Fuel 272 (2020) 117628

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A stepwise microwave synergistic pyrolysis approach to produce sludge- T

based biochars: Feasibility study simulated by laboratory experiments
Chaoqian Wanga, Wenlong Wanga, , Leteng Linb, , Fusen Zhanga, Runing Zhanga, Jing Suna,
⁎ ⁎

Zhanlong Songa, Yanpeng Maoa, Xiqiang Zhaoa

a
National Engineering Laboratory for Reducing Emissions from Coal Combustion, Engineering Research Center of Environmental Thermal Technology of Ministry of
Education, Shandong Key Laboratory of Energy Carbon Reduction and Resource Utilization, School of Energy and Power Engineering, Shandong University, Jinan,
Shandong 250061, China
b
Department of Built Environment and Energy Technology, Linnaeus University, 351 95 Växjö, Sweden

ARTICLE INFO ABSTRACT

Keywords: A stepwise microwave synergistic pyrolysis (SMSP) approach is proposed as a new way to relieve disposal
Sewage sludge problems of the sewage sludge. Here the sludge is first pre-pyrolyzed by a conventional heating stage, and then
Microwave rapidly pyrolyzed by a microwave-induced heating stage without any extra microwave absorbers or blending
Pyrolysis needed. Under simulated process pyrolysis conditions, the dried sludge, intermediate and final sludge-based
Biochar
biochar samples were prepared in the laboratory. Their chemical composition, microstructure and morphology,
Heavy metals immobilization
and leaching toxicity of heavy metals were carefully characterized and analyzed by various techniques such as
proximate and ultimate analysis, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy,
Brunauer-Emmett-Teller (BET), and scanning electron microscope equipped with energy-dispersive x-ray spec-
troscopy (SEM-EDX). Results showed that the pre-pyrolytic biochar can be rapidly heated up to 1100 °C within
5 min under microwave irradiation. The pre-pyrolytic stage increased the carbonization and ash enrichment
degree of the sludge which itself acted as a good microwave absorber while achieving a quick temperature rise
under microwave irradiation. The ash remaining ratio and the specific surface area of the biochar derived from
the SMSP approach (labelled as SBC2) are increased by 6.46% and 16.17% respectively, compared with the
conventional biochar sample (SBC1). And SBC2 still had diverse surface functional groups kept after SMSP. The
residual ratios of Ni, Cu, Zn, Pb, Cr and Cd in SBC2 was more noticeable than in SBC1 but the leaching ratios
quite the contrary. Vitrification is also well proved by the increment of quartz peak detected by XRD tests, and
the formation of melted glassy spheres with elemental composition of Si, Ca, Al observed by SEM-EDX. It can
favorably increase solidification level and decrease leaching toxicity of heavy metals in the SBC2. The feasibility
of this proposed SMSP concept has been positively supported by our experimental results. The properties of the
sludge-based biochar produced from the SMSP approach also show great potential to be utilized as precursors to
produce various adsorbents.

1. Introduction
Sewage sludge is an unavoidable and heterogeneous byproduct from
wastewater treatment, which contains, not only hazardous substances
(e.g. pathogens and heavy metals), but also organic matter with certain
useful chemical energy and nutrients (e.g. nitrogen and phosphorus
etc.) that can be used as fertilizers as well [1]. During the course of
urbanization and industrialization, the production of sewage sludge
escalates [1]. In China, over 30 million tons of the wet sewage sludge is
produced every year, which is also increasing by 10% annually [2,3].
Current technologies hardly treat and dispose of the sewage sludge in
an economic and ecological way. In order to avoid the secondary pol-
lution and energy waste, management and treatment of the sewage
sludge is becoming an important issue that relates to circular economy,
human health, environment and nature.
The environmental regulations and standards are continuously
getting stricter [1]. The goal of the sludge treatment is to find both
energy-efficient and environment-friendly methods to reduce its vo-
lume and stabilize its hazard components, recovery useful material or
energy, and/or upgrade into certain value-added products for further
utilization, rather than direct disposal or land-fill. Anaerobic digestion
is a typical treatment technology, which could reduce the sludge

⁎
Corresponding authors.
E-mail addresses: wwenlong@sdu.edu.cn (W. Wang), leteng.lin@lnu.se (L. Lin).

https://doi.org/10.1016/j.fuel.2020.117628
Received 11 September 2019; Received in revised form 13 February 2020; Accepted 12 March 2020
Available online 01 April 2020
0016-2361/ © 2020 Elsevier Ltd. All rights reserved.
C. Wang, et al.
volume and produce biogas fuel [4]. However, the conversion effi-
ciency of the process is very low, and the digestion reaction time is
rather long. Heavy metals left in the residues after the digestion still
need to be taken care of [5]. The installation and operation cost are still
quite high [6]. Currently the application of the anaerobic digestion
technology for the sewage sludge treatment is very rare in China [6].
Conventional disposal methods of sewage sludge mainly include land-
fill, compost and incineration. However, they all have profitability
limits while also having satisfying new requirements of resource reuse
and sustainable development goals. It is mainly limited by the high risk
of the secondary pollution by the heavy metals and other hazardous
components [1]. In recent years pyrolysis technology shows the po-
tential to meet those requirements, which has become a promising al-
ternative for the sewage sludge disposal [1,3].
Pyrolysis is a thermochemical decomposition process under inert
atmosphere, which could convert organic matter in the sewage sludge
such as proteins and its cellulosic fractions into gas, liquid and biochar.
Compared with sludge-based pyrolytic gas and liquid [7,8], sludge-
based biochar is a stable, cost-effective carbon material [9–11] in which
both carbon and heavy metals can be solidified. Sludge-based biochar
can be utilized as the precursor of adsorbent [11], catalyst [9] and soil
amendment [10]. One of the main determining factors is the leaching
toxicity of heavy metals in the sludge-based biochar, which could be
optimized and controlled through vitrification occurring under high
temperature pyrolysis [12]. Conventional way of heating (pyrolyzing)
the sludge to achieve the solidification target usually need reach around
1400 °C and retain for several hours. This, however, is a really energy-
and time consuming procedure [12–14]. Most heavy metal components
could be already vaporized during this heating process. As reported,
around 80% of heavy metals would release from sludge-based biochar
already at 1000 °C for 10 min [13,15]. Moreover, prolonged pyrolysis
time at high temperatures could possibly destroy char microstructures
due to the occurrence of pore collapse and ash melting. Researchers
have tried to stabilize heavy metals at low temperatures without vi-
trification by co-pyrolyzing the sewage sludge with chemical additives
[16] or biomass [17]. Results for lowering the toxicity of the heavy
metal are positive [15], but the mobility of heavy metals is still high
due to the low formation rate of the stable chemical speciation of heavy
metals [15,17]. The risk of the secondary pollution due to the applied
chemicals and movable heavy metals [16,17] is hard to control.
Microwave-induced pyrolysis has shown great potential for in-
dustrial application due to the advantages of lower energy consumption
and short processing time [2]. Microwave irradiation offers a unique
way of volumetric heating, which is also rapid, selective and non-con-
tacting [18]. Sludge-based biochars obtained from microwave pyrolysis
showed better properties of heavy metals immobilization [13,19] and
adsorptivity [14] than biochars produced by the conventional non-
microwave heating under similar pyrolysis temperatures. However, the
fast heating of the microwave can be realized only when the microwave
absorbers exist in the sample [20]. Usually the sludge that will be
treated by microwave irradiation will be blended with different types of
absorbers. Researchers also found that carbon-based material such as
carbon black, charcoal, active carbon or even biochars from pyrolysis
could be used as microwave absorbers to blend with the sludge to ef-
ficiently convert microwave energy into heat [20,21]. After pyrolysis,
some absorbers are supposed to be separated from sludge-based biochar
for recycling. However, this is very difficult and costly in practice and
might also aggravate leaching toxicity of heavy metals if absorbers with
heavy metals have been applied [22]. Blending of the extra microwave
absorbers with the sludge will always greatly increase the volume of the
final sludge-based product. All these factors prevent the microwave
pyrolysis from being commercialized.
In order to relieve the problem of extra microwave absorber needed
in the current research on microwave pyrolysis of sewage sludge, an
innovative stepwise microwave synergistic pyrolysis (SMSP) is pro-
posed which integrates the microwave pyrolysis with conventional pre-
2
Fuel 272 (2020) 117628
pyrolysis. It is a two-staged concept that is expected to be developed as
a continuous running process. This differs from previous research
concepts of blending biochars and/or extra microwave absorbers with
the sludge for microwave pyrolysis. In this proposed process, the dried
sludge feedstock is first pre-pyrolyzed by the conventional heating for a
relatively short time. This is to increase the dielectric properties of the
sludge through enrichment of fixed carbon and heavy metals during the
devolatilization. Continuously the pre-pyrolytic sludge-based biochar
with good microwave absorption ability is directly exposed to micro-
wave irradiation at the second stage. The high-energy sites [23] in-
duced by microwave irradiation can quickly heat up the sample to
enhance the in-situ carbonization of sludge-based biochar and the so-
lidification of heavy metals via vitrification. This new approach has
potential advantages of not needing any extra microwave absorbers,
shortened processing time, high value-added sludge-based biochar and
high energy efficiency of the whole process. In order to study the fea-
sibility of this proposed concept, the dried sludge feedstock and sludge-
based biochar products were prepared under simulated conditions in
laboratory batch experiments.
2. Experimental
2.1. Sewage sludge sample preparation
Raw sewage sludge sample was collected from a wastewater treat-
ment station, produced by about 27,000 inhabitants, located at the
campus of Shandong Jianzhu University in Jinan, China. Raw sewage
sludge sample had the initial moisture content about 85 wt%. After
being sun-dried for 7 days, the sewage sludge was further dried in an
electrical oven at 105 °C for 24 h. The moisture content of the sewage
sludge sample decreased to approximately 5 wt%. The sewage sludge
sample was then ground in a portable stainless-steel blade mill, and
sieved by using a 20-mesh screen. The sewage sludge that passed
through the screen was selected and properly mixed to ensure its
homogeneity. The selected sample denoted as DSS was stored in the
sealed bag for subsequent pyrolysis experiments.
2.2. Preparation of the sludge-based biochar samples
2.2.1. Preparation of sludge-based biochars via both conventional and the
SMSP procedures
In order to simulate and analyze the potential advantages of the
SMSP procedure, the sludge-based biochars were produced via two
different pyrolysis routes and used for further characterization and
properties comparisons. According to the literature [12,13,24,25],
pyrolysis conditions including the temperature, retention time and
heating rate would directly influence the immobilization of heavy
metals, microstructural properties of biochar products, as well as the
total energy consumption in the process. As a compromise to all those
aspects, we finally selected conditions at 700 °C with a retention time of
60 min as a reference to perform conventional pyrolysis.
The first group of the sludge sample (about 30 g) was pyrolyzed
through a slow conventional pyrolysis procedure. This pyrolysis system
consists of a tubular reactor (inner diameter: 50 mm, length: 1200 mm)
that was heated by an electrical oven (Jvjing Inc., China), a nitrogen
supply unit, a pyrolysis gas washing unit, and a pyrolysis oil con-
densation unit. The sludge filled porcelain boat with round bottom
(width: 40 mm, length: 150 mm, height: 20 mm) was set in the hot zone
of the tubular reactor. The reactor was purged by a 200 ml/min N2 flow
(99.99%, V: V) for 30 min to achieve an inert atmosphere before
heating started. Then the reactor was heated up to 700 °C with a
heating rate of 25 °C/min from room temperature. When the tem-
perature reached 700 °C, it was kept isothermal for 60 min. Then the
oven was switched off, and the sludge-based biochar was cooled to
room temperature in the reactor protected by flowing N2. The resulting
biochar was denominated as SBC1.
C. Wang, et al.
The second group of the sludge feedstock sample was first heated up
to 700 °C as described above in the conventional pyrolysis procedure.
But it was only kept for 5 min at the isothermal stage at 700 °C.
Thereafter the sample was cooled in the reactor by flowing N2. This pre-
pyrolytic sludge-based biochar was denominated as SBC0. The sample
SBC0 would later be partially used for further characterization, and
partially to expose for secondary microwave synergistic pyrolysis.
Secondary microwave synergistic pyrolysis of pre-pyrolytic biochar
of SBC0 was conducted in a multi-mode microwave oven which was
adjusted continuously from 0 to 3000 W under constant frequency
(2450 MHz). The microwave pyrolysis system consists of a vertical
cylindrical quartz reactor (diameter: 40 mm, height: 150 mm), K-type
thermocouple with a temperature display, and the pyrolysis gas and
liquid collection units similar to the ones used in the conventional
pyrolysis setup. The quartz reactor has two ports for gas inlet and outlet
with both ends covered with lids. About 20 g pre-pyrolytic sludge-based
biochar SBC0 was placed in the quartz reactor which was purged by N2
flow for 3 min before heating. The microwave was then switched on to
a power fixed of 900 W. After 5 min of pyrolysis, the microwave was
turned off and the sample was cooled in the reactor protected by
flowing N2. The resulting sludge-based biochar was denominated as
SBC2.
2.2.2. Temperature rise measurement of the dried sludge and biochar during
the microwave irradiation
Pyrolysis temperature is a key factor in influencing quality and
structure of sludge-based biochars. It is important to get ideas on how
the temperature develops when the sample is heated during microwave
irradiation. The temperature was measured by a K-type thermocouple
(measuring range: 0–1450 °C) with a temperature display. The ceiling
wall of the microwave oven has a small aperture made just for the
thermocouple passing through. The crucible filled with sludge sample is
located directly below this opening. Once the microwave is switched off
after the desired heating time, the thermocouple is simultaneously in-
serted into the sludge sample in the fixed crucible. The thermocouple is
then stirred stably during the course of temperature measurement. The
temperature indicated by the thermocouple under this circumstance is
not an accurate measurement and is always lower than the actual
sample temperature due to the time delay, system response and heat
loss. The temperature measurement was done to both the DSS and the
SBC0 samples. For each case, about 20 g of the sample was dispensed in
a quartz crucible and heated at 900 W.
2.3. Characterization of sludge and pyrolytic sludge-based biochars
2.3.1. General nature of the dried sludge and biochars
For both prepared sludge sample and pyrolytic biochar samples, the
elemental analysis of carbon, hydrogen, and nitrogen was performed
using an Vario EL III elemental analyzer (Elementar, Germany).
Elements C and H were tested by absorption method, element N was
tested by Kjeldahl method [26]. The proximate analysis of fixed carbon
and ash content was completed using an SDTGA 5000 analyzer (Sundy,
Hunan, China). Test conditions for about 1 g sample were as follows:
water content (105 °C, 1 h), ash content (815 °C, 1 h), volatile content
(900 °C, 7 min), and fixed carbon content calculated by difference.
They were mixed with deionized water with a ratio of 1: 20 (sample
weight: water volume) to identify the pH value of the sludge and bio-
char samples, and thereafter shaken for 24 h in a rotary drum shaker
and then centrifuged for solid separation. The pH value of the solutions
was measured using a PHS-3C standard pH meter (INESA, Shanghai,
China).
2.3.2. Fourier transform infrared (FTIR) spectra and X-ray diffraction
(XRD) tests
To distinguish the changes of surface functional groups, FTIR tests
were performed using a Spectrum GX spectrometer (Perkin Elmer,
3
Fuel 272 (2020) 117628
USA). The spectra of both sludge and biochar samples were investigated
in the 4000–400 cm−1 region with a resolution of 4 cm−1. This is based
on the principle of Fourier transform for interfered infrared light with
the advantages of high resolution and sensitivity. The raw data baseline
was adjusted and the modified data were then normalized by using
OMNIC 8.0.342 software (Thermo Scientific, USA).
To explore the changes in main chemical components of the sludge
and biochar samples, XRD tests were carried out using X-ray
Diffractometer (Thermo Scientific, USA), which works based on the
principle of correspondence between crystal structure and its diffrac-
tion pattern. XRD instrument run at 40 kV and 250 mA, a scanning
angle of 10°- 80°, and the scanning speed of 6°/min. The raw data
baseline was adjusted and the modified data were then normalized by
using MDI Jade 5.0 software.
2.3.3. Specific surface area and morphology
To analyze microstructural properties of the dried sludge and
sludge-based biochars, specific surface area was determined by ap-
plying the Brunauer-Emmett-Teller (BET) method that works according
to the N2 adsorption–desorption mechanism. The surface area and pore
volume were determined by the Density Functional Theory (DFT)
method, and the average pore size was calculated by the Nonlocal
Density Functional Theory (NLDFT). NLDFT model describes the be-
havior of the applied fluid confined in the pore at the molecular level.
And it is commonly used to calculate pore size distribution of carbon or
other porous materials such as biochars which contains micro- and
mesopore structures. The measurement was carried out using an
Autosorb-1-C gas sorption system (Quantachrome, USA) which was
running isothermally at 77 K. All samples were outgassed at 300 °C for
4 h before BET measurements. The morphology and local elemental
composition of all samples was characterized by using a S-5500 scan-
ning electron microscope equipped with energy-dispersive x-ray spec-
troscopy (SEM-EDX, Hitachi, Japan).
2.4. Total concentration and leaching toxicity of main heavy metals
Leaching property of heavy metals is a vital evaluation criterion for
further application of sludge-based biochars. Total concentration of
main heavy metals (Cu, Zn, Pb, Cr, Cd, Ni) in all sludge and biochar
samples were detected by microwave digestion method. For each test,
about 0.3 g sample was added to the polytetrafluoroethylene (PTFE)
digestion tank and sequentially mixed with hydrochloric acid (HCl,
1 ml), hydrofluoric acid (HF, 4 ml) and hydrogen nitrate (HNO3, 5 ml).
The lid covered tank was placed in the microwave digestion instrument
(CEM MARS-5, USA). The microwave power was fixed at 1200 W
during the heating process. When the digestion mixture reached 180 °C,
the microwave was switch off after a retention time of 15 min.
Leaching property of main heavy metals was tested according to the
Toxicity Characteristic Leaching Procedure (TCLP) method. An acetic
acid with a pH value of 2.88 ± 0.05 was used as an extraction fluid for
the four samples (DSS, SBC0, SBC1, and SBC2). About 2.0 g of each
sample was mixed with the extraction fluid at a ratio of 1:20 (sample
weight: liquid volume). The extractor vessels were then placed in a
rotary agitation device at a speed of 30 ± 2 rpm for 18 ± 2 h.
Thereafter, the extract solutions were separated by vacuum filtration.
Heavy metal concentrations in the solution were determined by using
an inductively coupled plasma mass spectrometry (ICP-OES) (Optima
7000 DV, PerkinElmer, USA). The Chinese standard (GB 4284–2018)
was adopted as the evaluation reference for the leaching toxicity of the
sludge and biochar samples.
Prior to the test, all containers were immersed in nitric acid (3 wt%)
for 24 h, then flushed by the deionized water at least three times and
dried in an electrical oven at 105 °C. Chemicals used in this test were all
at the analytical reagent (AR) level and containers used for handling
extraction liquid samples were made of polyethylene.
The residual ratio of heavy metal suggests that the total remaining
C. Wang, et al.
percentage of each target heavy metal in the biochars (SBC0, SBC1 and
SBC2), was calculated as follows [12]:
Residual ratio = (Cbiochar / Csludge feedstock ) × Ybiochar
where Cbiochar is the total concentration of the target heavy metal in
each biochar sample (unit: mg/kg); Csludge feedstock is the total con-
centration of the target heavy metal in the dried sludge (DSS) (unit:
mg/kg); and Ybiochar is the yield of the biochar sample (unit: %).
The leaching ratio of heavy metal suggests that the leaching per-
centage of each target heavy metal from the biochars (SBC0, SBC1 and
SBC2), was calculated as follows [12]:
Leaching ratio = Cleaching / Ctotal
where Cleaching is the leaching concentration of the target heavy metal
in each biochar sample (unit: mg/L), and Ctotal is the total concentration
of the same target heavy metal in the same biochar sample (unit: mg/L).
3. Results and discussion
3.1. Temperature rise measurement of the dried sewage sludge and biochar
For the same parental sludge feedstock, char characteristics such as
char yield, pore structure, and stability are rather dependent on the
conditions of pyrolysis process, that is to say, pyrolysis temperature
[27], heating rate [25,28] and retention time [25,28]. Generally, higher
pyrolysis temperature, faster heating rate and longer retention time
would enhance sample devolatization and produce char with less yield,
more porous structure and better stability [25,28,29]. Fig. 1(a) sum-
marized the heating histories of all our sludge and derived biochar
samples. Samples of SBC0, SBC1 and SBC2 had experienced the same
conventional pyrolysis heating process with a heating rate of 25 °C/min
up to 700 °C. Subsequently, the SBC0 was cooled directly after a re-
tention time of 5 min, and SBC1 continued to a retention time of
55 min. The cooled SBC0 was further microwave-induced pyrolyzed to
derive the biochar sample of SBC2. This is regarded as the final product
of the proposed SMSP process. During the second stage of microwave-
induced pyrolysis, the SBC2 sample experienced a 5 min microwave
exposure which heated the biochar sample up to 1100 °C with a heat
rate of around 213 °C/min. Due to the limitation of the applied tem-
perature measurement method [20,30,31], the final indication on the
thermocouple would always have a time delay. This made the final
reading to be probably lower than the actual sample temperature due to
the unavoidable heat loss and system response.
Fig. 1. Heating procedure applied for the sample preparation (a), and the temperature rise measurement for the dried sludge (DSS) and the sludge-based biochar
(SBC0) under microwave irradiation at a fixed 900 W (b).
4
Fuel 272 (2020) 117628
The major purpose of the pre-pyrolytic stage is to increase the
carbonization degree and ash enrichment degree of the pre-pyrolytic
sludge-based biochar (SBC0). During the second microwave-induced
stage, SBC0 could act as a good microwave absorber achieving a quick
temperature rise which could potentially melt ash component and so-
lidify heavy metals via vitrification [32]. This is proven by the com-
parison of the temperature rise between the SBC0 and DSS samples
under the same microwave-induced conditions (shown in Fig. 1b). The
pre-pyrolytic sludge-based biochar of SBC0 could rapidly reach up to
1100 °C due to the potential increased dielectric properties [2,20],
while the dried sludge sample, DSS, showed a much slower temperature
rise trend.
3.2. General nature of the dried sewage sludge and derived biochars
Table 1 summarized the basic physicochemical properties of the
dried sludge and derived biochars including the yield, proximate ana-
lysis, elemental analysis, pH value, and atomic ratios of H/C and N/C.
The increase of the severity of pyrolysis conditions would enhance the
devolatilization of the sludge sample and result in decreased yield of
biochar samples which contained fewer volatile components. This has
been indicated in the Table 1. Yields of the sludge-based biochars de-
creased from 67.53% for pre-pyrolytic biochar SBC0 to 55.45% for
SBC1 due to the prolonged retention time. It went further down to
54.12% for the SBC2 due to the higher temperature and heating rate
under microwave-induced environment. The loss ratios of the total
volatile matter and fixed carbon for three biochars were steadily in-
creased from 53.66% for SBC0 sample to 70.93% for SBC2 sample. The
volatile contents in the biochars were much less than that in the original
DSS sample. Only about 5.58% of the volatile matter was left in the
SBC2 sample.
The increased severity of pyrolysis condition could also reduce the
ash content of biochars, but not as much as the influence to the volatile
matter. Due to the big loss of the volatile matter, the ash content in the
specific pyrolytic biochars (SBC0, SBC1, SBC2) was actually enriched
compared to the original DSS, which was similar to the trend of the
fixed carbon content. Ash component is relatively stable and mostly
remains as indicated by the ash remaining ratios. Compared to the ash
content of the DSS sample, about 95.2% of ash remained in the SBC0
sample, and 81.56% in the SBC1 sample which is probably due to the
long pyrolysis retention time. The SBC2 sample showed a better ash
remaining ratio of 86.83% compared to the SBC1 sample, even though
it was pyrolyzed with a higher heating rate at a higher temperature.
C. Wang, et al. Fuel 272 (2020) 117628

Table 1
Physical and chemical properties of the dried sludge (DSS) and biochars (SBC0, SBC1 and SBC2) derived under different pyrolysis conditions.
DSS SBC0 SBC1 SBC2

Yield, wt.% 100 ± 0.05 67.53 ± 5.17 55.45 ± 3.22 54.12 ± 4.36
Moisture content, wt.% 4.82 ± 0.27 3.24 ± 0.08 0.92 ± 0.03 0.19 ± 0.07
Volatile content, wt.% 47.19 ± 1.62 19.33 ± 0.05 12.17 ± 0.15 5.58 ± 0.11
Fixed carbon content, wt.% 4.62 ± 1.44 16.29 ± 0.93 23.12 ± 0.32 24.65 ± 0.46
Volatile matter and fixed carbon loss ratiob, % 0 53.66 64.54 70.93
Ash content, wt.% 43.37 ± 4.73 61.14 ± 0.81 63.79 ± 1.25 69.58 ± 1.01
Ash remaining ratioa, % 100 95.20 81.56 86.83
Atomic ratio N/C 1.645 ± 0.21 0.387 ± 0.04 0.181 ± 0.11 0.127 ± 0.02
H/C 0.057 ± 0.04 0.043 ± 0.02 0.032 ± 0.03 0.029 ± 0.02
pH (S:L = 1:20) 5.94 ± 0.06 9.87 ± 0.47 10.67 ± 0.31 11.23 ± 0.11

a
Ash remaining ratio = ash content of biochar × biochar yield /ash content in the dried sludge × 100% [33]. Only the averaged values were used for the
calculation.
b
Volatile matter and fixed carbon loss ratio = 1-(1-ash content of biochar) × biochar yield/(1-ash content of sludge) × 100% [33]. Only the averaged values
were used for the calculation.

These results, on one hand, indicated that the release of inorganic ash
components could also be promoted together with the formation of
condensable hydrocarbons and gas product during the enhanced de-
volatilization stage [33]. On the other hand, the SMSP approach shows
a great potential of solidifying heavy metals and ash component within
the biochar structure. This is probably due to the vitrification that was
proved by XRD and SEM-EDX characterization discussed in the fol-
lowing related sections. A shorter pre-pyrolysis time could certainly
make the dried sludge feedstock (DSS) as a suitable microwave ab-
sorber, SBC0, for the second stage of microwave-induced pyrolysis
process. The total retention time needed by the two-staged process
could be shortened by a factor of about 5.5 compared to the conven-
tional pyrolysis process.
The lower the molar ratio of H/C becomes, the higher carbonization
degree the sludge-based biochar has reaches. All three biochars showed
a molar ratio of H/C below 0.5, suggesting those samples had good
thermal stability due to the high degree of carbonization and ar-
omaticity [34]. The molar ratio of N/C showed a similar trend as H/C
ratio, meaning, a decrease when the severity of pyrolysis increased. It
could be an indication of the loss of the surface functional groups in the
biochars [33].
The DSS showed an acidic pH level of 5.95. The pH level of the three
biochars (SBC0, SBC1, and SBC2) indicated a steady increasing in the
basicity as the severity of pyrolysis increased which is similar to results
reported by other researchers [29,35]. The inorganic ash content such
as metal oxides and minerals is maintained and enriched during pyr-
olysis which could contribute to the enhanced alkalinity of biochar
products. Some researchers pointed out the increase of the basicity of
sludge-based biochars was caused by the release of alkali salts from the
pyrolytic structure [36]. Others have also reported the transformation
of amine functionalities to pyridine-like compounds and that the de-
crease of acidic surface functional groups could enhance the surface
basicity [24].
3.3. XRD test
XRD spectra of the dried sludge and three biochar samples were
presented in Fig. 2. In general, higher pyrolysis temperature and longer
retention time could facilitate the formation of crystalline structure
[37]. The crystallinity of dried sludge (DSS) was low and was indicated
by less sharper peaks compared with other three samples. Crystal
substances in the DSS were mainly SiO2 and calcite, which originated
from large amount of sediment component and dewatering additive
during the process of sewage sludge treatment [2]. Two quartz sharper
peaks at 2θ = 20.9° and 50.2° initially appeared in the SBC0 but the
peaks were rather weak. As the retention time prolonged, the peaks
became slightly stronger in SBC1. These quartz peaks became most
distinguishable in the sample SBC2, suggesting the occurrence of the
Quartz
Calcite
Quartz Quartz
CuO
Al2O3
ZnO SBC2
SBC1
NaCl
SBC0
Fe2O3
DSS
10 20 30 40 50 60 70 80
2θ (degrees)
Fig. 2. XRD spectra of the dried sludge (DSS) and three sludge-based biochar
samples (SBC0, SBC1 and SBC2).
enhanced vitrification via the microwave synergistic pyrolysis stage.
Other peaks between 2θ = 10°- 40° also became more obvious in the
SBC2 sample than those in other samples. This implied that the pre-
pyrolytic process could effectively convert the DSS into an excellent
microwave absorber, SBC0. The microwave absorbing capability of
SBC0 can facilitate fast microwave heating and promote vitrification in
the sludge-based biochar within a short time. This would potentially
contribute to a new way of solidifying heavy metals with less energy
consumption due to the time-saving effect. Other dispersed phases such
as Al2O3 and Fe2O3 in three pyrolytic samples may also play a role in
being a precursor for vitrification to solidify heavy metals [32].
The behavior of calcite in this study differs from the result reported
in the other research paper, where the calcite was found completely
decomposed when the pyrolysis temperature went above 700 °C. In our
study, calcite was clearly detected in all investigated sludge and biochar
samples. This was also indicated by FTIR spectroscope, even though the
SBC2 has experienced high-temperature microwave synergistic pyr-
olysis. There are a few potential explanations. One aspect could be that
large amount of calcite already existed in the original sludge sample.
This formed partially from big quantity of dewatering additive (CaO)
and partially from rain-swept sediment during the treatment process.
Another aspect, the provided reaction conditions (i.e. high temperature
but short reaction time) may not be sufficient to decompose all carbo-
nates. In the reference [37], the pyrolysis retention time employed was
2 h for all biochar samples. In addition, effect of protective layers
formed during vitrification may also hinder the decomposition of cal-
cite [38].

5
C. Wang, et al.
SBC2
Absorbance
SBC1
SBC0
DSS
4000 3600 3200 2800 2400 2000 1600 1200 800 400
Wavenumber, cm-1
Fig. 3. Detailed evolution of FTIR spectra for the dried sludge (DSS) and three
biochar samples (SBC0, SBC1 and SBC2).
The NaCl peak disappearance in samples of SBC1 and SBC2 may be
due to the vaporization. Alkali chlorine could easily be vaporized when
the temperature goes above 700 °C. A similar phenomena of alkali re-
lease has been frequently investigated and reported in the field of
thermochemical conversion of biomass [39,40]. CuO existence is rela-
tively stable in all sludge biochars. Crystalline structure of ZnO became
weaker in the SBC2 sample which may be due to some high-tempera-
ture reaction, such as solid solution displacement [12].
3.4. FTIR spectra
FTIR spectra of the dried sludge and three biochars were presented
in the Fig. 3. The band between 3200 and 3600 cm−1 is similar as
reported in the reference [37]. It corresponds to the functional groups
of O–H and N–H stretching vibrations, which means the presence of
possible compounds such as phenols hydroxyl [41], alcohols, carboxylic
acids and amides/amines [37]. This band is rather stable for all three
pyrolytic sludge samples (SBC0 to SBC2) which indicates unchanged
inorganic links with hydroxyl [37].
Peaks at 2926 and 2853 cm−1 are the evidence for the C–H asym-
metrical stretching and symmetrical stretching, respectively, which
correspond to possible aliphatic structures formed from the methylene
groups [37,41]. These two peaks exist in the dried sludge sample DSS,
and disappear in the three biochar samples due to the decomposition of
aliphatic structure during pyrolysis.
The 2350 cm−1 peak corresponds to CO2 [42]. All four samples had
been deducted by the blank background of KBr. However, CO2 was still
found in all three biochar samples but not in the DSS. The main ex-
planation is because CO2 released from the partial decomposing of the
calcite during the pyrolysis process [42] got trapped in all three biochar
samples.
The 1642 cm−1 peak is related to Amide I band with potential
contributions from C = O stretching vibrations around 1700 cm−1
[37]. This peak for SBC1 and SBC2 shows a slightly increase than that
for DSS and SBC0, which is in accordance to the alkalinity increase of
the relevant sample.
The 1430 cm−1 peak is typically related to CH2 scissoring, for in-
stance, in the structure of cellulose or saturated fatty acids [35,37]. In
Table 2
Microstructure properties of the dried sludge and biochar samples presented on the air-dried basis.
DSS
Specific surface area, m2/g 10.74 ± 3.96
Average pore size, nm 8.32 ± 0.87
Pore volume, cm3/g 0.047 ± 0.16
Fuel 272 (2020) 117628
this band the contribution from calcium carbonate, which usually peaks
at around 1420 cm−1 and 873 cm−1 [37], cannot be neglected in this
study due to the proved existence of calcite from XRD tests. Bands at
1000–1150 cm−1 have been attributed to polysaccharides as claimed
by several authors [37]. However, it could also be C-O bonds existed in
phenols, carboxylic or alcohols [41], and/or some inorganic structure
for example the calcite [37]. These two bands became weaker in bio-
chars than in the DSS, which is probably caused by the decomposition
of organic compounds and inorganic carbonates. Even though SBC2
experienced the high temperature microwave-induced pyrolysis, the
oxygen-containing functional groups still exist in the final biochar
sample probably due to the short retention time. The diversity of the
functionalities is well reserved in the final SBC2 which would make it
usable for its potential adsorption and catalytic properties, for example,
the application of the denitration reaction [43].
3.5. Microstructure and morphology
Microstructure properties of the four sludge samples were presented
in Table 2. The dried sludge dominated with the mesopore structure
had the least specific surface area and pore volume among all four
samples. During devolatilization when the gas product is released from
the sludge [37,44], the specific surface area of the SBC0 increased four
times and the pore volume almost doubled than that of the DSS. This
could also be confirmed from the SEM images of the DSS and SBC0 in
the Fig. 4. An obvious microstructural evolution occurred for the SBC0
as proved by the reduction of the particle size and newly formed cav-
ities and openness. The DSS sample looks more like a dense block with
relatively flat morphology and nonporous structure. As the pyrolysis
retention time prolonged, the averaged pore size of the SBC1 became
smaller compared to the SBC0 while the surface area and pore volume
were decreased. Pore blockage caused by ash melting and pyrolytic
liquid [44] could partially explain this. As shown by the SEM image in
Fig. 4, particles in the SBC1 sample agglomerated and some granules
melted together.
The specific surface area of the SBC2 was larger than both the SBC0
and SBC1 samples. The pore volume of the SBC2 sample slightly in-
creased than that of the SBC1 sample. This was probably caused by the
secondary gas release occurring at a higher temperature during the
microwave-induced pyrolysis of the SBC2. Meanwhile, spherical parti-
cles with different particle sizes were formed from ash melting on the
surface of the SBC2 sample (shown in the SBC2 image in the Fig. 4). The
sludge-based biochar sample would experience fast heating and cooling
process [23] due to the character of the microwave selective heating.
This fast response high-temperature process could encourage the for-
mation of small size spherical particles [45]. Another important factor
to the formation of the spherical melt with different particle sizes at
high temperature is the chemical composition of the sample [46]. EDX
analysis was conducted to distinguish components of elements in the
sludge-based biochar samples, with one selected point tested in the
SBC1 and three selected points tested in the SBC2 (the precise position
marked by numbers in the Fig. 4). EDX results here are recommended to
be used as a qualitative indication. The absolute content of elements
that have been identified is not reliable due to the limitations of the
technology, the limited measuring spots and the heterogeneity of the
sludge composition. The ash melting mechanism is similar with the
formation of glassy materials from oxides of silicon, calcium, aluminum
SBC0 SBC1 SBC2
55.31 ± 3.24 53.87 ± 4.18 62.58 ± 3.22
4.77 ± 0.14 3.42 ± 0.21 3.86 ± 0.27
0.091 ± 0.25 0.076 ± 0.19 0.088 ± 0.31
6
C. Wang, et al.
Fig. 4. SEM images and EDX characterization results of the dried sludge and biochar samples. Applied magnification of the SEM-EDX: X10000 for a1-a4, X5000 for b1
and b2.
and iron [46]. As indicated by the EDX results in the Fig. 4, these ele-
ments (Si, Ca, Al) were well identified in the melted balls of the SBC2.
The ball size difference might be caused by the varied proportion of the
local content of silicon, calcium and aluminum. The formation of
melted glassy balls indicated the occurrence of vitrification [32,46]
which is also in agreement with the detection of the newly formed
quartz peaks in the XRD results.
3.6. Solidification and leaching toxicity of main heavy metals
The toxicity of heavy metals in all testing sludge and biochars is
evaluated by the heavy metal residual ratio and leaching ratio. The
lower the residual ratio of heavy metals is, the more the heavy metal
components released from the sludge-based biochar during the heating
procedure. The higher the leaching ratio is, the lower the solidification
degree of heavy metals reached for the specific sludge-based biochar
sample. In order to decrease the environment risk caused by heavy
metals [12], the toxicity of heavy metals in the sludge-based biochars
should be carefully evaluated and controlled.
Residual ratio and total concentration of heavy metals were pre-
sented in Fig. 5(a) and Table 3, respectively. The residual concentration
of Cd for all sludge-based biochars was very low, and almost vanished
in the SBC1 and SBC2. Cd would easily be volatilized when the tem-
perature went above 650 °C [15,47]. Except for Cd, all other targeted
heavy metals in all three biochar samples were relatively enriched with
the total residual concentrations. This is due to the devolatilization of
some hydrocarbons and inorganic components. However, the residual
ratios of all target heavy metals in the biochar samples decreased.
During pyrolysis process, heavy metals could be vaporized and forming
particulate matter through nucleation and condensation, and/or went
into pyrolytic liquid and gas products [15]. The longer pyrolysis
7
Fuel 272 (2020) 117628
retention time led to a lower residual ratio as indicated by the com-
parison between the SBC0 and SBC1. The residual ratio of target heavy
metals in the SBC2 was, however, higher than that in the SBC1. For
each targeted heavy metal Ni, Cu, Zn, Pb, Cr, and Cd, the residual ratios
in the SBC2 were 6.8%, 8.7%, 13.5%, 8.4%, 14.1% and 460% higher
than that in the SBC1, respectively. As discussed before, the pre-pyr-
olytic SBC0 could act as a good microwave absorber. When exposed to
the microwave irradiation to produce SBC2, the hot-spot effect would
rapidly heat up the sample, melt some ash components and solidify
heavy metals via vitrification [32]. That is to say, the SMSP approach is
more advantageous than the conventional pyrolysis method with regard
to both heating time and solidification of the heavy metals.
Leaching ratios and leaching concentrations of the targeted heavy
metals in all sludge and biochar samples were presented in Fig. 5(b) and
Table 4, respectively. Compared to the dried sludge sample, leaching
concentrations of all targeted heavy metals and leaching ratios (except
Cd) decreased to no < 50% in the three biochar samples. Looking at
DSS, SBC0 and SBC1 samples pyrolyzed with increasing retention time,
the leaching ratios of Cu, Zn, Pb and Cr showed a decreasing trend,
whereas the leaching ratios of Ni and Cd increased. It indicates that
longer retention time can stabilize better heavy metals during the
conventional pyrolysis. That condition, however, would lower the re-
sidual ratio of heavy metals as the other consequence. The SBC2 sample
had lower leaching ratios of Ni, Cu, Zn, and Cd than that of the SBC1,
about 83%, 12.5%, 85.2% and 87.4% lower, respectively. The leaching
ratio of Pb and Cr for the SBC2 was slightly higher than that of the
SBC1. However, both were almost equally good taking the error into
consideration. This implies the advantage of the SMSP approach being
able to solidify heavy metals within a short time. When looking at the
leaching concentration of heavy metals in Table 4, the SBC2 sample
gave lower leaching concentration of Ni, Zn and Cd than the SBC1. As
C. Wang, et al. Fuel 272 (2020) 117628

Leaching ratio of heavy metals in samples, %

30

Residual rate of heavy metals in samples, %

120 DSS SBC0 DSS
SBC1 SBC2 SBC0
100 SBC1
SBC2
80 20

60

40 10

20

0 0
Ni Cu Zn Pb Cr Cd Ni Cu Zn Pb Cr Cd
Heavy metals cointained in the sludge samples Heavy metals contained in the sludge samples
(a) Residual ratio of heavy metals (b) Leaching ratio of heavy metals
Fig. 5. Residual and leaching ratio of heavy metals in the dried sludge and biochar samples. Yield ratio of the biochar sample (Ybiochar) was selected from its average
value (shown in Table 1). For each targeted heavy metal, its total concentration in the dried sludge (Csludge feedstock) was average value of three tests, and its total
concentration in the biochar sample (Cbiochar) was three test results, respectively. The total concentration (Ctotal) was the average value of three tests, its leaching
concentration (Cleaching) in the sample was the three test results, respectively. Then error bar was calculated by standard deviation from those three relevant results.

Table 3 potential advantages of short processing time, low energy consumption,

Total concentration of tested heavy metals contained in the dried sludge and no-need for extra microwave absorbers, enhanced solidificaiton of
biochar samples. heavy metal via vitrification, and high value-added biochar products.
Metals, DSS SBC0 SBC1 SBC2 The improved properties of the sludge-based biochar (SBC2) pro-
(mg/Kg) duced from the SMSP approach gave good proof of the feasibility of the
concept. Compared to the sludge-based biochar (SBC1) produced from
Ni 43.3 ± 0.9 59.44 ± 1.17 63.41 ± 4.04 69.37 ± 1.49
the conventional pyrolysis conditions, the SBC2 shows increased ash
Cu 456.7 ± 0.21 637.1 ± 0.29 678.7 ± 0.69 756.1 ± 0.66
Zn 3197 ± 0.16 4019 ± 0.76 4047 ± 1.43 4708 ± 0.71
remaining ratio and specific surface area, well-reserved diversity of
Pb 186.7 ± 1.59 205.1 ± 1.28 219.5 ± 4.57 243.9 ± ×1.26 surface functional groups, and improved leaching toxicity of heavy
Cr 436.7 ± 0.55 486.3 ± 1.24 474.9 ± 1.04 555.2 ± 0.48 metals. The occurrence of vitrification during the microwave sy-
Cd 43.3 ± 3.33 14.04 ± 3.43 0.39 ± 1.20 2.24 ± 0.94 nergistic pyrolysis is proved by the formation of melted glassy spheres
observed by the SEM image. This is also supported by the EDX result of
elemental composition (Si, Ca, Al) and the XRD result of the newly
formed quartz peaks. From the preliminary laboratory test, the total
for the other three heavy metals of Cu, Pb and Cr, the leaching con- processing time by the SMSP approach can be potentially shortened
centrations in the SBC2 sample were higher than that in the SBC1 compared to the time needed by the conventional pyrolysis in order to
sample. Leaching, however, is a rather complex process which has not achieve the sludge-based biochar of high quality. This is a good sign of
been fully understood yet. It may be influenced by many factors such as the energy-saving potential in industrial application. However, the
material composition and structure, solution properties, detailed energy consumption and process efficiency will be closely related to the
chemistry, and transportation phenomena etc.[15]. Still, there is a big composition of raw sewage sludge, the dielectric property of the pre-
potential to further improve the solidification of heavy metals, micro- pyrolytic chars, the system scale, the selected technologies applied in
structural and physiochemical properties of biochars by continuously each step, as well as the potential integration use of waste heat from
optimizing the operation conditions of the SMSP approach. other industries. This will be discussed in another paper during the
demonstration phase. Pyrolysis conditions at both stages need to be
4. Conclusions further optimized which is going to be our next research topic.

In this study a SMSP approach is proposed. It is where the con-

ventional heating acts as a pre-pyrolysis stage to increase the dielectric CRediT authorship contribution statement
properties of the sludge feedstock. Microwave synergistic heating is
then applied at the sequential stage to rapidly heat up the sample to Chaoqian Wang: Conceptualization, Data curation, Formal ana-
solidify the heavy metal via vitrification. The SMSP approach has lysis, Investigation, Methodology, Software, Validation, Writing -

Table 4
Leaching concentration of tested heavy metals contained in the dried sludge and biochar samples.
Metals, (mg/Kg) DSS SBC0 SBC1 SBC2 Chinese standard (for the farmland)

Ni 10.86 ± 1.61 4.01 ± 1.97 6.35 ± 1.08 1.17 ± 1.53 < 100
Cu 93.03 ± 1.04 16.18 ± 1.11 5.17 ± 0.91 5.51 ± 0.91 < 500
Zn 554.1 ± 0.82 316.1 ± 0.93 248.5 ± 0.95 40.92 ± 1.31 < 1200
Pb 25.68 ± 4.52 6.85 ± 1.93 5.68 ± 2.36 8.35 ± 0.99 < 300
Cr 56.51 ± 0.92 24.53 ± 0.98 11.52 ± 0.54 17.18 ± 0.85 < 500
Cd 2.01 ± 2.81 0.67 ± 0.45 0.04 ± 0.92 0.03 ± 0.74 <3

8
C. Wang, et al.
original draft. Wenlong Wang: Conceptualization, Formal analysis,
Funding acquisition, Methodology, Project administration, Resources,
Supervision, Validation, Visualization, Writing - review & editing.
Leteng Lin: Formal analysis, Investigation, Methodology, Supervision,
Validation, Writing - review & editing. Fusen Zhang: Investigation,
Methodology, Software. Runing Zhang: Investigation, Methodology.
Jing Sun: Conceptualization, Methodology, Funding acquisition.
Zhanlong Song: Conceptualization, Methodology, Funding acquisition.
Yanpeng Mao: Conceptualization, Methodology, Funding acquisition.
Xiqiang Zhao: Conceptualization, Methodology, Funding acquisition.
Acknowledgements
The authors thank the support of National Natural Science
Foundation of China (Grant 51976110); the Young Scholars Program of
Shandong University (Grant No. 2018 WLJH75); and the Natural
Science Foundation of Shandong Province (ZR201808170119).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuel.2020.117628.
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Glossary
AR: analytical reagent
BET: Brunauer-Emmett-Teller
DFT: Density Functional Theory
DSS: the dried sewage sludge
FTIR: fourier transform infrared spectroscopy
NLDFT: Nonlocal Density Functional Theory
10
Fuel 272 (2020) 117628
SBC0: the pre-pyrolytic sludge-based biochar
SBC1: the biochar prepared via the conventional pyrolysis with longer retention time
SBC2: the final biochar of the proposed stepwise microwave synergistic pyrolysis process
SEM-EDX: scanning electron microscope equipped with energy-dispersive x-ray spectro-
scopy
TCLP: Toxicity Characteristic Leaching Procedure method
XRD: x-ray diffraction