun, Kinetics of the reactions of carbon dioxide and steam with [26] V.S. Semenov, N.A. Semenenko, Pattern of combustion and gasifica-
coke, Bur. Mines Bull. 598 (1961) (R622.05 v53-1 No. 598 – 605).
tion of coal in a cyclone chamber, Teploenergetika 16 (12) (1969)
[12] S.A. Quader, Natural Gas Substitutes from Coal and Oil, Coal Science 79 – 81.
and Technology, vol. 8, Elsevier, 1985.