Bioresource Technology 102 (2011) 3527–3534

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage:

Pyrolysis of biomass by thermal analysis–mass spectrometry (TA–MS)
Y.F. Huang a, W.H. Kuan b, P.T. Chiueh a, S.L. Lo a,⇑

Graduate Institute of Environmental Engineering, National Taiwan University, 71, Chou-Shan Road, Taipei 106, Taiwan, ROC
Department of Safety, Health and Environmental Engineering, Mingchi University of Technology, 84, Gung-Juan Road, Taishan, Taipei 243, Taiwan, ROC

a r t i c l e

i n f o

Article history:
Received 26 August 2010
Received in revised form 10 November 2010
Accepted 11 November 2010
Available online 4 December 2010
Reaction kinetics

a b s t r a c t
The kinetic parameters such as pre-exponential factor and activation energy of hemicellulose, cellulose,
and lignin were well determined by the linear regressions of selected, sufficient thermogravimetric data,
and close to literature values. The pyrolysis of biomass can be divided into four stages. There was only
drying in the zeroth stage (<150 °C). In the first stage (150–250 °C), some light hydrocarbons were produced with the early pyrolysis of biomass. The biomass was mainly pyrolyzed in the second stage (250–
500 °C) with higher reaction rates than those of other stages. The productions of H2 and CO2 in the third
stage (>500 °C) may be able to be the evidence of self-gasification of char existing at higher temperatures.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction
Nowadays biomass has been commonly seen as an alternative
and renewable energy source. By various conversion technologies
(e.g., pyrolysis, gasification, torrefaction, etc.) of biomass, many
kinds of bioenergy (biofuel) can be produced and used. Most of
the biomass is composed of numerous components and thus
has a heterogeneous property. In most cases, biomass is a mixture of hemicellulose, cellulose, lignin, ash, and minor amounts
of other organics, which each pyrolyze or degrade at different
rates and by different mechanisms and pathways (Bridgwater
et al., 1999). Biomass is a term for all organic material that stems
from plants including algae, trees, and crops (McKendry, 2002).
Wood, crops, agricultural and forestry residues, and biodegradable components of municipal solid waste (MSW) and commercial and industrial wastes are some of the main renewable
bioenergy resources available (Bridgwater, 2006). In Taiwan,
there are a lot of sugarcanes, coffees, and bamboos planted or
grown wildly, so residues of the plants are abundant. Thus this
study primarily focused on these feedstocks and their experimental results.
In recent years, the authors have presented some results on
microwave-induced pyrolysis of biomass, including properties of
three-phase products (Huang et al., 2008), further investigation

⇑ Corresponding author. Tel.: +886 2 23625373; fax: +886 2 23928821.
E-mail address: (S.L. Lo).
0960-8524/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.

on gas product (Huang et al., 2010), and related outcomes. According to the authors’ experience, it was hard to determine reaction
kinetics and detailed mechanism of microwave-induced pyrolysis.
This may be due to difficulties in real-time measuring of sample
weight and product analysis, and disturbance caused microwave
irradiation. However, perhaps the most critical limitation was
from the existing apparatus of microwave-induced pyrolysis. The
technology of thermogravimetric analysis (TGA) coupled with
mass spectrometry (MS) is able to provide the reaction kinetics
and products distribution of traditional pyrolysis, which may be
capable of being regarded as a reference for newly developed
pyrolysis technologies. There has been some literature concerning
the thermal analysis–mass spectrometry (TA–MS) of volatile
products from biomass (Varhegyi et al., 1988; Szabo et al., 1996;
Worasuwannarak et al., 2007; Meszaros et al., 2007; Gomez
et al., 2007; Barneto et al., 2009) and related materials (Materazzi,
1998; Otero et al., 2002; Li et al., 2003). According to the literature,
one of the most attractive advantages of TA–MS is that it is able to
afford the real-time and sensitive detection of evolved gases, which
is an important and often a difficult task in many thermal
Although the researches about the pyrolysis of biomass have
been quite a lot, such as kinetics and product analysis, detailed
studies on distribution of specific products with reaction temperature and time are relatively few. This study aimed to investigate
the thermogravimetric property, reaction kinetics, and gas product
distribution of pyrolysis of biomass by utilizing the TA–MS
technology, and then to further discuss characteristics and novel
discoveries in pyrolysis of biomass.

sugarcane peel.2 44. which can be seen as 3He (the less abundant isotope of the purge gas used).1 6.3 87. volatile matter. the biomass feedstock was air-dried. T is the average value of temperatures at which the thermogravimetric data best fit a straight line done by linear regression. VM. FC.0 18. CO.u.. tar production). 2010).0 77. and then heated in the TA–MS apparatus from room temperature to about 900 °C at the heating rate of 5 °C/min. Thus a straight line may be obtained from a plot of ln[ln(1  a)/T2] versus 1/T. and the results are listed in Table 1. Reaction kinetics of pyrolysis of biomass 3.3 0.1 9.. the reaction model in Eq.. 27.3. C2H6.6 1. and CO2.7 Dry basis.. and T is temperature. Thus rate equation for the kinetics analysis can be expressed as: By means of the TA–MS experiments. and mf is the final mass at the end of pyrolysis.3 52.u.2.1. a¼ ð1Þ m0  mt m0  mf ð2Þ where m0 is the initial mass of biomass sample. and various mechanisms and assumptions have been illustrated. respectively. Before being put into the TA–MS system.8 0. Eq. In this article.2 0. R is the universal gas constant (8.5 49.m. The mass spectrometer was in the electron impact (EI) ionization mode at the electron energy of 70 eV and provided mass spectra up to 512 a.74%). This study primarily discusses the mass spectra of 2.3528 Y. the pyrolysis of biomass was assumed to be a first-order reaction (i. the activation energy and the preexponential factor can be calculated by the slope and the intercept of the line. CH4. S1 (see Supplementary data in the online version of this article). 28. The biomass feedstocks except filter paper were all agricultural and forest residues in Taiwan. a skimmer coupling system was used to prevent the unnecessary condensation of evolved gases (i. and a is conversion ratio of biomass feedstock: This study focused on the pyrolytic behaviour of five kinds of biomass feedstocks. During the experiments. Proximate analysis (wt. Dry ash free basis.m.u.2 11. which are assigned to represent H2.2 0. 30. 18.3 5.0 8. under a constant heating rate b (= dT/dt). the term of ln[AR/bEa(1–2RT/Ea)] can be regarded as a constant (Zhou et al.7 0.e.5 11.2 0. O2.8 6. / Bioresource Technology 102 (2011) 3527–3534 2. 1964). and sieved (40 mesh) to yield powder samples. 44 a. It can be seen that under the temperature up to about 900 °C.b Coffee hulls Bamboo leaves Sugarcane bagasse Sugarcane peel Filter paper a b c d Ultimate analysis (wt. (1) can be rearranged to:   da A Ea ¼  exp   ð1  aÞ dT b RT ð5Þ By the Coats–Redfern integral method (Coats and Redfern.5 70. (5) can be integrated to: ln   lnð1  aÞ T2  ¼ ln    AR 2RT Ea  1 bEa Ea RT ð6Þ For most values of activation energy and for the temperature range of pyrolysis.%)c VM FC Ash C H N S Od 77. respectively.5 40.7 0. 1999).4 47.8 43. 15.2 10.7 4. In the interface between the two subunits. Results and discussion 2. From the linear regression of Eq. 2006). Besides. fixed carbon.. TA–MS experiment TA–MS measurements were performed by a simultaneous thermal analyzer (Netzsch STA-409CD) coupled with a quadrupole mass spectrometer (Balzers QMA 400).5 0. Huang et al.3 48. In all experiments.. Eq. the purge gas used was helium with a constant flow rate of 100 ml/min. From this may be concluded that the biomass feedstocks have a close to common composition. TGA results of biomass feedstocks There have been so many researches on the kinetics of pyrolysis of biomass. the compositions and thermal properties of biomass feedstocks will be further discussed by means of the TA–MS analysis. the C/H/O ratios of biomass feedstocks were nearly the same as one another and analogous to that of the rice straw discussed in the authors’ previous work (Huang et al. 2.0 11. (1) can be expressed as: f ðaÞ ¼ ð1  aÞn ð4Þ where n is order of reaction.. sugarcane bagasse.%)a.8 44.F.e. Methods da ¼ k  f ðaÞ dt 2. respectively.8 12. 32.5 6. The proximate and the ultimate analyses of biomass feedstocks were in accordance with American Society for Testing and Materials (ASTM) Standard Test Method D 5142 and D 5291. Biomass where k is rate constant.8 0. as shown in Fig.314 J/kmol). Excluding bamboo leaves. Calculated by difference. 3. C2H4. 2008). and bamboo Table 1 The proximate and the ultimate analyses of biomass feedstocks. (6). TGA results of the biomass feedstocks can be obtained. such as coffee hulls. f(a) represents a hypothetical model of reaction mechanism (Gil et al. n = 1). every 2 min.8 6. H2O. Therefore.3 89. The rate constant can be derived from the Arrhenius equation:   Ea k ¼ A  exp  RT ð3Þ where A is pre-exponential factor. The rate of reaction for the decomposition of a solid depends on the temperature and the amount of substance (Orfao et al. about 10 mg of sample (40 mesh sieved) was put in a ceramic crucible for each batch.1. Ea is activation energy. .2 48.0 45. Both the sensitivity of MS and the baseline of MS signals were checked by the measurement of 3 a. In many applications. and filter paper (Advantec).m.2 0. bamboo leaves. mt is the mass at time t or temperature T. there was the most overall mass loss possessed by filter paper (88. milled.

and mass-loss rate (RP) and temperature (TP) at the peak in the DTG diagram. The total mass losses (LT) represent the entire reactivity of the biomass feedstocks under the TGA Table 2 The TGA results of biomass feedstocks. 150–500 °C. 335. such as the thermal reactivity and relative proportions of components. / Bioresource Technology 102 (2011) 3527–3534 leaves owned the least (61.42%/min.14 11. several data (mass change by temperature or time) were selected to satisfy a best linear regression of Eq. respectively. and the operating conditions of experiments (e. respectively. cellulose. 3529 experiments. Results of kinetics analysis In the TGA result. 2006). From this and the result of ultimate analysis are concluded. such as accumulative mass losses (L1.67–85. the mass-loss rate at the peak (RP) in the DTG diagram also means the maximum mass-loss rate if there is only one peak. which were only 2. and the maximum mass-loss rates were 2. All the mass losses of the biomass feedstocks mainly occurred at the temperatures of 200–500 °C. and lignin. RP and TP. between which there was also an accumulative mass loss of around 20%. massloss rate and temperature at the peak in the DTG diagram.74 RP TP (%/min) (°C) 5. The mass losses of the third stage (L3).18% of the total mass losses (LT) during the TGA experiments happened in the second stage. the peak of filter paper was much higher and more concentrated at the temperature range of 300–400 °C. R2 (from 0. That the most part of the biomass reacted at the temperature range of 150–500 °C shall be recognized as the pyrolysis of its lignocellulose content. bamboo leaves. self-gasification. As above mentioned. but only part of the lignin can be reacted due to its low thermal reactivity. and 350 °C for coffee hulls. 3.F. Idris et al. For coffee hulls. The mass losses of the second stage (L2) were 54. total mass loss during TGA experiment (LT). It seems that these mass losses under different temperature range might come from thermal decompositions of corresponding components in sugarcane bagasse. at which the cellulose pyrolyzed as indicated by Yang et al. might come from the pyrolysis of lignin content. secondary reactions. The difference among the peak temperatures was not significant compared with that among the maximum mass-loss rates. Refer to the study by Yang et al. S2.73 78.81% and 4. Since the composition of biomass is complicated. The temperature at the peak (TP) in Table 2 also means the corresponding temperature of maximum mass-loss rate. sugarcane peel. heating rate. the overall mass loss was divided into three stages by temperature ranges of <150 °C.67 76.15 82.12 2.11 88.28 54. and >500 °C in this study.2. it is still believed that. total mass loss during TGA experiment. The curves of mass versus temperature are clearly S-shaped except sugarcane bagasse. and filter paper performed the best (88. However. the maximum mass-loss rates by the TGA experiments were 5. as Vyazovkin and Wight (1998) pointed out. 325. Meanwhile the overall mass losses of the other three biomass feedstocks were 75–82%.47 75..74%).96 1. the pyrolytic weight loss of hemicellulose. and L3) at temperatures of less than 150 °C. or something unknown.Y. 3. 150–500 °C.42 340 325 205/335 335 350 L1. which were 340. there was an obvious mass change at the temperature of around 200 °C. In this stage. Although the temperature ranges selected are small. filter paper might be mainly composed of the cellulose.14 5. (6). are listed in Table 2. and L3. Accumulative mass losses during the temperature ranges of the two peaks (170–230 and 295–380 °C) were about 18% and 32%.38 2. reaction atmosphere. bamboo leaves. so this means that 89. Huang et al.30  1015 1/s. etc.14%/min at the temperatures of 205 and 335 °C.42 0. The second stage of mass loss is supposed to be in which the pyrolysis of biomass feedstock mainly occurred. Their corresponding temperature range and results of kinetics analysis are listed in Table 3. respectively. As shown in Table 2. Combined diagrams presenting DTG results of the biomass feedstocks are shown in Fig. sugarcane peel. the moisture contents of the biomass feedstocks that were assigned as the mass loss of the first stage (L1) were only 0. and the pyrolytic degradation was mainly started from 180–200 °C till around 500 °C. This difference is highly coincident with that in the volatile matters of biomass feedstocks (Table 1). and higher than 500 °C. and ranged from 6.35 4. In addition to hemicellulose. most of the biomass is primarily composed of hemicellulose. it is supposed that the linear regressions with R2 as high as possible are able to prevent the disturbance of experimental errors (data noise) and provide the representative kinetic parameters at the corresponding temperature ranges. (2007). major constituents of biomass also consist of organic extractives and inorganic minerals (Mohan et al.78 kJ/mol.58 85.65 73.11– 3.81/4. or at least. and lignin. This difference was nearly coincident with that from the total mass losses of the biomass feedstocks discussed above.13 71.01 3. the kinetic parameters determined over a small temperature range may approach to those of a certain component. cellulose. Except the peak appearing at the temperature range coincident with the other feedstocks.14 5.14.73–5.15%). and filter paper. Thus the unique peak in the DTG diagram of sugarcane bagasse might be contributed by the constituent of less thermal-resistance part of hemicellulose or organic extractives. cellulose. To further discuss the difference among the TGA results of the biomass feedstocks.12. the capability of a mathematical model to .92 3. and lignin mainly happened at the temperature ranges of 220–315 °C.0000). L2.35% of original feedstock weights. that the compositions of biomass feedstocks are different to some extent with one another. there were two peaks in the DTG diagram of sugarcane bagasse.42% of original feedstock weights. 5.g. Generally. respectively. According to this consistency. thermal efficiency. Therefore. Several TGA results of the biomass feedstocks. Therefore. compared to the other biomass feedstocks.40–96. Biomass L1 L2 L3 LT (%) Coffee hulls Bamboo leaves Sugarcane bagasse Sugarcane peel Filter paper 0. and 11. The reactivity in the third stage was much less than that in the second stage.42 2. (2010) indicated that the moisture drying region in the pyrolysis oil palm biomass was at the temperature range of lee than 150 °C. Bamboo leaves showed the least pyrolytic reactivity (61.11 0. 315–400 °C. respectively.38 61.9949 to 1.68 to 210. respectively. The pre-exponential factors differed with different biomass feedstocks and temperature ranges. 150–500 °C.). respectively. derivative thermogravimetric (DTG) analysis was adopted. the assumption that pyrolysis of biomass undergoes a first-order reaction should be proper. the activation energy varied in the same manner and ranged from 22. (2007). and filter paper. Each of the DTG diagram shows only one peak excluding the diagram of sugarcane bagasse. and >500 °C.01.10 3. the TGA results of filter paper might be capable of representing some properties of the cellulose.15%).33  102 to 2. temperature.38% of original feedstock weights. It is supposed that the formation and separation of peaks may come from several factors. respectively. Except a negligible peak at the temperature of about 70 °C. L2.. The mass profile of sugarcane bagasse demonstrated that unlike the other biomass feedstocks. Besides. All the regression results have nearly extreme coefficients of determination. and 160–900 °C. accumulative mass loss at temperatures of <150 °C. Moreover. there was also a smaller peak at the temperature of about 200 °C in the diagram of sugarcane bagasse. LT. In Table 2. both the hemicellulose and cellulose contents are able to completely decompose.

and lignin concluded by some evidences and assumptions.42  102 6.91  105 1.9990 0.0  1019 1. Compared with other biomass feedstocks.3530 Y. as listed in Table 4. / Bioresource Technology 102 (2011) 3527–3534 Table 3 The kinetic analysis of biomass pyrolysis.7 244 210 231.0 7.90  101 4..68 71. and sugarcane peel shall be due to the composite reactions of multi-components.39  104 5. At the medium temperatures of 250–290 °C.28  104 2. parts of the components of biomass such as hemicellulose. According to the kinetics analyses of the biomass feedstocks discussed above.e. pre-exponential factor.65 kJ/mol.9980 0.g.33  102 8.9998 0. (1999) (cellulose) Vamvuka et al. there was also a positive correlation between the activation energy and the temperature. 2004). such as the preexponential factor of 1.14  1015 2.03 59. If the ratios of the mass loss after 385 °C and the residue after TGA experiment are both further excluded.38 210.27 96.3–103 5. 2003.30  1015 240 82.78 Lignin Varhegyi et al.9983 Filter paper 255–275 300–320 340–360 2.07 0. Ea (kJ/mol) R2 Biomass Temperature range (°C) A (1/s) Coffee hulls 195–220 250–280 330–350 6.9997 R2: coefficient of determination. Gronli et al. The positive correlation between the pre-exponential factor and the temperature may be due to that the pre-exponential factor is highly related with the temperature-dependent collision frequency described in the collision theory.41 b. the kinetics parameters determined at temperatures of 190–210 °C may be able to represent the pyrolysis characteristics of hemicellulose. As mentioned above.02 210.93  109 2.93 75. (2003) (straw) Yang et al. Xylan has been used by some researches (Varhegyi et al. However. produce meaningful information cannot be only characterized by the goodness of fit (italics added by the authors). Rao and Sharma. the lignin).74 66. In other words.9991 Bamboo leaves 195–220 245–280 310–330 2..0000 Sugarcane bagasse 190–210 250–305 325–345 1. However.29 0.9998 0.9981 Sugarcane peel 180–205 250–290 325–345 2. there was a very high peak at the temperature of about 350 °C in the DTG diagram of filter paper.108–2. Orfao et al.41 62..31 0. the unique peak of sugarcane bagasse may provide a message that there was a single reaction of a single component and/or with a single mechanism.16  1018 4.23 96. (1997) (cellulose) Rao and Sharma (1998) (cellulose) Gronli et al. Therefore.08  109 2. If the specific component is assumed to be one or some kinds of hemicellulose. at almost the same temperature range.g. According to the DTG diagram of sugarcane bagasse. and sugarcane peel may come from composite reactions of multi-components.76  101 2. (2004) (lignin) Present study (bagasse/filter paper) 10 20 10 10 5 100.78 0. and lignin were reacted at this temperature range. cellulose.64  104 1.68–48. Ea (kJ/mol) .30  1015 1/s and the activation energy of 210.64  104 1/s and the activation energy of 67.. the kinetics parameters of sugarcane bagasse and filter paper were relatively small and. which is a kind of interdependence between them.28 0.8 69.30  1015 48. and then this peak may be able to represent the pyrolytic result of cellulose.9959 0.9986 0. respectively.64  104 105. the mass loss was sum up into about 77%. (2004) (cellulose) Present study (filter paper) 10 20 5 5 10 10 5 3. the relatively low reactivity of coffee hulls. thermal decompositions of multi-components) at lower temperatures. therefore. (1997) (lignin) Rao and Sharma (1998) (lignin) Vamvuka et al. some of the literature used different integral methods with one another. 1999. (2003) (straw) Yang et al.10  103 4. These small disagreements may reflect in part simple differences in samples or result from unidentified. (2004) (xylan) Present study (bagasse) 20 10 10 5 1.58  100 2.0 31.9949 0. from the kinetics analysis of filter paper. 1997.17  103 31.10  101 5. However.45  103 67.8 227.65 Cellulose Varhegyi et al. In addition.0 120.48  105 50.6  1016 2. 2004) that all discussed the pyrolysis of lignocellulosic materials via firstorder reaction kinetics.23 kJ/mol. respectively.14 88. cellulose. Therefore. Yang et al.85  102 1. the accumulative mass loss during the peak period will be turned into around 94%. (1999) (cellulose) Orfao et al. Vamvuka et al. Furthermore. However. there were the pre-exponential factors and the activation energy of hemicellulose.F.69  105 1.08  101 4. Rao and Table 4 The first-order reaction parameters of biomass pyrolysis. Most of the pre-exponential factors and the activation energy showed an increasing tendency with the increase in temperature. During the peak period at the temperatures of 295–385 °C. The kinetics parameters of coffee hulls.. Lignocellulose literature (sample) b (°C/min) A (1/s) Hemicellulose Rao and Sharma (1998) (xylan) Vamvuka et al. A.10  103 1/s and 59.34  100 34–65 67. Most of the pre-exponential factors and the activation energy calculated by the present study do not differ much from the literatures (Varhegyi et al. At the temperatures of 190–210 °C.9996 1. there was a peak of mass-loss rate at the temperature of around 200 °C.9998 0. This high percentage provides an additional proof that the filter paper should be primarily composed of a kind of material which can be highly supposed to be cellulose. bamboo leaves.14 kJ/mol. Thus.58 1/s and 22. the pre-exponential factor and activation energy were 2.65 22.09  103 1. For the three biomass feedstocks pyrolyzed at the temperatures of 250–290 °C.90  105 28. bamboo leaves. 1999.. 1998). it seems that the extraordinary preexponential factor and activation energy may come from a thermal-decomposition reaction of some specific component in the sugarcane bagasse. 1997.13  1018 5..78 kJ/mol are supposed to be close to pyrolysis characteristics of cellulose. The pre-exponential factor and activation energy of the two were 0. (2003) (straw) Yang et al. Huang et al.. the pre-exponential factor of sugarcane bagasse at the temperatures of 190–210 °C was much higher and the activation energy of that was the highest. may be capable of being regarded as the thermal properties of a single material (e. heating rate. it will not be further discussed in this article. 1998. Ea.. However. since no explanation has yet been generally agreed for the widespread occurrence of KCE relationships (Galwey. the pre-exponential factor at the temperatures of 190–210 °C was also higher than that at the temperatures of 325–345 °C.27–75.80 35. both the pre-exponential factor and the activation energy were much higher than that at the temperatures of 250–305 °C. there was an exception for sugarcane bagasse.9986 0. hemicellulose) that can be pyrolyzed at lower temperature are supposed to have lower activation energy.39 67. both the preexponential factor of 2.. parts of the components of biomass (e. The kinetic parameters seem to show a kinetic compensation effect (KCE). systematic temperature measurement errors that are accentuated at high heating rates (Antal et al. Unlike the DTG results of other biomass feedstocks that showed a composite outcome (i. activation energy.42  102–8. the kinetics parameters of sugarcane bagasse and filter paper were much different from those of the other three biomass feedstocks.

where no obvious gas can be produced by the pyrolysis of other biomass feedstocks. Huang et al. it can be supposed that there was no pyrolysis of biomass at that time (temperature). and H2O. of 30 and 32 can be regarded as methanal (CH2O) and methanol (CH3OH) as well. respectively.m.0321. in the zeroth stage (<150 °C). 28. 32. Qualitative analyses can be easily achieved by interpreting the TA–MS results. or at least they are highly related. the second. the product analysis can be achieved with observations on ion-current changes in TA–MS results.. 1. The temperature range was selected for the purpose that to collect the conversion data of the biomass feedstocks at the same period where they were all highly reacted. Thus at this temperature range. Peaks at lower temperatures (<150 °C) expressed the drying of biomass feedstocks. The relationship was evaluated by calculating the correlation coefficients between the integral areas of ion-current peaks of gas products and the accumulative conversion ratios of biomass feedstocks at the temperatures of 300–350 °C. most of the gas products were primarily generated at the same temperature range of 250–500 °C. H2 was produced much more at higher temperatures (>500 °C).m.m. since no gas product but H2O was found in this stage. Firstly. or an atom that was generated by the electron-impact ionization of the mass spectrometry. Gas product analysis By means of TA–MS analysis. A signal of ion current can be seen as the existence of a compound. Besides. selection. with respective to the molecular weights of the gas compounds. which was coincident with the peak in the DTG diagram. the activation energy and the pre-exponential factor. in this study. and C2H6. Therefore. as listed in Table 6. respectively)..0670 and 0. This may imply that the earlier productions (compared to those in the second stage) of the light hydrocarbons and H2O are highly related to the pyrolysis of hemicellulose that has been discussed above. respectively. the permanent gases including H2. as shown in Table 5. In the result of mass spectrometry. Yang et al.9989) with the reactivity of biomass. there were some peaks at 3531 the temperature of about 200 °C. 44. there was only H2O detected in the spectrums of the biomass feedstocks except filter paper. Parenthetically. such as the zeroth. However. Orfao et al. and O2 were not found in the first stage of the pyrolysis of sugarcane bagasse. but there was lack of quantitative analysis of mass spectrometry. may come from the contributions of various atoms or molecules. Otherwise.g. Thus it can be thought that there was no moisture content in the filter paper. especially CH4 and CO2. CO2.u. 30. CO2. Therefore. by the temperatures of <150 °C. the result of correlation analysis may provide another proof that the productions of H2 . This study primarily focused on the production of permanent gases such as H2. the pyrolysis of cellulose can produce more both of H2 and CO. of 30 and 32 in the mass spectra where the abundances at the other a. 2004) to represent the pyrolytic behaviour of hemicellulose. both the peaks of H2 and CO are narrower than those of the other gas products. The a. The productions of the other gases showed moderate correlations with the reactivity of biomass. respectively. since there is still a possibility that the signal at an a. 3. This may be due to that by selecting part of the thermogravimetric data (at least five) that provided the best result of linear regression. respectively.u. and H2O. this study has referred to the database of National Institute of Standards and Technology (NIST) for the help of a. CO2. respectively. 1999. and >500 °C. In Fig. When a peak is formed in the ion-current profile.. and the third stage. some light hydrocarbons including CH4. the atomic mass units (a. of 15 and 27 instead of 16 and 28 were selected to represent CH4 and C2H4. 250–500 °C. C2H6. thermogravimetric data over a small interval of temperature or time can provide a good linear regression in the kinetics analysis as illustrated in this study. Secondly.u.8233.u. the interference among them (e. To further discuss the magnitude and distribution of the gas products. 150–250 °C.m. Since the cellulose is supposed to undergo pyrolysis at the temperature range including 300–350 °C where all the biomass feedstocks were reacted the most. C2H4.) of 2. Combined diagrams of the ion-current profiles versus temperatures of coffee hulls.m. there may be something different between the contents of sugarcane bagasse and the other biomass feedstocks. CO.8707 and 0.3. thermogravimetric data can be obtained as well as information about the product distribution. CO. bamboo leaves. This phenomenon was even clearer in the product distribution of filter paper. and O2. 2004). a corresponding product can be quantitatively determined by integrating the peak. Orfao et al. the first. To discuss the relationship between the gas production and the reactivity of biomass feedstock. and 18 represented H2. Besides. C2H6 and O2 have the highest relative abundance at the a. it is supposed to be appropriate to regard the a. 1. the kinetics parameters of hemicellulose and lignin can be well determined by the assumption that the pyrolysis of biomass feedstock accords with first-order reaction. and the productions of CO and CH4 were in strong ones (r = 0. / Bioresource Technology 102 (2011) 3527–3534 Sharma. a semiquantitative analysis was applied and can be accomplished by the integration of the ion-current peak. accumulated signals) is supposed to be inevitable. although the a. in spite of which method of integration or other calculation applied. the overall temperature range that the TA–MS proceeded was divided into four stages.m. C2H6. of 29 and 31 in the mass spectra.m.Y.u. for the purpose of preventing the interference from other atoms or molecules that have the same atomic or molecular weights. 1998. the Pearson product-moment correlation coefficient (r) was used: P Þ ðx  xÞðy  y rðx. According to the temperatures that the gas products appeared. C2H4. the productions of O2 and H2O were almost not related to the reactivity of biomass with the correlation coefficients of 0. (1999) had mentioned that the thermal decomposition of xylan and lignin can not be described by first-order reaction kinetics. it was named the zeroth stage with respect to the existence of the pyrolysis or none. Since the filter paper can be seen as a representative of cellulose as mentioned above. sugarcane bagasse. It can be regarded as that the pyrolysis of the biomass feedstocks mainly happened in this stage. an almost straight line can be achieved and its slope and intercept can be further calculated to obtain the kinetics parameters. of 30 and 32 as representatives of C2H6 and O2. Therefore. In the TA–MS diagram of sugarcane bagasse. since both the two compounds can easily release a hydrogen atom in the electric field of mass spectrometer.m.. Therefore. On the contrary. The thermal properties of lingocellulose (especially lignin) may change during the pyrolysis due to their complicated compositions. yÞ ¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi P 2P  Þ2 ðy  y ðx  xÞ ð7Þ where x and y are two data sets.F. However. most of the gas products except H2 were produced in the second stage (250–500 °C). sugarcane peel.m. CO. respectively. and the top lines represent their means. Not like this. However. it may be supposed that compared with hemicellulose and lignin. they generally have the highest relative abundance at the a. the gases such as CH4. This can be due to the difficulty to obtain commercial hemicellulose (Yang et al. and filter paper are shown in Fig. Thirdly. and H2O were produced by the pyrolysis of sugarcane bagasse in the first stage (150–250 °C). are quite low. It can be clearly seen that for all the biomass feedstocks.u.u. Unlike these light hydrocarbons and H2O.u. O2.u. the production of H2 was in very strong correlation (r = 0. Too many data may result in poor result of linear regression that comes from a composite effect of multi-components.

there was less biomass pyrolysis and almost no gas production except CO2 for the bamboo leaves and H2 for all the biomass feedstocks.E-08 1.E-08 1. Huang et al. Therefore.E-09 1.E-11 1. and CO are highly related to the cellulosic content in the biomass as above mentioned.E-10 1.E-11 1.E-12 0 100 200 300 400 500 Temperature 600 700 800 0 900 100 200 ( oC) 300 400 500 Temperature (c) Sugarcane bagasse 600 700 800 900 700 800 900 ( oC) (d) Sugarcane peel 1. For all the biomass feedstocks except filter paper. Otherwise.F.E-08 1. but their quantities were quite small. In the third stage.E-12 1.E-12 0 100 200 300 400 500 600 700 800 900 Temperature ( oC) Fig.E-10 1. CO2.E-10 1.E-12 1. the productions of H2 in the third stage were much higher than those in the second stage (about 4–12 times). there were CO. maybe there is some kind of relationship between the productions of CO2 and H2 at higher temperatures. / Bioresource Technology 102 (2011) 3527–3534 (b) Bamboo leaves 1.E-08 1. The unusual CO2 production had a maximum rate at the temperature of 597 °C and started at about 550 °C that H2 was also going to be produced for the second time. Bamboo leaves met the maximum rate earliest (668 °C) and sugarcane bagasse . there was a maximum rate of H2 production at the temperature about 700 °C. The TA–MS analyses of biomass feedstocks.E-11 1. 1.E-10 1. and C2H4 as well produced by the pyrolysis of bamboo leaves.E-12 0 100 200 300 400 500 Temperature 600 700 800 900 0 100 ( oC) 200 300 400 500 Temperature 600 ( oC) (e) Filter paper 1.E-08 Legends: H2O O2 C2H6 C2H4 CO2 CO CH4 H2 Ion current (A) 1.E-09 1.E-09 1.E-09 Ion current (A) Ion current (A) 1.E-11 1. At the temperatures more than 500 °C (the third stage). The quantities of H2 produced by the pyrolysis of filter paper were almost the same in both stages.3532 Y.E-10 1.E-11 1.E-09 Ion current (A) Ion current (A) (a) Coffee hulls 1. at the temperatures of 400– 500 °C.

0321 Very strong Strong Moderate Strong Moderate Weak Very weak Very weak the latest (749 °C).7790) and the integral areas of ion-current peaks of O2 and H2O produced in the second stage (r = 0.85@340 7. Four stages in pyrolysis of biomass According to the TA–MS results and relevant discussion mentioned above. / Bioresource Technology 102 (2011) 3527–3534 Table 5 The product analysis by TA–MS.0670 0. CO. CO was not found in the third stage for all the biomass feedstocks.17@205 7.56@749 10.33@474 8.63@340 C2H6 Table 6 The relationships between the reactivity of biomass and the productions of different gases in the second stage.64@319 9.92@349 3rd CH4 C2H4 1st 2nd 1st 2nd 7. The integral areas of ion-current peaks of H2 produced in the third stage were highly correlated with the conversion ratios of biomass feedstocks happened at the temperatures of 500–700 °C (r = 0. Menendez et al.89@330 7.8707 0.70@340 8. Then there is a new equation by combining Eqs.29@349 O2 2nd 7. further investigations are still needed to prove this phenomenon. CH4.09@205 8. In the second stage (250–500 °C). (8) and (9): C þ H2 O þ 0:5O2 ! CO2 þ H2 ð10Þ Therefore. 2.F. (2007) and Dominguez et al.37@340 8. Gas Correlation coefficient.4451 0. Thus the H2O and the char (represented as C) both generated in the second stage may interact as: C þ H2 O ! CO þ H2 ð8Þ which is the gasification of char with steam.27@319 9. Referring to the low reactivities of the biomass feedstocks at higher temperatures.57@700 10. Gomez et al. .16@349 8. the ion current of H2O remained nearly constant at the higher temperatures.96@718 CO 2nd 8.71@340 8. In the zeroth stage. pointed out a self-gasification of char by CO2 that is produced during microwave pyrolysis. (8): CO þ 0:5O2 ! CO2 ð9Þ where O2 can be obtained from the production in the second stage that is also highly correlated with the H2 production in the third stage. and most of the gas products will be produced then. as shown in Fig.9989 0.52@668 10.90@329 7.80@340 8. residual char generated in earlier stages. This may be attributed to an offset of self-gasification and charring processes.09@112 8.78@330 8. The productions of H2 and CO2 in the third stage may prove the possibility of self-gasification of biomass or. To take the production of CO2 from bamboo leaves at higher temperatures into account.3533 Y.23@319 9.57@330 7.02@ 68 7. the most part of the biomass (hemicellulose and cellulose) can be rapidly pyrolyzed.42@340 9. and CO2 at higher temperatures (above about 500 °C) as the products of charring process. the pyrolysis of biomass can be divided into four stages.93@319 10. However. 2. (2007) mentioned a selfgasification of cane trash by H2O as moisture in the trash or pyrolytic H2O.7905 and 0.07@330 8.15@340 8. such as self-gasification or the others.2593 0. (2007) and Barneto et al. where H2O should be generated as well.7027. The four stages in pyrolysis of biomass. On the other hand.4. Once the temperature is high enough (150–250 °C).95@339 H2O 0th 1st 2nd 8.25@68 8.75@330 8. Huang et al. This is the first stage in pyrolysis of biomass to produce light hydrocarbons.05@205 8. more precisely.15@340 9.76@340 8.07@319 8. This may provide evidence of some kind of secondary reaction. Tian et al.14@350 9.16@340 8. There are only a few literatures that discussed the self-gasification in the pyrolysis of biomass.35@709 10. there is no reaction of pyrolysis but moisture removal due to the low temperature (<150 °C).59@340 8. respectively). the second production of H2 was too high to be ignored.51@349 Oth stage (<150 ºC) 1st stage (150–250 ºC) 2nd stage (250–500 ºC) 3rd stage (>500 ºC) Moisture Removal Early Pyrolysis Main Pyrolysis Late Pyrolysis Reaction Temperature / Time Fig.33@319 8.35@330 8.68@330 8.12@597 8.00@360 9.04@349 9.63@464 9. (2008) 6. Although this study has presented the evidence of selfgasification by the TA–MS results.32@205 7. At higher temperatures (>500 °C).5436 0. Gas Stage Logarithmic ion current@temperature of peak (°C) Coffee hulls Bamboo leaves Sugarcane bagasse Sugarcane peel Filter paper H2 2nd 3rd 10.58@340 8.60@340 9. r Correlation H2 CO CO2 CH4 C2H4 C2H6 O2 H2O 0. Eq. (2009) regarded H2.34@349 CO2 2nd 8. still undergoes pyrolysis. In this study.09@329 7.07@433 1st 2nd 7.8233 0. there maybe exist a pathway that sink the CO by Eq. part of the biomass (like hemicellulose) can be thermally decomposed at lower reaction rate. only a little part of the biomass which should be the unreacted lignin.20@329 7.18@319 9.29@ 68 6. (10) may be capable of representing the self-gasification of biomass at higher temperatures. 3.

Pasadakis. G. Org. Barneto. J. Huang. Ismail. Szabo.. J. Bioresour. Kinetic parameters from thermogravimetric data. / Bioresource Technology 102 (2011) 3527–3534 4. Fuel Process.. 101. Z.. Li..F. Chem.. Energy Fuels 20. Pis. J. 1968–1973. .M... H. Li.. E. Y. Ferrer. 1267–1275.. D. Huang et al. Vyazovkin. Mohan. O.. W. Eng. A. L..P. J. McKenzie. 22. S.. 2002. Int.. Most of the gas products were generated in the second stage. S.. Bridgwater. 397–403. Otero.F. T. 38. Evidence of selfgasification during the microwave-induced pyrolysis of coffee hulls. 963–969. E. 1814–1821. B. 1998. Pyrolysis 79. Y. Yan. M... 101. E. Szabo. Rao. R. 73–87. M. 1997. 2238–2244. respectively. Rahman.R... Thermogravimetric characteristics and kinetic of plastic and biomass blends co-pyrolysis. 1781–1788. Appl. Diez.L.2010.. 2010. The gases found in the third stage may provide the evidence of self-gasification of char existing at higher temperatures. Jakab. Figueiredo.H. Use of thermogravimetry/mass spectrometry analysis to explain the origin of volatiles produced during biomass pyrolysis. 30. E. 17. Anal. Appendix A. Antal. A. 2008.. P. Wight. Sci. 2003. W.A. C. Thermogravimetric analysis-Fourier transform infrared analysis of palm oil waste pyrolysis. H. 1. References Antal.. Jakab.V. J. Energy 23. Moran.P..L.049. J. T. 349–358. Antal. C. 2010. Py-GC/MS and THM-GC/MS study of the composition and thermal behavior of extractive components of Robinia pseudoacacia.P... Hayashi.J. Chem. Appl. 973– 978. Pyrolysis 78. Chemosphere 70. Thermochim.J. Is the science of thermal analysis kinetics based on solid foundations? A literature appraisal. Appl. 4584–4592. Pyrolysis rates of biomass materials.. Res. T. Dominguez. Kuan. 87. Gomez.. A.. S..F. Meier.. Spectrosc. Res. 5601–5608. Res... 2004.. McKendry.. 2010.L. Technol. Conversion of fuel-N into HCN and NH3 during the pyrolysis and gasification in steam: a comparative study of coal and biomass. Coats.. C.. Wang. Supplementary data Supplementary data associated with this article can be found. A. Biomass for energy. C. G.. R..J... 189–218. Chin. Phys.. M. Bio-syngas production with low concentrations of CO2 and CH4 from microwave-induced pyrolysis of wet and dried sewage sludge. Redfern. Matuschek. M.. Alfonso. Thermogravimetry/ mass spectrometry study of woody residues and an herbaceous biomass crop using PCA techniques..M.. J.. rice husk.. Thermogravimetric mass spectrometric characterization of two energy crops. Isothermal and non-isothermal kinetics of thermally stimulated reactions of solids. 179–190. Varhegyi. 7430– 7436. Kettrup. Appl. Acknowledgements The authors gratefully acknowledge the financial support from the National Science Council of the Executive Yuan. 2004.F. Chem.I. 68–69. 37. Lee.P.W. 33. Casal. J.. Q. Till. Only water and light hydrocarbons were detected in the zeroth and the first stage. Pis. Nature 201. 37–46.. Pyrolysis 67. Fidalgo. J. Sonobe. Hydrogen-rich fuel gas from rice straw via microwave-induced pyrolysis. Pyrolysis behaviors of rice straw. Technol. Technol. in the online version. M..T. F.A. F. Wang. and corncob by TG-MS technique. Calvo.. 2006... Materazzi. Lo. Cai. H. Ind. C.Z. 2007. Acta 413. Chen.. Huang. Anal.H. after which there was no production of gas except H2 and CO2. Ind. Anal. Steele. Anal.1016/j.. Antal. A. Eng. C... Energy Fuels 21.. D.J. Conclusions The properties and characteristics of pyrolysis of biomass were researched by thermal analysis–mass spectrometry (TA–MS). Analysis of the cocombustion of sewage sludge and coal by TG-MS. 2007. 1999. Meszaros. 373–378.. Ind. Varhegyi..H. 549–558. Appl. Y. Jakab...J.K. A study on combustion of Chinese coals by TA/MS. Herrera.S. P. L. Rubiera. 2006.J. Sharma. T... Idris. Varhegyi. Orfao.. Energy Fuels 17... Liang. M.E. P. J. E. C. NSC 99-ET-E-002-009-ET). Chen. 1479–1493. Investigation on thermochemical behaviour of low rank Malaysian coal.V. Huang. A.P.. Pyrolysis 80. Appl. G. Jakab. Biomass Bioenerg.. Technol. Gronli.. Kinetic modeling of biomass pyrolysis. Pevida. Pis. Energy Fuels 21. TG/MS.J.J. 319– 329. N.J. S. Rev... Kinetic modeling of coal/agricultural by-product blends. Carmona. E. Arundo donax and Miscanthus sinensis. Rev.G. 517–521... 848–889. 139–183.. G.. Vamvuka.. 2006.11.. Energy Fuels 18. Thermal behaviour and kinetics of coal/biomass blends during co-combustion. C. D. Yu. Bioresour. E. Worasuwannarak. Varhegyi. 2002. F.. J. Velo. C. 101. 265–271. 1964.3534 Y. Fuel 86. Menendez. T. H.. M.J..A. A. M... Yang. Jakab.. Tanthapanichakoon.J. Zheng. Fuel 78. Geochem. Chem. Pittman.. Puigjaner. Yang. Tian. F. J. Kastanaki... A. L. 1998.biortech. cellulose and lignin pyrolysis.J. Taiwan (Contract No. Y. J. 2007. Appl.F. Energy production from biomass (part 1): overview of biomass. Bridgwater.. F. 48.. An overview of fast pyrolysis of biomass. P. 393–406. Aris. H.. 2009. Eng.G. J. S. Mass spectrometry coupled to thermogravimetry (TG-MS) for evolved gas characterization: a review. Garcia. Zhou. Meszaros.. Food Agric.. 2007. 1999. J.. 1755–1768. 1998. Kuan.. Simultaneous thermogravimetric–mass spectrometric studies of the thermal decomposition of biopolymers. Energy Fuels 2.. Radlein. Alias. Total recovery of resources and energy from rice straw using microwave-induced pyrolysis.J.. X. K. 1998. 2008. 2007. 416–426.B. 267–272.L. 1996. Pyrolysis 42.A. Bioresour.A. 61–70. J. Fernandez.. Zheng. Varhegyi..F. D.G. G.... J.. 99. Cellulose pyrolysis kinetics: revisited. E. Anal. Characteristics of hemicellulose. L. 83. Fernandez. A round-robin study of cellulose pyrolysis kinetics by thermogravimetry. G. Bioresour. 1999. 2007... Lin. J.. Dominguez. J. Rashid. Avicel cellulose in the presence and absence of catalysts. C. A.C. E. Gil. Antunes. 86. oil palm biomass and their blends during pyrolysis via thermogravimetric analysis (TGA). Szekely.A. at doi:10. A.. 2003. 8252–8258. Lin..A.. W. Pyrolysis 36..H.... Yan. Till.. Menendez. Y. Faix. Bioresour. 1988.A. N. Galwey. D. The pyrolysis of biomass can be divided into four stages.. The kinetics parameters of lignocelluloses determined by thermogravimetric data were close to literature values. G. 407–433. J. A. N.. J.. Technol. Pyrolysis kinetics of lignocellulosic materials – three independent reactions model. Anal. Lo. D. D. Varhegyi.U. Pyrolysis of wood/biomass for bio-oil: a critical review. M. Technol.