Journal of Analytical and Applied Pyrolysis 92 (2011) 4349

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Journal of Analytical and Applied Pyrolysis
j our nal homepage: www. el sevi er . com/ l ocat e/ j aap
Microwave pyrolysis of straw bale and energy balance analysis
Xiqiang Zhao
a,b
, Jian Zhang
a
, Zhanlong Song
b
, Hongzhen Liu
b
, Longzhi Li
b
, Chunyuan Ma
b,
a
School of Environmental Science and Engineering, Shandong University, 250061 Jinan, PR China
b
National Engineering Laboratory of coal-red pollution reduction, Shandong University, 250061 Jinan, PR China
a r t i c l e i n f o
Article history:
Received 29 December 2010
Accepted 8 April 2011
Available online 15 April 2011
Keywords:
Microwave pyrolysis
Straw bale
Energy balance
Electricity consumption
a b s t r a c t
The compressed wheat and corn strawbale were pyrolyzed on a microwave heating device self-designed
and built with respect to the time-resolved temperature distribution, mass loss and product properties.
Considering scale up and technology promotion of microwave pyrolysis (MWP), the investigations on
electricity consumption and energy balance of MWP were carried out emphatically. The results indi-
cated that MWP had obvious advantages over conventional pyrolysis, such as heating rapid and more
valuable products obtained. The distribution of pyrolysis products such as gas, liquid and char was close
to 1:1:1 due to the medium pyrolysis temperature and the slow heating rate, which was not favorable
for the formation of gas and/or liquid products. The content of H
2
attained the highest value of 35vol.%
and syngas (H
2
and CO) was greater than 50vol.%. The electricity consumption of MWP was between
0.58 and 0.65kWh (kg straw)
1
and with the increase of microwave power, the electricity consump-
tion required for pyrolysis of unit mass of straw increased. The minimum microwave power for MWP
was about 0.371kW (kg straw)
1
and the proportion of heat loss and conversion loss of electricity to
microwave energy occupied in the total input energy was 42%. Data and information obtained are useful
for the design and operation of pyrolysis of large-sized biomass via microwave heating technology.
2011 Elsevier B.V. All rights reserved.
1. Introduction
Pyrolysis is one of the most promising thermo-chemical conver-
sion routes to recover energy from biomass. Generally, pyrolysis
converts biomass to liquid, gaseous and solid fractions under an
oxygen absence condition [1]. At present, the pyrolysis, which
optimize the operating conditions and/or achieve the directional
conversion by means of innovative heating methods or catalysts
for improving the yields or quality of desired products, have been
gaining increasing interests [24]. MWP is one of the research
focuses and attracts widespread concern of domestic and foreign
researchers [58].
During microwave heating process, energy transfer occurs
through the interaction of molecules or atoms. Compared with
conventional heating methods, more uniform temperature distri-
bution can be achieved and the undesired secondary reactions may
be avoided. As a result, better control of the process and more
desired products will be obtained [9]. More importantly, since
heat is transformed by microwave energy within feedstock inter-
nally, the large-sized materials, such as wood block and strawbale,
can be processed [6,10]. Consequently, the drawbacks existed in

Corresponding author at: School of Energy and Power Engineering, National

Engineering Laboratory of coal-red pollution reduction, Shandong University,
250061 Jinan, PR China. Tel.: +86 531 88399369; fax: +86 531 88395877.
E-mail address: chym@sdu.edu.cn (C. Ma).
resource utilizationof cropstraw, suchas lower density, hightrans-
port costs, not easily broken and so on, could be overcome by
MWP.
Currently, the defect of MWP is the lower power conversion
efciency of electricity into microwave energy, which wastes a
lot of high-grade energy. In addition, the sample used in existing
researches are powders or granules and the amount is less than
20g usually [11,12], leading to the lower energy utilization ratio
and a lot of electricity consumed in the preparation of sample, such
as crushing and grinding. Also, the unique feature of integrity
of microwave heating is not fully displayed. Though energy con-
sumption of MWP has been involved [13], but only the energy
analysis carried out on a laboratory-scale experimental appara-
tus, which is not enough for the large-scale application. However,
these parameters are of great signicance for the design and opti-
mization of experimental devices and improvement of economy of
MWP. Therefore, it is urgent to investigate MWP of the large-sized
biomass, especially for the systems electricity consumption and
energy balance.
Based on the analyses above, the objectives of this study are to
experimentally investigate the pyrolysis characteristics of wheat
and corn straw bale on a microwave reaction system specially
designed and constructed. Furthermore, for investigating the econ-
omy of MWP of large-sized materials, the electricity consumption
and energy balance of entire system are analyzed and reasonable
suggestions on how to improve the economy of MWP are put for-
ward.
0165-2370/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2011.04.004
44 X. Zhao et al. / Journal of Analytical and Applied Pyrolysis 92 (2011) 4349
Fig. 1. Diagram of microwave pyrolysis system for straw bale. 1-N
2
; 2-ow meter; 3-microwave generator; 4-frame; 5-straw bale; 6-weighing tray; 7-weighing sensor;
8-weighing digital indicator; 9-beam; 10-chimney; 11-eletric heating tube; 12-furnace; 13-condenser; 14-pump; 15-collector; 16-gas bag.
2. Material and methods
2.1. Materials
The samples used are the straw of two common crops (wheat
and corn) in the north of China, which are from Liangshan County,
Shandong Province. Loose straws are mechanical compressed and
baled after air drying, and the baling density is about 80kgm
3
and
the size of straw bale is about 1000mm600mm600mm. The
proximate and ultimate analyses of sample are carried out after
grinding, and the results are shown in Table 1. Compared with coal,
the content of volatiles in straws is high and the content of ash
is very low. So combustion of straws would produce less ash and
the ash produced can be used as a soil additive on farm targets. In
addition, straws have negligible sulfur content and therefore, do
not contribute to sulfur dioxide emissions.
2.2. Apparatus
The batch scale MWP apparatus is constituted by microwave
heating furnace, microwave generating and control system, weigh-
ing and temperature measurement systemand products collection
system, as shown in Fig. 1. The apparatus is equipped with 20 sets
of magnetronandthe total microwave output power is 18kW. Nine
K-type thermocouples of 4mm diameter were arranged in two
groups: the rst one, containing 5 thermocouples spaced 60mm
apart horizontally, was positioned at the median section of the fur-
nace starting fromthe centreline, while the other one, containing 4
thermocouples spaced 80mm apart, was positioned at the vertical
axis of the furnace.
Table 1
Proximate and ultimate analyses of straw (wt.%, ad).
Item M
ad
A
ad
V
ad
FC
ad
C H O
a
N S
Wheat 7.4 5.9 69.3 17.4 41.41 5.86 45.22 1.44 0.17
Corn 7.5 4.7 70.2 17.5 43.51 6.23 43.88 1.52 0.16
M: moisture content, V: volatile matters, A: ash, FC: xed carbon; ad: on air dried
basis.
a
Subtraction.
The mass loss of stalk bale was measured and recorded continu-
ously as a function of time by a suspension systemand the accuracy
of mass detectionwas better than50g, i.e., approximately0.17wt.%
of the initial mass.
Straw bale was weighed and loaded on the tray 6 (for mass loss
experiments) or onthesupport frame4(for temperaturemeasuring
experiments), then the furnace was closed and tightly sealed. A
ow of N
2
(5L min
1
) was purged into the furnace continuously
for 30min to remove the air and then reduced to 1L min
1
during
the pyrolysis process to maintain an inert atmosphere and carry
the gaseous product out. Details on the experimental apparatus
and operation steps can be obtained in previous study [10].
3. Results and discussion
3.1. Mass loss and temperature rising characteristics
Time-dependent detection of the loss of mass is one of the most
important features in this work. It is a consequence of the gas pro-
duction which, in turn, depends on the current bales temperature,
which two are combined together to reveal the characteristics of
MWP [14].
The sizes of straw bale used in experiments were large, leading
to the uneven distribution of internal temperature. When carrying
out the thermogravimetric analysis, the temperature was expected
to be able to represent the temperature of whole package. As a
result, the average temperature of ve points in the direction of
microwave radiation was considered to be the overall temperature
of the strawbale, combined with weight loss curves, then the ther-
mal weight curve of wheat strawand corn stalks were obtained, as
shown in Fig. 2 and Fig. 3. The microwave energy absorbed by unit
mass of straw=total input microwave energy/mass of straw, unit:
kW (kg straw)
1
.
From the mass loss curves of Fig. 2 and Fig. 3, it can be found
that with the increase of microwave power, the duration of dry-
ing and violent pyrolysis stage was shortened. The reason was
that the higher the microwave power was, the higher the heat-
ing rate was. As a result, more water and volatiles were vigorously
releasedina short time [9,12]. At the microwave power of 0.668kW
X. Zhao et al. / Journal of Analytical and Applied Pyrolysis 92 (2011) 4349 45
Fig. 2. Microwave thermogravimetric curves for wheat straw bale at different microwave powers, (a). 0.334kW (kg straw)
1
. (b). 0.668kW (kg straw)
1
. Mass loss curve
(), mass loss rate curve ( ), temperature rising curve ().
(kg straw)
1
, the water evaporation of straw bale completed in
1520min and the straw bale entered the pyrolysis stage when
its temperature reached about 200

C. However, compared with

microwave power of 0.668kW(kg straw)
1
, the temperature of the
bale attened over a long period of time before entering the pyrol-
ysis stage at microwave power of 0.334kW (kg straw)
1
, which
could be explained by retardation due to endothermic reactions of
the outer layers of the bale and the different thermal conductivi-
ties and heat capacities of the charring layers, and the un-reacted
substrate: the effective thermal conductivity of the inner regions
of the sample was changing as the pyrolysis front was progressing
[14,15].
However, due to the same nal temperature of straw bale at
different microwave power, the residual mass of wheat and corn
strawunder different microwave power at the end of pyrolysis was
very close, respectively, which was between 35wt.% and 40wt.%,
higher than the sum of xed carbon and ash (about 23wt.%). It
could be attributed to the incomplete pyrolysis caused by the low
temperature of our experiments, which was about 625

C and at
local positions it might be cooler. Another reason was some impu-
rities had been interfused into the straw bale during the process of
collection and baling.
Due to the larger size of straw bale, the temperature showed
in Fig. 2 and Fig. 3 was the average temperature of ve points in
the direction of microwave irradiation. In addition, because the
microwave has a limited penetration depth into the straw bale,
the temperature distribution in the straw bale was uneven. Con-
sequently, the average temperature calculated was lower than the
value obtained by other researches. Also, as the characteristics of
penetrating heating of microwave, the bale was pyrolyzed from
outside to inside, so more straws were pyrolyzed at the rst stage.
But with the developing of pyrolysis, more microwave energy was
absorbed by the char produced by the outside straw. Therefore, the
straw inside the bale pyrolyzed slowly. Correspondingly, the mass
loss curve and the temperature curve were not in good consistence
at lower microwave power. However, if the microwave power was
larger enough, such as 0.668kW (kg straw)
1
, the mass loss curve
was in good consistence with the temperature rising curve.
The differential curve of mass loss had two distinct peaks, the
one corresponding to the water evaporation and the other one
corresponding to the release of volatiles vigorously. It was worth
noting that the maximal pyrolytic rate at different microwave
power of straw bale was double with double of microwave power
and the corresponding temperature of the maximal pyrolytic rate
was reduced gradually. When most volatiles had been released,
there were still many jagged peaks in the differential curve because
of the release of a small amount of volatiles and char formation.
Furthermore, limited by the accuracy of weighing sensor, the data
might uctuate repeatedly.
3.2. Analysis of gas products
3.2.1. Three-phase products
Three-phase products suchas gas, liquidandchar were obtained
by MWP. The yield of three-phase pyrolysis products at microwave
power 0.668kW (kg straw)
1
was shown in Fig. 4.
As can be seen from Fig. 4, in the nal pyrolysis products
obtained at microwave power 0.668kW (kg straw)
1
, the mass of
Fig. 3. Microwave thermogravimetric curves for corn straw bale at different microwave powers, (a). 0.334kW (kg straw)
1
. (b). 0.668kW (kg straw)
1
. Mass loss curve (),
mass loss rate curve ( ), temperature rising curve ().
46 X. Zhao et al. / Journal of Analytical and Applied Pyrolysis 92 (2011) 4349
Fig. 4. Products distribution at microwave power of 0.668kW (kg straw)
1
.
Table 2
Gas compositions at maximumheat value of pure pyrolysis gas at microwave power
0.334kW (kg straw)
1
(vol.%).
Item CO CO
2
H
2
CH
4
C
2
H
6
C
2
H
2
LHV/kJ Nm
3
Wheat straw 17.5 20.6 37.1 21.7 0.66 0.84 14908
Corn straw 18.4 18.4 35.2 23.0 0.83 1.1 15535
residual carbon was maximum, followed by liquid products, and
gas products was fewest, but the difference between them was
small. This was because the nal pyrolysis temperature of these
experiments was about 600

C, belonging to the medium temper-

ature zone, which was not favorable for gas formation and parts
of volatiles had not yet been released [16]. In addition, the heating
rate was not high enough and the temperature was not at the opti-
mal operation value for formation of liquid products [17]. Thus, the
nal distribution of three phases of pyrolysis products was close to
1:1:1.
3.2.2. Analysis of gas products
Theresults obtainedbyGCshowedthat thegas products of MWP
at microwave power 0.334kW (kg straw)
1
mainly contained CO,
CO
2
, H
2
, CH
4
, C
2
H
6
andasmall amount of unsaturatedhydrocarbon,
and the sum accounted for 95vol.% or more in pure pyrolysis gas
(nitrogen and oxygen removed), which was shown in Table 2.
As can be seen from Table 2, the contents of H
2
and syn-
gas (H
2
+CO) in pyrolysis gas were high. The concentration of H
2
was about 35vol.% and the concentration of syngas was higher
than50vol.%. Moreover, comparedwithconventional pyrolysis, the
temperatureneededfor MWPwas lower duetothefavorableness in
the dry reforming reactionof methane and the gasicationreaction
of carbon and CO
2
under microwave heating [11,18].
The contents of different gases in gas products at microwave
power 0.668kW (kg straw)
1
were shown in Fig. 5. CO and CO
2
were released rstly, while the release of other combustible com-
ponents such as H
2
, CH
4
, C
2
H
6
and C
2
H
2
lagged behind, which had
a closest relationship with their generation mechanisms [19,20].
When entering the pyrolysis stage, the content of H
2
in the pyrol-
ysis gas stabilized at 30vol.% and the content of syngas stabilized
at 45vol.% or even higher. It was noteworthy that the pyrolysis gas
contained about 15vol.% of CH
4
. If using CO
2
and H
2
O contained
in the pyrolysis gas to reform it by catalysis, more syngas could be
obtained [21,22].
3.3. Electricity consumption and energy balance analysis
3.3.1. Electricity consumption
The electricity consumption of MWP when 90wt.% of total mass
loss had been completed was investigated. By measuring the cur-
rents of MWP apparatus, the microwave power couldbe calculated.
Then the power of each microwave generator can be obtained and
the value was 1.127kW. In addition, the rated power of magnetron
was 0.9kW, so the conversionefciency of electricity to microwave
energywas about 0.8. Actually, theattenuationof magnetronwould
be inevitable in the course of using, so the actual conversion ef-
ciency was lower than 0.8. The results of electricity consumption
of MWP were shown in Table 3.
As canbe seenfromTable 3, the electricity consumptionof MWP
at our conditions was between 0.58 and 0.65kWh (kg straw)
1
.
Withthe increase of microwave power, the electricityconsumption
required for pyrolysis of unit mass of strawincreased, equivalent to
that if microwavepower was maintainedat acertainvalue, withthe
increase of mass of strawbale, the energy consumption of pyrolysis
of unit mass of straw would decrease, which was in consistence
with the study [6].
3.3.2. Energy balance analysis
The principled energy balance system of MWP was shown in
Fig. 6. To the entire system, the input energy include: (1) biomass
chemical energy Q
B
, (2) electricity energy Q
M
. The output energy
include: (1) chemical energy of gas products Q
G
, (2) chemical
energy of residual carbon Q
C
, (3) sensible heat of residual carbon
Fig. 5. Actual composition of different pyrolysis gases at microwave power of 0.668kW (kg straw)
1
. (a) Wheat straw. (b) Corn straw.
X. Zhao et al. / Journal of Analytical and Applied Pyrolysis 92 (2011) 4349 47
Table 3
Electricity consumption of microwave pyrolysis of straw bale.
Item Microwave power
(kW (kgstraw)
1
)
Time (min) Energy consumption
kWh (kgstraw)
1
Conversion efciency Electricity consumption kWh
(kgstraw)
1
Wheat 0.334 83 0.462 0.8 0.58
0.668 46 0.512 0.64
Corn 0.334 90 0.501 0.8 0.63
0.668 47 0.523 0.65
Table 4
Calculation of energy balance for microwave pyrolysis system.
Item Symbol Value/kJ (kg straw)
1
Wheat straw Corn straw
Biomass chemical energy QB [24] 16734 16950
Theoretical minimum microwave power QM 1336 1212
Residual carbon chemical energy Q
C
6750 6678
Residual carbon sensible heat Q
CA
262 259
Liquid chemical energy QL 4890 5265
Gas chemical energy Q
G
3289 3058
Heat absorbed by cooling water QH 2879 2902
Actual input electricity Q
M0
2304 2340
Heat loss +conversion loss QT 968 1128
Q
CA
, (4) heat loss and conversion loss in transform of electricity
to thermal energy Q
T
, (5) heat taken out by cooling water Q
H
, (6)
chemical energy of liquid products Q
L
[23].
The heat loss was difcult to estimate, so the calculation of
energy balance was carried out at Q
T
=0. In this case, the value of
Q
M
was the theoretical minimum electricity energy, and then the
subtract value of actual input electricity and the theoretical mini-
mumelectricity energy was considered as the sumof heat loss and
conversion loss of electricity transformed to thermal energy.
In a stability condition, the energy balance of entire systemwas
satised:
Q
B
+Q
M
= Q
G
+Q
C
+Q
CA
+Q
H
+Q
L
(1)
The total input energy of system was biomass chemical energy
and electricity energy:
Qr = Q
B
+Q
M
(2)
The conditions of the import and export of systemwere consid-
ered to be at a standard state (298.15K, 101.3kPa), and all energy
values were calculated according to per kg of biomass and products
obtained from per kg of biomass. The chemical energy of biomass,
residual carbon and gas products in Eq. (1) were their low heating
value (LHV).
The chemical energy value of liquid products was replaced by
the heat value of same amount of tar. In these cases, only electricity
Fig. 6. Energy balance system for microwave pyrolysis.
energy and the heat taking out by the cooling water were unknown
in Eq. (1), but these values were easily obtained by calculation.
According to energy balance system and the balance equations,
the energy balance of MWP was calculated, and the results were
shown in Table 4.
As can be seen from Table 4, if the heat loss and conversion loss
were ignored, the minimum electricity for MWP of wheat straw
was 1336kJ (kg straw)
1
, about 0.371kWh (kg straw)
1
. The pro-
portion of heat loss and conversion loss of electricity to thermal
energy occupied in the actual input electricity was 42%, which was
consistent with the ndings of Huang et al. [13]. If the scale of
experimental systemwas expanded and some improvements were
adopted, the energy efciency can be improved further. Because
the broken, grinding and other preprocessing steps could be saved,
MWP of large-sized materials would undoubtedly simplify the
intermediate processing steps, and then save a lot of electricity.
3.4. Means to improve economy of MWP
Fromanalyses of electricity consumption and energy balance of
MWP above, it can be found that energy consumption of MWP was
high and some measurements should be adopted to improve its
efciency. If using it as a key technology for application at present,
the following aspects should be improved:
(1) Design of special microwave cavity suitable for pyrolysis to
reduce the loss during the transmission process of microwave
and the loss in the pyrolysis furnace, and improve the absorp-
tion rate of materials to microwave [25]. For instance, the
absorption ability of microwave can be improved through
adding microwave receptors, suchas char andmetal oxides, but
which need further basic researches on dielectric properties of
materials.
(2) Improving processing technology, taking the microwave heat-
ing as a key node in the entire process to get the best economy.
For example, part of high-temperature pyrolysis gas could be
returned to the pyrolysis furnace for heat resource and inert
gas. In this case, the sensible heat loss can also reduce and the
energy efciency could be improved.
(3) Development of comprehensive utilization of pyrolysis prod-
ucts, increasing added value of products. By choosing optimal
operating conditions or appropriate catalysts, achieve the ori-
entation transformation and increase the production of the
48 X. Zhao et al. / Journal of Analytical and Applied Pyrolysis 92 (2011) 4349
Fig. 7. Diagram of microwave pyrolysis of straw bale for multi-target products.
target products. MWP of strawbale for multi-target products is
shown in Fig. 7.
If gas products were all used for electricity generation, only 45%
of the electricity could be self-sufcient for the energy requirement
of entire system by calculation. The residual products can be con-
verted to the multi-target products by various routes. For instance,
the raw pyrolysis gas can be converted to syngas on the carbon-
based catalyst (char can be used directly) through reheating by
microwave [26], while itself can be directly used as fuel; The char
after activation can be used as activated carbon [27,28], which can
also be converted to syngas by steam gasication [29,30]; syngas
is an important chemical material, and a variety of chemical prod-
ucts can be obtained through the catalytic synthesis, which could
be used directly as a fuel gas.
4. Conclusions
In our study, MWP of wheat and corn straw bale and investiga-
tions on the electricity consumption and energy balance analysis of
entirepyrolysis process werecarriedout. Thefollowingconclusions
were obtained:
(1) As the nal pyrolysis temperature belonged to the medium
temperature zone and the heating rate was not at the optimal
operation value for formation of liquid products, so the nal
distribution of three phases of pyrolysis products was close to
1:1:1.
(2) Pyrolysis gas was mainly composed of CO, CO
2
, H
2
, CH
4
, C
2
H
6
and a small amount of low-carbon unsaturated hydrocarbons.
The maximum volume content of pure H
2
in pyrolysis gas was
morethan35vol.%, andmaximumsyngas (H
2
+CO) content was
more than 50vol.%.
(3) The electricity consumption of MWP of straw bale under our
experiment conditions was at 0.580.65kWh (kg straw)
1
.
Withtheincreaseof mass of strawbale, electricityconsumption
for pyrolysis of unit mass of straw decreased.
(4) The ratio of heat loss and energy conversion losses occupied in
the energy balance of entire system was about 42%, and if the
energy efciency would be improved, the scale of experimental
systemshould be expanded and some improvements should be
adopted.
Acknowledgements
This research project was nancially supported by the National
Natural Science Foundation of China (No. 50906047), the Special-
ized Research Fund for the Doctoral Program of Higher Education
(No. 200804221027) and the Independent Innovation Foundation
of Shandong University (IIFSDU No. 2010GN056).
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