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Fuel Vol. 76, No. 10, pp. 945-949, 1997 1997 Elsevier Science Ltd. All rights reserved Printed in Great Britain 0016-2361/97 $17.00+0.00

Kinetic study of high-pressure pulverized coal char combustion: experiments and modelling
Vadim Banin, Roel Moors and Bram Veefkind
Eindhoven University of Technology, Faculty of Applied Physics, PO Box 513, NL-5600 MB Eindhoven, The Netherlands. E-mail: elegve@urc.tue.nl (Received 31 October 1996; revised 18 April 1997)
Reactivity of Grttelborn char over a broad range of particle temperature (1500-3000 K) and partial oxygen pressure (0-100% of 0.7-0.9 MPa) was measured using a shock tube. It was concluded that the contributions of combustion at the internal and external surfaces are of the same order of magnitude. An approximate analytical method based on the Thiele approach was used to calculate the kinetic parameters of the reaction rate with pore growth accounted for by introducing an external surface roughness factor. A computational model was developed to describe the reactions on the internal and external surfaces and the changes in the geometric structure of the char particle. The approximate kinetic results were used as a first approximation in calculations for the same conditions as in the experiments. The calculated values agreed with the measured apparent reaction rates within 27%. The influence of pore growth during burnout was shown to be significant; neglecting this growth would overestimate the total kinetic reaction rate and true activation energy. 1997 Elsevier Science Ltd.
(Keywords: pulverized char combustion; kinetics; mathematical modelling)

Investigations to determine the combustion and gasification characteristics of pulverized coals and chars are in progress in the EVE&M laboratory 1-6. A number of methods have been used in coal and char research to determine rates of combustion and gasification. The enormous complexity of the process can lead to large errors in applying experimental results to predict coal behaviour in real combustors and gasifiers. This paper is limited to presenting a new general approach to the interpretation of experimental results on the behaviour of char, taking into account the influence of the changing physical structure of a single particle during combustion and/or gasification. This method illustrated by results of combustion experiments in a shock tube with clouds of char particles in oxygen-nitrogen mixtures, partly reported earlier 5. A general method of calculating the true reaction characteristics from the apparent ones is presented by e.g. Mulcahy and Smith 7. A Thiele modulus approach has been used to evaluate the true reaction rate from the measured value. This approach has proved to be useful in calculations of reactions at the surfaces of porous catalysts. Its application to char combustion, although generally used, can cause significant errors. The source of these errors is the continuously changing size of the pores during the combustion process. A model which takes into account this pore growth is discussed below. EXPERIMENTAL Rapid creation (within 100/zs) of hot gas conditions is a

characteristic of the shock tube. Details of the experimental installation and techniques can be found elsewhere 2'5. The gas temperature was varied between 1200 andl800 K and the total gas pressure was - 0 . 8 MPa. The partial oxygen pressure in the mixture with nitrogen was varied from 0 to 0.8 MPa. The char was made from Grttelborn coal and provided by the International Flame Research Foundation. It was ground to a mean size of 5 #m. The particle temperature and relative size measurements were based on i.r. twowavelength pyrometry. A detailed description of the pyrometric measurements is given elsewhere 2'5. The particles reach thermal balance in a characteristic time of -20/~s, which is much shorter than the burnout time ( - 15 ms). Thus by measuring temperature and particle size, the energy balance equation can be used to calculate the rate of combustion, Rp.m:
K

Rp, m = aHc(Tp - T~)

(1)

where K is the thermal conductivity, Hc the energy release per kg of char, Tp the particle temperature, a is the particle radius ( - 2 . 5 #m) and T~ the gas temperature. The term for radiation cooling in the energy balance equation is small in comparison with that for cooling by heat conduction. The value of He was taken 8 as l0 M J kg -1, which corresponds to the surface combustion of C with 02 producing CO. EXPERIMENTAL RESULTS AND DISCUSSION The experimental results for char combustion are presented in Figure 1 as a three-dimensional graph of the measured

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High-pressure pulverized coal char combustion: V. Banin et al.


the pore. The rate is given by: Rp, m
m.

2o
10

"

~:

c~.Rp,s 1 + ~-~x~ e

(2)

i
-,o
a ~

with

Si 0 Rp do / as ~---ne = x.~j - Sex Rp, sPs VRp, s


where
X

(3)

(4)

~lb~ t~ve 04
_e~ o~r~

d~exV

a zvzo2

Figure 1 Measured combustion reaction rate as a function of oxygen partial pressure and reciprocal particle temperature (1 bar = 0.1 MPa)

where ~Te is the effectiveness (ratio of penetration depth to particle radius), Dp the diffusion coefficient (either Knudsen or bulk), rp the mean pore size, Mc and Me2 the molecular weights of carbon and oxygen, Ro the reaction rate as a function of oxygen density and p the oxygen density; subscript s denotes conditions at the surface. The external surface Sex is related by a roughness coefficient o~ to the geometric surface Sg:

Sex = o~.Sg
1.00

(5)

0.80

"e

O c; O

o.60

0.40

0.20

0.(X

vq'r
Figure 2

Reaction order as a function of oxygen partial pressure and reciprocal particle temperature (1 bar = 0.1 MPa)

reaction rate as a function of reciprocal particle temperature and the oxygen pressure. The reaction rate is related to the external surface. The measured reaction rate is 5 - 1 0 times lower than the calculated external diffusion limit 2's. It has been shown by Banin et al: how a change in the measured reaction order n with oxygen pressure and temperature can be used as an indication of whether internal diffusion limitation plays a significant role in combustion. If a measured reaction order is < 0.5, this would mean either that the measured reaction rate Rp,m is the same as the real one Rp,s (without influence of internal combustion) 9 or that combustion at the internal surface Si and at the external surface Sex are of the same order of magnitude 5. In both cases a particle burns in a shrinking-core regime, as observed experimentally. An expression for the measured reaction rate in the latter case consists of two parts: combustion at the external surface and combustion inside

The factor c~ is related not only to apparent geometric distortions from an ideal spherical shape but also to penetration of oxygen molecules within a pore before the first collision with the pore wall, which determines the Knudsen diffusion coefficient 10. This means that internal diffusion control does not play any role up to a distance equal to about the pore diameter. The factor u lies between 2 and 3 and has been taken equal to 2.5 for further calculations. A Langmuir type of equation is used to represent the reaction rate of surface combustion of 02 to CO: A'p'exp ( - ~PA) 1 + B.p.exp where A is the pre-exponential factor for oxygen adsorption, (6)

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High-pressure pulverized coal char combustion: V. Banin et al.


Table 1 Kinetic parameters for G6ttelbom char determined experimentally

ot 2.5

(m'Ss-5) 12

A (m s -t) 2480

B (m3kg-I) 10.3

El (K) 18 390

E2 (K) 1830

E A the activation energy of adsorption, B the pre-exponential factor for the adsorption-desorption equilibrium, Ea the equilibrium activation energy and p the oxygen density. The choice of the Langmuir type of equation instead of the Arrhenius one is explained by the wide variation of the oxygen partial pressure (0-1.0 MPa) in the experiments, which very likely causes a change in the real reaction order from 1 to 0. In this case the integral in Equation (3) can be solved analytically:

The scope of the computational model presented here is to describe the time-dependent behaviour of the oxidation or gasification of porous char particles in different regimes (zones I, II and III 14) without using semi-empirical parameters. The changes in pore size and shape depend on the oxygen partial pressure and thus on position and time. The main assumptions may be summarized as follows: The pores are initially cylindrical and all have the same size. The porosity of the spherical coal/char particle is initially uniform. The temperature of the particle is constant and intraparticle temperature gradients are negligibly small. Pores are parallel in the radial direction and all originate at the external surface of the particle. Radial differences in the reacting gas density over a crosssection in the pore are neglected. The density does vary with radial position in the particle. This reduces the calculation of the oxygen density to a one-dimensional problem. The assumption that the pores are parallel to the particle radius and that the porosity is initially uniform determines the length distribution of the pores. The number of pores, n(r), at a distance r from the centre of the particle is given by17:

\
p. .

G J
(7)

. . ~B exp ( - -~p-p)

The 3D representation of the dependence of the measured reaction order on the particle temperature and oxygen partial pressure is given in Figure 2. It can be seen that at high temperature and high oxygen partial pressure the reaction order is < 0.5, which means that internal combustion does not dominate the overall process. To find the value of the real reaction rate Rp from experiment is the reverse problem defined by Equations (2)-(7). Five values, X, A, B, El and E2, have to be determined. The use of two limiting cases simplifies the problem: (1) high pressure, where the real reaction rate is apparently dominated by desorption; (2) low pressure, where the real reaction rate is dominated by adsorption. The values of X, A, B, El and E2 determined from the experiment are given in Table 1. These values can be used as a first approach in an accurate computational model. DYNAMIC MODELLING OF CHAR OXIDATION In most previous models J1-13 describing the change in pore structure due to reaction, the expansion rate of each pore was assumed to be uniform. Therefore the physical properties and changes in these physical properties are also uniform. This assumption is valid only if the reaction rate is the same everywhere inside the particle, yielding a zero reaction order for oxygen partial pressures attained in the pores or if oxygen partial pressure differences can be neglected (zone I kinetics ~4). At high temperatures when the reaction rate is high and oxygen consumption is high, there will be a non-uniform oxygen pressure in the pores. Furthermore the reaction rate, which can be desorptionlimited at high partial oxygen pressures, can become adsorption-limited because of the low oxygen partial pressure in the pores, yielding a non-zero reaction order. The assumption of a uniform expansion rate of the pores is thus no longer valid at high temperatures when the depth of penetration of oxygen into the pores is smaller than the pore length (zone II kinetics). In the most models a semiempirical approach is used to describe the local internal surface area as a function of burnout ~5or the model contains a large number of adjustable parameters ]6.

n(r) = 40o(r/rpo) 2

(8)

where rp0 is the initial radius of the pore and 00 is the initial (surface) porosity of the char particle. The oxygen pressure is calculated using a quasi. 18, but taking stationary approach similar to that of Th]ele into account the curvature of the pore walls and the radial differences in pore diameter. The oxygen density profile is obtained by applying the law of conservation of mass over a cross-section with a length dr of a pore and can be written as follows:

l__(O v rp Or Drp~r)=2M2Jl+Mcv

(Orp)2Rp(p) \OrJ

(9)

where v is the stoichiometric ratio of the reaction (1/2 for combustion to CO). The term with the square root arises from the curvature of the pore surface. The diffusion coefficient D is determined as follows:
1 1

D - Dc

+ --

DKn

(10)

with the continuum diffusion coefficient Dc given byl9: D c = 5 . 1 1 0 - 4 ( ' 7Tg 51) 0'~ p (11)

and the Knudsen diffusion coefficient DK, given byW:

2rp 106) ( 2000"~

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High-pressure pulverized coal char combustion: V. Banin et al.

The gas temperature in the pores, Tg, is equal to the particle temperature Tp, and the total pressure in the pores is denoted by P. The boundary equations are given by:

Table 2 Particle parameters used in the calculations


Radius (gm) Porosity Pore diameter (nm) True density (kg m-3)

1.5
0.1 0.5 2000

p(a(t), t) = ps(t)

(13)

Pa~rr = 0

(14)

It should be noted that both the radius of the char particle and the density of oxygen at the external surface of the char particle are functions of time, since the total mass consumption is time-dependent. The density of oxygen at the external surface is calculated by solving a quasi-stationary mass balance for the reacting gas. The expansion of the pore cross-section is calculated by applying the law of conservation of mass in an infinite small radial control volume containing one pore. Since the pore expansion rate depends on the reaction rate, the pore expansion rate depends on the oxygen partial pressure and thus can be non-uniform. The rate of increase in pore radius can be written as:
Orp _

1 ~/1

[ Orp~ 2
+ ~-~-r) Rp(p) (15)

0-T-- ~ ,

with the true density of the particle denoted by Pc. Depending on the rate of reaction and geometric properties, burnout may take place due to combustion on the external surface or due to internal combustion, which occurs when the surface porosity becomes (locally) 1. To calculate the overlap of pores at high porosity, the centrelines of the pores are assumed to be positioned on a square mesh. The decrease in particle radius a due to external combustion/gasification can be written as follows:

da _
dt

Rp(Os)
Pc

(16)

MODEL RESULTS AND DISCUSSION Calculations were performed on the basis of the reaction kinetics obtained by the analytical method described above (Table 1). A typical result is shown in Figure 3, where the particle parameters given in Table 2, a particle temperature

10
E 8
"'"-. -....

3.0 2.s
o

"'""......
tO 4 2

"....
"-.. "'"......

2.0 ~ 1.5
1.0

.-~

0.5 I~.

o'., 0.'2 o'., 01,


Time, s

oi#

Figure 3 Combustion reaction rate and particle radius as a function of time for a particle temperature of 2000 K and an oxygen partial pressure of 0.8 MPa

of 2000 and an oxygen pressure of 0.84 MPa are used. In this figure the reaction rate per unit external surface and the particle radius are plotted versus time. Note from Table 2 that the pore size and the porosity are both small, but the pores of size 10-1000 nm are macropores for particle sizes of 1.5 #m and do not contribute significantly to the total rate of reaction. The fact that the porosity is low can be explained by noting that this is an effective porosity of only the small pores and not a total porosity, which consists to a large extent of macropores. As indicated in Figure 3, the burnout of the particle is divided into four stages, which will be analysed. In the first stage of burnout the reaction rate is increasing because of an increase in internal surface. Except for a slight decrease due to external combustion, the radius of the particle is almost constant. The maximum reaction rate is reached when the pores start to overlap. This process would be smoothed by a pore size distribution. To emphasize that this is not a computational instability, the time step in the computations was varied until the results did not depend on the time step. In the second stage of combustion the pores start to overlap. The internal surface of the particle decreases because of this overlap. The internal surface growth is (obviously) smaller than the surface decrease caused by overlap. The particle radius decreases due to internal burnout in a thin layer near the external surface. The decrease in particle radius is orders of magnitude larger than in stage 1. In stage three, after the decrease the reaction rate increases again. This is a result of new growth of internal surface, but now for a particle whose size has decreased (the reactant penetrates to places inside the particle that could not be reached at earlier stages of combustion). In this stage there is a continuous decrease in particle size. Thus there is also a continuous decrease in internal surface due to overlap of pores. For a long period the apparent reaction rate is constant, which is a consequence of the equilibrium between internal surface growth and internal surface loss. The observed reaction rate in this stage is higher (by a factor of - 4 ) than the calculated reaction rate neglecting pore growth. In stage four, at the end of burnout the reaction rate decreases. This can be explained as follows. The reaction rate in the first stages of burnout (<80%) is mainly dominated by internal combustion, because the effective internal surface is larger than the external surface. When the particle is small (combustion still occurs in the shrinkingcore regime), the ratio of the effective internal surface to the external surface decreases and thus the total reaction rate decreases. The apparent reaction rate can even be lower than the kinetic reaction rate, because the holes in the external surface can be larger than the gain in surface in the pores (rp > 21, where l is the effective penetration length of oxygen into the pores, or the pore length if that is smaller than the possible penetration length). This decrease in reaction rate would even be more drastic if mineral matter were to be taken into account. A decrease in reaction rate in the last

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Fuel 1997 Volume 76 Number 10

High-pressure pulverized coal char combustion: V. Banin et al.


Table 3 Results of calculations of apparent reaction rate for conditions similar to the shock tube experiments
Oxygen pressure (MPa) 0.83 0.82 0.80 0.47 0.43 0.40 0.23 0.19 0.13 Tp(K) Reaction rate (kg m-2s -t) Deviation (%)

Holten, A. W. M. van Iersel and H. F. Koolmees for their technical support and Prof. Dr W. R. Rutgers for fruitful discussions.

Measured 2850 2000 1480 2140 1725 2680 1640 1900 2550 14 4.7 1.1 4.5 1.6 9.5 0.8 1.7 2.9

Calculated 17 5.1 0.8 4.7 1.7 9.9 0.8 1.6 3.1 +18 +8 -27 +4 -3 +4 +3 -3 +7

REFERENCES 1 2 3 4 Banin,V. E., Veefkind, A., Ivanov, V. A. and Bityurin, V. A., in Proceedings of the Seventh International Conference on Coal Science, 1993, pp. 31-34. Banin,V. E., Shock tube research on kinetics of pulverised coal particles combustion and ignition. Ph.D. thesis, Eindhoven University of Technology, 1994. Commissaris,F. A. C. M., Banin, V. E. and Veefkind, A., in Proceedings of the Eighth International Conference on Coal Science, 1995, pp. 519-522. Banin,V. E., Commissaris, F. A. C. M. and Veefkind, A., in Proceedings of the Eighth International Conference on Coal Science, 1995, pp. 591-594. Banin,V. E., Commissaris, F. A. C. M., Moors, J. H. J. and Veefkind, A., Combustion and Flame, 1997, 108, 1. Commissaris,F. A. C. M., Banin, V. E., Roekaerts, D. J. E. M. and Veefkind, A., Combustion and Flame (accepted for publication). Mulcahy,M. F. R. and Smith, 1. W., Reviews of Pure and Applied Chemistry, 1969, 19, 81. Kapteijn,F. and Moulijn, J. A., in Carbon and Coal Gasification, NATO ASI Series E, Vol. 105, ed. J. L. Figueiredo and J. A. Moulijn. Martinus Nijhoff, Dordrecht, 1986. Smith, I. W., in Nineteenth Symposium (International) on Combustion. The Combustion Institute, Pittsburgh, 1982, pp. 1045-1065. Frank-Kamenetskii, D. A., Diffusion and Heat Transfer in Chemical Kinetics. Plenum Press, New York, 1969. Tseng,H. P. and Edgar, T. F., Fuel, 1988, 68, 114. Simons,G. A., Combustion Science and Techology, 1979, 20, 107. Gavalas,G. R., AIChE Journal, 1980, 26, 577. Essenhigh,R. H., in Chemistry of Coal Utilization, Second Supplementary Volume, ed. M. A. Elliott. Wiley Interscience, New York, 1981, p. 1153. Srinivas,B. and Amundson, N. R., AIChE Journal, 1980, 26, 487. Hashimoto,K. and Silvestone, P. L., AIChE Journal, 1973, 19, 268. Moors,J. H. J., Internal Report, Eindhoven University of Technology, 19~995. Thiele, E. W., Industrial & Engineering Chemistry, 1939, 31,916. Field,M. A., Gill, D. W., Morgan, B. B. and Hawksley, P. G. W., Combustion of Pulverised Coal. British Coal Utilisation Research Association, Leatherhead, 1967. Waters, B. J., High temperature kinetics of pulverisedcarbon combustion. Ph.D. thesis, Purdue University, 1988. Dutta,S. and Wen, C. Y., Industrial & Engineering Chemistry Process Design & Development, 1977, 16, 31.

stages of burnout was found in several coal combustion studies 1L]4,20,21. To validate the kinetics derived from the shock tube experiments, the apparent reaction rate was calculated for conditions similar to the experiments. Table 3 shows the data for these calculations. This (effective) pore size and (effective) porosity were chosen to minimize the difference between calculation and measurement, and this results in realistic values, keeping in mind that the porosity is only that of the micropores in the char. The particle temperature, the oxygen partial pressure, the measured apparent reaction rate, the calculated apparent reaction rate and the relative deviation between these rates are listed in Table 3. Over the whole range of temperature and oxygen partial pressure the calculated apparent reaction rate differs by no more than 27% from the measured reaction rate and thus it can be concluded that the method described earlier for approximately calculating the kinetics of coal combustion gives a good first estimate of the true kinetics considering pore growth during burnout. It can also be seen from Table 3 that the computations overestimate the apparent reaction rates at high values. As the activation energy for internal reactions is different from the true activation energy (by a factor of 2 for cylindrical pores), the apparent activation energy depends on the ratio of external and internal combustion. During combustion in this regime this ratio changes and thus the apparent activation energy changes. The growth of pores thus accounts for the small differences between the computations and the analytical method. ACKNOWLEDGEMENTS This work was supported by the Netherlands Technology Foundation (STW). The authors would like to thank A. P. C.

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