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Energy 116 (2016) 1e7

Contents lists available at ScienceDirect

Energy
journal homepage: www.elsevier.com/locate/energy

Co-torrefaction of sewage sludge and leucaena by using microwave


heating
Yu-Fong Huang, Hsuan-Te Sung, Pei-Te Chiueh*, Shang-Lien Lo
Graduate Institute of Environmental Engineering, National Taiwan University, 71, Chou-Shan Rd., Taipei 106, Taiwan, ROC

a r t i c l e i n f o a b s t r a c t

Article history: Microwave co-torrefaction of sewage sludge and leucaena can be a workable technique, because it not
Received 3 June 2016 only produces biofuels but also solves the problems in waste treatment. When the sewage sludge
Received in revised form blending ratio was 25e50 wt% and the microwave power level was 100 W, a synergistic effect was found
20 August 2016
to influence the mass and energy yields as well as product properties. The relatively small amount of
Accepted 17 September 2016
sewage sludge could play a role as a catalyst, since the synergistic effect was hard to be identified at
Available online 24 September 2016
higher sewage sludge blending ratios. Besides, it was difficult to find out the synergistic effect at higher
microwave power levels. This could be attributable to the effect of microwave heating which increases
Keywords:
Co-torrefaction
with its power level. The elemental compositions of biochar were close to those of anthracite and
Sewage sludge bituminous coal. The energy return on investment (EROI) of microwave co-torrefaction of the 25/75 (w/
Leucaena w) sewage sludge/leucaena blend at a microwave power level of 100 W in a processing time of 30 min
Microwave heating can be approximately 10.1 or 4.7, when the gaseous and liquid products are utilized or not. Therefore, the
Synergistic effect technique should be energetically and economically feasible.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction waste treatment and disposal.


Microwaves are located between infrared and radio waves in the
Because of heavy dependence on fossil fuels that are non- electromagnetic spectrum, and they have wavelengths from 1 mm
renewable and cause a great deal of carbon emissions, the use of to 1 m, corresponding to frequencies between 300 MHz and
nuclear energy that may lead to radioactive pollution for hundreds 300 GHz [5]. In order to avoid interference with telecommunica-
years, and global climate change that is leading to more and more tions and radar transmissions, domestic and industrial microwave
unexpected disasters, the research and development of clean, safe, ovens generally operate at either 900 MHz or 2.45 GHz [5,6]. Mi-
abundant, and low-cost renewable energy has been so important crowave technology has been used in various applications,
and urgent. Biomass, one of renewable energy sources, provides including organic synthesis [5e8], digestion [9,10], and food heat-
various advantages. Biomass is the only source of renewable liquid, ing [11,12]. Microwave heating provides a number of advantages
gaseous, and solid fuels [1]. The growth of plant biomass removes over conventional heating, including higher heating efficiency and
atmospheric carbon dioxide, which can offset the carbon dioxide power density, better heat transfer and process control, more uni-
emitted by the combustion of biofuels [2]. Biomass is an abundant, form heat distribution, and faster internal heating [13e16]. Mi-
carbon-neutral, and renewable resource for the production of crowave heating can reach high temperatures in a fraction of the
biofuels and biomaterials [3], and thus there has been increasing time required for conventional heating, and the unique features of
interest in producing biofuels from a range of biomass feedstocks in microwave heating can be used to improve processes, to modify
recent years [4]. Furthermore, most of the municipal and industrial selectivity, and to perform reactions that do not occur by conven-
wastes can be regarded as biomass feedstocks. In addition to the tional heating [17,18]. Microwave heating has been used for
advantage of biofuel production, the utilization of the organic biomass pyrolysis and torrefaction in several studies [19e29]. The
wastes can also reduce the cost and environmental impacts from dominant product of microwave pyrolysis can be liquid [20], solid
[27], or gases [28], depending on operational parameters such as
microwave power level, processing time, biomass characteristics,
and the presence of catalysts or microwave absorbers [29].
* Corresponding author.
Raw biomass feedstocks have high moisture content, low energy
E-mail address: ptchueh@ntu.edu.tw (P.-T. Chiueh).

http://dx.doi.org/10.1016/j.energy.2016.09.102
0360-5442/© 2016 Elsevier Ltd. All rights reserved.
2 Y.-F. Huang et al. / Energy 116 (2016) 1e7

densities, and hydrophilic nature, and they are bulkier with poorer There was a three-stub tuner in charge of regulating the incident
handling and transportation characteristics and is more tenacious angle of microwaves to make sure that microwave peak is located at
to make it difficult to comminute into small homogeneous parti- the center of reaction zone. At the end of microwave propagation
cles, resulting in complicated and expensive storage and trans- pathway, a short-circuit plunger was set to adjust the wavelength
portation [30e33]. In addition, the high oxygen content of biomass phase of microwaves. During the experiment induced by micro-
would result in a large amount of smoke formation during com- wave heating, both three-stub tuner and short-circuit plunger were
bustion [33]. All of the drawbacks have given rise to the research adjusted to minimize reflected microwave power. The heat caused
and development of new technologies for biomass modification in by the reflected microwave power was absorbed by a water load
order to ensure that its utilization as an energy source is environ- that was cooled down by a refrigerated circulator. Incident and
mentally friendly and economically efficient [31,34]. One poten- reflected microwave power was measured by a power meter. The
tially feasible way is a thermal processing step known as temperature of the biomass sample was measured by a thermo-
torrefaction [30,34,35]. Torrefaction is a low-temperature couple and an infrared thermometer. After passing through a
(200e300  C) thermal pretreatment of biomass operated at at- condenser, the vapor produced during the experiment was divided
mospheric pressure in the absence of oxygen [35e37], so it is also into condensable (tar) and non-condensable (gas) parts, and the
known as mild pyrolysis [30,31,33,38]. In addition to increasing flow rate of the gaseous product was measured by a digital flow
energy density and decreasing moisture and oxygen content, tor- meter.
refaction offers a great effect on the grindability and reactivity of
biomass [31]. Furthermore, biomass becomes hydrophobic after 2.3. Experimental details
torrefaction, which could be attributable to the formation of non-
polar unsaturated structures [35]. In this study, individual and blended biomass samples were
In this study, the co-torrefaction of sewage sludge and leucaena heated at microwave power levels of 100, 150, 200, 250, 300, and
was carried out by using microwave heating. The disposal of 350 W. The reaction cavity was purged with pure nitrogen gas at a
sewage sludge would be one of the most complex environmental flow rate of 25 mL/min to maintain its inert atmosphere. After
problems [39,40], whereas the organic fraction of sewage sludge sufficient purging, the power supply of the microwave heating
can be regarded as a resource of bioenergy [41,42]. Leucaena is a system was turned on and switched to the prescribed microwave
fast growing plant with high biomass production rate, so it has a power level for 30 min. reflected microwave power was controlled
high potential for bioenergy production and can be a satisfactory to be as low as possible during the entire experimental period by
alternative to the use of traditional biomass feedstocks [43,44]. The adjusting the three-stub tuner and the short-circuit plunger. The
purpose of this study was to investigate the biochar produced by actual working microwave power level was determined by sub-
microwave co-torrefaction of sewage sludge and leucaena. This tracting the reflected microwave power level from the incident
study also evaluated the energy usage of the technique. The origi- level. At microwave power levels of 100, 200, and 300 W, sewage
nality of this study was that a synergistic effect between the two sludge was heated to approximately 170, 280, and 350  C, and
very different biomass feedstocks was found to influence the leucaena was heated to approximately 230, 340, and 390  C,
properties of the biochar and the mass and energy yields of mi- respectively. When the prescribed processing time was reached,
crowave co-torrefaction. Consequently, even at relatively low mi- the power supply was turned off, the gas purging was stopped, and
crowave power levels, the performance of microwave co- the tar and gas collectors were removed and sealed. After self-
torrefaction was satisfactory. Besides, it was found that the en- cooled down to the room temperature, solid residues (biochar)
ergy usage benefit of microwave co-torrefaction was high, no remained in the crucible were removed and then placed in a
matter gas and liquid products were recovered or not. desiccator for hours. All of the experiments were performed in
triplicate at least to obtain average values for the results.
2. Material and methods
2.4. Analytical methods
2.1. Materials
Proximate analyses of biomass samples and torrefied products
Sewage sludge was obtained from the Dihua Sewage Treatment were performed according to the standards D7582-12 and D3172-
Plant, Taipei, Taiwan. The moisture content of the as-received 07a of the American Society for Testing and Materials (ASTM). Ul-
sewage sludge was approximately 85 wt%. To remove the mois- timate analyses were carried out by using a PerkineElmer 2400 II
ture, the raw sewage sludge was air dried for several months and CHNS/O elemental analyzer. Higher heating values (HHV) were
then dried in an oven (95  C) for three days. Leucaena wood was measured in a Parr 1341 adiabatic oxygen bomb calorimeter. Each
provided by the Kenting National Park, Pingtung, Taiwan. Before sample (approximately 1 g) was dried at 105  C in an oven for 24 h
applying to microwave torrefaction and relevant experiments, prior to heating value analysis. All of the samples were tested in
sewage sludge and leucaena was dried, shredded, and ground into triplicate at least to obtain average values for the results. Ther-
powder, and then it was sieved by using a 50-mesh screen mogravimetric analyses (TGA) were carried out by using a TA In-
(0.297 mm opening). The blended samples were obtained by struments SDT Q600 thermogravimetric analyzer with a nitrogen
mixing sewage sludge and leucaena at the ratios of 25:75, 50:50, flow rate of 100 ml/min, and each sample (approximately 10 mg)
and 75:25, named as SS25%, SS50%, and SS75%, respectively. was heated to 900  C at a rate of 10  C/min.

2.2. Experimental apparatus 3. Results and discussion

A single-mode (focused) microwave oven was used in this study. 3.1. Characteristics of biomass feedstocks
This microwave oven operates at a frequency of 2.45 GHz, and its
maximum output power is 2000 W. A schematic diagram of the The general characteristics of air-dried sewage sludge and leu-
overall microwave heating system can be found elsewhere [45]. caena samples are listed in Table 1. As can be seen, the moisture
Both reaction tube (40 cm length, 5 cm outer diameter) and sample contents of the two biomass feedstocks were approximately 9.0
crucible (3 cm height, 4 cm outer diameter) are made of quartz. and 10.5 wt%, respectively. The volatile matter content of leucaena
Y.-F. Huang et al. / Energy 116 (2016) 1e7 3

Table 1 3.2. Proximate analysis


Characteristics of air-dried sewage sludge and leucaena.

Sewage sludge Leucaena The proximate compositions of biochar produced at different


Moisture (wt%) 8.98 10.50
biomass blending ratios and at microwave power levels of
Proximate analysis (wt%)a 100e350 W are shown in Fig. 2. At higher microwave power levels
Volatile matter 52.31 78.80 (250e350 W), both volatile matter and fixed carbon contents
Fixed carbon 18.51 18.72 decreased whereas ash content increased with increasing sewage
Ash 29.18 2.48
sludge blending ratio. This phenomenon can be attributable to the
Ultimate analysis (wt%)b
Carbon 51.58 47.93 relatively high ash content of raw sewage sludge (Table 1). How-
Hydrogen 8.23 6.59 ever, this trend did not exist at lower microwave power levels
Oxygenc 31.40 38.27 (100e200 W). When the sewage sludge blending ratio was 50 wt%,
Nitrogen 8.79 7.21
the biochar produced at microwave power levels of 100e200 W
HHV (MJ/kg)a 15.04 19.27
had the lowest volatile matter content and the biochar produced at
a
Dry basis. a microwave power level of 100 W had the highest ash content. This
b
Dry ash-free basis.
c finding implies that there could be a synergistic effect between
Determined by difference.
sewage sludge and leucaena occurred during their co-torrefaction,
which might improve the reactivity of microwave torrefaction at
was up to 79 wt%, much higher than that of sewage sludge. On the lower microwave power levels and thus enhance the economic
contrary, the ash content of sewage sludge was much higher than viability of the technique due to lower energy consumption. On the
that of leucaena. The ash content of leucaena was only approxi- other hand, the trends in proximate compositions may imply that
mately 2.5 wt%. Coincidentally, the fixed carbon contents of the two the synergistic effect would be less substantial than the effect of
biomass feedstocks were almost the same (approximately 19 wt%). microwave power at higher power levels. Besides, volatile matter
The combustible fractions of sewage sludge and leucaena were content decreased whereas ash content increased with increasing
approximately 71 and 98 wt%, respectively. The sewage sludge microwave power level. However, there was no substantial rela-
sample had higher carbon, hydrogen, and nitrogen contents, tionship between fixed carbon content and microwave power level.
whereas the leucaena sample had higher oxygen content. The HHVs The fuel ratios of different biochar products are listed in Table 2.
of the sewage sludge and leucaena samples were approximately 15 Fuel ratio is the ratio of fixed carbon content to volatile matter
and 19 MJ/kg, respectively. The relatively low HHV of the sewage content. The typical fuel ratio of bituminous coal is approximately
sludge sample is attributable to its high ash content. 1.0e2.5 [46,47]. The fuel ratios of raw sewage sludge and leucaena
The thermogravimetric (TG) profiles of sewage sludge, leucaena, were 0.35 and 0.24, respectively. After microwave torrefaction, the
and their 1:1 blend are shown in Fig. 1. All the profiles can be fuel ratio can be highly increased due to the removal of volatile
divided into three stages. Firstly, the weight loss occurred mainly components. Generally, the fuel ratio increased with increasing
attributable to the removal of moisture. Secondly, the weight microwave power level, whereas the relationship between fuel
largely and quickly decreased because of the devolatilization of ratio and biomass blending ratio was difficult to define. Neverthe-
highly volatile components. Lastly, the weight slowly decreased less, when the sewage sludge blending ratio was 25 wt% and mi-
until the end of experiment. For sewage sludge and leucaena, the crowave power levels were 250e350 W, the fuel ratio of biochar
boundaries between stages 1 and 2 were almost the same was relatively high. At a microwave power level of 300 W, the
(approximately 200  C). However, the stage 2 of leucaena profile biochar produced by microwave torrefaction of SS25% sample had a
ended much earlier than that of sewage sludge profile. The fuel ratio of approximately 11. Besides, when the pure sewage
boundaries between stages 2 and 3 of leucaena and sewage sludge sludge was torrefied at a microwave power level of 350 W, the fuel
were located at approximately 370 and 500  C, respectively. This ratio of biochar was up to 14.
should be attributable to their difference in chemical compositions.
The volatile content of leucaena was much higher than that of 3.3. Ultimate analysis
sewage sludge, whereas the ash content of sewage sludge was
much higher than that of leucaena. Besides, the ultimate compo- The ultimate compositions of biochar are illustrated in Fig. 3. As
sitions of the two biomass feedstocks were different. Moreover, the can be seen, when the biochar was produced at higher microwave
TG profile of the blend was very similar to that of leucaena, power levels, it generally had higher carbon content but lower
although its final residual weight percent was nearly the average of hydrogen, oxygen, and nitrogen contents. This should be attribut-
sewage sludge and leucaena values. able to that oxygen- and nitrogen-contained hydrocarbons were
removed more at higher reaction temperatures. Therefore, the ra-
tios of hydrogen to carbon (H/C) and oxygen to carbon (O/C) were
substantially reduced. In general, the carbon content of biochar
increased with increasing microwave power level, but decreased
with increasing sewage sludge blending ratio. However, at a mi-
crowave power level of 100 W, the carbon contents of the biochar
produced from SS25% and SS50% were approximately 73 and 66 wt
%, much higher than that from SS0% (approximately 59 wt%). Once
again, an unexpected result happened when the sewage sludge
blending ratios were 25 and 50 wt% and the power level was 100 W.
Therefore, there could be a synergistic effect between sewage
sludge and leucaena to let microwave torrefaction severer at such
low microwave power level. Besides, the highest carbon content of
the biochar produced from blends was approximately 77 wt%,
which produced from SS25% at a microwave power level of 150 W.
Fig. 1. TG curves of sewage sludge, leucaena, and a 1:1 blend. The aforementioned H/C and O/C ratios are important
4 Y.-F. Huang et al. / Energy 116 (2016) 1e7

Fig. 2. Proximate compositions of biochar produced at different biomass blending ratios and different microwave power levels.

Table 2
Fuel ratios of biochar.

Microwave power level (W) Sewage sludge blending ratio (wt%)

0 25 50 75 100

100 0.57 ± 0.07 0.70 ± 0.18 2.16 ± 0.34 2.44 ± 0.25 1.06 ± 0.08
150 4.03 ± 1.39 2.02 ± 0.48 4.32 ± 0.83 5.06 ± 0.38 2.88 ± 0.44
200 4.94 ± 1.86 2.03 ± 0.09 3.99 ± 0.75 3.64 ± 1.04 3.36 ± 0.67
250 5.92 ± 1.73 6.42 ± 0.75 5.35 ± 1.30 5.00 ± 0.52 6.74 ± 1.25
300 5.97 ± 0.96 11.18 ± 1.97 3.62 ± 1.03 5.59 ± 1.43 5.78 ± 0.88
350 7.30 ± 0.51 9.38 ± 0.74 7.60 ± 1.71 8.79 ± 0.21 13.84 ± 2.21

indicators, because the combustion or gasification of biomass 350 W was approximately 0.34, which could be attributable to the
feedstocks with higher hydrogen and oxygen contents would lead severe microwave torrefaction carried out by the high microwave
to more formation of smoke [48]. The elemental composition of power level to sufficiently remove the hydrogen content of
biochar can be observed and discussed by using the van Krevelen biomass. In general, the atomic H/C ratio of biochar can be reduced
diagram, which is a plot of atomic H/C ratio versus atomic O/C ratio. to even lower than that of anthracite, but the lowest atomic O/C
The atomic ratios of raw sewage sludge and leucaena and biochar ratio was still higher than that of bituminous coal. Therefore, to
produced from different biomass blending ratios and at different produce biochar with elemental composition similar to that of
microwave power levels were compared with those of different anthracite, it would be necessary to further reduce the oxygen
ranks of coal [49], as illustrated in Fig. 4. It can be seen that both H/C content of biochar by modifying microwave torrefaction or adding
and O/C ratios were substantially reduced after microwave torre- another process, such as feedstock pretreatment and biochar
faction. Besides, the ratios increased with increasing microwave refinement.
power level, but decreased with increasing sewage sludge blending
ratio. The biochar produced from pure leucaena feedstock had 3.4. Heating value
relatively low atomic H/C and O/C ratios (approximately 0.40 and
0.14). Besides, the atomic H/C ratio of the biochar produced at The heating values of the biochar produced at different biomass
Y.-F. Huang et al. / Energy 116 (2016) 1e7 5

Fig. 3. Ultimate compositions of biochar produced at different biomass blending ratios and different microwave power levels.

Table 3
Higher heating values of biochar.

Microwave power level (W) Sewage sludge blending ratio (wt%)

0 25 50 75 100

100 23.50 23.23 18.92 17.87 16.16


150 29.18 24.88 20.28 16.66 13.07
200 29.19 24.43 18.50 16.46 12.67
250 29.72 21.01 17.34 15.13 12.23
300 29.83 23.37 18.87 13.80 10.30
350 30.27 24.41 15.60 13.39 10.32

* Unit: MJ/kg.

Fig. 4. Van Krevelen diagram for raw sewage sludge and leucaena, biochar, and coal.
The data for the coal are taken from Ref. [49]. Higher microwave power level also led to lower heating value.
However, there were some exceptions.
The experimental and theoretical heating values of biochar are
blending ratios and different microwave power levels are listed in shown in Fig. 5. The theoretical values were calculated according to
Table 3. As can be seen, the HHV of SS0% biochar was much higher biomass blending ratios:
than that of raw leucaena (approximately 19 MJ/kg). At microwave
power levels of 150e350 W, the HHVs of SS0% biochar were as high
Vtheoretical ¼ rS  VS þ ð1  rS Þ  VL (1)
as 29e30 MJ/kg. A power level of 100 W seems to be insufficient for
leucaena torrefaction. Besides, microwave torrefaction lowered the where rs is the sewage sludge blending ratio, Vs and VL are exper-
heating value of sewage sludge. The HHVs of SS100% biochar pro- imental values from individual torrefaction of sewage sludge and
duced at microwave power levels of 300e350 W were only leucaena, respectively. When the sewage sludge blending ratio was
approximately 10 MJ/kg. This is because that the ash content of the 25 wt%, the experimental HHV was higher than the theoretical HHV
biochar was approximately 68 wt%. The heating values of the at a microwave power level of 100 W. This could be attributable to a
blends decreased with increasing sewage sludge blending ratio. synergistic effect as aforementioned to let microwave torrefaction
6 Y.-F. Huang et al. / Energy 116 (2016) 1e7

100 W, the mass yields of SS25% and SS50% were approximately


36% and 44%, and the energy yields were approximately 46% and
48%, all much lower than those of SS0% and SS75%. The results
should be attributable to the synergistic effect as aforementioned to
let microwave torrefaction severer at the low power level. This
phenomenon did not exist at higher microwave power levels,
which could be attributable to that the effect of microwave power
level was stronger than the synergistic effect. Furthermore, the
mass and energy yields of SS25% at 250e350 W were only 18% and
23%, respectively. The low yields represent that approximately
80 wt% of biomass feedstock was converted into gaseous and liquid
products via severer torrefaction (i.e., pyrolysis). In conclusion,
Fig. 5. Heating values of biochar (exp: experimental; the: theoretical). when the sewage sludge blending ratio was not over 50 wt%, a
synergistic effect could occurred to enhance the performance of
microwave torrefaction at low microwave power levels. Thus, en-
severer. Otherwise, the experimental HHV of SS25% biochar was ergy requirement for microwave torrefaction can be lowered.
lower than the theoretical HHV at 100 W. This should be because
that, at this time, the effect of microwave power level was more 3.6. Energy return on investment
substantial. When the sewage sludge blending ratio increased to 50
and 75 wt%, the synergistic effect was hard to be identified. To evaluate the energy usage benefit of microwave co-
Therefore, the relatively small amount of sewage sludge could play torrefaction, an indicator called energy return on investment
a role as a catalyst. (EROI) was calculated. EROI is a ratio between the energy delivered
to society and the energy required to deliver that energy [51]:

3.5. Mass and energy yields Energy delivered


EROI ¼ (4)
Energy required
The mass and energy yields of sewage sludge and leucaena co-
torrefaction are listed in Fig. 6. The mass and energy yields can be EROI is an important indicator of potential energy benefit to
calculated by the equations as follows [50]: society [52]. The calculation details for the EROI of microwave co-
torrefaction are listed in Table 4. It should be noted that the
Mass of torrefied biomass maximum processing capacity of the microwave heating system
Mass yield ð%Þ ¼  100 (2) can be approximately 200 g, and the conversion efficiency from
Mass of raw biomass
electrical energy to microwave energy can be 50% [53]. The EROI of
HHV of torrefied biomass microwave co-torrefaction of SS25% at a microwave power level of
Energy yield ð%Þ ¼ Mass yield  100 W in a processing time of 30 min can be approximately 4.7,
HHV of raw biomass
without the recovery of gaseous and liquid products. Since the
(3)
minimum EROI for a sustainable society is 3 [54], the technique
In general, both mass and energy yields increased with under the conditions should be energetically and economically
increasing sewage sludge blending ratio, but decreased with mi- feasible. Besides, if all the byproducts of microwave torrefaction
crowave power level. However, at a microwave power level of (condensable liquids and non-condensable gases) can be totally
recovered (i.e., the chemical energy of the blend is completely
utilized), the EROI will be as high as approximately 10.1. Further-
more, when the treatment cost of sewage sludge and the carbon
absorption by leucaena growth are considered, the economic and
environmental benefits of the technique can be even higher.

4. Conclusions

In this study, the co-torrefaction of sewage sludge and leucaena


was carried out by using microwave heating. The power level of
100 W was not high enough for microwave torrefaction. However,
with the addition of sewage sludge not over 50 wt%, the reaction
performance would be satisfactory possibly attributable to the ex-
istence of a synergistic effect. The relatively small amount of

Table 4
Calculation details for the EROI of microwave co-torrefaction.

Energy required Energy delivered

 Microwave power level: 100 W  Sewage sludge


blending ratio: 25 wt%
 Processing time: 30 min  Feedstock weight:
200 g (maximum capacity)
 Conversion efficiency from  Energy yield: 46%
electrical energy to
microwave energy: 50%
Fig. 6. Mass and energy yields of sewage sludge and leucaena co-torrefaction.
Y.-F. Huang et al. / Energy 116 (2016) 1e7 7

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