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Energy Fuels 2009, 23, 42694277 Published on Web 08/21/2009

: DOI:10.1021/ef900205d

Comparison of the Combustion Reactivity of TGA and Drop Tube Furnace Chars from a Bituminous Coal
Katherine Le Manquais,*,, Colin Snape,, Ian McRobbie, Jim Barker, and Victoria Pellegrini
Fuels and Power Technology Research Division, Faculty of Engineering, University of Nottingham, NG7 2RD, U.K., Innospec Limited, Oil Sites Road, Ellesmere Port, Cheshire, CH65 4EY, U.K., and Current address: Department of Chemical & Environmental Engineering, Faculty of Engineering, University of Nottingham, Nottingham, NG7 2RD, U.K.

Received March 9, 2009. Revised Manuscript Received July 8, 2009

Although thermogravimetric analysis (TGA) is a widely accepted technique for assessing coal combustion, conflicting trends have often been reported when relating apparent TGA reactivities to pulverized fuel (PF) burner conditions. Therefore, this paper compares the reactivity of chars generated in a drop tube furnace (DTF) to those from TGA. The implications of devolatilization temperature, heating rate and residence time are considered. For the smaller particle size ranges of the bituminous coal investigated (ATC), optimized devolatilization procedures were used to generate corresponding TGA burnout rates between the two char types. However, with fractions of >75 m, the DTF chars showed an increased burnout propensity when moving from combustion regime II to combustion regime III. Scanning electron microscope (SEM) images and internal surface areas indicate that this is because of incompatible char morphologies. Thus, while chars produced under the conditions of TGA pyrolysis strongly resemble raw coal and display an undeveloped pore network; the DTF chars are highly porous, extensively swollen and possess considerably larger internal surface areas. Subsequently, char burnout variability was quantified, with the reactivity distribution for the DTF samples found to be up to an order of magnitude more significant than for the TGA chars. This is attributed to a fluctuating devolatilization environment on the DTF. Finally, a TGA study observed a robust particle size based compensation effect for the TGA chars, with the relative reaction rates and activation energies demonstrating the presence of internal diffusion control. However this phenomenon was partly alleviated for the DTF chars, since their higher porosities reduce mass transfer restrictions. Moreover, it should be realized that DTF char fractions of <38 m, including those required to ensure true intrinsic control under the investigated burnout conditions, cannot be produced directly. This is because of bridging and sloughing in the DTFs screw-feeder. Instead, such samples must be created by grinding larger particles, which destroys the chars existing porosity.

1. Introduction Although thermogravimetric analysis (TGA) is a well established1,2 and extensively used3 technique for investigating the thermal reactions of coal, extrapolation of the resultant reactivity parameters to larger scale systems remains a controversial issue. In the past, this was partly because of the assumption that inherent char reactivity is not a limiting factor at the high temperatures experienced in a pulverized fuel (PF) furnace, allowing diffusion processes to dominate (combustion regime III).4 However, as small particle sizes promote boundary layer diffusion5 and since char deactivation can cause low intrinsic reactivity to occur after a relatively

*To whom correspondence should be addressed. E-mail: enxkl1@ nottingham.ac.uk. (1) Yu, J.; Lucas, J. A.; Wall, T. F. Prog. Energy Combust. Sci. 2007, 33, 135170. (2) van Heek, K. H. Fuel 2000, 79, 126. (3) Kok, M. V.; Pamir, M. R. J. Anal. Appl. Pyrolysis 1995, 35, 145 156. (4) Backreedy, R. I.; Habib, R.; Jones, J. M.; Pourkashanian, M.; Williams, A. Fuel 1999, 78, 17451754. (5) Lu, L.; Kong, C.; Sahajwalla, V.; Harris, D. Fuel 2002, 81, 1215 1225. (6) Beeley, T.; Crelling, J.; Gibbins, J.; Hurt, R.; Lunden, M.; Man, C.; Williamson, J.; Yang, N. Symp. (Int.) Combust. 1996, 26, 31033110. (7) Essenhigh, R. H.; Klimesh, H. E.; Fortsch, D. Energy Fuels 1999, 13, 826831.
r 2009 American Chemical Society

short heat treatment time,6 a combination of diffusion and chemical control now seems extremely likely (regime II).7 This implies that combustion rate is the result of three interacting factors: the intrinsic reaction rate of the internal surface of the coal particles, the size of this surface, and the extent to which oxygen diffusion through the pores restricts the reaction.8 Subsequently, to compare the reactivities of different coals and chars, it is preferable to decouple mass and heat transfer effects from those of the chemical reaction.9 Thereby, TGA based experiments have become a common analytical choice; providing a convenient, rapid and quantitative means of examining sample mass changes during combustion. TGA techniques for assessing char reactivity have generally fallen into two main categories, isothermal runs, where a pseudofirst order reaction rate constant can be assumed,10-12 and the quicker but more kinetically complicated nonisothermal methods. Nevertheless even for simple isothermal studies the operating temperatures, heating rates, and particle sizes investigated have varied widely. Furthermore, a wide variety of rate constants have been used to express combustion
(8) Smith, I. W. Proc. Combust. Inst. 1982, 10451065. (9) Valix, M. G.; Trimm, D. L. Chem. Eng. Sci. 1992, 47, 16071617. (10) Ceylan, K.; Karaca, H.; Onal, Y. Fuel 1999, 78, 11091116. (11) Russell, N. V.; Beeley, T. J.; Man, C. K.; Gibbins, J. R.; Williamson, J. Fuel Process. Technol. 1998, 57, 113130. (12) Hurt, R. H.; Calo, J. M. Combust. Flame 2001, 125, 11381149.

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Table 1. Proximate, Ultimate, and Maceral Analyses of ATC PF
ultimate analysis volatiles C H N S O (wt % daf) (% daf) (% daf) (% daf) (% daf) (% daf) 31 85 5 2 1 7 vitrinite (% daf) 45

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proximate analysis moisture (wt %) ATC 5 ash (wt %) 13 fixed carbon (wt % daf) 69

maceral analysis liptinite (% daf) 4 semifusinite (% daf) 43 fusinite (% daf) 8

activity including maximum reactivity,13,14 average reactivity,15 reactivity at a fixed conversion,16,17 and combinations thereof.18 Unsurprisingly this diversity, especially when coupled with an incomplete understanding of the fundamental interactions occurring, has repeatedly resulted in the absence of true kinetic control (regime I).19,20 In addition, TGA burnout data has occasionally been used in conjunction with chars produced on medium scale devices, such as drop tube furnaces (DTFs)21 and other laminar flow reactors.22 DTFs are capable of creating an environment that closely simulates industrial conditions; in particular the short residence times, high temperatures, fast heating rates, and dilute particle phases.23 These operating variables are known to have a significant influence on char morphology, including pore structure and internal surface area, and are consequently critical factors in determining a coals carbon burnout propensity.1,24 Unfortunately, such work has frequently led to conflicting reactivity trends being reported and further confusion pertinent to the combustion regimes being observed.21,22,24-26 This paper, therefore, evaluates the reactivity of a single coal by conducting TGA burnout analyses on DTF chars and their TGA counterparts. Hence, the ability of traditional TGAs and more recent infrared furnaces to mimic the devolatilization conditions of the DTF and produce realistic coal chars is considered. To this end, the combustion behaviors of both char types are explained in terms of their physical characteristics, which are supplied in the form of scanning electron microscope (SEM) images and internal surface areas. The repeatability and reproducibility of the char production methods is then examined. Finally, as the effects of temperature and coal particle size are known to be fundamentally important during TGA studies,8,27,28 a detailed investigation into their influences and the impact of char type has been conducted.
(13) Naredi, P.; Pisupati, S. V. Energy Fuels 2008, 22, 317320. (14) Cai, H. Y.; Guell, A. J.; Chatzakis, I. N.; Lim, J. Y.; Dugwell, D. R.; Kandiyoti, R. Fuel 1996, 75, 1524. (15) Tsai, C. Y.; Scaroni, A. W. Fuel 1987, 66, 14001406. (16) Gale, T. K.; Bartholomew, C. H.; Fletcher, T. H. Energy Fuels 1996, 10, 766775. (17) Floess, J. K.; Longwell, J. P.; Sarofim, A. F. Energy Fuels 1988, 2, 1826. (18) Chen, Y.; Mori, S.; Pan, W. P. Energy Fuels 1995, 9, 7174. (19) Essenhigh, R. H.; Misra, M. K.; Shaw, D. W. Combust. Flame 1989, 77, 330. (20) Hamor, R. J.; Smith, I. W.; Tyler, R. J. Combust. Flame 1973, 21, 153162. (21) Biswas, S.; Choudhury, N.; Sarkar, P.; Mukherjee, A.; Sahu, S. G.; Boral, P.; Choudhury, A. Fuel Process. Technol. 2006, 87, 191199. (22) Zolin, A.; Jensen, A.; Pedersen, L. S.; Dam-Johansen, K.; Torslev, P. Energy Fuels 1998, 12, 268276. (23) Ulloa, C.; Borrego, A. G.; Helle, S.; Gordon, A. L.; Garcia, X. Fuel 2005, 84, 247257. (24) Cloke, M.; Lester, E.; Thompson, A. W. Fuel 2002, 81, 727735. (25) Biswas, S.; Choudhury, N.; Ghosal, S.; Mitra, T.; Mukherjee, A.; Sahu, S. G.; Kumar, M. Energy Fuels 2007, 21, 31303133. (26) Barranco, R.; Cloke, M.; Lester, E. Fuel 2003, 82, 18931899. (27) Chen, Y.; Mori, S.; Pan, W.-P. Thermochim. Acta 1996, 275, 149 158. (28) Lu, L.; Sahajwalla, V.; Harris, D. Energy Fuels 2000, 14, 869876.

2. Experimental Procedure
2.1. Coal Preparation. The coal used in this study is from the Arthur Taylor Colliery (ATC) in South Africa. Its proximate, ultimate and maceral analyses are set out in Table 1. ATC has been ground using a ball mill, before being sieved into <20, <38, 38-53, 53-75, 75-106, and 106-150 m particle size fractions. Any entrained fines were removed using an Alpine Jet Sieve. The sieved coal was then separated into 3 g samples for firing on the DTF or 5 mg portions for TGA work. 2.2. DTF. The DTF consists of a coal screw-feeder, watercooled feeder and collector probes, a controllable gas system and a 2 m ceramic work tube, with an internal diameter of 50 mm and 5 mm thick walls. The DTF was heated to 1300 C using three programmable heaters (a preheater, a main heater and a trim heater). An atmosphere of 1% oxygen in nitrogen (mol mol-1) was maintained, rather than true pyrolysis conditions, to allow for the combustion of any tars formed. A variety of furnace residence times were used when producing the chars, 200, 400 and 600 ms, and these were achieved by lowering the DTFs collector probe and correcting the inlet gas flows. Particle heating rates of approximately 104-105 C s-1 can be assumed. 2.3. TGA. Char samples were also produced by TGA, in nitrogen and at a range of devolatilization temperatures between 900 and 1300 C. This involved using a conventional electrically heated TA SDT Q600 although, for the investigation of higher heating rates, a TA Q5000IR infrared furnace was utilized (where indicated). The Q5000IR is capable of a ballistic heating rate of approximately 1800 Cmin-1, with a maximum controllable heating rate of 500 Cmin-1, which is far greater than the 150 Cmin-1 achievable on the SDT Q600. This should also cause a significant reduction in the diffusion based lag-time at the start of the burnout period. Once produced, the combustion activities of the different chars were assessed using isothermal TGA burnouts at 525 C. To do this, the DTF chars were heated at a rate of 50 Cmin-1 to 525 C under nitrogen, the furnaces atmosphere was switched to air and the samples were isothermally combusted for 80 min. For the TGA chars, the furnace was cooled to 525 C after pyrolysis and the samples were immediately burnt out. From the resultant carbon burnout profiles, two quantitative measures of reactivity were then taken. First a time until 90% carbon conversion and, second, pseudo-first order kinetics were applied between 5 and 95% carbon burnout to allow for the calculation of a composite rate constant (k) using DR k1 -R 1 Dt Here R = (1 - C/C0) is the fractional weight conversion, with C as the remaining carbon mass and C0 as the original carbon mass.29 The solution of eq 1 by integration, subject to the initial condition R = 0 at t = 0, yields -ln1 -R kt 2

The rate constant can be determined graphically from the gradient of a plot of -ln(1 - R) versus t and, subsequently, the values of the activation energy (E) and the pre-exponential factor (A) can be estimated from the slope and intercept of an Arrhenius plot ln k ln A -E=RTisothermal 3

(29) Sima-Ella, E.; Yuan, G.; Mays, T. Fuel 2005, 84, 19201925.

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Table 2. Influence of Devolatilization Residence Time on the Reactivity of DTF Char


residence time (ms) 200 600 400 burnout time to 10% carbon remaining (min) 47.3 54.6 57.0 composite 1st order rate constant (min-1) 0.055 0.046 0.045

Therefore, the activation energy of the coal combustion can be determined by completing isothermal TGA runs at a range of temperatures. 2.4. Char Characterization. While a sufficient amount of DTF char was produced to allow for a direct characterization, a great number of TGA runs would be required to create a similar quantity of material. Instead TGA chars were imitated using a horizontal tube furnace (HTF) at 900 and 1100 C, where a pushing rod and a thermocouple were used to replicate the 150 Cmin-1 heating rate. The combustion activities of the HTF pyrolyzed chars were then assessed by TGA burnout and found to be consistent with the TGA devolatilized samples. Subsequently, SEM images of the DTF and HTF chars were taken by a FEI Quanta 600 instrument at x400 and x800 magnifications. BET surface areas were also measured from nitrogen adsorption isotherms at -196 C using a Micromeritics ASAP 2000. Carbon dioxide adsorption isotherms were not used, as there remains some uncertainty as to whether micropores are available for oxidation above 1000 C.7,8,30-32

Figure 1. Carbon burnout profiles for TGA chars with different devolatilization temperatures and the DTF char baseline.

3. Results and Discussion 3.1. Comparing Devolatilization Heating Procedures. As a first step in comparing TGA and DTF chars, it is necessary to develop an optimized TGA devolatilization heating procedure that can produce char with a combustion reactivity apparently akin to that from PF boilers. This is problematic because, although conventional TGAs can easily achieve the temperatures of an industrial furnace, even when using a state of the art infrared TGA heating rates are still hundreds or thousands of degrees Celcius per minute. In contrast, tens or hundreds of thousands of degrees Celcius per minute can be achieved on the DTF or in an industrial PF boiler. Nevertheless with the advent of this new technology, a reassessment of optimum devolatilization temperatures, heating rates and residence times seems prudent. As such, Table 2 illustrates the effect of devolatilization residence time on the burnout reactivity of DTF char to develop a credible reactivity baseline from which a suitable TGA devolatilization method might be obtained. These results were collected using the 53-75 m coal fraction which is most similar in composition to PF. Table 2 shows that the 200 ms DTF char is the most active, with the shortest time until 90% carbon conversion and the highest combustion rate constant. Char reactivity then decreases for the 400 ms sample, where a greater degree of thermal deactivation or annealing6 and a reduction in the amount of retained volatile matter can be assumed. Specifically, this has a strong effect on char reactivity because the residual hydrogens that remain as a consequence of incomplete devolatilization and reduced thermal annealing, provide the active sites by which the combustion
(30) Kulaots, I.; Aarna, I.; Callejo, M.; Hurt, R. H.; Suuberg, E. M. Proc. Combust. Inst. 2002, 29, 495501. (31) Lorenz, H.; Carrea, E.; Tamura, M.; Haas, J. Fuel 2000, 79, 1161 1172. (32) Alonso, M. J. G.; Borrego, A. G.; Alvarez, D.; Menendez, R. Fuel Process. Technol. 2001, 69, 257272. (33) Alonso, M. J. G.; Borrego, A. G.; Alvarez, D.; Menendez, R. Fuel 1999, 78, 15011513.

proceeds.33 Conversely an unexpected increase in combustion activity is witnessed for the 600 ms char, indicating that the 1% oxygen present might provide an artificial activating side effect that can influence mesopore surface area.34-36 The 400 ms sample is therefore most similar to the unreactive char that is customarily found in the oxygen deprived zones of an industrial furnace and it will thus be used as standard. To replicate this carbon burnout profile using a TGA, Figure 1 depicts combustion curves for TGA chars that have been generated at a variety of devolatilization temperatures. These temperatures were intentionally chosen to be above the values normally used, in the anticipation of ensuring a more authentic devolatilization of the coal analogous to that experienced on the DTF. All the runs were conducted at the SDT Q600s maximum achievable heating rate of 150 C min-1. Subsequently, the burnout profiles in Figure 1 reaffirm that the intrinsic reactivity of char from high temperatures is generally lower than that from low temperatures. This is attributed to an increase in thermal annealing as enhanced mobility gives rise to extensive repolymerizations, the growth of regions with turbostatic carbon structure and the collapse of micropores. In turn, this causes a reduction in the amount and accessibility of active sites.5,16,33,37 However, the trends in Figure 1 also indicate that a devolatilization temperature of 1100 C is most suitable for generating TGA chars with a burnout propensity that corresponds to the 1300 C, 400 ms DTF char baseline. As such, a higher devolatilization temperature produces a char that is more unreactive than the standard DTF sample. But, while the opposite is also probably true for lower devolatilization temperatures, the observed trend is not as distinctive because of a change in the shape of the combustion profile. This suggests that char deactivation could be partially due to a combination of heating rate and residence time with temperature not, per se, controlling the extent of annealing. Additional information can also be surmised by studying the time based derivates of these burnouts, commonly referred to as reactivity profiles, which are shown in Figure 2. Such maxima have been encountered by many researchers and they are thought to arise from intraparticle diffusion
(34) Guerin, H.; Siemieniewska, T.; Grillet, Y.; Francois, M. Carbon 1970, 8, 727740. (35) Senneca, O.; Salatino, P.; Masi, S. Exp. Therm. Fluid Sci. 2004, 28, 735741. (36) Gale, T. K.; Fletcher, T. H.; Bartholomew, C. H. Energy Fuels 1995, 9, 513524. (37) Tsai, C.-Y.; Scaroni, A. W. Fuel 1987, 66, 200206.

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Figure 2. Rate of carbon combustion for TGA chars with different devolatilization temperatures and the DTF char baseline.

limitations. This is because of either physical properties, such as surface area and porosity,8,38 or the carbons structural ordering.13 In Figure 2, the rate peaks are shown to be strongly dependent on the temperature of TGA devolatilization, with the smallest maximum rate being exhibited for the highest temperature and shifted toward the latest burnout time. However, of most interest in Figure 2, is the considerably higher combustion rate that is realized by the DTF char compared to the TGA char generated at the same temperature. This indicates a significant change in the underlying char structure. First, this might be from different extents of graphitization, because of the dissimilar heating rates and treatment times experienced. Or, second, since devolatilization is likely to be incomplete, it could be from volatiles being retained in the DTF char and burnt early on in the subsequent combustion.39 Or, third, enhanced porosity might be permitting a faster burnout rate, but only if the combustion is being controlled by oxygen pore diffusion (i.e., regime II).1,32 Hence, to determine which of these explanations is behind the profiles in Figures 1 and 2, it is necessary to examine the physical characteristics of the samples. Figure 3 shows surface SEM images of two HTF chars, which have been produced under identical conditions to the corresponding TGA samples and exhibit consistent burnout profiles, and the DTF baseline char. Both the HTF samples closely resemble raw coal; they are heterogeneous, irregular, sharp-edged, and angular. In fact, the only evidence of devolatilization is that the particles are slightly swollen, with the occasional surface crack and degassing pore. This implies that a proportion of the coals inherent volatiles could remain trapped in the presented char structure. Moreover, there appears to be little variation between the sample produced at 900 C and that at 1100 C, although the char particles from the higher temperature are slightly more rounded and glassy in appearance. In contrast, the DTF sample closely resembles industrial PF char.8,40As such, there is a predominance of irregular, but rounded, ellipsoidal particles with few sharp edges and corners. The majority of the char is highly porous with abundant degassing holes.
(38) Arenillas, A.; Rubiera, F.; Pevida, C.; Ania, C. O.; Pis, J. J. J. Therm. Anal. Calorim. 2004, 76, 593602. (39) Sadhukhan, A. K.; Gupta, P.; Saha, R. K. Fuel Process. Technol. 2009, 90, 692700. (40) Liu, G.; Benyon, P.; Benfell, K. E.; Bryant, G. W.; Tate, A. G.; Boyd, R. K.; Harris, D. J.; Wall, T. F. Fuel 2000, 79, 617626.

Figure 3. Morphology of 53-75 m chars obtained from devolatilization at (a) 900 C on the HTF, (b) 1100 C on the HTF, and (c) 1300 C on the DTF.

This alteration in morphology arises from the very different heating rates experienced by the chars, which will in turn have caused considerable changes to the speed and degree of devolatilization. Thus, when a liquid film is formed on the outside of a char particle, it can be responsible for the formation of an approximately closed porosity as in the HTF chars. However, by increasing the heating rate, volatiles are released faster and the liquid film layer becomes thinner allowing the formation of both more and larger pores, which gives a morphology akin to that from
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DTF char BET surface areas (m2g-1) 14.7 9.7 17.3 18.9

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Table 3. BET Surface Areas of the Different HTF and DTF Chars
particle size (m) 38-53 53-75 75-106 106-150 HTF char BET surface areas (m2g-1) 3.0 3.1 1.6 0.2

the DTF.31,41 This is except for some inertinite, fusinite and mineral derived particles whose structures remain almost unaltered. Additionally, as well as containing a greater population of pores, chars from rapid heating are expected to possess larger internal surface areas and, accordingly, a higher availability of active sites.14,41 To this end, BET surface areas of the HTF and DTF chars are displayed in Table 3. Here the 53-75 m DTF char exhibits an internal surface area that, although relatively small, is in agreement with similar industrial chars and other frequently used laboratory imitations.31,39 However, the DTF chars surface area is over three times greater than that of its HTF counterpart. Presumably, this also occurs from the unlike heating rates, although the DTF chars surface area might have been further increased through a mild activation from the oxygen present.36 In summary, while the chars produced on the TGA and DTF exhibit somewhat similar burnout profiles, they possess very different physical characteristics. Therefore a conventional TGA cannot be used to realistically mimic DTF devolatilization, simply because it cannot provide sufficient heating. This explains why a different maximum temperature is required in the two systems in Figure 1 and also accounts for the altered reactivity profiles in Figure 2. It now seems obvious that an infrared TGA should be used to study the impact of heating rate and residence time over a wider range of values than previously possible. However, a direct comparison of these new results to the existing data is difficult, because of different furnace configurations. Altered process variables, such as the furnace volume, flow direction, and flow rate, lead to changes in the shape of the generated burnout profiles requiring the 400 ms DTF char and the 1100 C, 150 C min-1 TGA char baselines to be rerun. The most obvious of these modifications is a reduction in the diffusion lag-time detected at the start of the burnout period, which decreases from 4-8 min in Figure 1 to approximately 2.5 min on the Q5000IR in Figure 4. As such, Figure 4 gives a standalone summary of the implications of TGA devolatilization heating rate, where the chars intrinsic combustion reactivity is shown to decrease with a sufficient increase. Nevertheless, even though this effect has already been acknowledged,16 its impact is much smaller than that of devolatilization temperature, with only the ballistic heating rate showing any significant adjustment in the burnout profile. Consequently any enhancement in the realism of the chars reactivity profile and, in all probability, its physical characteristics can be considered as slight. Although, in contrast, TGA volatile yield was found to strongly dependent on the pyrolysis heating rate, showing a 10% increase between the standard 150 C min-1 rate of the SDT Q600 and the ballistic 1800 C min-1 of the Q5000IR. This is consistent with the
(41) Arenillas, A.; Rubiera, F.; Parra, J. B.; Pis, J. J. Fuel Process. Technol. 2002, 77-78, 103109. (42) Jamaluddin, A. S.; Truelove, J. S.; Wall, T. F. Combust. Flame 1986, 63, 329337. (43) Anthony, D. B.; Howard, J. B.; Hottel, H. C.; Meissner, H. P. Fuel 1976, 55, 121128.

Figure 4. Carbon burnout profiles for TGA chars produced using different devolatilization heating rates and the DTF char baseline (from the TA Q5000IR).

Figure 5. TGA char burnout profiles highlighting the importance of particle size.

findings of previous laminar flow42 and wire mesh reactor studies,14,43 which accredited the extra weight loss to enhanced thermal fragmentation of the coals molecular structure. Yet, while this might improve the realism of the TGA chars physical properties to some extent, an appreciable lack of heating rate remains compared to the DTF, making vast porosity and surface area developments unlikely. 3.2. TGA Char vs DTF Char. Having identified a benchmark TGA devolatilization procedure, albeit one derived from relative burnout profiles and not the authenticity of the chars physical characteristics, it is now possible to examine the influence of particle size on combustion activity. This is important as coal is not a homogeneous material, causing differently sized fractions to exhibit a range of pore structures and chemical properties. Figure 5 shows burnout profiles for various TGA chars, where the smallest fraction tested is the most reactive and the largest particles take the longest to burn. This confirms the existence of mass transfer limitations and, consequently, some level of internal diffusion control must be supposed, given that the inherent rate of reaction is implicitly constant with unvarying combustion temperature. Such behavior is characteristic of a char possessing large microporous domains, because these restrictions rarely occur in samples with developed macropore networks.17 Moreover, since a similar pore diffusion limitation is also present when the samples are burnt at 425 C, this constraint cannot be circumvented, principally because,
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Figure 6. Mean 1st order rate constants from the burnout of various TGA and DTF chars.

when the temperature is lowered any further, combustion ceases. Likewise, the burnout rates recorded at 425 C are much slower than those observed at 525 C, signifying a kinetic element to the overall reaction rate too. This places the TGA burnouts in combustion regime II. Besides, previous literature indicates that much smaller particles would be required to gain true intrinsic control during isothermal TGA burnouts at these temperatures.8 But such particle sizes are unsuitable for work on the DTF, with the fines causing bridging and sloughing in the silo of the screw feeder.44 For this reason, Figure 6 compares the mean burnout rate of TGA and DTF chars for the previously described size fractions only. In Figure 6, although the first order combustion rates equate over the two smaller particle sizes, a reactivity divergence emerges for the larger ones with the TGA chars becoming less active than their DTF counterparts. This advocates that the chars textural properties play an important role in determining the rate of reaction.8,41 Accordingly, cross-sectional SEM images of the different chars have been taken and a selection of these are displayed in Figure 7. In images a and b, the HTF samples are shown to be predominantly molten and unmolten type III char particles.1 These exhibit <50% porosity and consist of mixed dense and solid unfused particles that are not fully devolatilized, along with the expected inertoids and fusinoids. Despite this, the 53-75 m fraction does display the preliminary stages of macropore development, which will eventually result in the formation of thick-walled Cenospheres, mesopheres, and mixed porous particles. Whereas the 106-150 m particle size range exhibits smaller but more frequent pores, probably indicative of the early phases of a mesophere or tenuine network. Presumably, these underdeveloped pore networks are also behind the very small internal surface areas recorded for the HTF chars in Table 3. Thus, these calculated values appear to be strongly dominated by external surface area, causing average combustion rate to demonstrate a robust association to particle size. This implies that active site availability remains a rate limiting factor for the HTF chars, particularly the two largest particle size fractions. Conversely the pore structures of the DTF chars, Figure 7c and d, are well developed, because of the greater devolatilization rate experienced. Although, like most industrial chars, they do not conform to a single, simple configuration.8 As such, the DTF samples mainly consist of type I and II
(44) Carpenter, A. M.; Skorupska, N. M. IEA Coal Res. 1993, 52-67.

Figure 7. Particle cross sections showing the pore distribution of HTF chars of (a) 53-75 and (b) 106-150 m and DTF chars of (c) 53-75 and (d) 106-150 m.

char particles, with >80% and >50% porosity respectively.1 These include Cenospheres with multiple degassing vesicles in their walls, tenuinetworks, mesospheres and rounded, subangular single chambered particles with secondary porosity. In addition, the chars have also been subjected to extensive swelling, which occurs during the plastic softening of the coal.45,46 As a result, particle diameters increase by up to 50% during DTF pyrolysis, because of the rapid heating encountered and/or the presence of gases other than nitrogen and oxygen.47 Smaller particles are also expected to swell more comprehensively under consistent heating conditions, fundamentally from the higher likelihood of them being monomaceral.48 However, in this study, the swelling behavior of ATC is most noticeable from the relative particle sizes of images a and b in Figure 8, rather than from those in Figure 3. This could be caused by sieving or grinding phenomena, since maceral and mineral matter fractionations can cause some particle sizes to exhibit unexpected combustion properties.49,50 Moreover, some inertinite and fusinite based particles are present in all of the char samples. These macerals demonstrate limited swelling and porosity, but they do suggest the development of anisotropy in images c and d of Figure 7, reaffirming that the coal has passed through a plastic stage.33 Overall, this increased porosity and swelling results in both larger pores and substantially increased BET surface areas in Table 3, aiding combustion in two main ways. First, the bigger macropores and mesopores increase the rate of pore diffusion, thus reducing any mass transfer restrictions.32 Second, the enlarged internal surface areas improve
(45) Gale, T. K.; Bartholomew, C. H.; Fletcher, T. H. Combust. Flame 1995, 100, 94100. (46) Yu, J. L.; Strezov, V.; Lucas, J.; Liu, G. S.; Wall, T. Proc. Combust. Inst. 2002, 29, 467473. (47) Fletcher, T. H. Fuel 1993, 72, 14851495. (48) Yu, J.; Lucas, J.; Strezov, V.; Wall, T. Energy Fuels 2003, 17, 11601174. (49) Yu, D.; Xu, M.; Sui, J.; Liu, X.; Yu, Y.; Cao, Q. Thermochim. Acta 2005, 439, 103109. (50) Mendez, L. B.; Borrego, A. G.; Martinez-Tarazona, M. R.; Menendez, R. Fuel 2003, 82, 18751882.

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Le Manquais et al. Table 4. TGA Char Variability, Expressed As Standard Deviations in the Burnout Reactivity Criteria
particle size burnout time to 10% carbon (m) remaining (min) >38 38-53 53-75 75-106 106-150 2.1 0.9 1.3 0.6 0.8 composite 1st order rate constant (min-1) 0.005 0.002 0.002 0.001 0.001

Figure 8. Morphology of 106-150 m chars obtained from devolatilization at (a) 1100 C on the HTF and (b) 1300 C on the DTF.

Table 5. DTF Char Variability, Expressed As Standard Deviations in the Burnout Reactivity Criteria and the Chars Carbon Contents
burnout time to particle 10% carbon size (m) remaining (min) 38-53 53-75 75-106 106-150 14.1 9.7 3.4 9.7 composite 1st order rate constant (min-1) 0.028 0.014 0.008 0.012 carbon content carbon content by by EA TGA proximate (%) analysis (%) 1.0 4.0 1.7 0.7 2.2 2.8 3.3 0.6

active site accessibility. In fact, this latter occurrence is potentially the more important, since the DTF chars surface areas in Table 3 closely reflect the average burnout rates of the coal fractions in Figure 6. This again establishes the availability of surface active sites as a critical factor in determining combustion reactivity. But, particularly for the smaller particle sizes investigated, diffusion is still partially rate determining. This means that the observed DTF char burnout activities do not increase above those of the TGA chars, irrespective of some greatly enhanced internal surface areas. However, such an argument assumes consistent intrinsic reactivity between the samples produced by TGA and DTF, which is probably not the case. As explained previously, this is from variations in the extent of thermal annealing as a result of the different heating rates, temperatures and treatment times experienced. Next, it seemed sensible to assess the repeatability and reproducibility of these char production methods, quantifying the likely error in the reactivity data displayed in Figure 6. Thus Table 4 illustrates the variability occurring in TGA chars, by using standard deviations in the two benchmark reactivity measures as indicators of data spread. These values are based on 5 repeats in each of the particle size fractions. Table 4 indicates that most of the standard deviations are very small compared to the average activities recorded in Figure 6, merely representing 1-3% alterations in the established means. Such slight deviations are easily accounted for by irregular particle distributions within the fractions, an issue which is exacerbated by the small mass of coal tested per run. However, a more substantial variability exists within the <38 m coal portion where the standard deviation accounts for approximately 6-7% of the mean value. This occurs from the lack of a lower size boundary and the consequent reduction in sample homogeneity - specifically regarding particle size, maceral composition and mineral matter content. Nevertheless, the reactivity distribution for TGA chars can be considered as moderately small. Unfortunately the data spread experienced for the DTF chars is far greater, as demonstrated by the much larger standard deviations listed in Table 5. These values represent a variability of 13-38% in the established mean rates. This unpredictability could again be from sieving or grinding related maceral and mineral matter fractionations, but this type of occurrence should also have been depicted in the existing TGA data, which was not the case. Instead, it is suggested that the inconsistency originates from process variables fluctuating during DTF devolatilization. These variables are fundamental to determining a carbons burnout propensity, since they can disturb the furnaces anticipated
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flow patterns, altering the assumed near-laminar configuration and thus changing the particles residence time.51 Likely candidates include the gases flow rates and pressures, the recycle flow rate as applied by the vacuum pump, the coal feed rate and any automatic adjustments to the furnaces temperature. To summarize, although variability is obviously far greater than for the TGA chars, given the large number of process variables involved and the innate uncontrollability of some aspects of the DTF system, it is not particularly unreasonable. However, it remains difficult to substantiate any of the reactivity trends from Figure 6 without completing more repeats or locating the source of this unpredictability. Hence, the final step in assessing variability was to monitor the DTF chars carbon contents, also clarifying whether they directly relate to particle size as has been proposed.49 Thus a breakdown of the standard deviations in these carbon contents is displayed in Table 5, where the variation is approximately 2-4% via both TGA proximate analysis and EA. Therefore, the chars produced by DTF devolatilization have a relatively constant carbon content, with no indication of the previously recorded discrepancies. Carbon content is also consistent between the particle size fractions and the overall inconsistency between all twenty samples is only slightly greater than the error inherent to the EA technique (0.65%). This indicates that while the carbon content of the char produced by DTF devolatilization is quite reproducible, the chars structure and burnout reactivity is much more unpredictable. Unfortunately, the process instabilities behind this variability cannot be easily eliminated from DTF systems. Therefore these errors must be calculated and considered during any investigation. Significantly this large variation in reactivity, which is plausibly typical of chars produced by older manually controlled DTFs, has not been accounted for in previous papers.24,26,51-53 3.3. TGA Combustion Regime Study. To measure the intrinsic kinetics of the oxidation of a porous particle, it has been well established that the combustion needs to be
(51) Brewster, B. S.; Smoot, L. D.; Barthelson, S. H.; Thornock, D. E. Energy Fuels 1995, 9, 870879. (52) Gilfillan, A.; Lester, E.; Cloke, M.; Snape, C. Fuel 1999, 78, 1639 1644. (53) Lester, E.; Cloke, M. Fuel 1999, 78, 16451658.

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Figure 9. Evidence of how the compensation effect alters for different char types.

reaction controlled,9,54 in real terms implying the burnout of small particles at relatively low temperatures (i.e., regime I).11 However the TGA operating boundaries that define the combustion regimes are unique for a given sample, reflecting both the coals properties and the char preparation conditions.8 This has led many researchers to use combinations of particle sizes, temperatures and atmospheres that have not been unequivocally in regime I.8,9,20 Subsequently, as in Figure 5, mass transfer limitations have frequently been observed.17 As such, with the TGA and DTF chars produced in this study only capable of undergoing an isothermal TGA burnout in air under regimes II and III, a direct measurement of the intrinsic kinetics of the occurring reaction is not achievable.55 Nevertheless an investigation into the impact of particle size, char morphology and temperature on burnout rate, combustion regime, and the reactions apparent activation energy does remain possible. Therefore, in accordance with the availability of char for SEM and BET, the following discussion is based on the chars initial postdevolatilization structures. Although it should be noted that the combustion regime can also change with conversion, as the chars pore structure develops and the intrinsic reactivity of the carbon matrix declines.8 Figure 9 demonstrates two compensation effects. A series of comparable reactions can be said to exhibit a compensation effect when they display systematic variations of activation energy and pre-exponential factor according to the straight line relationship demonstrated. Examples of this association have been reported for many diverse reaction systems under kinetic control, including TGA carbon pyrolysis and combustion,56-58 but hitherto it is not understood if this phenomenon is mechanistically important or just statistically significant. As such, it has even been implied that the behavior might arise from the TGA methodology and be an artifact of the data processing.58-60 Figure 9 shows that a similar compensation effect can occur during the regime II combustion of different particle sizes of the same
(54) Bews, I. M.; Hayhurst, A. N.; Richardson, S. M.; Taylor, S. G. Combust. Flame 2001, 124, 231245. (55) Valix, M. G.; Harris, D. J.; Smith, I. W.; Trimm, D. L. Symp. (Int.) Combust. 1992, 24, 12171223. (56) Cuesta, A.; Martinez-Alonso, A.; Tascon, J. M. D. Energy Fuels 1993, 7, 11411145. (57) Jones, J. M.; Agnew, J.; Kennedy, J.; Watts, B. Fuel 1997, 76, 12351240. (58) Essenhigh, R. H.; Misra, M. K. Energy Fuels 1990, 4, 171177. (59) Zsako, J. J. Therm. Anal. 1996, 47, 16791690. (60) Wilson, M. C.; Galwey, A. K. Nature 1973, 243, 402404.

coal. Mechanistically this could be from mass transfer restrictions or surface area availability, although an underlying autocorrelation cannot be fully dismissed.58 Starting with the TGA char, the 106-150 m ATC fraction is located in the middle of the plot, with the smaller particle size ranges displayed further up in descending order. This gives the 106-150 m particles the lowest observed activation energy, 52 kJ mol-1, concurring with the smallest recorded surface area in Table 3. In contrast, at the other end of the compensation effect line, the finely ground <20 m particles exhibit the highest apparent activation energy of 94 kJ mol-1. These activation energies are considerably smaller than those of impure carbons burning under kinetic control, since ATCs true activation energy is probably somewhere between 120 and 160 kJ mol-1, depending on the catalytic contributions of its inherent mineral matter.8 This reaffirms that all of the reactions are occurring under regime II conditions and that diffusion limitations are present in all of the investigated chars.8 Accordingly, having established that the <20 m particle size range is closest to true kinetic control for ATCs TGA char, the upper temperature limit of regime II combustion was then examined for this fraction. It is 575 C. The same compensation effect line is also observed for the DTF char activation energies and pre-exponential factors, with any slight gradient change easily accommodated for by the DTF char burnout variability that was presented in Table 4. However, the relationship between particle size and activation energy is not as well-defined. The <38 m DTF char, which was created by grinding a larger particle size fraction thereby destroying most of the samples inherent porosity, has the highest activation energy of 100 kJ mol-1. But the 38-53 m fraction exhibits a similarly high value of 99 kJ mol-1, implying that a porous structure can diminish the impact of mass transfer on the apparent activation energy. Furthermore, this might be why all the DTF chars have higher activation energies than their TGA equivalents; chiefly from the very restricted internal surface areas and underdeveloped pores of the HTF/TGA chars. Alternatively, these elevated thresholds could also be indicative of enhanced thermal deactivation, resulting from the faster heating rates and higher temperatures encountered.42 4. Conclusions By optimization of the devolatilization heating procedures, the mean burnout rates of TGA and DTF chars from a single bituminous coal (ATC) were correlated for coal particle size fractions of <75 m. However, with particles of >75 m, a reactivity divergence was evident and the TGA chars became less combustible than their DTF counterparts. SEM images and BET surface areas indicate that this is because of conflicting char morphologies. In fact, when the preferred TGA pyrolysis program was imitated using a HTF, the samples produced strongly resembled raw coal; that is, they were heterogeneous, sharp-edged and angular. These chars also display signs of an undeveloped pore network, resulting in very small BET surface areas that are governed by relative particle size. In contrast, the DTF samples manufactured closely resemble industrial char: they are both highly porous and extensively swollen. As such, the DTF chars also possess substantially larger internal surface areas. This suggests that the availability of surface active sites is a crucial factor in determining TGA burnout rates. Although, for the smaller particle sizes investigated, mass transfer remained a
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predominant influence. However, such an argument assumes consistent intrinsic char reactivity and this is questionable, principally because of the impact of heating rate on the severity of thermal deactivation. Subsequently, the implications of pyrolysis heating rate were examined using an infrared TGA. But, even though volatile yield was shown to be strongly dependent, only a 10-fold increase caused an appreciable change in the chars combustion reactivity. This implies that significant porosity, surface area or thermal annealing developments are unlikely, even when using state of the art equipment. Accordingly, TGA cannot be used to realistically imitate the char particles produced by DTF devolatilization, simply because it cannot provide a sufficient heating rate. Next, the variability associated with the TGA and DTF char samples was explored and TGA char was shown to have a very limited reactivity distribution. Unfortunately, the data spread experienced during the burnout of DTF chars was up to ten times more significant, even though these chars displayed a moderately constant carbon content. It is therefore suggested that DTF char unpredictability originates from fluctuating process variables and their influence on the created char morphology. This variability is advocated as being characteristic of char samples that have been devolatilized using older, manually controlled DTF setups. Finally, a comprehensive TGA study demonstrated that both operating temperature and particle size have an extensive impact on the control regime and the apparent activation energy of ATCs burnout. Thus, a strong compensation effect was witnessed for TGA chars of different particle sizes, with the relative reaction rates and activation energies indicating

the presence of internal diffusion control. This phenomenon was partially mitigated for the DTF chars, since their higher porosities reduce mass transfer restrictions, but they otherwise exhibit a very similar compensation effect. Subsequently, TGA char particles of <20 m were used to identify an upper temperature boundary for regime II combustion as 575 C, above which mass transfer limitations totally dominate the burnout rate constant. Below this temperature, such a coal fraction gives ATC an activation energy of 94 kJ mol-1 and a pre-exponential factor of 5.85, whereas <38 m DTF char has an activation energy of 100 kJ mol-1 and a pre-exponential factor of 6.38. Nonetheless, these values are considerably smaller than would be expected for an impure carbon burning under kinetic control, reaffirming that the reaction is occurring under regime II conditions. As such, it should be realized that DTF char fractions of <38 m, for example, those that would be required to ensure true intrinsic control, cannot be produced directly. This is because of bridging and sloughing phenomena in the silo of the DTFs screw-feeder. Instead, these samples must be created by grinding larger particles, which destroys the chars inherent porosity.
Acknowledgment. The authors are grateful to Innospec Inc. for their financial support of this PhD studentship. Supporting Information Available: Tables confirming consistent burnout reactivity between the various TGA and HTF samples and seting out reactivity criteria from the burnout of TGA chars at 425 C. This material is available free of charge via the Internet at http://pubs.acs.org.

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