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Bioresource Technology 92 (2004) 187–195

Investigations into the pyrolytic behaviour of coal/biomass blends using thermogravimetric analysis
H.B. Vuthaluru
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Department of Chemical Engineering, Curtin University of Technology, GPO Box 1987, Perth, WA 6845, Australia Received 10 April 2003; received in revised form 24 May 2003; accepted 10 August 2003

Abstract Investigations into the pyrolytic behaviour during co-pyrolysis of coal, biomass materials and coal/biomass blends prepared at different ratios (10:90, 20:80, 30:70 and 50:50) have been conducted using a thermogravimetric analysis (TGA) apparatus. The coal sample selected was Collie sub-bituminous coal from Western Australia, while wood waste (WW) and wheat straw (WS) were used as biomass samples. Three thermal events were identified during the pyrolysis. The first two were dominated by the biomass pyrolysis, while the third was linked to the coal pyrolysis, which occurred at much higher temperatures. No interactions were seen between the coal and biomass during co-pyrolysis. The pyrolytic characteristics of the blends followed those of the parent fuels in an additive manner. Among the tested blends, 20:80 blends showed the lowest activation energies of 90.9 and 78.7 kJ molÀ1 for coal/ WW and coal/WS blends respectively. The optimum blend ratio for pyrolysis of coal/WS was 50:50 with a high degradation rate in all the thermal events and a higher mass loss over the course of the co-pyrolysis compared to coal/WW blends examined. The reaction orders in these experiments were in the range of 0.21–1.60, thus having a significant effect on the overall reaction rate. Besides the pyrolysis of coal alone, the 50:50 coal/biomass blends had the highest reaction rate, ranging 1 · 109 –2 · 109 minÀ1 . The experimental results may provide useful data for power generation industries for the development of co-firing options with biomass. Ó 2003 Elsevier Ltd. All rights reserved.
Keywords: Coal; Biomass; Thermal degradation; Co-pyrolysis co-firing

1. Introduction Pyrolysis is the thermal degradation of fuels in the absence of oxygen. As a renewable energy source, biomass has been considered as a potential feedstock for co-firing options for power stations. Additionally, cofiring of coal and biomass fuels (wood waste, wheat straw, peat and municipal solid waste) is being presently considered as an alternative means of reducing CO2 emissions (Werther et al., 2000; Williams et al., 2001; Sami et al., 2001). The rationale is that the thermal utilisation of biomass can contribute to the reduction of CO2 emissions as the same amount of CO2 is extracted from the atmosphere during the growth period of the plants as is released by combustion (CO2 balance). Various types of renewable energy sources such as biomass could be used for power production. For achieving
Tel.: +61-8-9266-4685; fax: +61-8-9266-2681. E-mail address: h.vuthaluru@exchange.curtin.edu.au (H.B. Vuthaluru). 0960-8524/$ - see front matter Ó 2003 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2003.08.008
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a significant CO2 reduction, as well as fossil fuel substitution, it is desirable to use fairly large quantities of biomass for power generation. Besides as single fuel, it is also considered sensible to utilise biomass in co-combustion in existing firing systems, such as coal-firing power stations. Whereas the construction of new decentralised plants fired exclusively with biomass would require high investment costs, the retrofit for co-combustion in an existing coal-firing plant requires less supplementary investments. In many parts of the world a major reason for considering co-combustion is the difficulty associated with disposing of wastes in landfills because of the volume and the environmental constraints. Co-firing of coal and biomass is a relatively new area. Despite the simplicity of the co-firing concept, its application in pulverised coal-fired boilers is associated with many technical issues, which require further attention. Most of the experimental information is derived from pilot-scale equipment (Abbas et al., 1990; Swanekamp, 1995) where it is often difficult to cover a

A (minÀ1 ) is the pre-exponential factor (frequency factor). operation. 2000. Pyrolysis is slower for biomass than coal. Thermogravimetric analysis (TGA) is one of the most common techniques used to investigate thermal events and kinetics during pyrolysis of coal or coal/ biomass mixtures (Hatakeyama and Quinn. Methods 2. Caballero et al. Mansaray and Ghaly.B. Mansaray and Ghaly (1999) investigated the behaviour of rice husks in a similar manner and two thermal events were identified in the firing process. combustion efficiency. 1999): 1 da A ÀEðT Þ n ¼ e R ð1 À aÞ dt / ð1Þ where a is the conversion of reactant. Kastanaki et al. 1996. and impacts on system performance need to be understood in closely controlled simulated combustion environments and must be fully quantified. Moreover.. repeat experiments and validate the reported trends. The information pertinent to thermal events and kinetics plays an important role in the efficient design. The application of co-combustion technologies involving biomass and coal for power generation requires a proper understanding of the thermal properties and reaction kinetics of coal/biomass blends. Nassar (1999) identified two thermal events during the pyrolysis of both bagasse and rice straw by assuming a pseudo first-order reaction. and modelling of co-fired boilers. The thrust of this paper therefore was to identify the thermal events taking place during pyrolysis of coal/biomass blends and obtain kinetic data based on TGA. 1997. The kinetics of these thermal events has been determined by the application of the Arrhenius equation corresponding to the separate slopes of constant mass degradation (Nassar. kinetic parameters from TG data were obtained from the following rate expression (Hatakeyama and Quinn. R (J/mol/K) is the universal gas constant (8. and few data are required for obtaining kinetics over an entire temperature range in a continuous manner. / is the heating rate (°C). Several researchers have investigated co-pyroloysis of coal/biomass mixtures (Pedersen et al. rather than individual reactions. Although TGA provides general information on the overall reaction kinetics. 1999. the large part of biomass and coal combustion history involves char oxidation.314). Other advantages include only a single sample. n is the reaction order.188 H. Vuthaluru / Bioresource Technology 92 (2004) 187–195 Nomenclature A a ms mf m da=dt Pre-exponential factor (minÀ1 ) fraction of starting material consumed: ðms À mÞ=ðms À mf Þ initial mass of sample final mass of sample actual mass of sample rate of reaction E N U R T t activation energy (kJ/mol) reaction order constant heating rate (°C or K/min) gas constant (J/mol/K) temperature (K) time (min) wide range of conditions. 1999). In the present work. Eq. 2002). 1999. Pan et al.. Theory The kinetics of thermal decomposition reactions of carbonaceous materials is complex. The interesting fact that emerges out of studies conducted in thermogravimetric analysis (TGA) to date is that the understanding of kinetics of the thermal decomposition of fuels or fuel blends is crucial to the designing and operation of conversion systems. It provides a measurement of weight loss of the sample as a function of time and temperature. Heinzel et al. 1996... Helsen and Van den Bulck. it could be used as a tool for providing comparison of kinetic data of various reaction parameters such as temperature and heating rate. t (min) is the time. Pan et al. A larger fraction of biomass is likely to be released as volatile gases during combustion. 1998.1. This large volatile yield occurs over a relatively short time and can influence the time required for complete combustion when compared to a coal particle of similar size (Rudiger et al. in that decomposition of carbonaceous materials involves a large number of reactions in parallel and in series. T (K) is the temperature. 1999. 2. Generally it is much shorter than either drying or combustion of char. Nassar. (1) relates the fraction of material consumed with time in the form of an Arrhenius expression comprising of ac- . 1999. 1994). In addition. Meesri and Moghtaderi. E (J/mol) is the activation energy. Mansaray and Ghaly. (1996) examined the combination of pine chips with poor grade coals and reported that the two fuels pyrolyzed together displayed an overlapping of the two individual behaviours in the thermogravimetric analysis. Coal and biomass are consumed by both thermal decomposition (devolatilisation) reactions and char oxidation.. 2002). emissions..

The resultant plot d½lnðda=dT ފ= d½lnð1 À aފ versus dð1=T Þ=d½lnð1 À aފ of Eq.2. WS and WW samples were dried in crucibles in an oven set at 110 °C for 20 h. preferably in existing pulverised coal-fired boilers.1. After determining activation energy and order of reaction for a given temperature range.2 0. Argon flowed through the combustion chamber at 50 cc minÀ1 . biomass and coal/biomass blends were performed at a heating rate of 20 °C minÀ1 . As these fuels burn quite effectively in pulverised form.01 37.1 0. (1) was employed in conjunction with the data of T . Experimental 2. (2) is lnðda=dT Þ ¼ lnðA=/Þ À E=RT þ n lnð1 À aÞ ð2Þ Table 1 Analysis of coal and biomass materials (in wt. up to 1250 °C to establish the temperature range required for the present investigations. From the rate of mass loss. Approximately 1 kg of 10 mm coal (mixture of samples from several seams) was crushed to a top size of 1 mm.2 0. (3) for several time intervals should provide a straight line with an intercept of n and a slope of ðÀE=RÞ. all the TGA-MS runs on coal. 9. 1974). Percent residual mass increased with increasing coal content for both blends comprising of coal/WW and coal/WS. pre-exponential factor ðAÞ and reaction order ðnÞ. Approximately 100 mg of samples of coal and biomass materials were chosen for testing in TGA. This trend is due to the high volatile content and low fixed carbon content in biomass samples compared to the coal. 2. Wheat straw used for the present tests is local soft wheat.6 19. Initial TGA-MS test runs employed the 50:50 mix of coal/ biomass of each biomass at a heating rate of 10 °C minÀ1 . These biomass fuels. The logarithmic form for Eq. Residual mass and char yields Observed thermal behaviour of coal/biomass blends during co-pyrolysis performed in argon atmosphere at a heating rate of 20 °C minÀ1 is shown in Fig.3 75. (3) for different time intervals.6 54. Wood waste samples were collected from a local wood-based industry. Synergistic effects also were deduced from the comparisons of mass loss versus temperature and char yield profiles of coal. the above equation simplifies to:  À Áà À1Á d ln da d T E dt ð3Þ ¼nÀ R d½lnð1 À aފ d½lnð1 À aފ The data from the TGA on measured mass loss with time for the tested samples was used to determine the left and right hand parameters of Eq.9 0. Thermogravimetric analyzer (TGA) A NETZSCH Simultaneous Thermal Analyzer STA 409 C (TGA-MS) was used to measure and record the sample mass change with temperature over the course of the pyrolysis reaction. biomass materials and coal/ biomass blends. 2001). Eq. being man-made waste materials.B.0 0.7 50. reflecting the thermal behaviour and composition of the initial sample.2.9 2. for it was the only coal used for power generation in Western Australia and had yet to be well investigated.03 38. The details of the thermal analyzer are presented elsewhere (Netzsch. Once these were defined.2 0. which is a unique blend of white. Wood waste (WW) was obtained locally derived from old seasoned trees containing no bark. hemicellulose and . soft-grained club wheat varieties. which presumably derived from hard wood without bark from a seasoned tree. are discarded at alarming rates and create grave landfill concerns.9 By differentiating with respect to lnð1 À aÞ. the kinetics of pyrolysis for different coal/biomass blends was determined. TGA experiments generated mass loss versus temperature or time graphs. thus enabling determination of kinetic parameters (E and n). The main characteristics of the coal and biomass materials are presented in Table 1. they were selected as potential fuels for co-combustion with coal. The striking difference is also attributed to the difference in the strength of the molecular structure of the fuels. For all the pyrolysis runs 100 mg samples were used. d½lnðda=dT ފ= d½lnð1 À aފ versus dð1=T Þ=d½lnð1 À aފ and d½lnðd=dT ފ= d½lnð1 À aފ versus dð1=T Þ=d½lnð1 À aފ=dT to determine the frequency factor A. 3.1 80. The samples were then ground and homogenised by mixing in appropriate proportions and subsequent rolling for 24 h. Coal.7 5.2. intermediate species and final residue (Wendlandt.6 10.0 3.1 47.7 35.%) Coal Proximate analysis (db) Ash Volatile matter Fixed carbon Chlorine Ultimate analysis Carbon (total) Hydrogen Nitrogen Sulfur Oxygen (by difference) Wood waste 0.H. Choice and preparation of samples Collie coal from Western Australia was chosen for the study. 1.9 42. Vuthaluru / Bioresource Technology 92 (2004) 187–195 189 tivation energy ðEÞ. The biomass fuels selected were wood waste (WW) and wheat straw (WS).2. Results and discussion 3.7 20.1. Coal samples were supplied from seams from Premier mine located at Collie in Western Australia.9 Wheat straw 3.4 5. The polymers of cellulose.

. 6–0:100 (biomass). 3–80:20. 1993). 4–60:40. Additionally the amount of char generated during copyrolysis decreased with increasing biomass content in the blend. Therefore by increasing the coal content in the blend. which constitute the macromolecular structure of the biomass and other woody materials. As a consequence. are linked together with relatively weak ether bonds (R–O–R. Keys 1–100 (coal):0. with either biomass. The coal considered for the present study was a sub-bituminous coal. 1993).. To confirm the absence of synergistic effects measured data for char yield are plotted against the blending ratio for coal/WW and coal/WS blends in Fig. 2–90:10. (a) Coal/WW. Percent residual mass versus temperature. which mostly comprises dense polycyclic aromatic hydrocarbons linked together by C@C (aromatic ring) bonds with bond energy of 1000 kJ molÀ1 (Blazej and Kosik. This suggests that there are no synergistic effects (lack of chemical interactions) between the two fuels. It can be seen that there is linear relationship between the char yield and the amount of biomass in the blend. 1994).B.190 100 H. 2. the volatile content decreases and the fixed carbon increases. Hence the mass loss was lower (high residual mass) than from co-pyrolysis of blends involving biomass samples. Hence an increased residual mass with blends containing a higher proportion of coal would result during co-pyrolysis. are more resistant to the heat (Smith et al. In contrast the immobile phase present in the coal structure. 5–50:50. 1. a small amount of fragmented polycyclic aromatic compounds would be expected to result from the immobile phase. bond energy of 380–420 kJ molÀ1 ). lignin. Vuthaluru / Bioresource Technology 92 (2004) 187–195 (a) 80 % Residual Mass 60 1 2 3 4 40 5 20 6 0 0 200 400 600 800 1000 1200 1400 Temperature (˚C) 100 90 80 70 (b) % Residual Mass 1 60 50 40 5 30 6 20 10 0 0 200 400 600 800 1000 1200 1400 2 3 4 Temperature (˚C) Fig. (b) coal/WS. These bonds are less resistant to the heat at low temperatures (400–500 °C) (Blazej and Kosik. which was expected to have a high aromatic content.

2983BR + 64. This was not taken into account for the determination of thermal events.H.381) 20 800˚C (CY = -0.B. 3 shows a typical plot showing thermal events observed during co-pyrolysis of 50:50 blend samples. A major shift in the slope of TG curve was thus treated as the end of a thermal event and commencement of a new thermal event.4568BR + 89. It should be noted be noted here that all the measurements were done only once except 50:50 coal/biomass blends. Tables 2 and 3 present the summary of thermal events and corresponding temperatures observed during . Similar pyrolytic behaviours of coal/biomass mixtures have been reported in the literature (Meesri and Moghtaderi.2791BR + 61. CY refers to char yield in the fitted equations given in the legend).2. (b) coal/WS.666) Blending ratio of wood waste (%wt/wt) 100 (b) 90 80 70 Char yield (%wt/wt) 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 80 90 100 400˚C (CY = -0.3618BR + 71. 2002). 2.175) 1000˚C (CY = -0. Thermal events and synergistic effects Thermogravimetric curves showed an initial decrease in the weight of samples between 100 and 150 °C due to the release of moisture remaining in the samples. 3.3395BR + 64. (BR refers to blending ratio. Char yield versus blending ratio of biomass (a) coal/WW.488) 600˚C (CY = -0. It should be noted that each thermal event is defined as the region where the slope of TG curve is constant.3185BR + 61. Repetitive runs with both blends (50:50) suggested that the reproducibility was within ±5%.567) 30 600˚C (CY = -0.635) Blending ratio of wheat straw (%wt/wt) Fig.4415BR + 89. Vuthaluru / Bioresource Technology 92 (2004) 187–195 100 191 (a) 90 80 70 Char yield (%wt/wt) 60 50 40 400˚C (CY = -0.3837BR + 72.764) 800˚C (CY = -0. Fig.417) 10 0 0 10 20 30 40 50 60 70 80 90 100 1000˚C (CY = -0.

As can be seen that the residual mass could be predicted from the parent fuels under these conditions. 2002) in dictating thermal behaviour of fuels. However. Nassar. suggesting no interaction between coal and WS during co-pyrolysis.1 along with TGA data. It is evident from the data that activation energies and preexponential factors increased with increasing levels of coal in the blends (i. 2002). Both thermal events in the pyrolysis of the single WS commence at a temperature 30 °C lower than those observed with WW (Table 2). but for the coal/WS blend there was a slight fall in order. This suggests some effect on the behaviour of the wheat straw by the addition of the coal. the gas–solid or gas phase interactions during pyrolysis also play an important role (Kastanaki et al.4 kJ molÀ1 . coal component 0–50%) for the first thermal event.% mixture of biomass in coal is recommended. 3. Thermal events for a 50:50 blend sample. suggesting lack of synergistic effects between the fuels. The completion of respective thermal events followed similar trend of rising through a range of 30 °C with increasing coal content. Helsen and Van den Bulck. 1997. There is a gradual increase for the commencement of thermal events with coal content in the blend.. the activation energy of the reaction for second thermal event is at a minimum.192 10 0 -10 H.% wood content. This implies that to ensure lower activation energy and so lower temperatures required for promotion of the forward pyrolysis reaction. 2002. It is evident from the data in Tables 2 and 3 that the pyrolysis of coal displayed a single thermal event as opposed to two distinct thermal events with single biomass samples. Kinetic analysis Kinetic analysis has been performed using equations detailed in Section 2. The results of the kinetic analysis are summarised in Table 4.. the pyrolysis of coal/WW and coal/WS mixtures. Kastanaki et al. The activation energy requirement then rises to a peak of 135. Therefore under inert conditions the two fuels undergo independent thermal degradation process without any chemical interactions in the solid phase. 2000. 3. Calculated weighted average values of residual mass loss presented in Fig. During co-pyrolysis of both coal/biomass mixtures (with a 20% biomass). Caballero et al. A range of values obtained for Ôn’ justifies the dismissal of the assumption that the reactions are all first order. 1999. Similar observations during pyrolysis of individual feed stocks (bagasse.3. The commencement of thermal event of 50:50 blends for pyrolysis increased by 15 °C. Vuthaluru / Bioresource Technology 92 (2004) 187–195 Thermal event 1 Thermal event 2 -20 -30 -40 -50 -60 -70 0 10 20 30 40 50 60 70 Thermal event 3 Time (min) Fig. This requires further attention in future studies. It may be seen that the first thermal event of single WW pyrolysis is only evident during pyrolysis of 50:50 blend (Table 2). occurring at the 50 wt. 4c and d). calculated weighted average values of residual mass corresponded with experimental data (Fig. Comparison of activation energy data has been the common method of analysing the suitability of the various biomass types in similar Table 2 Observed thermal events and corresponding temperatures (°C) for the tested coal/WS mixtures Blend coal:WS (wt/wt) 0:100 50:50 70:30 80:20 90:10 100:0 Event 1 Initial 260 276 316 322 366 426 Final 312 326 359 355 406 488 Event 2 Initial 316 326 419 416 414 – Final 355 356 485 482 488 – Event 3 Initial – 368 – – – – Final – 494 – – – – Table 3 Observed thermal events and corresponding temperatures (°C) for the tested coal/WW mixtures Blend coal:WW (wt/wt) 0:100 50:50 70:30 80:20 90:10 100:0 Event 1 Initial 291 281 345 350 350 426 Final 328 327 384 394 430 488 Event 2 Initial 350 343 403 410 430 – Final 379 388 472 485 485 – Event 3 Initial – 401 – – – – Final – 470 – – – – Mass loss (mg) .e. a 20 wt. However.B. The order of the reaction increased for the coal/WW blend runs. 4 for tested blends also confirmed the absence of synergistic effects. The third thermal event commenced at a temperature of 50 °C lower than that of single coal firing. woody biomass and rice straw) are reported in the literature (Meesri and Moghtaderi. A similar trend of thermal events is evident during copyrolysis of coal/WS blends (Table 3)..

47E+04 4.27E+07 7.22E+06 4.9 76.46E+06 2.92E+07 6.15E+09 2.85E+07 1. Ahmed and Clements.77E+09 4.60E+07 Blend ratio E (kJ molÀ1 ) n A (minÀ1 ) Reaction rate ðda=dtÞ at a given temperature (°C) (minÀ1 ) 280 3.4 0.95E+06 WW Coal/WS WS Overall Event 3 Coal Coal/WW Coal/WS experiments that have been performed to date (Nassar.38E+08 1.52E+05 340 7.9 68 1. Ramaiah.11E+09 1.39 4.9 114.21 0.94E+06 2.9 64. Table 4 Summary of kinetic parameters and reaction rates for tested samples Feed Overall Event 1 Coal/WW WW Coal/WS WS Overall Event 2 Coal/WW 90:10 80:20 70:30 50:50 100 90:10 80:20 70:30 50:50 100 115.9 68.9 99.7 119.3 78. 4.8 9.41E+04 2.08E+05 1.85 0.10E+02 3.05E+03 1.07 0. Comparison of residual mass with calculated weighted average values for typical coal/WW (a and b) and coal/WS (c and d) blends of 50:50 and 80:20.00E+02 3.1 135.82E+03 6.05E+03 1.44 0.90E+05 7.54E+03 1.48E+04 1.86E+12 5.38 0.00E+02 3.48 0.3 90.52E+05 380 7.60E+08 480 1. kinetic parameters in their studies were estimated based on the assumption of the reaction order of 1.10E+09 1.24 0.4 0.60E+08 420 100:0 10:90 20:80 30:70 90:10 80:20 70:30 183.B.42E+08 1.24E+06 4.46 0.59E+02 1.64E+10 3.4 59.6 0.39E+08 1.91E+02 1.H. Vuthaluru / Bioresource Technology 92 (2004) 187–195 100 90 80 70 60 50 40 30 20 10 0 0 100 90 80 70 60 50 40 30 20 10 0 0 193 % Residual Mass 50:50 Coal/WW Weighted average WW 200 400 600 800 1000 1200 1400 % Residual Mass (a) Coal (b) Coal Weighted average 80:20 Coal/WW WW 200 400 600 800 1000 1200 1400 Temperature (˚C) 100 90 80 70 60 50 40 30 20 10 0 0 100 90 80 70 60 50 40 30 20 10 0 0 Temperature (˚C) % Residual Mass % Residual Mass (c) Coal Weighted average Coal (d) Weighted average 80:20 Coal/WS WS 200 400 600 800 1000 1200 1400 50:50 Coal/WS WS 200 400 600 800 1000 1200 1400 Temperature (˚C) Temperature (˚C) Fig.12E+11 2.6 123.23E+06 4.62 0.95E+06 2.58E+02 320 3.4 118 124.53E+05 2.90E+10 4. .86E+07 400 7.42 0.46E+01 5.9 49.86E+07 1.20E+05 9.47E+04 4.90E+05 7.52 4.54E+05 2.04E+09 1.8 1.04E+09 1.6 76. 1970).12E+11 2.90E+05 7.36 0.70E+09 50:50 100 50:50 100 46. However.54E+05 2.47E+01 5.9 54.57E+04 2.57E+04 2.03E+03 1.91E+02 1.42 0.82E+03 6.7 80.43E+08 1.22 0.48E+08 1.63E+03 8.38 0. 1988. 1999.41 0.2 0.39E+08 1.03E+05 1.10E+02 3.90E+09 3.19E+03 4.

50:50 blend appears to be the optimum fuel with high degradation rates (1 · 109 –2.0E+10 H. suggesting lack of interaction between the fuels during co-pyrolysis. 5. Fractional mass loss rate for second thermal event at 340 °C. Based on this TG analysis it can also be concluded that the second thermal event represents the period of fastest degradation for all feeds examined.86 · 1012 minÀ1 for the tested blends.0E+06 1. Conclusion The pyrolytic behaviour of coal/biomass blends has been investigated using a TGA apparatus. However. The first two are linked to the firing of biomass.0E+05 0 10 20 30 40 50 60 70 80 90 100 Biomass content of feed (%) Fig.0E+09 Fractional mass loss rate 1.0E+08 Wood Waste Wheat Straw 1. Temperature range of between 280 and 480 °C has been selected as representative of the thermal event region.B. The conclusions drawn from the present work are as follows: . The degradation temperature of coal decreased with increasing biomass content in the blend possibly due to the massive decomposition of biofuels. activation energies and pre-exponential factors were found to be in the range of 46. pyrolytic behaviour of the blends can be predicted from those of parent fuels. In the second thermal event. which justifies the dismissal of the assumption of first order for co-pyrolysis reactions. 20:80 blends showed the lowest activation energies irrespective of the type of biomass sample. The lowest average rate of reaction can be seen at 20% (Fig. • Three thermal events are observed during the copyrolysis of coal/biomass blends.0E+07 1. based on the estimated reaction rate. Also highlighted in Table 4 are the degradation rates derived from the kinetic parameters. such a method of analysis is insufficient to describe the overall reaction behaviour.54 · 103 – 4. The rate of degradation was derived from the following equation proposed by Hatakeyama and Quinn (1999): 1 da A ÀEðT Þ ¼ e R ð1 À aÞn dt / ð4Þ It is evident from the Table 4 that coal has the highest rate of degradation. suggesting lack of synergistic effects between the fuels.. 5).9–183. Vuthaluru / Bioresource Technology 92 (2004) 187–195 1. but the trend is similar throughout the temperature range examined (26– 1247 °C). Acknowledgements The author gratefully acknowledges the financial and other support received for this research from Curtin University of Technology. while the third event occurred at a higher temperature as a result of coal firing.1 · 109 minÀ1 ).194 1.6 kJ molÀ1 and 1. • Among the tested blends. The orders of reactions were in the range of 0. The author also likes to ac- 4. The second highest degradation rate is observed during the pyrolysis of the 50:50 coal/ WW blend. Given that this assumption has not been deemed appropriate based on the variety of values found by Mansaray and Ghaly (1999).21–1. • Measured TGA data indicated a linear relationship between the char yield and the proportion of biomass in the blend. • Calculated kinetic parameters viz. The pyrolysis of 50:50 coal/WS blend is the next highest.6. there is a trend in reaction rate with respect to ratio apparent in both biomass samples. Hence.

Caballero. Annamalai.. Clements. 1998. Energy Combust. 14. R.. Ahmed. J. Anal.M.. 27.G. L. L.. Full-scale cofiring of straw and coal. Technol. Kuester. Z. 1993. E. J. 1995. H. Lack of synergetic effects in the pyrolytic characteristics of woody biomass/coal blends under low and high heating rate regimes. K... 1994. 1994. bol 3. J.. P. Pyrol.. Ogada... C4. Sami. M. 159–166. Combustion of agricultural residues. Chichester. Energy Sources 21. Ellis Horwood. Blyth of Chemistry Department for assisting with TGA experiments.. Grammelis.W. T.. 1999. 2001.. 1997. Marcilla. K. E.. U. Pan. Kinetics of the low-temperature pyrolysis of chromated copper arsenate-treated wood.A. A. Kiil. Appl. K.A. Fletcher..L... Hein.. Netzsch. Appl.R.. K. Sci.B. M.. Kinetics of the thermal degradation of rice husks in nitrogen atmosphere. 51. Pyrolysis of blends of biomass with poor coals. 2002.. P. 2000. Blazej.. References Abbas. Kosik.. 1970. W. Rudiger. F. Mansaray. Lockwood. Costen.. H. Sydney. M. B. In: Bridgwater. Puigjaner. Smoot. Nassar.. Prog. Ramaiah. Opie and K. Conesa. John Wiley & Sons. L. Germany... pp. 2001.. Kilsig.N. 2002. Research in Thermochemical Biomass Conversion. Velo. Phytomass.X. Thermal analysis––Fundamentals and applications to polymer science. L.. 1323–1337.. Pourikashanian. Wendlandt. pp. Quinn. Vuthaluru / Bioresource Technology 92 (2004) 187–195 195 knowledge J. Greul..M.. Wittelsbacherstrasse 42. England. 1988. J. Siegle. Hein. Swanekamp. Selb. Kinetics of biomass pyrolysis with radiant heating. 2001. Biomass co-firing technology debuts in recent test burn. Christensen. Sci.. Helsen. 109– 125. Energy Combust. A. hemicellulose and lignin. Energy Combust. 1990. 26. H.. Fuel 75.. 77–78. T. A. D. Hatakeyama. Hartge. London. Hansen. 587– 610...G. A. 51–79. Wooldridge..V. E. E. Thermal analysis of kinetics of Bagasse and Rice Straw.. 131–137. J. Saenger. 171–214.U. Fuel Process. Biomass and Bioenergy 23. 1584–1590.. 295–309. Werther. 773–784. Pyrol. T. M. Thermal methods of analysis. Appl.E. V.P..D. Fuel Process. Vamvuka. T.. Spliethoff. Plenum Press.. Dam-Johansen. 1999. C..D. A. Technol. Netzsch––Ger€tebau Gmbh.. . Co-firing of coal and biomass fuel blends. Solid fuel utilisation: from coal to biomass.. Ghaly.. Combustion of pulverised coal and biomass. Jones. John Wiley and Sons. Energy Sources 21. F. T. J. J. M. 412–418.) 139 (2). The structure and reaction process of coal.. Jespersen. Power (Boilers Combust. H. L. Pedersen. Moghtaderi. Kastanaki.. Sci. 1974. 54. M. Investigation of slagging in pulverized fuel co-combustion of biomass and coal at a pilot-scale test facility. 2000. Williams. New York. Y.H. Smith. 1–27. Copyrolysis of coal/biomass and coal/sewage sludge mixtures in an entrained flow reactor.).. Elsevier Science Publishers. M. In: APAS clean coal technology programme.. Polym. 3041–3058. Thermogravimetric and differential thermal analysis of cellulose. 75–88. K. In: Twenty-Sixth Symposium (International) on Combustion. L.H.. L. S... E. P. Anal.G... Prog.. Thermogravimetric analysis of olive stones with sulphuric acid treatment. Siagi. J. (Eds.S. 1999. Meesri.. 44. Van den Bulck.G. 1996. Nielsen. F. USA. S.A. Sci.H. Heinzel. Fuel 75. Prog. J. 27. 55– 66. Kakaras.V.. Splithoff. a DE-95100. Syst.. Thermogravimetric studies of the behavior of lignite-biomass blends during devolatilization.R. 53.C.G. 1996.