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Abstract
With the application of induction heating, a fast pyrolysis was used for producing valuable products from rice straw, sugarcane bagasse and
coconut shell in an externally heated fixed-bed reactor. The effect of process parameters such as pyrolysis temperature, heating rate and holding
time on the yields of pyrolysis products and their chemical compositions were investigated. The maximum yield of ca. 50% on the pyrolysis liquid
product could be obtained at the proper process conditions. The chemical characterization by elemental (CHNO), calorific, Fourier transform
infrared (FT-IR) spectroscopy and gas chromatography/mass spectrometry (GC–MS) showed that the pyrolysis liquid products contain large
amounts of water (>65 wt.%), and fewer contents of oxygenated hydrocarbons composing of carbonyl groups, resulting in low pH and low heating
values. The results were very similar to bio-oils obtained from other biomass materials. The residual solid (char or charcoal) was also characterized
in the present study.
# 2006 Published by Elsevier B.V.
Keywords: Rice straw; Sugarcane bagasse; Coconut shell; Fast pyrolysis; Biomass and agricultural wastes
2. Experimental
2.3. Characterization
Fig. 4. Dependence of water, bio-oil and char yields based on a wet basis from
(a) rice straw, (b) bagasse, and (c) coconut shell on holding time at a heating rate
of 200 8C/min, pyrolysis temperature of 500 8C, particle size of <0.50 mm,
nitrogen flow rate of 1000 cm3/min, and condensation temperature of 10 8C.
Table 2
Calorific values and pH of the yrolysis productsa
Biomass waste Pyrolysis conditions Liquid productc Residual solid
d
Calorific value (MJ/kg) pH Calorific value (MJ/kg)
b
Rice straw 200 8C/min, 400 8C, 1 min 18.43 2.89 20.43
200 8C/min, 500 8C, 1 min 20.40 2.78 20.74
200 8C/min, 700 8C, 1 min 5.06 3.25 22.48
400 8C/min, 500 8C, 1 min 6.10 3.34 20.97
200 8C/min, 500 8C, 8 min 5.85 2.98 19.78
Sugarcane bagasse 200 8C/min, 400 8C, 1 min 3.79 2.10 24.57
200 8C/min, 500 8C, 1 min 4.43 2.32 24.80
200 8C/min, 700 8C, 1 min 3.72 2.04 25.24
400 8C/min, 500 8C, 1 min 4.88 2.28 26.47
200 8C/min, 500 8C, 8 min 5.12 2.24 27.00
Coconut shell 200 8C/min, 400 8C, 1 min 7.75 3.15 26.18
200 8C/min, 500 8C, 1 min 8.99 3.11 25.97
200 8C/min, 700 8C, 1 min 10.32 3.25 26.89
400 8C/min, 500 8C, 1 min 9.67 3.26 28.63
200 8C/min, 500 8C, 8 min 9.55 3.28 27.06
a
All pyrolysis products were derived from the same conditions: particle size of <0.50 mm, nitrogen flow rate of 1000 cm3/min, and condensation temperature of
10 8C.
b
200 8C/min, 400 8C, 1 min means that the pyrolysis products were obtained at heating rate of 200 8C/min, pyrolysis temperature of 400 8C, and holding time of
1 min.
c
The liquid product is mainly composed of water (Figs. 2–4), and fewer amount of bio-oil.
d
On the wet basis.
feeding precursors listed in Table 1. It is obvious that conventional fuels, and also resulting in the low energy content of
considerable amounts of carbon organized in the combustible the pyrolysis liquid product listed in Table 2.
matters of feeding precursors are still present in the residual The FT-IR spectra of the pyrolysis liquid products produced
solids, not pyrolyzed to produce condensable components in the from the fast pyrolysis of rice straw, sugarcane bagasse and
fast pyrolysis system. On the other hand, the water contents in the coconut shell are given in Fig. 5. It can be seen that their peak
pyrolysis liquid products, which result from the original moisture patterns are very similar, showing that their corresponding
in the feedstock and the product of the dehydration reactions functional groups should be also close. The presence of the
occurring during pyrolysis, could be high up to 30% [10], thus significant peaks between 1640 and 1700 cm 1 could be
lowering its heating value and bio-oil yield. Table 2 also shows ascribable to C–O (carbonyl) stretching vibration indicative of
that the pH values of the pyrolysis liquid products are in the the ketones, phenols, carboxylic acids or aldehydes, and/or
ranges of 2.1–3.3. The finding is in agreement with the results in represent C C stretching vibrations indicative of alkenes and
the literature; that is, pyrolysis liquid products generally contain aromatics. The peak at around 1517 cm 1 could be the cause of
substantial amounts of organic acids, mostly acetic acid and C C stretching vibrations indicative of alkenes and aromatics.
formic acid, which results in a pH of 2–3 [10,23]. The results Below 1500 cm 1, all bands are complex and have their origin
described above were further demonstrated with the elemental in a variety of vibrational modes. C–H stretching and bending
analyses of pyrolysis liquid products. From the data in Table 3, vibrations between1380 and 1465 cm 1 indicate the presence
the carbon, hydrogen and oxygen contents of the pyrolysis liquid of alkane groups in pyrolysis oils derived from biomass.
products are 8–10%, 7–8% and 43–48%, respectively. Therefore, the band at 1395 cm 1 is ascribable to bending
Obviously, the pyrolysis liquid product contains considerable vibrations for CH3 groups. Absorptions possibly due to C–O
amounts of water and oxygenated component, resulting in higher vibrations from carbonyl components (i.e., alcohols, esters,
H/C molar ratios than the feeding precursors (see Table 1) and carboxylic acids or ethers) occur between 1300 and 900 cm 1.
Table 3
Comparisons on major element analysis of the pyrolysis productsa
Element Liquid (wt.%) Residual solid (wt.%)
Rice straw Sugarcane bagasse Coconut shell Rice straw Sugarcane bagasse Coconut shell
Carbon 8.39 10.36 10.29 49.29 71.41 69.33
Hydrogen 7.21 7.68 7.01 2.83 3.32 3.26
Nitrogen 0.08 0.18 0.27 1.32 1.77 0.94
Oxygen 49.85 46.19 43.22 15.15 15.46 15.29
a
Obtained at heating rate of 200 8C/min, pyrolysis temperature of 500 8C, holding time of 8 min, particle size of <0.50 mm, nitrogen flow rate of 1000 cm3/min,
and condensation temperature of 10 8C.
W.T. Tsai et al. / J. Anal. Appl. Pyrolysis 76 (2006) 230–237 235
Fig. 6. GC–MS chromatogram of the pyrolysis liquid products from (a) rice
straw, (b) sugarcane bagasse, and (c) coconut shell.
Table 4
Tentative GC–MS characterization of pyrolysis liquid products from biomass wastesa
Peak no. tRb (min) Component % Area
Rice straw Sugarcane bagasse Coconut shell
1 14.4 Acetic acid (C2H4O2) 0.9 7.6 3.6
2 21.8 Furan, 2,5-dimethyl- (C6H8O) 3.1 0.4 0.5
3 23.1 2-Furanmethanol (C5H6O2) 1.6 1.3 1.1
4 24.5 2H-pyran, 3,4-dihydro (C5H8O) 1.6 1.2 1.1
5 25.7 2(3H)-furanone, 5-methyl- (C5H6O2) 1.4 1.6 1.1
6 27.8 Phenol (C6H6O) 1.7 1.3 7.8
7 29.7 1,2-Cyclopentanedione-3-methyl- (C6H8O2) 4.9 2.5 2.6
8 32.1 Phenol, 2-methoxy- (C7H8O2) 3.1 1.5 1.3
9 32.7 Maltol (C6H6O3) 0.8 0.4 1.3
10 33.0 2-Cyclopentan-1-one, 3-ethyl-2-hydroxy- (C7H10O2) 1.2 0.8 0.6
11 34.3 Phenol, 4-ethyl- (C8H10O) 1.8 1.3 0.7
12 35.2 1,2-Benzenediol (C6H6O2) 1.5 5.7 8.6
13 35.9 Benzofuran, 2,3-dihydro- (C8H8O) 3.1 5.7 1.6
14 37.2 1,2-Benzenediol, 3-methyl- (C7H8O2) 2.4 2.8 2.7
15 37.7 1,2-Benzenediol, 3-methoxy- (C7H8O3) 1.1 1.9 1.5
16 38.2 Phenol, 4-ethyl-2-methoxy- (C9H12O2) 0.9 0.3 0.2
17 39.2 4-Hydroxy-3-methylacetophenone (C9H10O2) 1.3 0.6 0.7
18 40.0 Phenol, 2,6-dimethoxy (C8H10O3) 2.0 2.9 2.8
19 41.7 Benzaldehyde, 3-hydroxy-4-methoxy (C8H8O3) 0.7 0.2 0.5
20 44.0 Phenol, 2-methoxy-4-(1-propenyl)- (C10H12O2) 0.4 0.2 0.2
21 44.9 Ethanone, 1-(4-hydroxy-3-methoxyphenyl)- (C9H10O3) 0.1 0.1 0.2
22 46.1 2-Propanone, 1-(4-hydroxy-3-methoxypheny)- (C10H12O3) 0.4 0.3 0.8
23 49.1 Benzeneacetic acid, 4-hydroxy-3-methoxy- (C9H10O4) 0.2 0.3 0.2
24 51.1 Phenol, 2,6-dimethoxy-4-(2-propenyl)- (C11H14O3) 0.1 0.2 0.5
Total 37.6 41.1 42.2
a
Obtained at heating rate of 400 8C/min, pyrolysis temperature of 500 8C, holding time of 1 min, particle size of <0.50 mm, nitrogen flow rate of 1000 cm3/min,
and condensation temperature of 10 8C.
b
See Fig. 6.
the capture in the present cryogenic system. Further studies on It was found that the yield of liquid tar product from sugarcane
the GC–MS analyses of the resulting gases would be helpful to bagasse was higher than those of rice straw and coconut shell.
elucidate the fast pyrolysis system. From the results of FT-IR Employing the higher pyrolysis temperature of >500 8C, faster
and GC–MS analyses, it can be concluded that the pyrolysis heating rate of >200 8C/min, and longer holding time of
liquid products are extremely complex and may be composed of >2 min, the pyrolysis tar yield reached a maximum of ca. 50%.
hundreds of organic compounds. The main components of the All analytical results of the resulting pyrolysis products
pyrolysis liquid products include acids, phenols, ketones, analyzed by elemental analyzer, pH meter and bomb
aldehydes, ethers, and some species of aromatics, which are in calorimeter are in consistence with those analyses by FT-IR
accordance with those obtained from the fast pyrolysis of spectroscopy and GC–MS. However, it was noted that the
woods [25–27]. The presence of these aromatic and oxygenated pyrolysis liquid product contains a significant amount (>65%)
compounds is attributable to its biopolymer textures such as of water, and fewer contents of complex compounds mostly
cellulose and hemicellulose. These results are consistent with composed of aromatic and carbonyl structures, resulting in low
the elemental compositions and chemical characterization of pH and low heating values. The results therefore indicate that a
the pyrolysis liquid products previously presented in Tables 2 large quantity of water evolves within a short time due to the
and 3 and Figs. 2–4, that showed high water and oxygenated water content of biomass feedstock and dehydration reaction in
contents and low heating values. Obviously, the highly the fast pyrolysis process. GC–MS analyses have shown that
oxygenated organic components would need to be first carboxylic acids, phenols, alcohols and branched oxygenated
separated from the water phase, and then upgraded using hydrocarbons are the main compounds of the bio-oil. It is
hydrotreating–hydrocracking process in order to further raise necessary that the resultant liquid product would need further
their heating values and reduce the corrosiveness when they are processing to remove the condensed water for chemical
used as a potential fuel. feedstock and/or biofuel production.
4. Conclusions Acknowledgement
In this study, fast pyrolysis experiments of three biomass This research was partly supported by NSC (National
wastes including rice straw, sugarcane bagasse and coconut Science Council), Taiwan, under contract no. NSC 92-2623-7-
shell were conducted in a fixed-bed induction-heating system. 041-001-ET.
W.T. Tsai et al. / J. Anal. Appl. Pyrolysis 76 (2006) 230–237 237
References [15] W.T. Tsai, Y.H. Chou, Y.M. Yang, Renew. Sustain. Energy Rev. 8 (2004)
22.
[1] P. McKendry, Bioresour. Technol. 83 (2002) 37. [16] A.E. Putun, A. Ozcan, E. Putun, J. Anal. Appl. Pyrol. 52 (1999) 33.
[2] J.M. Ebeling, B.M. Jenkins, Trans. ASAE 28 (1958) 898. [17] O. Onay, S.H. Beis, O.M. Kockar, J. Anal. Appl. Pyrol. 58/59 (2001) 995.
[3] B.M. Jenkins, L.L. Baxter, T.R. Miles Jr., T.R. Miles, Fuel Process [18] Y. Shinogi, Y. Kanri, Bioresour. Technol. 90 (2003) 241.
[19] C. Acikgoz, O. Onay, O.M. Kockar, J. Anal. Appl. Pyrol. 71 (2004) 417.
Technol. 54 (1998) 17.
[4] D.L. Klass, Biomass for Renewable Energy, Fuels, and Chemicals, [20] F. Ates, E. Putun, A.E. Putun, J. Anal. Appl. Pyrol. 71 (2004) 779.
Academic Press, San Diego, 1998, pp. 225–331. [21] M.F. Laresgoiti, B.M. Caballero, I. de Marco, A. Torres, M.A. Cabrero,
[5] A. Demirbas, Energy Convers. Manage. 42 (2001) 1357. M.J. Chomon, J. Anal. Appl. Pyrol. 71 (2004) 917.
[22] W.T. Tsai, C.Y. Chang, S.L. Lee, Carbon 35 (1997) 1198.
[6] P. McKendry, Bioresour. Technol. 83 (2002) 47.
[7] R. Gross, M. Leach, A. Bauen, Environ. Int. 29 (2003) 105. [23] A.V. Bridgwater, D. Meier, D. Radlein, Org. Geochem. 30 (1999) 1479.
[8] A.V. Bridgwater, S.A. Bridge, in: A.V. Bridgwater, G. Grassi (Eds.), [24] A. Torres, I. de Marco, B.M. Caballero, M.F. Laresgoiti, M.A. Cabrero,
M.J. Chomon, J. Anal. Appl. Pyrol. 58/59 (2001) 189.
Biomass Pyrolysis Liquids Upgrading and Utilization, Elsevier Applied
[25] J. Piskorz, D.S. Scott, D. Radlein, in: E.J. Soltes, T.A. Milne (Eds.),
Science, London, 1991, pp. 11–92.
[9] G. Maschio, C. Koufopanos, A. Lucchesi, Bioresour. Technol. 42 (1992) Pyrolysis Oils from Biomass—Producing, Analyzing, and Upgrading,
219. ACS Symposium Series 376, American Chemical Society, Washington,
DC, (1988), pp. 168–178.
[10] S. Czernik, A.V. Bridgwater, Energy Fuels 18 (2004) 228.
[11] D. Meier, O. Faix, Bioresour. Technol. 68 (1999) 71. [26] D.S. Scott, J. Piskorz, D. Radlein, in: R.M. Rowell, T.P. Schultz, R.
[12] S. Warnijati, I.B. Agra, Sudjono, Renew. Energy 9 (1996) 934. Narayan (Eds.), Emerging Technologies for Materials and Chemicals from
[13] P.T. Williams, N. Nugranad, Energy 25 (2000) 493. Biomass, ACS Symposium Series 476, American Chemical Society,
Washington, DC, (1992), pp. 422–436.
[14] M. Garcia-Perez, A. Chaala, C. Roy, J. Anal. Appl. Pyrol. 68 (2002)
111. [27] X. Dai, C. Wu, H. Li, Y. Chen, Energy Fuels 14 (2000) 552.