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J. Anal. Appl.

Pyrolysis 76 (2006) 230–237


www.elsevier.com/locate/jaap

Fast pyrolysis of rice straw, sugarcane bagasse and coconut shell in


an induction-heating reactor
W.T. Tsai a,*, M.K. Lee b, Y.M. Chang a
a
Department of Environmental Engineering and Science, Chia Nan University of Pharmacy and Science, Tainan 717, Taiwan
b
Department of Occupational Safety and Health, Chia Nan University of Pharmacy and Science, Tainan 717, Taiwan
Received 11 April 2005; accepted 9 November 2005
Available online 24 January 2006

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

1. Introduction combustion. The biomass energy led to the developments of


various thermo-chemical processes for producing bio-fuels
Since the energy crisis in the mid-1970s, the energy from lignocellulosic biomass [4–7].
utilization from biomass resources (called biomass energy) has Pyrolysis, a promising route for biomass utilization, has
received considerable attention. The energy obtained from been widely used for converting biomasses into fuel gases,
agricultural wastes or agricultural by-products is a form of liquids and solids among the thermo-chemical technologies.
renewable energy; in principle, utilizing this energy does not Generally, there are two approaches for the conversion
add carbon dioxide, which is a greenhouse gas, to the technology. One approach, referred to as conventional or
atmospheric environment, in contrast to fossil fuels [1]. Like traditional pyrolysis, is to maximize the yield of fuel gas at the
other biomass wastes, agricultural wastes contain a high preferred conditions of high temperature, low heating rate and
amount of organic constituents (i.e., cellulose, hemicellulose long gas resistance time, or to enhance the char production at
and lignin) and possess a high-energy content [2,3]. Therefore, the low temperature and low heating rate. Another approach,
it can be recognized as a potential source of renewable energy known as flash or fast pyrolysis, is to maximize the yield of
based on benefits of both energy recovery and environmental liquid product at the processing conditions of (1) very high-
protection. Due to the lower contents of sulfur and nitrogen in heating rate (>100 8C/min) and heat transfer rate, (2) finely
biomass wastes, its energy utilization also creates less ground biomass feed (<1 mm), (3) carefully controlled
environmental pollution and health risk than fossil fuel temperature (around 500 8C), and (4) rapid cooling of the
pyrolysis vapors to give the bio-crude products. Fast pyrolysis
of biomass solid-waste is at present considered as an emerging
* Corresponding author. Tel.: +886 6 2660393; fax: +886 6 2669090. energy technology for liquid-tar and solid-char production [8–
E-mail address: wwtsai@mail.chna.edu.tw (W.T. Tsai). 11]. However, the pyrolysis oil from biomass was found to be
0165-2370/$ – see front matter # 2006 Published by Elsevier B.V.
doi:10.1016/j.jaap.2005.11.007
W.T. Tsai et al. / J. Anal. Appl. Pyrolysis 76 (2006) 230–237 231

highly oxygenated and complex, and chemically unstable. Table 1


Main characteristics of biomass wastes fed
Thus, the liquid products still need to be upgraded by lowering
the oxygen content and removing residues. Characteristics Rice Sugarcane Coconut
In addition, induction heating has been applied in various straw bagasse shell
technological and scientific fields such as preheating, thermal Proximate analysisa (wt.%)
treatment, melting and welding processes because of its Moisture 13.61 16.07 11.26
characteristics of rapid heating, direct heating, non-contact Combustible matter 76.85 79.59 85.36
Ash 9.54 4.34 3.38
heating, and precision control. Therefore, induction heating has
also been considered as an alternative to carry out the pyrolysis Ultimate analysisb (wt.%)
in comparison with other fast/flash pyrolysis systems due to its Carbon 50.93 58.14 63.45
Hydrogen 6.04 6.05 6.73
high-energy efficiency and low air pollution [11]. With respect Nitrogen 0.83 0.69 0.43
to the production of bio-crude from the fast pyrolysis of Sulfur 0.23 0.19 0.17
agricultural wastes using induction heating, the information Chlorine 0.36 0.36 0.95
published is limited. The pyrolysis of coconut shells was Oxygenc 41.61 34.57 28.27
studied in a concentric three tubes reactor using a combination Heating value analysis (MJ/kg) 16.35 18.61 22.83
of external and internal heating method [12]. It was found that a
As prepared (air-dried, sand and fines free and ground <0.5 mm).
the less charcoal and light oil, the more tar were produced at the b
Elemental composition in the combustible matter, on a dry basis.
higher temperature and longer time of pyrolysis. The pyrolysis c
Calculated by difference.
of rice husk was investigated in a fluidized bed reactor with and
without ZSM-5 catalyst at 400–600 8C [13], showing that the 2.2. Pyrolysis experiments
uncatalyzed pyrolysis bio-oil was found to be highly
oxygenated and chemically complex. In the presence of the The fixed-bed fast pyrolysis experiments were performed in
catalyst the yield of bio-oil was markedly reduced; however, the a horizontally and externally heated tubular reactor (3.67 cm
oxygen content of the bio-oils was significantly reduced due to i.d. and 60 cm long), constructed from 310 stainless steel and
the evolution of catalytic gases such as H2O, CO and CO2. The heated by high-frequency generator (i.e., induction heating),
vacuum pyrolysis of sugarcane bagasse was performed at which is shown schematically in Fig. 1. For all experiments, the
bench- and pilot-scale plants [14]. In comparison with the yield mass (10 g, in each set of experiments) of the sample was
of charcoal at about 20 wt.%, the resulting bio-oil with the placed into a crucible made of stainless steel, and then housed at
recovery of about 30 wt.% (bagasse anhydrous basis) could be the center of the tubular reactor. During the experiments,
found to be a potential liquid fuel. In this study, the fast temperature was measured above the bed, with a K-type
pyrolysis of rice straw, sugarcane bagasse and coconut shell, thermocouple in the middle of the tubular reactor in order to
which are the most primary agricultural wastes in Taiwan [15], control and monitor the reactor temperature.
was investigated in an externally heated fixed-bed furnace to The sweep gas from a nitrogen cylinder was dried and
assess the product yield. The influences of pyrolysis purified by a molecular sieve tube. The constant nitrogen flow
temperature, heating rate and holding time at specified rate (ca. 1000 cm3/min) was precisely metered to the
temperature were studied so as to obtain useful data for the experimental system using a mass flow controller. The
optimal design in the induction-heating process. In addition, the experimental conditions in the fast pyrolysis system were as
pyrolysis products obtained at the conditions of the maximum follows: pyrolysis temperature of 400–800 8C, heating tem-
product yields were further analyzed, using elemental, Karl– perature of 100–500 8C/min, and holding time (at the specified
Fischer, thermal and spectroscopic methods, to determine its
possibility of being a potential source of renewable fuels.

2. Experimental

2.1. Feed materials

The biomass samples used as the feedstock for experi-


mental runs were rice straw, sugarcane bagasse and coconut
shell that were mainly obtained from a farm in southern
Taiwan. These samples were first dried in the sunshine for the
purpose of removing most of moistures, and then separated
from physical impurities such as sand and fine fraction.
Finally, the samples that were ground in a rotary cutting mill Fig. 1. Schematic diagram of the fast pyrolysis system: (1) nitrogen gas
were further screened into fractions of particle diameter cylinder; (2) regulator; (3) molecular sieve column; (4) mass flow controller;
(5) flexible heating tape; (6) power system (high-frequency generator); (7)
<0.50 mm. Each prepared sample was closely stored in glass tubular reactor (including induction coil); (8) temperature controller; (9) K-type
bottles. Their results of proximate, ultimate and thermal thermocouple; (10) temperature recorder; (11) cryogenic condensation (ethy-
analysis are given in Table 1. lene glycol/water system); (12) liquid product collectors.
232 W.T. Tsai et al. / J. Anal. Appl. Pyrolysis 76 (2006) 230–237

pyrolysis temperature) of 1–8 min. The resulting products after


fast pyrolysis were cooled to room temperature using a
cryogenic system ( 10 8C) with ethylene glycol solution, and
then taken from holding crucible and condensable collectors in
order to weigh the masses of residual solid and liquid tar,
respectively. The yields of the resulting products were thus
calculated based on the mass of the sample fed.

2.3. Characterization

Elemental analyses of elements of C/H/N and O were carried


out on the resulting products (i.e., liquid and residual solid) with
a CHN-O-RAPID Element Analyzer (Heraeus Co., Germany).
Prior to the measurement, the standard sample was first
analyzed for checking the experimental error within 1%. The
water content of the liquid product was measured using Karl–
Fischer moisture titrator (Model: MKS-510; Kyoto Electronics
Manufacturing Co., Japan) at least twice. The calorific values of
the liquid product and residual solid were also determined by
using a bomb calorimeter (Model: C2000 basic, IKA Co.,
Germany). Regarding the corrosion of the liquid product, the
pH of the pyrolysis liquid product was measured using a pH
meter (Model: SP-701, Suntex Co., Taiwan).
In order to settle down char traces from liquid phase in the
crude pyrolysis liquids, the pyrolysis liquid products were first
decanted and then centrifuged for 15 min at about 2000 rpm
prior to the chromatographic and spectrometric analyses.
Functional group analysis of the pretreated pyrolysis liquid
product was carried out using Fourier transform infrared (FT- Fig. 2. Dependence of water, bio-oil and char yields based on a wet basis from
(a) rice straw, (b) bagasse, and (c) coconut shell on pyrolysis temperature at a
IR) spectrometry (Model: DA8.3, Bomen Co., Canada).
heating rate of 200 8C/min, holding time of 1 min, particle size of <0.50 mm,
The gas chromatography/mass spectroscopy (GC–MS) nitrogen flow rate of 1000 cm3/min, and condensation temperature of 10 8C.
analysis of the pretreated pyrolysis liquid product was
performed with a Hewlett-Packard HP 5890-Series II gas
chromatograph equipped with a Hewlett-Packard HP 5972A a declining trend as the final pyrolysis temperature increased
mass selective detector (MS), using a 60 m  0.25 mm HP-1 from 400 to 800 8C because of the progressive pyrolysis
capillary column (0.25 mm film thickness). The following conversion at the higher temperature. However, the rate of
temperature program was adopted: initial, intermediate and declination in the ranges of 500–800 8C is not so fast as that in
final temperatures were 35, 200 and 350 8C, respectively, times the ranges of 400–500 8C (i.e., 74–38% versus 38–21% in rice
at initial, intermediate and final temperatures were 5, 5, and straw; 65–33% versus 33–21% in sugarcane bagasse; 75–38%
2 min, respectively, and heating rates were 5 and 10 8C/min, versus 38–25% in coconut shell). On the other hand, the total
respectively. The injector temperature and detector temperature yield of liquid products (water and bio-oil) slightly increased in
were 250 and 280 8C, respectively. The following parameters the rages of the pyrolysis temperature. As expected, the total
were used for the integration of the GC–MS chromatograms: yield of liquid products significantly increased as the pyrolysis
initial area rejection = 0, initial peak width = 0.058, and initial temperature was raised from 400 to 500 8C (i.e., 15% versus
threshold (to determine the sensitivity of the integrator) = 14.9. 38% in rice straw; 23% versus 47% in sugarcane bagasse; 12%
The oil sample (ca. 0.2 ml) was injected with a Hamilton versus 36% in coconut shell). The results showed that most of
syringe. The MS operated in scan mode and its mass range was volatile pyrolysis products from the feeding samples were
45–500 amu. evolved at temperatures lower than 500 8C, which was also
observed at other biomass wastes in the literature [16–21].
3. Results and discussion Further, the pyrolysis liquid products contained large amounts
of water (73–92 wt.%) obtained from the measurements by the
3.1. Product yield Karl–Fischer moisture titrator, resulting in the low yield of bio-
oil from these biomass wastes as shown in Fig. 2. The high
The yields of resulting products from fast prolysis of rice water content in the pyrolysis liquid product may be due to the
straw, sugarcane bagasse and coconut shell were discussed for high moisture content in the feeding biomasses and the release
examining the effect of pyrolysis temperature, heating rate and of volatile organic products during the preparation of
holding time. As shown in Fig. 2, the yield of residual solid had condensed liquid sample.
W.T. Tsai et al. / J. Anal. Appl. Pyrolysis 76 (2006) 230–237 233

To determine the effect of heating rate on the yields of the


pyrolysis products, the experiments were conducted at a
heating rate of either 100, 200, 300, 400 or 500 8C/min at the
final pyrolysis temperature of 500 8C and its holding time of
1 min. Fig. 3 shows that the variations of yields in the liquid
products and residual solid were observed in the cases of rice
straw, sugarcane bagasse or coconut shell. It can be seen that the
larger yield of solid product was generally obtained at the
higher heating rate, which was also consistent with the
literature [16–21]. The pyrolysis liquid products still contained
large amounts of water (70–86 wt.%). The bio-oil liquid yields
(lower than 14 wt.%) seemed to be extremely lower than those
(60–80 wt.%) carried out by other fast pyrolysis just because
the former is based on wet basis in comparison to the later based
on wet basis. However, it was reported that the yield of bio-oil
ranging 13–17 wt.% was obtained from the fast pyrolysys of
rape seed at 100–800 8C/min [17].
As shown in Fig. 4, it seems that the holding time at the final
prolysis temperature of 500 8C and heating rates of 200 8C/min
plays a somewhat important role in the manufacture of
pyrolysis products from rice straw, sugarcane bagasse, or
coconut shell. Obviously, the lower yield of pyrolysis char
product was observed at the longer holding time, which should
be attributed to the progressive gasification and/or thermal
cracking of the pyrolysis product [22]. On the other hand, the

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.

pyrolysis liquid products again contained large amounts of


water (65–87 wt.%), resulting in the low yield of bio-oil (below
16 wt.%). It was also found that the total yield of liquid product
produced from sugarcane bagasse was higher than that from
rice straw and coconut shell.

3.2. Chemical characterization

The liquid products obtained in the fast pyrolysis of rice


husk, sugarcane bagasse and coconut shell, which are usually
termed crude bio-oils, are red-brown-colored products with
irritable odor. The appearance and odor are common to all
pyrolysis liquid products from biomass wastes [23]. The
calorific values and pH of the liquid products obtained at typical
pyrolysis conditions are presented in Table 2. The results listed
in Table 2 also present the calorific values of the residual solids.
It can be seen that the calorific values (i.e., 4.6–10.3 MJ/kg on
the wet basis) of the pyrolysis liquid products are not as high as
those of commercial heating oils (30–40 MJ/kg on the dry
basis), showing that they should contain lots of non-
Fig. 3. Dependence of water, bio-oil and char yields based on a wet basis from
(a) rice straw, (b) bagasse, and (c) coconut shell on heating rates at a pyrolysis hydrocarbons and condensed water as described above.
temperature of 500 8C, holding time of 1 min, particle size of <0.50 mm, However, the calorific values (i.e., 20–29 MJ/kg) of the
nitrogen flow rate of 1000 cm3/min, and condensation temperature of 10 8C. residual solids are rather high, even higher than those of their
234 W.T. Tsai et al. / J. Anal. Appl. Pyrolysis 76 (2006) 230–237

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.

liquid products are such an unknown and complex mixture of


organic compounds that no calibration of the MS detector was
set, mainly due to the lack of an appropriate standard mixture
for calibration [21,24]. Table 4 lists the tentative compounds of
pyrolysis liquid products, which are the most probable
Fig. 5. FT-IR spectra of the pyrolysis liquid products from (a) rice straw, (b) compounds identified by the MS search file (HP MS
sugarcane bagasse, and (c) coconut shell.
ChemStation). The compounds have been numbered in
Fig. 6 so that each compound has the same number in
Notably, the band at 1278 cm 1 may be connected with –C–O– Table 4. The empirical formulae and their molecular weights
C– (e.g., ethers). In the study of this spectral region described are also included in Table 4. In view of the results presented in
above, FT-IR analysis might be used as a fast screen technique Table 4, it can be seen that, as expected, the chemical
to observe the extent of carbonyl group or oxygen content. compositions of pyrolysis bio-oils are very similar to the
Furthermore, some features in the elemental, calorific, pH and inclusion of a lot of aromatics and oxygenated compounds such
FT-IR analyses could be further demonstrated with the GC–MS as carboxylic acids, phenols, ketones, etc. For a preliminary
analysis. study, a corresponding GC–MS of pyrolysis gas sample was
GC–MS analysis was carried out in order to get an idea of also performed in order to investigate the presence of
the nature and type of organic compounds in the pyrolysis condensable or non-condensable compounds in the vent gas.
liquid products. Due to the rather similar peak patterns of It was found that the pyrolysis gas still contains a comparatively
chromatograms of the pyrolysis liquid products obtained at the small amount of condensable organic compounds such as
other pyrolysis parameters, Fig. 6 shows, for example, the GC– aromatic hydrocarbons (e.g., benzene, 2-methyl-furan and
MS chromatograms of the pyrolysis liquid products obtained at toluene). This result explains why at the pyrolysis conditions
a heating rate of 200 8C/min, pyrolysis temperature of 500 8C, total yields of water, bio-oil and char were about 75%, since at
holding time of 1 min, particle size of <0.50 mm, and the pyrolysis conditions, all noncondensable and few con-
condensation temperature of 10 8C. Clearly, the pyrolysis densable products were vented, resulting in the difficulty with
236 W.T. Tsai et al. / J. Anal. Appl. Pyrolysis 76 (2006) 230–237

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

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