Fuel 85 (2006) 10761082 www.fuelrst.

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Reaction kinetics of pulverized coal-chars derived from inertinite-rich coal discards: Gasication with carbon dioxide and steam
Raymond C. Everson a,*, Hein W.J.P. Neomagus a, Henry Kasaini b, Delani Njapha c
a

Separation Science and Technology Research Group, North-West University, Potchefstroom Campus, Private Bag X6001, Potchefstroom 2520, South Africa b Department of Chemical and Metallurgical Engineering, Tshwane University of Technology, Arcadia Campus, Pretoria 0001, South Africa c Department of Chemical Engineering Technology, University of Johannesburg, P.O. Box 17011, Doornfontein 2082, South Africa Received 14 January 2005; received in revised form 25 October 2005; accepted 25 October 2005 Available online 18 November 2005

Abstract An investigation was undertaken to determine the kinetics of gasication of coal-chars (pulverized) derived from typical South African inertinite-rich (high-ash) coals involving char reactions with carbon dioxide and steam and the effects of carbon monoxide and hydrogen. The chars used were characterized with respect to structural, chemical, mineralogical and petrographic (maceral content) properties and gasication experiments were conducted in a TGA at atmospheric pressure with different gas mixtures within a temperature range of 10731223 K. The shrinking core model with a controlling surface reaction was shown to be applicable for the gasication of pulverized coal-chars consisting of essentially of carbon-rich particles. The validity of this model can be attributed to the core having an exceptional low porosity (high inertinite parent coal) and consequently negligible penetration of the gases. It was found that the gasication intrinsic reaction rates could be adequately described by LangmuirHinshelwood type rate equations and that established equations have been validated with corresponding constants according to new data processing procedures. It was found that the reaction rate constants for coal-chars derived from inertinite-rich (7680%) coal discards were different to results published in the literature and that the intrinsic reaction rates differed only slightly (order of magnitude) for coal-chars with similar maceral (inertinite) compositions and different total ash contents. The marked inhibiting effect of the carbon monoxide and hydrogen on the carbon dioxide/carbon monoxide and steam/hydrogen gasication reactions is shown and relevant constants are reported. Experiments were done and models evaluated for a multi-component gasication mixture consisting of a feed mixture of carbon dioxide, carbon monoxide, steam and hydrogen. Reaction constants determined with results from binary mixtures were used to predict results and it was found that the overall rate is best described with the assumption that the important reactions proceed on separate sites. q 2005 Elsevier Ltd. All rights reserved.
Keywords: Inertinite-rich discards; High ash coal-chars; Gasication model

1. Introduction The advantages of uidised bed gasication using poor quality coal feed stocks (high sulphur content and low caloric value) are well known [1] and since the operation occurs at moderate temperatures (10731223 K) it is essential to evaluate the reaction kinetics for the relatively slow gasication reactions. For coal feed stocks with a high ash content it would be necessary to investigate the effect of the minerals present on the properties of the coal-chars formed and the subsequent reaction rates. [2,3]. The characteristics of the coal-char that affected the reaction rate are essentially: (1) the structural properties, which
* Corresponding author. Tel.: C27 18 299 1986; fax: C27 18 299 1535. E-mail address: chirce@puk.ac.za (R.C. Everson).

0016-2361/$ - see front matter q 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2005.10.016

include the surface area and porosity [46], and (2) the intrinsic reactivity dependant on the surface chemistry and catalytic effect of the inorganic compounds. Several coal-char structure models for gasication have been developed to incorporate the structural changes occurring during reaction and which can be included in a reaction rate equation [713]. The well-known shrinking core model is considered by Bhatia and Gupta [14] as the limiting case (dense particle with negligible intraparticle diffusion) of the reaction-diffusion model (random pore model with diffusion) and has been shown to be applicable for the gasication of many different coal-char samples under different conditions [15,16]. Since the minerals are included in the coal matrix it was found convenient to consider a reduction of available active surface area (structural effect) and an equation has been proposed in terms of conversion of carbon and the volume ratio of carbon to minerals [5]. It has also been shown that the minerals present can enhance gasication rates (intrinsic rates) due to a catalytic effect at moderate temperatures,

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Notation Cf dp Ei f(X) F(X) HCO2 HH2 O ik jk ki kio free carbon site pore diameter, A activation energy for reaction (forward) i, kJ moleK1. structure factor, m2 mK3 Eq. (5). adsorption enthalpy for carbon dioxide, kJ moleK1 adsorption enthalpy for steam, kJ moleK1 specic rate constants of mechanistic reactions, msK1 specic rate constants of mechanistic reactions, msK1 reaction rate constant for reaction (forward) i, m sK
1

Ki Kio Pi r r1 r2 r3 So T T X

adsorption constant for component i, PaK1 pre-exponential factor for component i, PaK1 partial pressure of component i, Pa general reaction rate, m sK1 reaction rate for carbon dioxide gasication, m sK1 reaction rate for steam gasication, m sK1 reaction rate for multi-component gasication, m sK1 calculated initial particle surface area, m2 mK3 temperature, K time, s fractional conversion of carbon

pre-exponential factor for ki, m sK1

Greek letters 30 initial porosity

especially for coal-chars derived from low-rank coals [17]. Huttinger and Nattermann [18] reported results on the catalytic effect of particularly calcium and iron (present in minerals) on gasication rates involving carbon dioxide and steam. Macerals present in the parent coal have been found to play a signicant role in determining the char activity [1921]. It is well known that coal-chars from vitrinite-rich coals are more active than coalchars derived from inertinite-rich coals, because of the highly porous structure formed. However, the reactivity of the coal-char surface (active sites) produced from different maceral coals needs to be examined especially for gasication [22]. LangmuirHinshelwood reaction rate equations have been derived and successfully evaluated by many investigators for the gasication of coal-char with both carbon dioxide and steam [2236] and at moderate temperatures (9001300 K). Many investigators have reported suitable reaction models especially for carbon dioxide gasication, and reaction rate constants (over a range) have been proposed following analyses of many published results [35,36]. With respect to the gasication with a mixture of carbon dioxide, carbon monoxide, steam and hydrogen two possible mechanisms have been proposed consisting of the two reactions carboncarbon dioxide and carbon steam occurring either on the same active site or on different sites [30,33]. An investigation was undertaken to determine the reaction rate kinetics for gasication of coal-chars, prepared from readily available South Africa discards in order to develop a process model for circulating uidised bed gasication (CFBG). The coal-chars used were the same as those used for an investigation involving combustion, the results of which have been reported in another publication [37]. The aim of this paper is to: (1) show that the shrinking core model with a controlling surface reaction, incorporating initial structural properties, together with LangmuirHinshelwood type intrinsic reaction rate equations is applicable, (2) present reaction rate constants characteristic of the coal-chars, and (3) show that the constants evaluated from binary mixtures can be used to predict

the behaviour of a multi-component mixture. The results involved gasication within a temperature range of 1073 1223 K and at atmospheric pressure (0.875!105 Pa).

2. Experimental 2.1. Char preparation and characterisation The coal-chars used were prepared by heating the parent coal in an atmosphere of owing nitrogen at 973 K for 60 min following an initial heating rate of 20 K/min [37]. The chemical-and maceral compositions are shown in Table 1 for the two parent coal samples and the structural properties of the resulting coal-chars are given in Table 2. It can be seen that the coal-chars have a very low porosity, which is characteristic of chars derived from inertinite-rich coal. The presence of a large amount of kaolinite and quartz in the parent coal could also contribute to the low overall porosity. Furthermore, it was found from a microscopic analysis (CCSEM) that the
Table 1 Analysis of parent coal Property Coal-char A Coal-char B 2.2 53.1 18.7 26 34.2 1.7 0.7 3.0 3.3 18 2 80

Proximate analysis Moisture (%) 2.4 Volatile matter (%) 20.4 Ash (%) 36.3 Fixed carbon (%) 40.9 Ultimate analysis C total (%) 49.1 H total (%) 2.6 N total (%) 1.1 S total (%) 1.7 O total (%) 6.9 Maceral compostion (mineral free) Virinite (%) 21 Liptinite (%) 3 Inertinite (%) 76

1078 Table 2 Properties of coal-chars Property BET surface area (m2 gK1) Pore volume (cm3 gK1) dp!1000 A Average pore diameter (A) by BET Bulk density (g cmK3) Total porosity, (dp!1000 A), 30 (%) Ash content (mass %) Average particle size mm (malvern analyser) Particle external surface areaa, S0, m2 mK3 Initial structural parameter, S0/(1K30), m2 mK3
a

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1400
CO

1.2 1

Coal-char A 12.1 0.015 50 1.94 2.92 47 70 8.57!104 8.83!104

Coal-char B 3.5 0.016 182 2.58 4.13 67 20 3.0!105 3.13!105

1200 1000

800 600
Temp CO2 O2

H2 Steam

0.6 0.4 0.2 0 1000

400 200 0 0

200

400

600

800

Time (min)
Fig. 1. Coal-char gasication with different gases.

Initial surface area of spherical non-porous char particles (calculated).

pulverized coal-char consisted of mainly carbon rich and mineral rich particles and that kaolinite and quartz was preferably included in the carbon matrix. The details of the techniques used for characterisation and more detailed results are fully described in the publication referred to above [37]. 2.2. Reactivity measurements The thermogravimetric analyser used was a TGA 951 model supplied by Du Pont Instruments Company (USA), which could handle essentially powders at atmospheric pressure up to 1500 K. Non-isothermal and isothermal experiments were carried out as described elsewhere [37] with different binary and multicomponent mixtures consisting of carbon dioxide, carbon monoxide, steam, hydrogen and nitrogen which were prepared on-line with a calibrated mixing manifold. The purity of the gases was greater than 99.5% (v/ v) and was supplied by Afrox (South Africa). The experiments involving steam were carried out by saturating a gas stream in glass bubblers containing water at a controlled temperature, which was also carefully calibrated by means of a material balance. The total gas ow over the sample in the sample pan was adjusted at a rate of 40 ml/min, which was sufcient to ensure the absence of lm diffusion. Reactivity experiments were performed at temperatures similar to that used in uidised bed combustion. 3. Results and discussion 3.1. Coal-char reactivity with different gases Experiments were performed to illustrate the relative reactivities of the coal-chars with pure carbon dioxide, carbon monoxide and hydrogen and a 18% steam in nitrogen mixture over a temperature range of 5731273 K. Thermogrammes (normalised mass) for experiments with coal-char A in the presence of a linear temperature ramp is shown in Fig. 1. It can be seen that the combustion reaction rate is many orders of magnitude greater than for the gasication reaction and that the coal-char reacts much

faster with carbon dioxide and steam than with carbon monoxide and hydrogen. Steam is more reactive than carbon dioxide and this can be attributed to weak hydrogen bonds forming water molecules compared to the double bonds forming the carbon dioxide molecules. This is also in accordance with results obtained by Bliek [33]. 3.2. Evaluation of overall reaction rate models and parameters 3.2.1. Evaluation procedure Overall reaction rate models were evaluated using isothermal reaction experimental results obtained at atmospheric pressure within the temperature range 10731223 K. The following general model was used to demonstrate the procedure used: dX Z rf X dt (1)

with r being the intrinsic reaction rate and f(X) the structure factor [2]. It was shown in another study [37] using the same coal-chars that the shrinking core model with a surface reaction was valid for combustion following a detailed characterisation of the coal-char. In this study, which involved much slower reactions, the same model was evaluated together with well-established LangmuirHinshelwood intrinsic reaction rate equations. The low porosity of the coal-chars, which restricts diffusion of reactants into the internal structure of the coal-char particle, causes the reactions to occur on the surface of a shrinking core. For this model, the structure factor depends on the initial surface area, porosity and the conversion only. The respective structure factor is the following: f X Z S0 1KX2=3 1K30 (2)

In order to evaluate this model with experimental results the following procedure was adopted. Eq. (1) can be written as follows: dX 1 S0 Zr 2=3 dt 1KX 1K30 (3)

Mass frac (-)

Temp (K)

0.8

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After separation of variables and integration the following is obtained: FX Z r with dX FX Z f X

0 X

0.45 0.4 0.35 0.3

S0 t 1K30

(4)
F(X)

0.25 0.2 0.15 0.1 0.05 0 0 50 100 150 200 250

CO2 gasification at 1173 K 100% CO2 70% CO2 40% CO2 30% CO2 20% CO2

(5)

Thus, a linear plot of F(X) versus t (for constant partial pressures of the gas) is a suitable test for the validity of the shrinking core model. The slope of these lines at different conditions will give the value of the intrinsic reaction rate r for known values of S0 and 30. The method for determining reaction rate constants (LangmuirHinshelwood equation LH) using the reaction r determined above is described in the next section with particular reference to carbon dioxide and steam gasication. 3.2.2. Reaction with carbon dioxide and the effect of carbon monoxide A reaction rate equation (LH) applicable to low pressures [2224] was used in this investigation. The reaction mechanism and reaction rate equation are the following [22] Cf C CO2 4 CO C CO CO/ CO Reaction 2 Reaction 1

Time (min)
Fig. 2. Validation of shrinking core model for coal-char A with carbon dioxide gasication at 1173 K.

The determination of the structure factor f(X) and the reaction rate r1 (Eq. (4)) from results obtained in this investigation are shown in Figs. 2 and 3 for both coal-chars A and B at 1173 K and for different concentrations of carbon dioxide. It was found that shrinking core model was valid and that the reaction rates (slopes) increased with temperature as expected. The reaction rate constants were evaluated by rearranging Eq. (6) in the form given by Eq. (9) and plotting r1 =PCO2 versus r1, which should be linear for a valid kinetic model: r1 ZK 1 KCO2 C k2 KCO2 r PCO2 (9)

with i1 (forward), j1 (backward) and j2 as the specic rate constants of reactions (1) and (2), respectively, the following rate equation can be derived: r1 Z k2 KCO2 PCO2 1 C KCO2 PCO2 C KCO PCO (6)

with k2Zj2; KCO2 Z i1 =j2 and KCOZj1/j2 also   K2 E 0 k2 Z k2 exp RT

0 KCO2 Z KCO2 exp

(7)

  K CO2 H RT

Linear plots were obtained at temperatures ranging from 1073 to 1223 K with carbon dioxide concentrations varying from 20 to 100% (mole), which conrmed the validity of the intrinsic rate equation used. From these linear plots the parameters k2 and KCO2 (also k1) were determined and the temperature dependence of these constants determined by linear regression methods using Eqs. (7) and (8), respectively. The results are shown in Table 3. For a comparison of the behaviour of the different coal-chars, it was considered meaningful to calculate the relevant constants at a particular temperature. Results at 1173 K are shown in Table 3, which is a typical temperature for uidised bed gasication. On comparing the results, it is seen that there are small differences (orders of magnitude) between the results for the two coal-chars
1.8 1.6 1.4 1.2

(8)

Almost all published results [22,35] based on this mechanism use a rate equation with an equivalent lumped constant k1 (equal to i1) instead of k2 KCO2 appearing in Eq. (6). The constants k1 (activation energy E1) and k2 (activation energy E2) are the specic rate constants for reactions (1) and (2), respectively, and the resulting reaction rate equations (r1) being obviously equivalent. In order to evaluate the parameters for the intrinsic reaction rate (r1) it was convenient to execute two sets of experiments, (1) with carbon dioxide and an inert (nitrogen), and (2) with carbon dioxide and carbon monoxide. For the carbon dioxide/inert experiments, Eq. (6) reduces to an equation without the term KCOPCO.

F(X)

1 0.8 0.6 0.4 0.2 0 0 50 100 150 200 250

CO2 gasification at 1173 K

100% CO2 60% CO2 50% CO2 30% CO2 20% CO2

Time (min)
Fig. 3. Validation of shrinking core model for coal-char B with carbon dioxide gasication at 1173 K.

1080 Table 3 Reaction rate results for carbon dioxide gasication

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This study Coal-char A Activation energy reaction 2 E2 kJ/mol Activation energy reaction 1 (forward) E1 kJ/mol Enthalpy of adsorption,HCO2 kJ/mol Reaction rate constant, k2 at 1173 K sK1 Adsorption constant, KCO2 at 1173 K PaK1 Adsorption constant, KCO at 1173 K and 1223 K PaK1 Reaction rate, r1 at 1173 K and 20% CO2 sK1 109 (G11) 93 (G9) 16 (G2) 5.53 (G0.6)!10K9 1.62 (G0.2)!10K5 1.0 (G0.1)!10K4 1.9 (G0.2)!10K5 1.22(G0.2)!10K9 Coal-char B 137 (G12) 96 (G9) 41 (G4) 2.00 (G0.25)!10K9 1.98 (G0.2)!10K5 2.6 (G0.3)!10K4 1.4 (G0.1)!10K4 5.15(G0.6)!10K10

Literature Coal-char 170187 [35] 170250 [32] 147.9 [35] 23 [38]

investigated. Coal-char A is only slightly more reactive and the carbon dioxide adsorption constant for coal-char B is larger and consequently more temperature dependent (same for steam gasication reported below). A comparison between reactivity experiments with mixtures of carbon dioxide with nitrogen (inert) and carbon dioxide with carbon monoxide at 1173 K is shown in Fig. 4, which illustrates the inhibiting effect of carbon monoxide. With the carbon dioxide kinetic constants determined for the carbon dioxide nitrogen mixtures reported in Table 3 the adsorption constants associated with carbon monoxide were calculated using the intrinsic reaction rate equation (Eq. (6)) incorporating the effect of carbon monoxide. The adsorption constants are shown (for two experiments only) in Table 3 and are slightly larger than for carbon dioxide at a corresponding temperature. A comparison of the results obtained in this investigation with published results are also shown in Table 3 and it can be seen that the results are very much different to that which have been published [32,35,36]. The results reported by Hampartsoumian et al. [35], Liu et al. [36] also include results published by other investigators, but do not include information concerning the parent coal maceral content. It appears, however, that the carbon rich coal-chars particles derived from inertinite-rich coals have much lower activation energies, even less than the lowest value reported for coal-chars derived from coals with unknown maceral concentrations. It should also be noted that the enthalpy of adsorption for carbon dioxide is also much low than that reported by Magge et al. [38]. 3.2.3. Reaction with steam and the effect of hydrogen The procedure followed for evaluation of the overall reaction rate model for the gasication with steam without and with hydrogen was the same as that for the carbon dioxide and carbon monoxide mixtures described above. A Langmuir Hinshelwood-type reaction rate equation used by many other investigators [32] similar to the reaction rate equation for carbon dioxide was also used for stream gasication with and without the presence of hydrogen. The reaction mechanism and overall reaction rate equation are the following [22] Cf C H2 O4 CO C H2 CO/ CO Reaction 4 Reaction 3

with i3 (forward), j3 (backward) and j4 as the specic rate constants of reactions (3) and (4), respectively, the following rate equation can be derived: r2 Z k4 KH2 O PH2 O 1 C KH2 O PH2 O C KH2 PH2 (10)

with k4Zj4;KH2 O Z i3 =j4 and KH2 Z j3 =j4 also   K4 E 0 k4 Z k4 exp RT

0 KH2 O Z KH2 O exp

(11)

  K H2 O H RT

(12)

Again almost all published results [34] based on this mechanism use a rate equation with an equivalent lumped constant k3 (equal to i3) instead of k4 KH2 O appearing in Eq. (10). The constants k3 (activation energy E3) and k4 (activation energy E4) are the specic rate constants for reactions (3) and (4), respectively. Results from experiments without hydrogen showing the validity of the shrinking core model, Eq. (4), are shown in Figs. 5 and 6 and the respective reaction rate constants are given in Table 4. Reaction rate constants were also calculated at 1173 K in order to achieve a meaningful comparison of the behaviour of the coal-chars at a typical uidised bed
1.2

60% CO2/40% N2
1 0.8

60% CO2/40% CO

X (-)

0.6 0.4 0.2 0 0 100 200 300 400 500 600 700

Time (min)
Fig. 4. Inhibition effect of carbon monoxide during carbon dioxide gasication at 1173 K.

R.C. Everson et al. / Fuel 85 (2006) 10761082

1.4 1.2 1 1 0.8 0.6

1081

20% H2O/80% N2

F(X)

X (-)

0.8 0.6 0.4 0.2 0 20 30 40 50 60 70 80 90 100

Steam gasification at 1173 K

20% H2O 15% H2O 10% H2O

20% H2O/80% H2
0.4 0.2 0 0 100 200 300 400 500 600 700

Time (min)
Fig. 5. Validation of shrinking core model for coal-char A with steam gasication at 1173 K.
1.8 1.6 1.4 1.2

Time (min)
Fig. 7. Inhibition effect of hydrogen during steam gasication at 1173 K.

1 0.8 0.6 0.4 0.2 0 0 20 40 60 80

Steam gasification at 1173 K

20% H2O 15% H2O 10% H2O

Time (min)
Fig. 6. Validation of shrinking core model for coal-char B with steam gasication at 1173 K.

coal-chars are more reactive with steam, which agrees with published results for many different chars. Results from experiments in the presence of hydrogen and a comparison with a corresponding experiment without hydrogen are shown in Fig. 7 with adsorption constants (two experiments only) reported in Table 4. The inhibiting effect is evident and the adsorption constants are greater than for steam adsorption at a corresponding temperature. The activation energies (Table 4) for the two coal-chars for gasication with steam are close to the values (126250 kJ/ mol) published by Liu et al. [36] whose results also included results published by other investigators. These results also do not include the petrographic properties of the parent coals and results from different LangmuirHinshelwood models are considered. 3.2.4. Reaction with a multi-component mixture Experiments were carried out with a mixture consisting of carbon dioxide, carbon monoxide, steam and hydrogen (equilibrium gas composition) at 1173 K in order to validate the constants determined above and to elucidate the surface mechanism. According to published results [30,33] there are two possible surface mechanisms that can occur: (1) the carbon-steam and carboncarbon dioxide reactions occur at a common active site, and (2) the carbon dioxide and steam reactions occur at separate active sites. Both reactions are surface reaction controlled and the respective rate equations are the following Rate 1 : r3 Z k2 KCO2 PCO2 C k4 KH2 O PH2 O 1 C KCO2 PCO2 C KCO PCO C KH2 O PH2 O C KH2 PH2 (13)

gasication temperature. Again, the constants do not differ very much, especially the intrinsic reaction rate, for the two coal-chars, with coal-char A having a slightly more reactive surface reaction than coal-char B and the steam adsorption constant KCO2 for coal-char B being larger. These trends are similar to that observed with the carbon dioxide gasication reported above and can be attributed to the presence of different surface chemical structures formed from coal samples with different included minerals in the carbon matrix. Also both
Table 4 Reaction rate results for steam gasication Coal-char A Activation energy reaction 4 E4 kJ/mol Activation energy reaction 3 (forward) E3 kJ/mol Enthalpy of adsorption HH2 O kJ/mol Reaction rate constant, k4 at 1173 K sK1 Adsorption constant, KH2 O at 1173 K PaK1 Adsorption constant, KH2 at 1173 K and 1223 K PaK1 Reaction Rate, r2 at 1173 K and 20% H2O sK1
a

F (X)

Coal-char B 204 (G12) 102G10a 102 (G9) 3.15 (G0.4)!10K9 6.50 (G0.7)!10K5 7.59 (G0.7) 4.23 (G0.4) 1.67 (G0.2)!10K9

212 (G12) 143G14a 69 (G7) 7.97 (G0.9)!10K9 8.07 (G0.9)!10K5 9.36 (G0.9) 4.07 (G0.4) 4.67(G0.5)!10K9

Rate 2 :   k2 KCO2 PCO2 k4 KH2 O PH2 O r3 Z C 1 C KCO2 PCO2 C KCO PCO 1 C KH2 O PH2 O C KH2 PH2 (14) Fig. 8 shows a comparison between experimental results for coal-char A and predictions using the two mechanisms and the constants reported in Tables 3 and 4. The overall model

Published results 126250 kJ/mol [36].

1082
0.8 0.7 0.6 0.5

R.C. Everson et al. / Fuel 85 (2006) 10761082

Case 2

X (-)

0.4 0.3 0.2 0.1 0 0 10 20 30

Case 1

gasication and these rates decreased signicantly in the presence of the hydrogen and carbon monoxide, respectively. For both gasication reactions (carbon dioxide and steam) occurring simultaneously in the presence of carbon monoxide and hydrogen, the overall reaction rate is best described with the assumption that the reactions proceed on separate sites. References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] Harris DJ, Patterson JH. Aust Inst Energy J 1995;13:22. Lu GQ, Do DD. Carbon 1994;32(2):247. Lu GQ, Do DD. Carbon 1992;30(1):21. Dutt S, Wen CY, Belt RJ. Ind Eng Chem Process Des Dev 1977;16(1):20. Ballal G, Zygourakis K. Ind Eng Chem Res 1987;26:911. Liu G, Benyon P, Benfell KE, Tate AG, Boyd RK, Harris DJ, et al. Fuel 2000;79:617. Bhatia SK, Perlmutter DD. AIChE J 1980;26:379. Bhatia SK, Perlmutter DD. AIChE J 1981;27:247. Gavalus GR. AIChE J 1980;26(4):577. Gavalus GR. Combust Sci Technol 1981;24:197. Ballal G, Zygourakis K. Ind Eng Chem Res 1987;26:1787. Chi WK, Perlmutter DD. AIChE J 1989;35:1791. Zygourakis K, Sandman CW. AIChE J 1988;34:1411. Bhatia SK, Gupta JS. Rev Chem Eng 1992;(34):177. Szekely J, Evans JE, Sohn HY. Gas-solid reactions. New York: Academic Press; 1976. Kwon TW, Kim SD, Fung DPC. Fuel 1988;67:530. Beamish BB, Shaw KJ, Rodgers KA, Newman J. Fuel Process Technol 1998;53:243. Huttinger KJ, Nattermann C. Fuel 1994;73:1682. Bailey JG, Tate AG, Diessel CFK, Wall TF. Fuel 1990;(96):225. Hurt RH, Davis KA, Yang NYC, Headley TJ, Mitchel GD. Fuel 1995;74: 1297. Rosenberg P, Petersen HI, Thomsen E. Fuel 1996;9:739. Walker PL, Kusinko F, Austin LG. Adv Catal 1959;11:590. Laurendeau NM. Prog Energy Combust Sci 1978;4:22. Kapteijn F, Meijer R, Moulijn JA. Energy Fuel 1992;6:494. Matsui L, Kojima T, Kunii D, Furusawa T. Ind Eng Chem Res 1987;26:9. Glasby J, Long FJ, Sleightholm P, Sykes KW. Proc R Soc 1948;193:357. Bliek A, Lont JC, Van Swaaij WPM. Chem Eng Sci 1986;41:1895. Blackwood JD, Ingeme AJ. Aust J Chem 1960;13:194. Blackwood JD, McGrory F. Aust J Chem 1958;11:16. Muhlen HJ, Van Heek KH, Juntgen H. Fuel 1985;64(7):944. Nozaki T, Adschira T, Fujimoto K. Fuel 1992;71(3):349. Liu G-S, Tate AG, Bryant GW, Wall TF. Fuel 2000;79:1145. Bliek, A. Mathematical modelling of a concurrent xed bed coal gasier. Doctoral Thesis. Eindhoven University, Netherlands; 1984. Huttinger KJ, Merdes WF. Carbon 1992;30(6):883. Hampartsoumian E, Murdoch PL, Pourkashanian M, Trangmar DT. Combust Sci Technol 1993;92:105. Liu, G-S. Mathematical modeling of coal char reactivity in a pressurized entrained ow gasier. Doctoral Thesis. The University of Newcastle, Australia; 1999. Everson RC, Neomagus HWJP, Njapha D. Fuel; 2006, doi: 10.1016/j.fuel.2005.10.025 Mugge J, Bosch H, Reith T. Chem Eng Sci. 2001;56:5351.

40

50

60

Time (min)
Fig. 8. Coal-char gasication with multi-component mixture for coal-char A at 1223 K. Case 1 involves Rate 1 (same site) and Case 2 involves Rate 2 (separate sites), full lines represent models and the symbol represents experimental points.

incorporating a mechanism involving reactions on separate sites is seen to be applicable and that the constants determined with binary mixtures can be used to predict multi-component gasication. This result was also found for coal-char B. 4. Conclusions The gasication of coal-chars derived from typical South African discards with carbon dioxide and steam was studied between 1073 and 1223 K at atmospheric conditions and reaction rate equations evaluated. For the pulverized coal-chars examined which consisted of a large fraction of carbon-rich particles it was found that the shrinking unreacted core model with a controlling surface reaction together with Langmuir Hinshelwood reaction kinetics was applicable. This implies that for coal-chars derived from discarded coal reserves with a high inertinite content (carbon rich particles), the variation of the internal porosity and internal surface area of the particles during the gasication reaction is not important and that the shrinking external surface area of the particle is a determining structural property. Intrinsic reaction rate constants were evaluated and it was found that on comparing with published results that these results are somewhat different (especially for carbon dioxide) which is attributed to the different chemical structure of the coal-chars surfaces formed from the inertinite rich coals. The effect of the minerals on the reaction rates was found to be minimal when the results are compared for two chars with different mineral contents and derived from coals with the same inertinite concentration. The intrinsic reaction rate equations involving steam predicted higher reaction rates than the corresponding equations involving carbon dioxide

[37] [38]