The Reactivity and Kinetics of Yanzhou Coal Chars From Elevated Pyrolysis Temperatures During Gasification in Steam at 900 - 120088888C
The Reactivity and Kinetics of Yanzhou Coal Chars From Elevated Pyrolysis Temperatures During Gasification in Steam at 900 - 120088888C
The Reactivity and Kinetics of Yanzhou Coal Chars From Elevated Pyrolysis Temperatures During Gasification in Steam at 900 - 120088888C
00
# 2006 Institution of Chemical Engineers
Trans IChemE, Part B, November 2006
Process Safety and Environmental Protection, 84(B6): 420 428
www.icheme.org/psep
doi: 10.1205/psep06031
his paper studied on the steam gasification reactivity and kinetics for Yanzhou coal
chars prepared at elevated pyrolysis temperatures, using a fixed-bed reactor at the
atmospheric pressure and gasification temperature ranging from 9008C to 12008C.
The following conclusions were reached mainly. The effect of gasification temperatures on
the gasification reactivity was stronger than that of pyrolysis temperatures under the condition
of elevated pyrolysis temperatures. Changes of reaction rate and surface area had a similar
trend, but the relationship between the change of surface area and that of reaction rate was
not proportional during the reaction process. While simulating the steam gasification reaction
of Yanzhou coal chars at the temperatures of 900 12008C, the shrinking un-reacted core
model (SUCM) was superior to the volume reaction model (VRM) and the reaction diffusion
model based on the shrinking un-reaction core model was more favourable, which suggested
that the diffusion had an effect on the reaction process, but its effect was not rather strong.
Therefore, it may be considered that the reaction process was mainly controlled by the chemical reaction. Apparent activation energies obtained for the steam gasification of Yanzhou coal
chars ranged from 127.17 kJ mol21 to 196.55 kJ mol21. Moreover, it was also found that kinetic parameters were in accord with the isokinetic relationship, according to which the calculated isokinetic temperature for all the reactions was 11978C.
Keywords: coal char; elevated temperature pyrolysis; steam gasification; kinetics model.
INTRODUCTION
Coal gasification is an efficient technology for coal utilization and becomes increasingly important, due to its high
carbon conversion and reduction of air pollutant emision.
The operation temperature in some gasfiers is as high as
14008C and even higher. Thus, coal particles in the gasifier
undergo elevated pyrolysis temperatures. It is well-known
that pyrolysis conditions strongly affects the reactivity of
resulting chars and hence the overall performance of a
coal gasifier. Comparing with low pyrolysis temperatures,
elevated pyrolysis temperatures as one of pyrolysis conditions, may result in the deformation or fusion of ash,
the change in intra-particle pore structure, a decrease of
active surface area of resulting chars and a better crystallinity of the carbonaceous part (Skodras and Sakellaropoulos,
2002; Leboda et al., 1998; Sekine et al., 2005; Jan et al.,
1998; Kajitani and Matssuda, 1998; Liu et al., 2004; Cetin
et al., 2004), and consequently a different behaviour or
mechanism of gasification reaction for resulting chars.
Accordingly, the clarification of gasification characteristics
EXPERIMENTAL
Preparation of Coal Chars
Correspondence to: Professor J. Gao, Department of Chemical Engineering for Energy Resources, East China University of Science and Technology, 200237 Shanghai, China.
E-mail: [email protected]
421
SP950
SP1200
SP1300
SP1400
17.22
0.76
82.02
17.28
0.62
82.10
17.31
0.60
82.09
81.7
0.21
2.35
0.11
81.75
0.18
2.21
0.12
81.78
0.17
2.00
0.09
Where tn is the reaction time, X(tn) is the carbon conversion at tn, MC is the atomic weight of carbon, f is the correctional factor of the wet flowmeter, Vi is the reading of
the wet flowmeter at ti, Vmol is the mole volume of gas at
the environmental temperature and the atmospheric
pressure, W represents the initial weight of coal char and
FCad is the content of fixed carbon in char. yi1,1 and
yi1,2 are respectively the volumetric contents of CO
and CO2 in the No. (i 1) gasbag.
Measurement of BET Surface Area
The analysis of BET surface area was conducted by N2
adsorption technique using the pore structure analyser
(ASAP 2400) produced by Micrometrics Instrument Co.
RESULTS AND DISCUSSION
In this study, experimental runs of the steam gasification
reaction for four chars, which were SP950, SP1200,
SP1300 and SP1400, were conducted at temperatures ranging from 9008C to 12008C, as shown in Figure 2. The
figure shows that the basic carbon conversion is very sensitive to gasification temperature variations, which suggests
that the chemical reaction is probably the rate controlling
step.
Effects of Gasification Temperatures and Pyrolysis
Temperatures on the Reactivity
The average reaction rate constant (KS), which was calculated through simulating the gasification reaction with
the SUCM (seen in the third part of Results and Discussion), was used as a reactivity index in this study to characterize the gasification reactivity of different char samples
for quantitative comparison. Figures 3 and 4 show respectively the effects of gasification temperatures and pyrolysis
temperatures on the average rate constant. From Figure 3, it
can be seen that with respect to any of resulting chars, its
Trans IChemE, Part B, Process Safety and Environmental Protection, 2006, 84(B6): 420 428
422
WU et al.
Figure 2. Effect of gasification temperatures on basic carbon conversion of various chars (gasification temperature: B 9008C; 10008C; O 11008C; P
12008C). A: SP950; B: SP1200; C: SP1300; D: SP1400.
Trans IChemE, Part B, Process Safety and Environmental Protection, 2006, 84(B6): 420 428
0a
0.89
36.28
30.81
63.90
40.09
73.34
49.08
91.60
43.12
effect of gasification temperatures on resulting char gasification reactivity is stronger than that of pyrolysis temperatures
under the condition of elevated pyrolysis temperatures.
423
pores disappearing, which were caused from the carbonaceous part of chars being consumed.
It is generally thought that the reaction rate of the char
changes with conversion. Here, it can also be seen that
the reaction rate increases initially with the increase of
carbon conversion, reaches a maximum at a certain conversion, and then declines after that (see Figure 5). Normally,
the change of the reaction rate would be related to changes
of surface area during reaction and the increasing surface
area can result in the increasing reaction rate, but it is not
the case. For example, making a comparison of the data
presented in Figure 5(d) and Table 2, those could be
found that at the temperature of 11008C, the reaction rate
of the SP1400 presents a maximum at the conversion of
about 30%, while after the point the surface area still
increases and the reaction rate decreases due to the
decrease of the active sites. The results indicate that
changes of reaction rate and surface area have the similar
trend, but the relationship between the change of surface
area and that of reaction rate is not proportional during
the gasification reaction process. The relationship between
surface area and reaction rate has been widely investigated,
but there is no general agreement. Adshiri et al. (1986) considered that the gasification rate is proportional to the surface area during gasification. Adanez and DeDiego
(1993) found that the reaction rate changed as the reaction
advances, while there was not any variation of surface
areas. As a matter of fact, most of studies (Yang and Watkinson, 1994; Alvarez et al., 1995; Kasaoka et al., 1987;
Hashimoto et al., 1986) found that surface area and reaction
rate were not proportional and proportionality was rather
found between reaction rate and active surface area related
to the number of active sites.
Figure 5. Changes of the reaction rate as the carbon conversion for four chars at different temperatures (gasification temperature: B 9008C; 10008C;
O11008C; P12008C). A: SP950; B: SP1200; C: SP1300; D: SP1400.
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WU et al.
Figure 6. 2 ln(1 2 X) versus t for various coal chars at different temperatures (gasification temperature: B 9008C; 10008C; O11008C; P12008C).
A: SP950; B: SP1200; C: SP1300; D: SP1400.
(2)
Figure 7. 1 2 (1 2 X)1/3 versus t for various coal chars at different temperatures (gasification temperature: B 9008C; 10008C; O11008C; P12008C).
A: SP950; B: SP1200; C:SP1300; D: SP1400.
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Table 3. Correlative indexes obtained using the SUCM (RSUCM) and the VRM (RVRM), respectively.
SP950
SP1200
SP1300
SP1400
Gasification temperature
RSUCM
RVRM
RSUCM
RVRM
RSUCM
RVRM
RSUCM
RVRM
9008C
10008C
11008C
12008C
0.9878
0.9969
0.9889
0.9915
0.9864
0.9921
0.9758
0.9654
0.9922
0.9964
0.9932
0.9767
0.9918
0.9923
0.9834
0.9393
0.9885
0.9962
0.9940
0.9766
0.9881
0.9941
0.9881
0.9361
0.9940
0.9918
0.9961
0.9894
0.9938
0.9892
0.9893
0.9678
Ks
t
3
(3)
In equations (2) and (3), KV, KS, X and t are respectively the volume reaction rate constant, the surface reaction rate constant, the basic carbon conversion and the
reaction time.
Figures 6 and 7 respectively, show that the experimental
data of the gasification for four chars with steam fitted to
the VRM and the SUCM, and correlative indexes (R) calculated are shown in Table 3. The table represents that the fitting extent of the SUCM is better than that of the VRM for
any one of Yanzhou coal chars at any gasification temperature, which indicates that the SUCM is superior to the
VRM for simulating the steam gasification reaction for
Yanzhou coal chars at gasification temperatures ranging
from 9008C to12008C.
Moreover, from Figure 7 it can be found that the plots
show worse and worse linearity as the reaction temperature
increases, meaning that the gas diffusion affects the gasification reaction of coal chars with steam.
Szekely et al. (1979, 1980) and Park and Levenspiel
(1975) considered that a porous spherical pellet of solid
was made up of a large number of spherical grains with uniform initial radius, and proposed that while considering the
effect of the diffusion on reaction process, the relationship
of the conversion and the reaction time is approximately
expressed as the equation (4) based on the SUCM.
t A{1 (1 X))1=3 s2 1 3(1 X)2=3
2(1 X)}
1=2
3 r m Vg
Vp 3(1 1)k Ag
1
A
; s
1
2De
KE
kCA0 Ag
Ap
Fg Vg
(4)
where Ag and Ap are respectively surface area of grain and
external surface area of pellet, Vg and Vp are respectively
volume of grain and pellet, rm is molar density of chars,
1 is porosity of chars, CA0 is concentration of gaseous reactant, k is reaction rate constant, De represents effective diffusivity of gases in porous chars and KE is equilibrium
constant. s2 reflects the influencing extent of the diffusion
on the reaction. The larger value of s 2 indicates that the
gas diffusion has a stronger effect on the reaction. A and
s 2 are calculated by the least-square.
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WU et al.
Figure 8. Carbon conversion versus time of reaction for various chars using the reactiondiffusion model (gasification temperature: B 9008C; 10008C;
O 11008C; P 12008C). A: SP950; B: SP1200; C: SP1300; D: SP1400.
Char samples
SP950
Gasification
temperature
SP950
SP1200
SP1300
SP1400
9008C
10008C
11008C
12008C
0.0133
0.0356
0.0390
0.0898
0.0028
0.0279
0.0646
0.1376
0.0044
0.0227
0.0560
0.1252
0.0024
0.0200
0.0286
0.0788
21
SP1200
2
9.27 10
K0, min
Ea, kJ mol21 124.17
SP1300
4
5.19 10
172.72
SP1400
5
2.18 10
190.71
3.39 105
196.55
(5)
Ea
ln (Ki )
RTi
(6)
where Ti is the isokinetic temperature for the reaction process and Ki is the reaction rate constant at Ti. Equation (6)
means that at the isokinetic temperature, all the reactions
with a given gasification agent proceed at the same rate.
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Table 6. Apparent activation energies reported by some literatures for the steam gasification reaction of coals and coal chars.
Samples
Reaction temperatures
coal residue
In-situ and ex-situ coal chars
1040 14308C
1000 14008C
Lignite char
750 8908C
890 9308C
800 10008C
,10008C
1000 14008C
1000 14008C
750 9008C
82.84 kJ mol21
56 85 kJ mol21 (in-situ chars)
63 99 kJ mol21 (ex-situ chars)
176 kJ mol21
75 kJ mol21
165.27 kJ mol21
159193 kJ mol21
91 107 kJ mol21
121125 kJ mol21
200 kJ mol21
1
;
RTi
b ln (Ki )
(7)
Literatures
Jensen (1975)
Peng et al. (1995)
Linares-Solano et al. (1979)
Schmal et al. (1983)
Kasaoka et al. (1985)
Tamhankar et al. (1982)
Bhat et al. (2001)
on gasification temperature. The influencing of gasification temperatures on resulting char gasification reactivity is stronger than that of pyrolysis temperatures at
elevated pyrolysis temperatures.
(2) BET surface area of resulting chars increases gradually
and then decreases as the carbon conversion, as does
the reaction rate of resulting chars. Although changes
of reaction rate and surface area have a similar trend,
the relationship between surface area and reaction
rate is not proportional during the gasification reaction
process.
(3) For simulating the steam gasification reaction process
of Yanzhou coal chars, the SUCM is superior to the
VRM, and under considering the effect of the diffusion
on the reaction, the reaction diffusion model based on
the SUCM is more favourable. However, the effect of
the diffusion on the reaction process at experimental
temperature range is quite limited and only appears a
little at the higher temperature. Thereby, it can be considered that the reaction process is mainly controlled by
the chemical reaction at the temperature ranging from
9008C to 12008C.
(4) Apparent activation energies obtained for resulting
char gasification reaction range from 127.17 kJ mol21
to 196.55 kJ mol21, which are at the higher end of all
those reported. It is also found that the activation
energy and pre-exponential satisfy the isokinetic
relationship and the isokinetic temperature calculated
is 11978C for all the reactions. The isokinetic temperature is close to the top of the experimental temperature
range and this finding is different from those reported
in literatures.
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ACKNOWLEDGEMENTS
The authors thank National Basic Research Program of China for
financial support for this work under Project No.2004CB217704.
The manuscript was received 5 June 2006 and accepted for publication
after revision 30 August 2006.
Trans IChemE, Part B, Process Safety and Environmental Protection, 2006, 84(B6): 420 428