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Char gasication in mixtures of CO2 and H2O: Competition and inhibition

D.G. Roberts *, D.J. Harris
Cooperative Research Centre for Coal in Sustainable Development, CSIRO Division of Energy Technology, PO Box 883, Kenmore, Queensland 4069, Australia Received 12 December 2006; received in revised form 8 March 2007; accepted 12 March 2007 Available online 9 April 2007

Abstract Our understanding of char gasication reaction kinetics at high pressures is generally limited to analyses of data generated using pure reactants, or reactants diluted with inert gases. This paper presents data generated for the reaction of coal chars with mixtures of CO2 and H2O at high pressures, to determine how existing pure-gas rate data can be applied to more realistic gasication systems. The data presented here show that the rate of reaction in a mixture of CO2 and H2O is not the sum of the two pure-gas reaction rates; rather, it is a complex combination of the two that appears to be dependant on the blocking of reaction sites by the relatively slow CCO2 reaction. Analysis of the results using a LangmuirHinshelwood (LH) style of rate equation with the assumption that both reactions compete for the same active surface, produces a model that explains the experimental data. This model allows reaction rates in mixtures of CO2 and H2O to be estimated based on existing, measured pure-gas reactivity data or from rst principles using knowledge of the rate constants for the LH equation. Crown Copyright 2007 Published by Elsevier Ltd. All rights reserved.
Keywords: Gasication; Char reactivity; Competition; Inhibition

1. Introduction The emergence of high pressure, gasication-based technologies as a high eciency, lower emissions option to help meet future energy needs has increased the requirement for knowledge and understanding of the gasication process. This has led to, inter alia, an increase in our understanding of the kinetics of the char gasication reactions an important aspect of coal conversion due to the relative slowness of the char gasication step. Previous work by the authors [14] and others [510] (including the many references therein) has built on more fundamental studies of the carbon gasication reactions [1120] and extended analysis of the reactions between coal chars at CO2 and H2O to high pressures. This collection of work has led to a much-

Corresponding author. Tel.: +61 7 3327 4444; fax: +61 7 3327 4455. E-mail address: Daniel.Roberts@csiro.au (D.G. Roberts).

improved understanding of the fundamentals of the high pressure char gasication reactions, and how they can aect coal performance in full-scale applications. Most published gasication reactivity investigations studied reactions of coal chars with pure gases (some with inert gases used as a diluent) at temperatures low enough to ensure that chemical processes alone controlled the reaction rates. The generation of such intrinsic reactivity data allows detailed analyses of the reaction system of interest, without complication from processes that are less-quantiable or that interfere with the measurements. Such intrinsic data generated are, typically, of high quality, and are of the form that allows direct application through mechanistic and process models of a range of gasication systems. Gasication and process models, however, usually do not consider how these pure-gas kinetics should be applied in systems where both of the key gasication reactions (CCO2 and CH2O) are occurring simultaneously. Implied in most (and explicitly described as such in Liu

0016-2361/$ - see front matter Crown Copyright 2007 Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2007.03.019

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and Niksas [21] and Blieks [22] char gasication models, for example) is the assumption that the rate of reaction of a char in a system containing CO2 and H2O is the sum of the rates of reaction of the char in the same amount of each reactant separately. There are very few publications that provide experimental data to assist researchers in assessment of such an assumption. Koba and Ida [23] studied the gasication reactivities of metallurgical cokes in CO2, H2O, and their mixtures. They used large amounts of large coke particles (10 g of 36 mm diameter pieces) and studied these reactions at high temperatures (1473 K) in order to simulate conditions in blast furnaces. These conditions, however, introduce unquantiable eects of inter- and intra-particle diusion into the results; this makes it dicult to use the data as the basis of an analysis of the gassolid reaction processes. Mu hlen et al. [6] studied high pressure reaction rates of a German bituminous coal char in complex mixtures of CO2, H2O and the product gases H2 and CO. They used previously published atmospheric- and high-pressure-derived LangmuirHinshelwood style rate equations to describe these data. Implied in their analysis and description of their data is an addition of the contributions of the separate CO2 and H2O reactions. The complicating eect of the inclusion of the eects of H2 and CO make the nature of the interactions between the CO2 and H2O reactions alone dicult to isolate from their analysis. The question remains: is the net reaction rate the sum of the individual (pure-gas) reaction rates when a char is reacting with a mixture of CO2 and H2O? Underlying this question is the issue of whether or not the reactions occur on separate sites, whereby the rate would be additive; or if they compete for the same active surface, in which case the outcome might be less predictable. The purpose of this paper is to present new data on the gasication reactivity of coal chars at high pressures, in mixtures of CO2 and H2O. These data will demonstrate whether or not the overall rate in a mixture is simply the sum of the rates in pure gases, or if there is some interaction on the surface that makes the implementation of the data more complex. 2. Experimental 2.1. Char samples Chars were made from three coal samples (proximate and ultimate analyses of the parent coals are presented in Table 1). These chars were produced from three Australian bituminous coals (coals CRC252, CRC272 and CRC281) by heating 1.0 + 0.6 mm coal samples in ceramic containers to 1373 K at 10 K min1 under dry nitrogen, and holding that temperature for 3 h. These preparation conditions are consistent with those used in previous work by these authors [1,2]. It is acknowledged that char preparation under such conditions produces char samples with dierent structure and morphology to

Table 1 Proximate and ultimate analyses of the parent coals of the chars used in this work CRC252 Proximate analysis (%, air-dried basis) Moisture 6.7 Ash 12.1 Volatiles 40.2 Fixed carbon 41.0 Ultimate analysis (%, dry, ash-free basis) Carbon 78.6 Hydrogen 6.1 Nitrogen 1.7 Sulfur 0.5 Oxygen 13.7 CRC272 3.4 6.6 38.6 51.4 82.9 5.95 1.83 0.88 8.4 CRC281 1.5 10.4 8.8 79.3 90.6 3.64 1.87 0.67 3.2

those generated under more realistic entrained-ow gasication conditions. It has been shown, however [3], that if treatment temperatures are kept constant, high pressure and rapid heating aects primarily the structure and surface area of the char produced, and the intrinsic reactivity properties of the char are not signicantly aected. Furthermore, preparation under consistent, well-dened conditions techniques provides, in a practical timeframe, the large quantities of char required for a study such as this. Surface areas of unreacted and selected post-reaction char samples were determined from CO2 adsorption and subsequent analysis using the DubininRadushkevic equation. 2.2. Reaction rate measurements Reaction rate measurements were performed in a high pressure thermogravimetric analyser, described in detail in previous work by the authors [1,2] and similar to that used by others [6,24]. This facility is capable of measuring mass proles of char samples at high pressures during reaction with mixtures of CO2, H2O and N2 (as well as other gases such as H2 and CO). Approximately 150 mg of dried char sample of particle size 1.0 + 0.6 mm was used in the experiments. Char samples were lowered into a preheated reaction zone to initiate reaction; to quench the reaction the sample was raised into an environment of inert, water-cooled gas. Specic reaction rates (qs) were calculated from mass versus time proles using Eq. (1): qs 1 dw g g 1 s 1 w dt 1

where w is the mass of char (dry, ash-free) at reaction time t. Intrinsic reaction rates (g m2 s1) were calculated from specic data by normalising to the measured surface area of the char. As with most investigations that aim to study the char gasication reactions, it is important that the data measured be free of any inuence of inter-particle and pore diusion, and that the reactor conditions be dierential. Previous work [25] has established a range of experimental

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12 CRC252
Specific Rate (g/g/s) x10 5

Table 2 Experimental program used to generate data presented in this paper P CO2 (MPa) 0.5 1.0 1.5 0.0 0.5 1.0 1.5 0.0 0.5 1.0 P H2 O (MPa) 0.0 0.0 0.0 0.5 0.5 0.5 0.5 1.0 1.0 1.0 P total (MPa) 5.0 1.0 1.5 5.0 1.0 1.5 2.0 1.0 1.5 2.0 Temperatures (K) 1173 1173 1173 1123 1123 & 1173 1123 & 1173 1123 1123 1123 & 1173 1123

10 8
(b) (a)

6 4 2 0 12 CRC272
(c)

This program was completed on each of the three char samples.

Specific Rate (g/g/s) x10 5

10 8

(a)

conditions over which these requirements are fullled for the char gasication system on samples such as these. Consequently, measurements of reaction rates in pure H2O were performed at 1123 K, and rates in pure CO2 at 1173 K (this higher temperature was required to generate a reaction rate that was within the acceptable range of the TGA apparatus). Rates in mixtures of CO2 and H2O were measured at 1123 K, with some extra measurements made at 1173 K. To allow direct comparison between reaction rate measurements made in gas mixtures and rate data obtained for individual reactants, the individual CO2 reaction rates were recalculated at the temperature of comparison (1123 K) using experimentally-determined activation energies. These activation energies were determined using established techniques at atmospheric pressure [26]; it has been shown that these true activation energies are not aected by reactant pressure within Regime I conditions [2]. Table 2 summarises the experimental work program discussed in this paper, showing the range of partial pressures used for the reaction rate measurements for each char sample. As shown in previous work by the authors [2] variations in total pressure between the individual measurements reported here do not aect the consideration of the data: under the conditions in this work, the partial pressure alone is the key pressure variable, being solely responsible for variations in reaction rates. This has been conrmed in the current work for experimentation with gas mixtures. 3. Results 3.1. Conversion proles in reactant gas mixtures Fig. 1 shows conversion proles for the three chars reacting in (separately) 0.5 MPa of CO2 and 0.5 MPa of H2O, compared with the reaction in a mixture of 0.5 MPa CO2 and 0.5 MPa H2O (total pressure of 1.0 MPa). These data are all presented at 1123 K. As expected from previous work, the rate of reaction of each of the chars with H2O alone is faster than the rate with CO2 alone. The data in Fig. 1 also show that the reaction rates in the mixture of CO2 and H2O are denitely not

(b)

6 4 2
(c)

0
12 CRC281 Specific Rate (g/g/s) x10 5 10
(a)

8 6 4 2
(c)

(b)

0 0 5 10 Conversion (%, daf) 15

Fig. 1. Example conversion proles for the samples used in this work reacting at 1123 K in (a) 0.5 MPa H2O, (b) a mixture of 0.5 MPa H2O + 0.5 MPa CO2, and (c) 0.5 MPa CO2.

the sum of the two pure-gas rates: for CRC252, the initial rate in the mixture is slightly less than the average of the single-gas rates, increasing to approximately 80% of the H2O rate by 10% conversion. The reaction rate in the gas mixture for the other char samples remained closer to the average of the rates in pure gases, increasing to approximately 60% of the CH2O rate by 10% conversion. Results consistent with these were obtained for the same chars reacting in 1.0 MPa of reactant, as well as 1.0 and 0.5 MPa of reactants, and are not shown here. 3.2. CO2 Inhibition of the charH2O reaction It is apparent from the data reported above that the rate of reaction of a char with a mixture of CO2 and H2O is not simply the sum of the rates of reaction of the char with the

D.G. Roberts, D.J. Harris / Fuel 86 (2007) 26722678

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CO2 DR Surface Area (m2/g)

pure reactants separately: it seems that the presence of CO2 may inhibit the faster CH2O reaction. Fig. 2 shows reaction rate data (determined at 10% conversion and two temperatures, 1123 and 1173 K) for the chars reacting with 0.5 and 1.0 MPa H2O, and the eect of incrementally adding CO2 to this system. It is clear that the addition of CO2 to the system decreases the measured specic reaction rate, and that this eect is similar at the two temperatures. It has been shown (e.g. [25]) that, when chemical rate control is predominant, reaction of porous carbons with H2O generally produces a larger surface area than reaction with CO2. Having the two reactions occur in parallel, and in particular with one eectively inhibiting the other, is likely to aect how the surface of the char develops during reaction. Table 3 (and Fig. 3) contains CO2 adsorption (DubininRadushkevich) surface area data for a selection of chars following reaction in CO2/H2O mixtures at 1123 K. As expected, surface areas following reaction in
45 40 CRC252

Table 3 CO2 (DR) adsorption surface areas of unreacted char samples and selected post-reaction (10% conversion, reacted at 1123 K) char samples Mix (MPa) CO2 H2O CO2 SA (m2/g) CRC252 13.6 112 336 357 143 326 330 225 CRC272 9.00 55.6 230 236 85.7 214 216 189 CRC281 2.82 99.1 195 181 98 209 194 211

Unreacted char 0.5 0.0 0.5 0.5 0.0 0.5 1.0 0.0 1.0 0.5 0.5 1.0 0.0 1.0

400

300

200

Specific Rate (g/g/s x 10 5 )

35 30 25 20 15 10

100

0 CRC252 1.0:0.0 1.0:0.5 CRC272 0.5:1.0 CRC281 0.1:0.0

400
5 0 45 40 CRC272

CO2 DR Surface Area (m2/g)

300

Specific Rate (g/g/s x 10 )

35 30 25 20 15 10 5 0 45 40 CRC281

200

100

0 CRC252 0.5:0.0 CRC272 0.5:0.5 CRC281 0.0:0.5

Fig. 3. CO2 adsorption surface areas of chars made from the three coals used in this work. The ratios in the legend refer to the CO2:H2O ratio, expressed in MPa.

Specific Rate (g/g/s x 10 )

35 30 25 20 15 10 5 0 0 0.5 1 1.5 CO2 Partial Pressure (MPa) 2

Fig. 2. Eect of CO2 addition on the specic rate of the charH2O reaction. Closed symbols = 0.5 MPa H2O; open symbols = 1.0 MPa H2O. Triangles = 1123 K; circles = 1173 K.

CO2 are less than those generated under the same conditions in H2O. This is true for all char samples used in this study. Addition of CO2, whilst inhibiting the H2O reaction as discussed, in general does not increase the surface area produced after reaction. This is consistent with the assumption that the mechanism of inhibition is based on both reactants competing for the same surface reaction sites. The specic reaction rates presented and discussed above are inuenced by both the true or intrinsic rate of the carbongas reaction and the amount of available surface on which this reaction can take place. By normalising

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7

D.G. Roberts, D.J. Harris / Fuel 86 (2007) 26722678

CRC252

Intrinsic Rate (g/m2/s x 10 7)

6 5 4 3 2 1 0 8

Intrinsic Rate (g/m2/s x 10 7)

7 6 5 4 3 2 1 0 6 CRC272

1.0 MPa H2O 0.5 MPa H2O

(up to 3.0 MPa) could be described using the Langmuir Hinshelwood rate equation based on generally-accepted atmospheric pressure reaction schemes. That work also presented calculations and measurements of reactive surface saturation by reaction intermediates, demonstrating the link between reaction rate and degree of surface saturation for both charH2O and charCO2 reactions. The experimental data presented here suggest that there is competition between CO2 and H2O for the same active surface. If this is true, then the reduction in surface available to the H2O reaction by adsorbed C(O) species from the CO2 reaction is a likely reason for the decrease in the H2O reaction rate upon addition of CO2. If we assume that the available surface for both reactions is the same, then this reduction in available surface for the CH2O reaction can be represented as Ct H2 O Ct COCO2 2

Intrinsic Rate (g/m2/s x 10 )

CRC281 5 4 3 2 1 0 0 0.5 1 1.5 CO2 Partial Pressure (MPa) 2

where Ct H2 O is the surface available for the H2O reaction, [Ct] is the total available surface of the char, and COCO2 is the concentration of intermediate surface complexes from the charCO2 reaction. A similar equation can be written to describe the surface available to the CCO2 reaction which has been reduced by the reaction intermediates of the CH2O reaction. As a rst analysis of this system, and to avoid potentially unnecessary complications and iterations, the scenario described in Eq. (2) will be assumed to be the dominant eect (likely to be a valid assumption due to the relatively slow rate of the CCO2 reaction). Using the generally-accepted LH style rate equation for the CO2 reaction in the absence of CO, the rate of reaction of CO2 at the carbon surface qCO2 is qCO2 Ct k 1 P CO2 1 1k P k 3 CO2 3

Fig. 4. Eect of CO2 addition on the intrinsic rate of the charH2O reaction at 0.5 and 1.0 MPa H2O and 1123 K.

the specic reaction rate to the measured surface area, data can be compared on an intrinsic reaction rate basis. This allows a more useful comparison of the actual chargas reaction kinetics. Using intrinsic reaction rate data to describe the eect of CO2 inhibition on the CH2O reaction generates similar trends to those discussed above. Fig. 4 shows how intrinsic reaction rates of chars reacting with H2O are also inhibited by addition of CO2. The similarity in the trends between specic and intrinsic reaction rate data are consistent with a competing active site concept for char gasication. That is, even though reaction with steam produces a greater surface area (presumably containing more active sites), this area is available to both reactants, and competition for that surface continues. 3.3. Interpretation using LH rate equations Previous work by the authors [4] demonstrated how reaction rates of chars with pure gases at high pressures

Since the rate of mass loss equals the rate at which the intermediate C(O) complexes desorb from the surface, we can express the overall rate as a function of the desorption rate constant and the concentration of intermediate surface complexes [19,20]: qCO2 k 3 CO 4

we can therefore arrive at an expression for the concentration of reaction intermediates from the CO2 reaction: COCO2 Ct k 1 =k 3 P CO2 1 k 1 =k 3 P CO2 5

Combining Eqs. (2) and (5) gives an expression for the total surface area available for the charH2O reaction: Ct k 1 =k 3 P CO2 Ct H2 O Ct 1 k 1 =k 3 P CO2   k 1 =k 3 P CO2 Ct 1 1 k 1 =k 3 P CO2

Substitution of this [Ct] term directly into the LH rate equation for the steam reaction, and including the contri-

D.G. Roberts, D.J. Harris / Fuel 86 (2007) 26722678

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Specific Rate (g/g/s x 10 )

bution of the CO2 reaction, results in a combined rate expression which can be used to calculate a reaction rate in a mixture of H2O and CO2:   k 1 =k 3 P CO2 7 qmixture qCO2 qH2 O 1 1 k 1 =k 3 P CO2 Given an adequate knowledge of the rate constants that are contained within this equation (as well as within the qCO2 and qH2 O terms) one is able to determine the reaction rate in a gas mixture from rst principles. However, such knowledge of the available surface and rate constants is often not available nor simple to determine. Eq. (7) is also of the form, however, that can be applied to existing reaction rate data determined for chars reacting with H2O and CO2 separately that is, the existing rate data (qCO2 and qH2 O ) be used directly in Eq. (7) and adjusted using the factor relying on the k1/k3 ratio. Fig. 5 shows measured rate data in mixtures of CO2 and H2O, compared with a estimated rate based on rate data obtained in pure gases [1,4] modied using Eq. (7). The inhibiting eect of increasing the CO2 partial pressure observed in the experimental data is reected well by Eq. (7). This suggests that the competing reaction model developed in this work represents well the nature of interaction of CO2 and H2O on a reacting char surface. Furthermore, the simplifying assumption that the inhibition by steam of the (small) contribution of the CO2 reaction need not be included in this analysis. The ratio k1/k3 used is the same at both temperatures in the absence of rate v pressure data at both temperatures from which temperature-specic ratios can be calculated, it is assumed that the ratio is the same at 1123 K and 1173 K. The t of the calculated rate to the measured rates indicates that over a 50 K temperature range this assumption is valid. Given the dierence in activation energies determined by other authors for these constants, however (e.g. [6,27]) it is unlikely that this assumption will be true over a wider temperature range. Ongoing work in this laboratory aims to measure temperature sensitivities of reaction rates in mixtures to further understand the competitive inhibition phenomenon described here. 3.4. Applications and future work This method of determining reaction rates in a mixture of reactants has two modes of application. One is from rst principles, whereby the qCO2 and qH2 O terms in Eq. (7) can be determined from a knowledge of the individual rate constants for the LangmuirHinshelwood rate equations. This allows calculation of the reaction rate of a given sample in a mixture of CO2 and H2O. A more practical application of Eq. (7), however, lies in its ability to be used on existing rate data obtained from pure-gas experiments, such as those reported previously by the authors [1]. With knowledge of the k1/k3 ratio (which, depending on the degree of accuracy required,

45 40
5

CRC252

35 30 25 20 15 10 5
(d) (a) (b) (c)

0 45 40 CRC272

Specific Rate (g/g/s x 10 )

35 30 25 20 15 10 5 0 40 35 CRC281
(d) (c) (a) (b)

Specific Rate (g/g/s x 10 )

30 25 20 15 10
(c) (a) (b)

5 0 0 0.5 1 1.5 CO2 Partial Pressure (MPa)

(d)

Fig. 5. Measured reaction rates (points) in mixtures of CO2 and H2O compared with those calculated (lines) based on pure-gas reaction rates and a correction factor derived from a LH analysis of the data, with the contribution of the measured charCO2 reaction rate included. (a) 1.0 MPa H2O, 1173 K; (b) 0.5 MPa H2O, 1123 K; (c) 1.0 MPa H2O, 1123 K; (d) 0.5 MPa H2O, 1123 K.

can be determined from a small number of experiments [4], estimated based on knowledge of relative char reactivity properties, or assumed based on knowledge of coal char reactivity in general) the rate of reaction in a mixture of gases can be calculated from known (measured) reaction rates in pure gases. This makes the pure-gas reactivity data that currently exist applicable to the determination of reaction rates in mixtures, thus enhancing their application to advanced coal char gasication models. The ability of this analysis to describe the experimental data suggests that the underlying hypothesis that CO2 and H2O compete for reactive surface on char, and the slower CCO2 reaction inhibits the H2O reaction by decreasing the availability of reactive surface is applicable under the conditions examined here. This is an important

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D.G. Roberts, D.J. Harris / Fuel 86 (2007) 26722678

nding, as such a phenomenon is not typically reected in models of the gasication process that regularly use intrinsic reactivity data. The work presented in this paper forms a rst step in our understanding of how interactions between CO2 and H2O inuence the overall reaction rate of a char particle during gasication. The data presented here were generated at two temperatures both within the reaction regime where chemical rates alone control the conversion rate and are presented at a single level of conversion. This provided the necessary data for interrogation and understanding of the reaction mechanisms; however the eects of temperature over a more practical range, and how these results vary as chars react (both under regime I conditions, as presented here, but also under higher temperature conditions more relevant to gasication applications) require further work. 4. Conclusions This work has presented intrinsic reaction rate data for three chars reacting in mixtures of CO2 and H2O at reactant partial pressures from 0.1 to 1.0 MPa. The data showed that the presence of CO2 reduced the rate of the CH2O reaction. These data were analysed using the LangmuirHinshelwood form of the individual rate equations, using the assumption that both reactions competed for the same active surface. Using this hypothesis, the LH rate equations were able to describe the experimental data well. This provides the basis of a means by which the competition between the two reactants can be incorporated into char gasication models, either from rst principles (using values of the LangmuirHinshelwood rate constants) or as a technique to determine the net reaction rate from known, measured pure-gas reaction rates. Acknowledgements The authors would like to thank Ms Jade Tinney (CSIRO) for her eorts in making the high pressure reac-

tion rate measurements. The authors also wish to acknowledge the support of the Cooperative Research Centre for Coal in Sustainable Development, which is funded in part by the Cooperative Research Centres Program of the Commonwealth Government of Australia. References
[1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] Roberts DG, Harris DJ. Energy Fuels 2000;14:483. Roberts DG, Harris DJ, Wall TF. Fuel 2000;79:1997. Roberts DG, Harris DJ, Wall TF. Energy Fuels 2003;17:887. Roberts DG, Harris DJ. Energy Fuels 2006;20:2314. Laurendeau NM. Prog Energy Combust Sci 1978;4:221. Mu hlen H-J, van Heek KH, Ju ntgen H. Fuel 1985;64:944. Nozaki T, Adschiri T, Fujimoto K. Energy Fuels 1991;5:610. Nozaki T, Adschiri T, Fujimoto K. Fuel 1992;71:349. Dutta S, Wen CY, Belt RJ. Ind Eng Chem Proc Des Dev 1977;16:20. Hampartsoumian E, Murdoch P, Pourkashanian M, Trangmar DT, Williams A. Combust Sci Technol 1993;22:105. Ergun S. J Phys Chem 1956;60:480. Blackwood JD, McGrory F. Aust J Chem 1958;11:16. Walker Jr PL, Rusinko Jr F, Austin LG. In: Eley DD, Selwood PW, Weisz PB, editors. Advances in catalysis, vol. 11. NY and London: Academic Press; 1959. p. 133. Blackwood JD, Ingeme AJ. Aust J Chem 1960;13:194. Ergun S, Mentser M. In: Walker Jr PL, editor. Chemistry and physics of carbon, vol. 1. NY: Marcel Dekker, Inc.; 1965. p. 203. Biederman DL, Miles AJ, Vastola FJ, Walker Jr PL. Carbon 1976;14:351. Strange JF, Walker PL. Carbon 1976;14:345. Ju ntgen H. Carbon 1981;19:167. Hu ttinger KJ. Carbon 1990;28:453. Hu ttinger KJ, Nill JS. Carbon 1990;28:457. Liu G-S, Niksa S. Prog Energy Combust Sci 2004;30:679. Bliek A. PhD thesis. University of Twente, 1984. Koba K, Ida S. Fuel 1980;59:59. Mu hlen H-J, Sulimma A. Thermochim Acta 1986;103:163. Roberts DG. PhD thesis. University of Newcastle, 2000. Harris DJ, Smith IW. Proc Combust Inst 1990;23:1185. Aderibigbe DA, Szekely J. Carbon 1979;17:431.

[14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27]