Catalytic effects of eight inorganic additives on pyrolysis of pine wood

sawdust by microwave heating

Ming-qiang Chen
a,
*, Jun Wang
a
, Ming-xu Zhang
a
, Ming-gong Chen
a
, Xi-feng Zhu
b,
**,
Fan-fei Min
a
, Zhi-cheng Tan
c,***
a
Department of Chemical & Material Engineering, Anhui University of Science and Technology, Huainan, Anhui 232001, China
b
Laboratory of Biomass Clean Energy, University of Science and Technology of China, Hefei 230026, China
c
Thermochemistry Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
1. Introduction
Biomass is a kind of renewable energy source. The forestry
residues and crop stalks are rich biomass resources in rural areas of
China and they are mostly burned directly or abandoned. We are
suffering from not only the low biomass resource utilization
efciency but the severe environmental pollution at present.
Among many efforts being made to solve this problem in China,
efcient and clean technologies for the biomass utilization are
greatly encouraged.
As a matter of fact, conversion routes for producing energy
carriers from biomass are plentiful. Main conversion options for
biomass to secondary energy carriers fall into two categories, one is
thermochemical conversion technologies which include combus-
tion, gasication and pyrolysis and the other is biochemical
conversion technologies which include digestion and fermentation.
Pyrolysis converts biomass at temperatures around 500 8C in
absence of oxygen to liquid (bio-oil), gaseous and solid (char)
fractions whose yields depend on pyrolysis condition, however.
With fast pyrolysis technology the liquid fraction can be
maximized. Pyrolysis now receives increasing attention as a
pre-treating step for long distance transport of bio-oil that can be
used in further conversion (e.g. efcient power generation or
gasication for syngas production). In addition, pyrolysis is also an
inseparable initial process of combustion and gasication.
Gasication as a means to covert a diversity of solid fuels to
combustible gas or syngas is receiving increasing attention
worldwide. Tar from gasication process through initial pyrolysis
is an undesired fraction for it can cause corrosion and blocking of
the successive apparatuses and also pollution of the producer gas.
Tar can also be utilized as elementary fuels or chemical resources.
J. Anal. Appl. Pyrolysis 82 (2008) 145150
A R T I C L E I N F O
Article history:
Received 3 August 2007
Accepted 4 March 2008
Available online 13 March 2008
Keywords:
Pyrolysis
Pine wood
Biomass
Microwave
Additives
A B S T R A C T
In this paper, pyrolysis of pine wood sawdust was carried out by microwave heating at ca. 470 8C under
dynamic nitrogen atmosphere. Eight inorganic additives (NaOH, Na
2
CO
3
, Na
2
SiO
3
, NaCl, TiO
2
, HZSM-5,
H
3
PO
4
, Fe
2
(SO
4
)
3
) were investigated in terms of their catalytic effects on the pyrolysis. All of the eight
additives have increased yields of solid products greatly and decreased yields of gaseous products more
or less. Yields of liquid products have not subjected to dramatic change. The incondensable gases
produced frompyrolysis consist mainly of H
2
, CH
4
, COand CO
2
. All of the eight additives have made these
gases evolve earlier, among which the four sodium additives have the most marked effect. All the
additives have made the amount of CH
4
and CO
2
decrease, while all of them except NaCl, TiO
2
and
Fe
2
(SO
4
)
3
have made that of H
2
increase and all of themexcept Na
2
SiO
3
and HZSM-5 have made that of CO
decrease. Alkaline sodium compounds NaOH, Na
2
CO
3
and Na
2
SiO
3
favor H
2
formation most. The most
abundant organic component in the liquid products from pyrolysis of untreated sample and samples
treated by all the additives except H
3
PO
4
and Fe
2
(SO
4
)
3
is acetol. All the four sodium compounds favor
acetol formation reaction and the selection increasing effect follows the order of
NaOH > Na
2
CO
3
Na
2
SiO
3
> NaCl. TiO
2
goes against the formation of acetol, HZSM-5 has no marked
effect on acetol formation. The two dominant organic components identied in the liquid products from
pyrolysis of H
3
PO
4
and Fe
2
(SO
4
)
3
treated samples are both fufural and 4-methyl-2-methoxy-phenol. A
possible pathway for acetol formation is tentatively proposed.
2008 Elsevier B.V. All rights reserved.
* Corresponding author. Tel.: +86 554 6668742; fax: +86 554 6668900.
** Corresponding author. Tel.: +86 551 3600040; fax: +86 551 3606689.
***Corresponding author. Tel.: +86 411 84379199; fax: +86 411 84685940.
E-mail addresses: mqchen@aust.edu.cn (M.-q. Chen), xfzhu@ustc.edu.cn
(X.-f. Zhu), tzc@dicp.ac.cn (Z.-c. Tan).
Cont ent s l i st s avai l abl e at Sci enceDi r ect
Journal of Analytical and Applied Pyrolysis
j our nal homepage: www. el sevi er . com/ l ocat e/ j aap
0165-2370/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2008.03.001
Removing tar in the biomass via pyrolysis at low temperature can
give rise to a tar free biomass semi-coke as further gasication
feedstock [15].
Since pyrolysis is an inevitable process of thermochemical
conversion technologies for biomass and plays a signicant role in
the biomass conversiontechnology development, in-depthresearch
for pyrolysis is of great importance. Pyrolysis of biomass can be
investigated focusing on various aspects among which catalytic
pyrolysis is gaining increasing interest. The use of catalysts or
additives to improve the yield or quality of gas or liquid fuels from
biomass is still in its infancy. While there is extensive fundamental
work underway [611] and more research is necessary to explore
the wide range of conventional and unconventional catalysts.
Another important aspect is heating source selection for
pyrolysis of biomass. Most research is conducted using conven-
tional heating method, i.e. external heating by conduction,
convection or radiation. Recently a novel heating method, i.e.
microwave heating has been employed by Miura et al. [12] to
pyrolyze wood blocks and interesting results which is different
from conventional heating has been obtained. Mcirowave irradia-
tion has also been applied by El har et al. [13] and Bilali et al. [14]
in the pyrolysis of oil shales and rock phosphate, respectively. The
former found that the oils produced by microwave heating is more
maltenic, less polar and contains less sulfur and nitrogen than
those obtained by conventional pyrolysis and the latter found that
more parafnic. Domnguez et al. [15] carried out microwave-
assisted pyrolysis of different sewage sludges and found that the
pyrolyzing oils have a high caloric value and a low proportion of
compounds of considerable environmental concern such as
polycycle aromatic hydrocarbons (PAHs).
Few studies have been conducted combining microwave
heating and additives adding[16]. Catalytic pyrolysis of pinewood
sawdust by microwave heating applying inorganic additives with
different basicity or acidity has been carried out in this study to
investigate their effects on yield distribution in gas, liquid and solid
phases and on composition and distribution of the uid phases.
2. Experimental
2.1. Biomass and catalysts
Proximate analysis and main component content of the pine
wood sawdust from Dabieshan mountain area, Anhui Province of
China determined by concentrated sulfuric acid method [17] are
given in Table 1.
Purity and properties of the additives employed are as
follows.
Na
2
CO
3
, A.R.; NaOH, A.R.; NaCl, A.R.; (Fe)
2
(SO
4
)
3
, A.R.; H
3
PO
4
,
A.R.; Na
2
SiO
3
, C.P., liquid product, provided by Huainan Inorganic
Chemical Plant; TiO
2
, anatase, average particle size = 30 nm,
specic area > 120 m
2
/g, purchased from Hehai Nanotechnology
Co. Ltd.; HZSM-5, 0.51.5 mm, SiO
2
/Al
2
O
3
= 59, specic area = 400
600 m
2
/g, purchased from Shanghai Huaheng Chemical Plant; SiC,
0.51 mm, provided by Shanghai Milling Material & Tool Co. Ltd.
2.2. Preparation of samples
6 g certain additive was put into 400 mL distilled water in a
beaker to make a solution or suspension, into which 60 g dry pine
wood sawdust was poured followed by vigorous stirring for ca.
5 min at room temperature. The mixture in the beaker was then
transferred to a tray to evaporate water and the left mixture was
subjected to drying at 105 8C until constant weight. The bare
sample was also subjected to drying in the same way. So the
samples thus prepared were water free.
2.3. Microwave pyrolysis
The heating source was a microwave generator with a frequency
of 2450 MHz. A quartz beaker-shaped reactor with a diameter of
12 cm and a height of 13 cm was put in the microwave cavity. The
reactant was 15 g untreated pine wood sawdust or 16.5 g treated
sawdust (15 g sawdust plus 1.5 g additive). 25 g SiC was used as the
microwave absorber for each run. Athin layer of sawdust was put at
the bottomof the reactor, and then it was covered by a thin layer of
SiC, which then was covered by another thin layer of sawdust. The
sawdust and SiC were put into the reactor alternatively like this in
order to obtain a uniform heating of sawdust samples. Each charge
contained about 15 layers of sawdust sample and 15 layers of SiC.
The condensable volatile was collected with three U-shaped tubes
immersed in the ice water. The permanent gases were collected
intermittently with several sampling bags. (The sampling timetable
was as indicatedinTable3.) Thereactor andtubesystemwas purged
byN
2
withaowrateof 0.2 m
3
/hfor 15 mintodriveawayair prior to
heating. The initial microwave power was controlled at 1 kW and
after the temperature measured by the pyrometer reached the set
temperature (350 8C) the power was regulated to a lower level
(about 0.3 kW) to maintain the set temperature. The temperature in
the inner part of the sample was about 120 8C higher than that
measured by the pyrometer. So the real pyrolysis temperature was
about 470 8C in average. (At the end of each run, a portable
thermocouple was inserted into the sample immediately after
microwave irradiation was shut off. The temperature measured this
way, which was ca. 120 8C higher than that measured by the
pyrometer, can reect the actual reaction temperature.) Most tar
was removedwithin8 min. Sothe total runtime was set at 12 minto
ensure all the tar removed.
2.4. Bio-oil from fast pyrolysis of pine wood
The bio-oil from fast pyrolysis of pine wood sawdust used in
this paper for comparison was provide by East China University of
Science and Technology, which was the crude bio-oil obtained by
fast pyrolysis in a conduit-spouting uidized reactor at 480 8C.
2.5. Analysis of gaseous and liquid products
The permanent gases were determined using a gas chromato-
graph GC9160 (Shanghai Huaai Gas Chromatograph Co. Ltd.) with a
TCD detector. A 5A molecular sieve column was employed for H
2
,
CH
4
andCOmeasurement andaPorapakRcolumnwas employedfor
CO
2
measurement. Temperature setting was as follows: injection
port: 100 8C, coloum: 100 8C, detector: 120 8C. The chromatogram
was calibrated with gases at known concentrations as standard
mixtures. Arepresentative fraction of the liquid product was diluted
by anhydrous-ethanol quantitatively to make the water content
lower than3 wt%andt for its measurement byGas Chromatograph
GC9160 employing the Porapak R column. Water measurement
condition was as follows: injection port: 260 8C, column: 170 8C,
detector (TCD): 260 8C. The real water content can be obtained by
multiply the measured value with the diluting ratio. The organic
composition of the liquid product was analyzed by GCMS (QP
Table 1
Proximate analysis and main components of pine wood sawdust on dry basis
V
d
(%) A
d
(%) FC
d
(%) Q
b, d
(MJ/kg) CL
d
(%) HC
d
(%) LN
d
(%)
81.98 2.16 15.86 19.92 40.32 26.73 30.97
V
d
, A
d
, FC
d
and Q
b, d
stand for volatile, ash, xed carbon and bomb caloricc value on
dry basis, respectively; and CL, HC and LN stand for cellulose, hemicellulose and
lignin, respectively.
M.- Chen et al. / J. Anal. Appl. Pyrolysis 82 (2008) 145150 146
5050A, Japan) after dehydrationby absorbent cotton and anhydrous
sodium sulfate. A capillary column (DB-17, 30 m 0.25 mm
i.d. 0.25 mm) was employed to separate organic mixtures.
Acetone was used as solvent to dilute the dehydrated liquid product
to a concentration appropriate for analysis. The detector tempera-
ture was set to 230 8C and that of injection was set to 300 8C. The
solvent cut time was set to 2 min. The temperature programwas as
follows: The temperature was kept constant at 60 8C for 4 min, then
raised to 140 8C with a heating rate of 10 8C/min. After that, the
temperature was raised to 148 8C with a slow heating rate of 1 8C/
min (to obtain a good separation at this stage). Finally the
temperature was raised to 280 8C with a fast heating rate of
33 8C/min and kept constant at 280 8C for 5 min.
The relative concentration of six identied compounds was
obtained by integrating the corresponding TIC peak area in the
chromatogram of the liquid pyrolysis product of each sample.
3. Results and discussion
3.1. Yields of gaseous, liquid and solid products
Table 2 shows that all of the eight additives, whether they are
basic, neutral or acidic, water soluble or insoluble, have increased
yields of solid products greatly and decreased yields of gaseous
products more or less. Liquid yields depend on the additive types.
Both NaCl and Fe
2
(SO
4
)
3
seemfavor liquid formation while Na
2
SiO
3
seemsgoagainst that. Therelativehighliquidyieldfor H
3
PO
4
treated
sample might be partly due to transfer of considerable part of added
H
3
PO
4
to the liquid since the boiling point of H
3
PO
4
is only slightly
higher than 200 8C. Other additives manifest no dramatic effect on
liquid yields. The solid yields increasing is in agreement with our
previous study [11] and is due to the char formation enhancing
effects of additives. The opposite changing direction of char and gas
yields and relative stable liquid yields can be partly explained by
Bradburyet al. model [18] sincethe formationof char andlight gases
is a competitive process bythis model. Comparedwithfast pyrolysis
of wood [19], liquid yields of this study is much lower. This might be
ascribedtotwofactors. Oneisthelower heatingrateinthis study(ca.
300 8C/min), which favors coke formation, and the other is the
relatively long vapor residence time (ca. 2.7 s gured out from
carrier gas owrate and the reactor size), which is an adequate time
period for a secondary decomposition of some heavy components
into light gases.
3.2. Catalytic effects on gas evolving
The incondensable gases produced from pyrolysis consist
mainly of H
2
, CH
4
, CO and CO
2
. All of the eight additives have
made these gases evolve earlier, among which the four sodium
additives have the most markedeffect (see Table 3). They have made
the maximum concentration of each gas species appear 4 or 6 min
(for NaOH and CO
2
) earlier compared with the bare pine wood
sawdust sample. Other additives have less apparent effect, however.
If we look upon the average concentration of each gas species
collected during the ve sampling periods as that of corresponding
gas species evolved during the total pyrolyzing period, we shall nd
the effects of different additives on yield of each gas species (see
Table 4). Interestingly, though the total yields of all gas species have
been decreased by additives, that of individual gas species is
subjected to different changing trend. Specically, all the additives
have made the yields of CH
4
and CO
2
decrease, while all of them
except NaCl, TiO
2
andFe
2
(SO
4
)
3
havemadethat of H
2
increaseandall
of them except Na
2
SiO
3
and HZSM-5 made that of CO decrease. It
also should be noted that alkaline sodium compounds NaOH,
Na
2
CO
3
and Na
2
SiO
3
favor H
2
formation most.
Pyrolysis process reactions can be expressed as follows [9].
Basic pyrolysis gasication reaction:
C
n
H
m
O
k

m
2
H
2
kCO n kC (1)
Further secondary gasication reactions:
C H
2
O H
2
CO (2)
C CO
2
2CO (3)
CO H
2
O H
2
CO
2
(4)
CH
4
H
2
O CO 3H
2
(5)
The inorganic additives inuence the basic pyrolysis reactions
resulting in earlier gas evolving and more semi-coke formation and
also leading to variation of primary gas composition, which would
then inuence the equilibria of the secondary gasication
reactions. Since all additives have decreased the yields of CO
2
and CH
4
, it might be inferred that CO
2
reduction reaction (3) and
CH
4
steam reforming reaction (5) had been intensied in the
catalytic pyrolysis gasication.
3.3. Catalytic effects on organic components of the liquid products
The total ion chromatograms (TICs) can be classied into three
types in terms of the organic component distribution. Type I are
those for bare sample and TiO
2
HZSM-5 treated samples; Type II
are those for NaOH, Na
2
CO
3
, Na
2
SiO
3
and NaCl treated samples,
characterized with large acetol peak area; Type III are those for
H
3
PO
4
and Fe
2
(SO
4
)
3
treated samples, characterized with two
dominant organic components. TICs for the bare sample, Na
2
CO
3
and Fe
2
(SO
4
)
3
treated samples were given in Figs. 13 to illustrate
the three types of TICs. In contrast, TIC of liquid product from fast
pyrolysis in a conduit-spouting uidized reactor is given in Fig. 4.
The peak areas of the 25 main organic components of each
liquid product have been obtained by integration of theTICs for
comparison of the catalytic effects of different additives on main
organic components of the liquid products.
Firstly, although the composition of the organic products is
complex, only a couple of components dominate in the organic
liquid products frompyrolysis by microwave heating. The type and
concentration of the dominant components are governed by
additive types. Table 5 shows the effects of different additives on
the relative concentration of the six organic components in the
liquid products, i.e. acetol (1-hydroxy-2-propanone), furfural, 2-
furanmethanol, 4-methyl-2-methoxy-phenol (4-methyl-guaiacol),
2-methoxy-phenol (guaiacol) and levoglucosan (LG), respectively.
These six organic components were identied in the liquid
Table 2
Liquid, gas and solid yields from pyrolysis of pinewood sawdust by microwave
heating
Catalyst Liquid yield (%)
a
Solid yield (%)
b
Gas yield (%)
c
Water (%)
d
Untreated 22.7 17.3 60.0 30.1
NaOH 20.0 36.0 44.0 31.1
Na
2
CO
3
22.0 33.3 44.7 28.2
Na
2
SiO
3
16.0 34.0 50.0 29.6
NaCl 26.0 34.7 39.3 28.9
TiO
2
22.7 40.3 36.7 26.8
HZSM-5 17.3 26.7 56.0 28.8
H
3
PO
4
25.3 38.7 36.0 30.5
Fe
2
(SO
4
)
3
26.0 36.7 37.3 27.7
a
Liquid yield = liquid weight/net weight of biomass 100%.
b
Net weight of char residue/net weight of biomass 100%.
c
By difference.
d
Water content in liquid product.
M.- Chen et al. / J. Anal. Appl. Pyrolysis 82 (2008) 145150 147
products with very high similarity of their mass spectra to the
corresponding pure substances ones in NIST107. The most
abundant organic component of the liquid products frompyrolysis
of untreated sample and samples treated by all the additives
except H
3
PO
4
and Fe
2
(SO
4
)
3
is acetol. All the four sodium
compounds favor acetol formation reaction and the selection
increasing effect follows the order of NaOH > Na
2
CO
3

Na
2
SiO
3
> NaCl, which indicates that the more basic the sodium
compound is, the more abundant the corresponding acetol is.
However, strong bases (NaOH, Na
2
CO
3
and Na
2
SiO
3
) can restrain
the formation of furfural, 2-furanmethanol, 4-methyl-2-methoxy-
phenol and levoglucosan. TiO
2
goes against the formation of acetol,
HZSM-5 has no marked effect on acetol formation. 2-Methoxy-
phenol was identied in the liquid products from pyrolysis of all
the nine samples and all the additives except Na
2
SiO
3
, HZSM-5,
H
3
PO
4
and Fe
2
(SO
4
)
3
have not changed its relative concentration
percentages to a large degree. The two dominant organic
components identied in the liquid products from pyrolysis of
H
3
PO
4
and Fe
2
(SO
4
)
3
treated samples are both fufural and 4-
methyl-2-methoxy-phenol (4-methyl-guaiacol). The total relative
concentration of these two components is up to 80%. Other
components are much less abundant.
Secondly, we can nd that the dominant components in the
liquid products from catalytic and non-catalytic pyrolysis by
microwave heating are quite different from those from conven-
tional fast pyrolysis of the bare sample. It was found that
levoglucosan (18.93%) is the dominant component in the bio-oil
from conduit-spouting uidized bed reactor. Compared with the
pyrolysis by microwave heating, the distribution of the organic
components in the liquid product from the uidized reactor is
more dispersive. Some other studies concerning pyrolysis of
lignocellusic biomass by conventional heating also show quite
different distribution of organic components from ours. For
example, Liao et al. [20] and Wang et al. [21] found that the most
abundant organic component in the liquid product obtained by fast
pyrolysis of cellulose (the most abundant component in wood)
is levoglucosan (LG), followed by acetaldehyde and acetol.
Table 3
Concentration of gases evolved during different period (%mol/mol)
S.T.P.
a
(min) 2.003.50 4.005.50 6.007.50
H
2
CH
4
CO CO
2
H
2
CH
4
CO CO
2
H
2
CH
4
CO CO
2
Untreated 0.0162 0.0000 1.3104 1.9935 1.5834 1.2849 3.1612 2.5799 4.5623 1.4116 3.0742 1.3581
NaOH 0.0155 0.3348 3.3623 3.8808 9.4856 1.9044 3.4335 2.2252 4.7847 0.9650 1.6777 1.0970
Na
2
CO
3
0.0081 0.1664 2.3718 3.8817 16.080 3.0190 8.4031 4.9980 7.4339 1.1763 3.4282 1.9930
Na
2
SiO
3
0.0112 0.2317 3.3002 2.8451 11.094 2.5230 6.8318 3.2833 3.5540 1.1047 1.9614 1.3380
NaCl 0.0061 0.0000 0.9084 1.4563 5.1740 1.7389 5.1450 3.1236 4.5968 1.1874 2.5937 1.1990
TiO
2
0.0066 0.0000 0.3420 0.8781 0.1269 0.8675 2.1983 1.9563 12.0640 2.1826 9.1624 2.0366
HZSM-5 0.0042 0.0000 0.2242 0.5785 0.1641 0.6893 2.1986 2.1093 3.7066 0.9007 2.9017 1.1154
H
3
PO
4
0.0038 0.0000 1.9787 2.6913 6.4860 0.8269 3.9397 1.4009 7.7293 0.7252 4.6446 1.4918
Fe
2
(SO
4
)
3
0.0011 0.0000 0.4363 0.5991 0.0220 0.3260 1.1614 1.9286 5.4433 1.6216 5.4763 1.8879
S.T.P.
a
(min) 8.009.50 10.0011.50 A.T.S.P.
b
H
2
CH
4
CO CO
2
H
2
CH
4
CO CO
2
H
2
CH
4
CO CO
2
Untreated 5.0861 1.5837 3.5840 4.7571 2.9082 1.1211 2.2039 1.9541 2.8312 1.0803 2.6667 2.5285
NaOH 3.1801 0.4330 0.6493 1.0039 1.1377 0.3040 0.5340 3.1476 3.7207 0.7882 1.9314 2.2709
Na
2
CO
3
2.9578 0.5624 1.2121 1.2026 1.5740 0.4923 1.0204 0.6899 5.6108 1.0833 3.2871 2.5530
Na
2
SiO
3
1.9393 0.8160 1.2892 0.7424 1.3396 0.6377 0.9563 0.7947 3.5876 1.0626 2.8678 1.8007
NaCl 4.3927 0.7222 3.5787 1.5706 1.9034 0.6468 1.1555 0.7619 3.2146 0.8591 2.6763 1.6223
TiO
2
2.1646 0.5320 1.4682 0.7619 1.5193 0.4282 1.1487 0.5638 3.1763 0.8021 2.8639 1.2393
HZSM-5 3.0063 0.5314 2.0783 0.7282 2.0849 0.4004 1.4852 0.7481 1.7932 0.5044 1.7780 1.0559
H
3
PO
4
2.1220 0.3784 1.4229 0.5743 1.0875 0.2975 0.8576 0.0000 3.4857 0.4456 2.5687 1.2317
Fe
2
(SO
4
)
3
5.5093 0.9021 3.9852 1.4197 1.6401 0.3914 1.4898 0.6501 2.5232 0.6482 2.5098 1.2971
a
S.T.P., Sampling time period.
b
A.T.S.P., Average concentration of the total sampling period.
Table 4
Estimated yield of each gas species evolved from pyrolysis of pine wood sawdust
treated with various additives by microwave heating (wt%)
H
2
CH
4
CO CO
2
Total
Untreated 1.6 5.0 21.5 32.0 60.1
NaOH 1.9 3.2 13.7 25.3 44.1
Na
2
CO
3
2.2 3.3 17.6 21.5 44.7
Na
2
SiO
3
1.9 4.6 21.8 21.6 49.9
NaCl 1.5 3.2 17.7 16.9 39.3
TiO
2
1.5 3.1 19.1 13.0 36.7
HZSM-5 1.9 4.2 25.8 24.1 56.0
H
3
PO
4
1.8 1.8 18.5 14.0 36.1
Fe
2
(SO
4
)
3
1.3 2.0 18.4 15.0 36.7
Fig. 1. TIC for liquid product from microwave pyrolysis of bare sample.
M.- Chen et al. / J. Anal. Appl. Pyrolysis 82 (2008) 145150 148
Kawamoto et al. [22] conducted pyrolysis of cellulose in sulfolane
(an aprotic polar solvent) and found it is a method for selective
formation of levoglucosan and other low molecular weight
substances. In our experiments, however, levoglucosan was either
not detected or found in trace amount. Dobele et al. [23] studied
the fast pyrolysis of pine wood treated with Fe
2
(SO
4
)
3
(about
11.8 wt%) and found 14.5% (area) LG, while in our microwave
pyrolysis of similar sample, LG was not detected and the most
abundant organic components were furfural (50%) and 4-methyl-
2-methoxy-phenol (29.04%). Dobele et al also studied the fast
pyrolysis of pinewood samples treated by H
3
PO
4
solution with the
concentration of 0.53% and found that the relative amount of LG
and LGone (levoglucosenon) varies with the concentration, while
in our microwave pyrolysis of pine wood treated with H
3
PO
4
,
whichaccounted for 10%of the pinewood sample weight, we found
that the main components are 4-methyl-2-methoxy-phenol
(52.76%) and furfural (27.05%) and both LG and LGone are absent.
Miura et al. [12] obtained considerable amount of LG from
pyrolysis of wood blocks by microwave heating, whereas we
obtained considerable amount of acetol instead of LG in the
pyrolysis of untreated sawdust by microwave heating.
Why levoglucosan is present only in a small fraction or even
absent in the organic products from pyrolysis of sawdust by
microwave heating in this study? Kawamoto et al. [24] proposed a
pathway for cellulose pyrolysis in which levoglucosan is believed
to be a key main initial intermediate and it can be further
transformed to solid carbonized products and volatile low
molecular weight products. The nal product distribution is
controlled by the actual pyroysis conditions, however. Levoglu-
cosan, once formed, might undergo further decomposition [25].
Fig. 5 illustrates a possible cleavage way from LG to acetol in the
pyrolysis of pine wood sawdust by microwave heating of this
study, induced by microwave eld and catalyzed by sodium
additives, since LG is absent, while the concentration of acetol is
increased, in the liquid products frommicrowave pyrolysis of these
four sodium-containing additives treated samples compared with
the untreated one.
H
3
PO
4
and Fe
2
(SO
4
)
3
favor furfural and 4-methyl-2-methoxy-
phenol formation by an acidic catalysis process fromhemicellulose
Fig. 2. TIC for liquid product from microwave pyrolysis of Na
2
CO
3
treated sample.
Fig. 3. TIC for liquid product frommicrowave pyrolysis of Fe
2
(SO
4
)
3
treated sample.
Fig. 4. TIC for liquid product from uidized bed pyrolysis of bare sample.
Table 5
Catalytic effects of various additives on the ve components of the liquid products from pyrolyis of pine wood sawdust by microwave heating (area%)
Acetol Furfural 2-Furanmethanol 4-Methyl-guaiacol Guaiacol LG
Untreated (m) 26.60 5.72 4.81 5.05 5.12 1.04
Untreated (f) 0 0 0 0 2.83 18.93
NaOH 53.30 0 2.08 0.94 7.53 0
Na
2
CO
3
45.28 1.03 2.58 0.84 8.33 0
Na
2
SiO
3
45.92 0 4.68 1.24 1.01 0
NaCl 30.95 3.62 5.62 2.90 6.99 0
TiO
2
19.40 9.46 2.21 4.28 4.38 3.25
HZSM-5 27.38 9.61 0 3.40 2.77 4.17
H
3
PO
4
0 27.05 0 52.76 1.43 0
Fe
2
(SO
4
)
3
0 50.00 0 29.04 0.93 0.43
m, Microwave pyolysis; f, fast pyrolysis in a conduit-spouted uidized reactor.
M.- Chen et al. / J. Anal. Appl. Pyrolysis 82 (2008) 145150 149
and lignin, respectively. So far, pyrolysis mechanism of cellulose
has been widely investigated while that of hemicellulose and
lignin has been studied much less, which is partly due to the more
complex structure of these two components. But it is well known
that furfural is the product of dehydration product of xylose [26
28], which is a main monomer unit of hemicellulose. So furfural is
likely formed from hemicellulose via an intermediate like xylose.
2-Methoxy-4-methyl-phenol is certainly from lignin since in the
model of the large molecular structure of conifer lignin contains
lots of monomer units of 4-methyl-2-methoxy-phenol. Detailed
pathway for furfural and 2-methoxy-4-methyl-phenol formation
remains unclear and further study is needed.
Lastly, it should be pointed out that the composition of organic
liquid products from pyrolysis is very complex. Some components
still remain unknown. Considering that the pyrolysis process is so
complicated a process, these unknown components can be new
substances and how to identify them remains to be a challenge
for us.
4. Conclusions
Catalytic pyrolysis of pine wood sawdust by microwave heating
carried out in this study gave some interesting results. Specically,
the following conclusions can be obtained:
(1) All of the eight additives, whether they are basic, neutral or
acidic, water soluble or insoluble, have increased yield of solid
products greatly and decreased yield of gaseous products more
or less. Liquid yield undergoes no dramatic change.
(2) The gases produced from pyrolysis consist mainly of H
2
, CH
4
,
CO and CO
2
. All of the eight additives have made these gases
evolve earlier, among which the four sodiumadditives have the
most marked effect. All the additives have made the yields of
CH
4
and CO
2
decrease, while all of them except NaCl, TiO
2
and
Fe
2
(SO
4
)
3
have made the yield of H
2
increase and all of them
except Na
2
SiO
3
and HZSM-5 have made that of CO decrease.
Alkaline sodium compounds NaOH, Na
2
CO
3
and Na
2
SiO
3
favor
H
2
formation most.
(3) Additives can change the composition of the organic products.
The most abundant organic component of the liquid products
from pyrolysis of untreated sample and samples treated by all
the additives except H
3
PO
4
and Fe
2
(SO
4
)
3
is acetol. All the four
sodium compounds favor acetol formation reaction and the
selection increasing effect follows the order of NaOH >
Na
2
CO
3
Na
2
SiO
3
> NaCl. TiO
2
goes against the formation of
acetol, HZSM-5 has no marked effect on acetol formation. The
two dominant organic components identied in the liquid
products from pyrolysis of H
3
PO
4
and Fe
2
(SO
4
)
3
treated
samples are both fufural and 4-methyl-2-methoxy-phenol.
(4) Levoglucosan is absent or presents only in trace amount in the
liquid products from pyroysis of sawdust by microwave
heating, which can be ascribed to its secondary decomposition.
Acknowledgements
This research project was nancially supported by the National
Natural Science Foundation of China (20676002), the National
Basic Research Program of China (973 Program) (2007CB210203,
2004CCA07300) and Anhui Young Teacher Foundation
(2006jq1075).
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M.- Chen et al. / J. Anal. Appl. Pyrolysis 82 (2008) 145150 150