Bioresource Technology 92 (2004) 187195

Investigations into the pyrolytic behaviour of coal/biomass blends using thermogravimetric analysis
H.B. Vuthaluru
*
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 dierent 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 identied during the pyrolysis. The rst 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 mol1 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 0.211.60, thus having a signicant eect 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 min1 . The experimental results may provide useful data for power generation industries for the development of co-ring options with biomass. 2003 Elsevier Ltd. All rights reserved.
Keywords: Coal; Biomass; Thermal degradation; Co-pyrolysis co-ring

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-ring options for power stations. Additionally, coring 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 2003 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2003.08.008
*

a signicant 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 ring systems, such as coal-ring power stations. Whereas the construction of new decentralised plants red exclusively with biomass would require high investment costs, the retrot for co-combustion in an existing coal-ring plant requires less supplementary investments. In many parts of the world a major reason for considering co-combustion is the diculty associated with disposing of wastes in landlls because of the volume and the environmental constraints. Co-ring of coal and biomass is a relatively new area. Despite the simplicity of the co-ring concept, its application in pulverised coal-red 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 dicult to cover a

188

H.B. Vuthaluru / Bioresource Technology 92 (2004) 187195

Nomenclature A a ms mf m da=dt Pre-exponential factor (min1 ) fraction of starting material consumed: ms m=ms mf initial mass of sample nal 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, repeat experiments and validate the reported trends. In addition, emissions, combustion eciency, and impacts on system performance need to be understood in closely controlled simulated combustion environments and must be fully quantied. Several researchers have investigated co-pyroloysis of coal/biomass mixtures (Pedersen et al., 1996; Pan et al., 1996; Heinzel et al., 1998; Meesri and Moghtaderi, 2002). Coal and biomass are consumed by both thermal decomposition (devolatilisation) reactions and char oxidation. A larger fraction of biomass is likely to be released as volatile gases during combustion. This large volatile yield occurs over a relatively short time and can inuence the time required for complete combustion when compared to a coal particle of similar size (Rudiger et al., 1994). Moreover, the large part of biomass and coal combustion history involves char oxidation. Pyrolysis is slower for biomass than coal. Generally it is much shorter than either drying or combustion of char. 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. The information pertinent to thermal events and kinetics plays an important role in the ecient design, operation, and modelling of co-red boilers. 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, 1999; Nassar, 1999; Mansaray and Ghaly, 1999; Caballero et al., 1997; Helsen and Van den Bulck, 2000; Kastanaki et al., 2002). It provides a measurement of weight loss of the sample as a function of time and temperature. 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, 1999; Mansaray and Ghaly, 1999). Nassar (1999) identied two thermal events during the pyrolysis of both bagasse and rice straw by assuming a pseudo rst-order reaction. Mansaray and Ghaly (1999) investigated the behaviour of rice husks in a similar manner and two thermal events were identied in the ring process. Pan et al. (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. 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. 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.

2. Methods 2.1. Theory The kinetics of thermal decomposition reactions of carbonaceous materials is complex, in that decomposition of carbonaceous materials involves a large number of reactions in parallel and in series. Although TGA provides general information on the overall reaction kinetics, rather than individual reactions, it could be used as a tool for providing comparison of kinetic data of various reaction parameters such as temperature and heating rate. Other advantages include only a single sample, and few data are required for obtaining kinetics over an entire temperature range in a continuous manner. In the present work, kinetic parameters from TG data were obtained from the following rate expression (Hatakeyama and Quinn, 1999):
1 da A ET n e R 1 a dt /

where a is the conversion of reactant, t (min) is the time, A (min1 ) is the pre-exponential factor (frequency factor), / is the heating rate (C), E (J/mol) is the activation energy, R (J/mol/K) is the universal gas constant (8.314), T (K) is the temperature, n is the reaction order. Eq. (1) relates the fraction of material consumed with time in the form of an Arrhenius expression comprising of ac-

H.B. Vuthaluru / Bioresource Technology 92 (2004) 187195

189

tivation energy E, pre-exponential factor A and reaction order n. The logarithmic form for Eq. (2) is lnda=dT lnA=/ E=RT n ln1 a 2

Table 1 Analysis of coal and biomass materials (in wt.%) Coal Proximate analysis (db) Ash Volatile matter Fixed carbon Chlorine Ultimate analysis Carbon (total) Hydrogen Nitrogen Sulfur Oxygen (by dierence) Wood waste 0.1 80.6 19.2 0.1 47.4 5.2 0.01 37.9 Wheat straw 3.3 75.7 20.1 0.9 42.7 5.2 0.03 38.9

By dierentiating with respect to ln1 a, the above equation simplies to: 1 d ln da d T E dt 3 n R dln1 a dln1 a 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. (3) for dierent time intervals. The resultant plot dlnda=dT = dln1 a versus d1=T =dln1 a of Eq. (3) for several time intervals should provide a straight line with an intercept of n and a slope of E=R, thus enabling determination of kinetic parameters (E and n). After determining activation energy and order of reaction for a given temperature range, Eq. (1) was employed in conjunction with the data of T , dlnda=dT = dln1 a versus d1=T =dln1 a and dlnd=dT = dln1 a versus d1=T =dln1 a=dT to determine the frequency factor A. 2.2. Experimental 2.2.1. Choice and preparation of samples Collie coal from Western Australia was chosen for the study, for it was the only coal used for power generation in Western Australia and had yet to be well investigated. The biomass fuels selected were wood waste (WW) and wheat straw (WS). These biomass fuels, being man-made waste materials, are discarded at alarming rates and create grave landll concerns. As these fuels burn quite eectively in pulverised form, they were selected as potential fuels for co-combustion with coal, preferably in existing pulverised coal-red boilers. Coal samples were supplied from seams from Premier mine located at Collie in Western Australia. Wood waste (WW) was obtained locally derived from old seasoned trees containing no bark. Wheat straw used for the present tests is local soft wheat, which is a unique blend of white, soft-grained club wheat varieties. Wood waste samples were collected from a local wood-based industry, which presumably derived from hard wood without bark from a seasoned tree. Approximately 1 kg of 10 mm coal (mixture of samples from several seams) was crushed to a top size of 1 mm. Coal, WS and WW samples were dried in crucibles in an oven set at 110 C for 20 h. The samples were then ground and homogenised by mixing in appropriate proportions and subsequent rolling for 24 h. Approximately 100 mg of samples of coal and biomass materials were chosen for testing in TGA. The main characteristics of the coal and biomass materials are presented in Table 1.

9.7 35.6 54.7

50.0 3.0 0.9 0.6 10.9

2.2.2. 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. The details of the thermal analyzer are presented elsewhere (Netzsch, 2001). Initial TGA-MS test runs employed the 50:50 mix of coal/ biomass of each biomass at a heating rate of 10 C min1 , up to 1250 C to establish the temperature range required for the present investigations. Once these were dened, all the TGA-MS runs on coal, biomass and coal/biomass blends were performed at a heating rate of 20 C min1 . For all the pyrolysis runs 100 mg samples were used. Argon owed through the combustion chamber at 50 cc min1 . TGA experiments generated mass loss versus temperature or time graphs, reecting the thermal behaviour and composition of the initial sample, intermediate species and nal residue (Wendlandt, 1974). From the rate of mass loss, the kinetics of pyrolysis for dierent coal/biomass blends was determined. Synergistic eects also were deduced from the comparisons of mass loss versus temperature and char yield proles of coal, biomass materials and coal/ biomass blends.

3. Results and discussion 3.1. 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 min1 is shown in Fig. 1. Percent residual mass increased with increasing coal content for both blends comprising of coal/WW and coal/WS. This trend is due to the high volatile content and low xed carbon content in biomass samples compared to the coal. The striking dierence is also attributed to the dierence in the strength of the molecular structure of the fuels. The polymers of cellulose, hemicellulose and

190
100

H.B. Vuthaluru / Bioresource Technology 92 (2004) 187195

(a)

80

% Residual Mass

60

2 3 4

40

20

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. 1. Percent residual mass versus temperature. (a) Coal/WW; (b) coal/WS. Keys 1100 (coal):0; 290:10; 380:20; 460:40; 550:50; 60:100 (biomass).

lignin, which constitute the macromolecular structure of the biomass and other woody materials, are linked together with relatively weak ether bonds (ROR, bond energy of 380420 kJ mol1 ). These bonds are less resistant to the heat at low temperatures (400500 C) (Blazej and Kosik, 1993). In contrast the immobile phase present in the coal structure, which mostly comprises dense polycyclic aromatic hydrocarbons linked together by C@C (aromatic ring) bonds with bond energy of 1000 kJ mol1 (Blazej and Kosik, 1993), are more resistant to the heat (Smith et al., 1994). The coal considered for the present study was a sub-bituminous coal, which was expected to have a high aromatic content. As a consequence, a small amount of fragmented polycyclic aromatic compounds would be expected to result from the immobile phase. Hence the mass loss was

lower (high residual mass) than from co-pyrolysis of blends involving biomass samples. Therefore by increasing the coal content in the blend, with either biomass, the volatile content decreases and the xed carbon increases. Hence an increased residual mass with blends containing a higher proportion of coal would result during co-pyrolysis. Additionally the amount of char generated during copyrolysis decreased with increasing biomass content in the blend. This suggests that there are no synergistic eects (lack of chemical interactions) between the two fuels. To conrm the absence of synergistic eects measured data for char yield are plotted against the blending ratio for coal/WW and coal/WS blends in Fig. 2. It can be seen that there is linear relationship between the char yield and the amount of biomass in the blend.

H.B. Vuthaluru / Bioresource Technology 92 (2004) 187195

100

191

(a)
90 80 70

Char yield (%wt/wt)

60 50 40 400C (CY = -0.4415BR + 89.567) 30 600C (CY = -0.3837BR + 72.381) 20 800C (CY = -0.3395BR + 64.417) 10 0 0 10 20 30 40 50 60 70 80 90 100 1000C (CY = -0.3185BR + 61.666)

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 400C (CY = -0.4568BR + 89.488) 600C (CY = -0.3618BR + 71.764) 800C (CY = -0.2983BR + 64.175) 1000C (CY = -0.2791BR + 61.635)

Blending ratio of wheat straw (%wt/wt)

Fig. 2. Char yield versus blending ratio of biomass (a) coal/WW; (b) coal/WS. (BR refers to blending ratio; CY refers to char yield in the tted equations given in the legend).

Similar pyrolytic behaviours of coal/biomass mixtures have been reported in the literature (Meesri and Moghtaderi, 2002). 3.2. Thermal events and synergistic eects 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. This was not taken into account for the determination of thermal events. It should be noted be noted here that all

the measurements were done only once except 50:50 coal/biomass blends. Repetitive runs with both blends (50:50) suggested that the reproducibility was within 5%. Fig. 3 shows a typical plot showing thermal events observed during co-pyrolysis of 50:50 blend samples. It should be noted that each thermal event is dened as the region where the slope of TG curve is constant. 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. Tables 2 and 3 present the summary of thermal events and corresponding temperatures observed during

192
10 0 -10

H.B. Vuthaluru / Bioresource Technology 92 (2004) 187195

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. 3. Thermal events for a 50:50 blend sample.

the pyrolysis of coal/WW and coal/WS mixtures. 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. Similar observations during pyrolysis of individual feed stocks (bagasse, woody biomass and rice straw) are reported in the literature (Meesri and Moghtaderi, 2002; Nassar, 1999; Caballero et al., 1997; Helsen and Van den Bulck, 2000; Kastanaki et al., 2002).

It may be seen that the rst thermal event of single WW pyrolysis is only evident during pyrolysis of 50:50 blend (Table 2). There is a gradual increase for the commencement of thermal events with coal content in the blend. The completion of respective thermal events followed similar trend of rising through a range of 30 C with increasing coal content, suggesting lack of synergistic eects between the fuels. Calculated weighted average values of residual mass loss presented in Fig. 4 for tested blends also conrmed the absence of synergistic eects. As can be seen that the residual mass could be predicted from the parent fuels under these conditions. A similar trend of thermal events is evident during copyrolysis of coal/WS blends (Table 3). Both thermal events in the pyrolysis of the single WS commence at a temperature 30 C lower than those observed with WW (Table 2). The commencement of thermal event of 50:50 blends for pyrolysis increased by 15 C. The third thermal event commenced at a temperature of 50 C lower than that of single coal ring. This suggests some eect on the behaviour of the wheat straw by the addition of the coal. However, calculated weighted average values of residual mass corresponded with experimental data (Fig. 4c and d), suggesting no interaction between coal and WS during co-pyrolysis. Therefore under inert conditions the two fuels undergo independent thermal degradation process without any chemical interactions in the solid phase. However, the gassolid or gas phase interactions during pyrolysis also play an important role (Kastanaki et al., 2002) in dictating thermal behaviour of fuels. This requires further attention in future studies. 3.3. Kinetic analysis Kinetic analysis has been performed using equations detailed in Section 2.1 along with TGA data. The results of the kinetic analysis are summarised in Table 4. A range of values obtained for n justies the dismissal of the assumption that the reactions are all rst order. It is evident from the data that activation energies and preexponential factors increased with increasing levels of coal in the blends (i.e. coal component 050%) for the rst thermal event. The order of the reaction increased for the coal/WW blend runs, but for the coal/WS blend there was a slight fall in order. During co-pyrolysis of both coal/biomass mixtures (with a 20% biomass), the activation energy of the reaction for second thermal event is at a minimum. The activation energy requirement then rises to a peak of 135.4 kJ mol1 , occurring at the 50 wt.% wood content. This implies that to ensure lower activation energy and so lower temperatures required for promotion of the forward pyrolysis reaction, a 20 wt.% mixture of biomass in coal is recommended. 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)

H.B. Vuthaluru / Bioresource Technology 92 (2004) 187195

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. 4. 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.

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 50:50 100 115.3 90.9 99.1 135.4 118 124.3 78.7 119.6 123.9 114.8 1.6 0.46 0.4 0.62 0.42 0.41 0.21 0.42 0.44 0.52 4.48E+08 1.27E+07 7.92E+07 6.64E+10 3.90E+09 3.77E+09 4.46E+06 2.15E+09 2.90E+10 4.70E+09 50:50 100 50:50 100 46.9 64.9 68.7 80.2 0.22 0.4 0.85 0.8 9.19E+03 4.20E+05 9.03E+05 1.60E+07 Blend ratio E (kJ mol1 ) n A (min1 ) Reaction rate da=dt at a given temperature (C) (min1 ) 280 3.91E+02 1.57E+04 2.47E+04 4.52E+05 340 7.22E+06 4.53E+05 2.94E+06 2.10E+09 1.42E+08 1.38E+08 1.90E+05 7.85E+07 1.04E+09 1.60E+08 420 100:0 10:90 20:80 30:70 90:10 80:20 70:30 183.6 76.9 54.4 59.9 76.9 49.9 68 1.07 0.38 0.38 0.36 0.48 0.24 0.39 4.86E+12 5.41E+04 2.63E+03 8.03E+03 1.08E+05 1.54E+03 1.48E+04 1.12E+11 2.05E+03 1.00E+02 3.10E+02 3.82E+03 6.46E+01 5.58E+02 320 3.91E+02 1.57E+04 2.47E+04 4.52E+05 380 7.23E+06 4.54E+05 2.95E+06 2.11E+09 1.43E+08 1.39E+08 1.90E+05 7.86E+07 1.04E+09 1.60E+08 480 1.12E+11 2.05E+03 1.00E+02 3.10E+02 3.82E+03 6.47E+01 5.59E+02 1.39E+08 1.90E+05 7.86E+07 400 7.24E+06 4.54E+05 2.95E+06

WW Coal/WS

WS Overall Event 3 Coal Coal/WW

Coal/WS

experiments that have been performed to date (Nassar, 1999; Ahmed and Clements, 1988; Ramaiah, 1970).

However, kinetic parameters in their studies were estimated based on the assumption of the reaction order of 1.

194
1.0E+10

H.B. Vuthaluru / Bioresource Technology 92 (2004) 187195

1.0E+09

Fractional mass loss rate

1.0E+08 Wood Waste Wheat Straw 1.0E+07

1.0E+06

1.0E+05 0 10 20 30 40 50 60 70 80 90 100

Biomass content of feed (%)

Fig. 5. Fractional mass loss rate for second thermal event at 340 C.

Given that this assumption has not been deemed appropriate based on the variety of values found by Mansaray and Ghaly (1999), such a method of analysis is insucient to describe the overall reaction behaviour. Also highlighted in Table 4 are the degradation rates derived from the kinetic parameters. Temperature range of between 280 and 480 C has been selected as representative of the thermal event region, but the trend is similar throughout the temperature range examined (26 1247 C). The rate of degradation was derived from the following equation proposed by Hatakeyama and Quinn (1999):
1 da A ET e R 1 an dt /

It is evident from the Table 4 that coal has the highest rate of degradation. The second highest degradation rate is observed during the pyrolysis of the 50:50 coal/ WW blend. The pyrolysis of 50:50 coal/WS blend is the next highest. In the second thermal event, there is a trend in reaction rate with respect to ratio apparent in both biomass samples. The lowest average rate of reaction can be seen at 20% (Fig. 5). 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.

Three thermal events are observed during the copyrolysis of coal/biomass blends. The rst two are linked to the ring of biomass, while the third event occurred at a higher temperature as a result of coal ring, suggesting lack of interaction between the fuels during co-pyrolysis. The degradation temperature of coal decreased with increasing biomass content in the blend possibly due to the massive decomposition of biofuels. Measured TGA data indicated a linear relationship between the char yield and the proportion of biomass in the blend, suggesting lack of synergistic eects between the fuels. Hence, pyrolytic behaviour of the blends can be predicted from those of parent fuels. Calculated kinetic parameters viz., activation energies and pre-exponential factors were found to be in the range of 46.9183.6 kJ mol1 and 1.54 103 4.86 1012 min1 for the tested blends. The orders of reactions were in the range of 0.211.6, which justies the dismissal of the assumption of rst order for co-pyrolysis reactions. Among the tested blends, 20:80 blends showed the lowest activation energies irrespective of the type of biomass sample. However, based on the estimated reaction rate, 50:50 blend appears to be the optimum fuel with high degradation rates (1 109 2.1 109 min1 ). Acknowledgements The author gratefully acknowledges the nancial and other support received for this research from Curtin University of Technology. The author also likes to ac-

4. Conclusion The pyrolytic behaviour of coal/biomass blends has been investigated using a TGA apparatus. The conclusions drawn from the present work are as follows:

H.B. Vuthaluru / Bioresource Technology 92 (2004) 187195

195

knowledge J. Opie and K. Blyth of Chemistry Department for assisting with TGA experiments. References
Abbas, T., Costen, P.G., Lockwood, F.C., 1990. Solid fuel utilisation: from coal to biomass. In: Twenty-Sixth Symposium (International) on Combustion. USA, pp. 30413058. Ahmed, S., Clements, L.D., 1988. Kinetics of biomass pyrolysis with radiant heating. In: Bridgwater, A.V., Kuester, J.L. (Eds.), Research in Thermochemical Biomass Conversion. Elsevier Science Publishers, London, pp. 295309. Blazej, A., Kosik, M., 1993. Phytomass. Ellis Horwood, England. Caballero, J.A., Marcilla, A., Conesa, J.A., 1997. Thermogravimetric analysis of olive stones with sulphuric acid treatment. J. Anal. Appl. Pyrol. 44, 7588. Hatakeyama, T., Quinn, F.X., 1999. Thermal analysisFundamentals and applications to polymer science. John Wiley & Sons, Chichester. Heinzel, T., Siegle, V., Splietho, H., Hein, K.R.G., 1998. Investigation of slagging in pulverized fuel co-combustion of biomass and coal at a pilot-scale test facility. Fuel Process. Technol. 54, 109 125. Helsen, L., Van den Bulck, E., 2000. Kinetics of the low-temperature pyrolysis of chromated copper arsenate-treated wood. J. Anal. Appl. Pyrol. 53, 5179. Kastanaki, E., Vamvuka, D., Grammelis, P., Kakaras, E., 2002. Thermogravimetric studies of the behavior of lignite-biomass blends during devolatilization. Fuel Process. Technol. 7778, 159166. Mansaray, K.G., Ghaly, A.E., 1999. Kinetics of the thermal degradation of rice husks in nitrogen atmosphere. Energy Sources 21, 773784.

Meesri, C., Moghtaderi, B., 2002. Lack of synergetic eects in the pyrolytic characteristics of woody biomass/coal blends under low and high heating rate regimes. Biomass and Bioenergy 23, 55 66. Nassar, M.N., 1999. Thermal analysis of kinetics of Bagasse and Rice Straw. Energy Sources 21, 131137. Netzsch, 2001. NetzschGertebau Gmbh, Wittelsbacherstrasse 42, a DE-95100, Selb, Germany. Pan, Y.G., Velo, E., Puigjaner, L., 1996. Pyrolysis of blends of biomass with poor coals. Fuel 75, 412418. Pedersen, L.S., Nielsen, H.P., Kiil, S., Hansen, L.A., Dam-Johansen, K., Kilsig, F., Christensen, J., Jespersen, P., 1996. Full-scale coring of straw and coal. Fuel 75, 15841590. Ramaiah, M.V., 1970. Thermogravimetric and dierential thermal analysis of cellulose, hemicellulose and lignin. J. Appl. Polym. Sci. 14, 13231337. Rudiger, H., Greul, U., Splitho, H., Hein, K.R.G., 1994. Copyrolysis of coal/biomass and coal/sewage sludge mixtures in an entrained ow reactor. In: APAS clean coal technology programme, bol 3. C4. Sami, M., Annamalai, K., Wooldridge, M., 2001. Co-ring of coal and biomass fuel blends. Prog. Energy Combust. Sci. 27, 171214. Smith, L.H., Smoot, L.D., Fletcher, T.H., 1994. The structure and reaction process of coal. Plenum Press, New York. Swanekamp, R., 1995. Biomass co-ring technology debuts in recent test burn. Power (Boilers Combust. Syst.) 139 (2), 51. Wendlandt, W.W.M., 1974. Thermal methods of analysis. John Wiley and Sons, Sydney. Werther, J., Saenger, M., Hartge, E.U., Ogada, T., Siagi, Z., 2000. Combustion of agricultural residues. Prog. Energy Combust. Sci. 26, 127. Williams, A., Pourikashanian, M., Jones, J.M., 2001. Combustion of pulverised coal and biomass. Prog. Energy Combust. Sci. 27, 587 610.