Waste Management 80 (2018) 175–185

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Effect of inherent minerals on sewage sludge pyrolysis: Product

characteristics, kinetics and thermodynamics
Siqi Tang a, Chunmiao Zheng a,b, Zuotai Zhang b,c,⇑
a
Department of Energy and Resources Engineering, College of Engineering, Peking University, Beijing 100871, People’s Republic of China
b
School of Environmental Science and Engineering, Southern University of Science and Technology, Shenzhen 518055, People’s Republic of China
c
Key Laboratory of Municipal Solid Waste Recycling Technology and Management of Shenzhen City, Shenzhen 518055, People’s Republic of China

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

Article history: Inherent minerals in sludge influence sludge pyrolysis behaviors and the final products. In this study, the
Received 17 December 2017 effects of inherent minerals on sewage sludge pyrolysis were systematically investigated by studying the
Revised 29 May 2018 pyrolysis behaviors of raw sewage sludge (RS) and HCl-washed sludge (WS), and in combination with
Accepted 4 September 2018
thermodynamic equilibrium simulations for the hypothetical mineral-free sludge (AS) assumed. The
pyrolysis of RS and WS was performed with a novel online thermogravimetric analyzer equipped with
an infrared spectrometer and a gas chromatograph coupled with a mass spectrometer (TG-IR-GC/MS).
Keywords:
It was found that inherent minerals influenced both the release of volatile products as a function of pyrol-
Sewage sludge pyrolysis
Inherent minerals
ysis temperature, and the development of the physicochemical properties of the derived char. In the tem-
Products distribution perature range of 300–500 °C, hydrocarbons with more than 4 carbon atoms as well as aromatic
Pyrolysis kinetics compounds showed an increased release during WS pyrolysis, with respect to RS, while hydrocarbons
Gibbs free energy minimization with less than 3 carbon atoms such as CH4 and C3H6 exhibited a decreased release. In addition, the inher-
ent minerals enhanced the release of HCN and NH3, both leading to increased NO2 release, and the release
of H2S and COS was also promoted while the release of CH3SH, SO2 and CS2 was mitigated. Kinetic anal-
ysis confirmed that a catalytic effect induced by the inherent minerals decreased the activation energy at
300–500 °C. Thermodynamic simulations suggested that inherent minerals influenced sludge pyrolysis
and the derived products formation by increasing the total Gibbs energy of the sludge pyrolysis system.
Therefore, considerations of sludge inherent minerals should be taken into account during pyrolysis for
the purpose of value-added commodity production and pollutant mitigation.
Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction methods are restricted by various degrees in practice (Fytili and

Sewage sludge, a byproduct generated from the biological pro-
cessing of municipal wastewater in a wastewater treatment plant,
has attracted increasing attention due to the difficulty in dealing
with the substantial amounts of dewatered sludge in an environ-
mentally friendly and economically feasible way. Conventional
treatments or disposals for sludge include incineration (Werther
and Ogada, 1999), landfilling (Lo et al., 2002), and soil utilization
(Pritchard et al., 2010) and as a feedstock for making other materi-
als such as ceramics (Almeida et al., 1997), cement paste (Lin and
Tsai, 2006), and activated carbon (Smith et al., 2009). Since the
sources of sewage sludge are diverse and a certain amount of water
still remains in the dewatered sludge cake, those conventional
⇑ Corresponding author at: School of Environmental Science and Engineering,
Southern University of Science and Technology, Shenzhen 518055, People’s
Republic of China.
E-mail address: zhangzt@sustc.edu.cn (Z. Zhang).
Zabaniotou, 2008). The emerging pyrolysis technology exhibits
great potential in sludge treatment, due to the fast and significant
reduction of sludge volume, production of value-added products
and mitigation of contaminant formation (Fonts et al., 2012). Thus,
the technology of sludge pyrolysis has been studied intensively in
the literature.
It has been generally acknowledged that two factors, pyrolysis
conditions and sludge composition dominate the progress of
sludge pyrolysis and attributes of the derived products (Chen
et al., 2014; Nowicki and Ledakowicz, 2014; Zielińska et al.,
2015). In the case of pyrolysis conditions, pyrolysis temperature
has been verified as the most significant condition (Chen et al.,
2014; Fonts et al., 2012). The increase in pyrolysis temperature
can make sludge components completely decomposed to release
volatile products, while the formation and nature of the derived
products depends on the heating rate during pyrolysis. The pyrol-
ysis with a high heating rate, for example, is often adopted for the

https://doi.org/10.1016/j.wasman.2018.09.012
0956-053X/Ó 2018 Elsevier Ltd. All rights reserved.
176 S. Tang et al. / Waste Management 80 (2018) 175–185
purpose of recovering liquid product rich in aromatics, at the
expense of gas and char production (Alvarez et al., 2016;
Atienza-Martínez et al., 2015; Sánchez et al., 2009). For the factor
of sludge composition, organic matter and inherent minerals are
two main fractions constituting the matrix of sludge (Gascó
et al., 2005; Zielińska et al., 2015). The organic fraction is often
composed of three biomass gradients, i.e., hemicellulose, cellulose
and lignin, the thermal decomposition of which contributes to the
behavior of sludge during pyrolysis (Thipkhunthod et al., 2007),
while the sludge-inherent minerals, accounting for almost 23.4–
52.8 wt.% (dry basis) (Shao et al., 2010; Thipkhunthod et al.,
2006), are composed of various inorganic compounds such as sili-
cates, aluminates, oxides and trace heavy metals such as Cu, Zn, Pb,
Pd, Cr and Mn (Shao et al., 2010). Many studies have investigated
the effects of inherent mineral matters on the pyrolysis of solid
fuels including biomass, coal and sewage sludge by means of dem-
ineralization and/or impregnation (Jiang et al., 2013; Sert et al.,
2011; Shao et al., 2010). Those studies revealed that inherent min-
eral matters showed hybrid effects on the pyrolysis of solid fuels,
depending on the type and content of the metal element and pyrol-
ysis temperature (Ellis et al., 2015; Raveendran et al., 1995; Shao
et al., 2010; Yang et al., 2006). Yang et al. (2006) demonstrated that
the addition of K2CO3 catalyzed the pyrolysis of the synthesized
biomass pyrolysis under low temperature (200–315 °C), while
others showed little influence. Shao et al. (2010) found that the
addition of Al2O3 and TiO2 reduced the total pyrolysis time while
the addition of CaO, Fe2O3 and ZnO delayed the pyrolysis time.
Removing sludge minerals by the acid washing method is com-
monly adopted to obtain a purified sludge that contains mostly
organics (Shao et al., 2010). Then, the ash-free sludge is impreg-
nated with various metal-containing compounds to attain specific
sludges, in order to study the effects of metal elements contained
in sludge minerals on sludge pyrolysis (Shao et al., 2010). By com-
paring the pyrolysis performance between raw sludge and metal-
impregnated sludge, the effects of inherent metals on the progress
of sludge pyrolysis have been revealed. It should be mentioned that
the sludge matrix has been modified after acid washing to some
degree. The acids commonly used are hydrogen chloride (HCl), sul-
furic acid (H2SO4) and nitric acid (HNO3), all displaying strong
acidities leading to the dissolution of sludge components
(Asadieraghi and Wan Daud, 2014; Wigley et al., 2015). It is known
that the acid-washing method was usually used to remove the
minerals contained in coal (Roets et al., 2015; Samaras et al.,
1996; Sert et al., 2011) and biomass (Asadieraghi and Wan Daud,
2014; Das et al., 2004; Eom et al., 2011; Jiang et al., 2013;
Raveendran et al., 1995), and their results showed that the diluted
acid could remove the minerals while it altered the structure of the
coal and/or biomass slightly. Although the pretreatment by the
diluted acid washing method may slightly alter the structure of
the sludge sample, the acid-washed sample could be used as a ref-
erence to aid the understanding of the inherent minerals
(Asadieraghi and Wan Daud, 2014; Das et al., 2004; Jiang et al.,
2013). In the study of Shao et al. (2010), they removed the minerals
by the acid washing method, and then added the chemicals into
the sludge to study the catalytic effects induced by the metals con-
tained in sewage sludge during pyrolysis. However, the effect of
the acid-washing pretreatment should be considered when study-
ing the effect of inherent metal elements on sludge pyrolysis. The
present study was therefore motivated to some extent by these
reasons. Furthermore, considering the limitations of experimental
methods for sludge demineralization during which the sludge
structure may be slightly modified, thermodynamic equilibrium
simulation can be regarded as an alternative approach to predict
the effects of inherent minerals on sludge pyrolysis without dam-
age to the sludge matrix. It has been confirmed that thermody-
namic equilibrium simulation performed well in modeling the
thermochemical reactions and predicting products formation
(Bale et al., 2016; Kangas et al., 2014; Schreiner et al., 2011). With
the merits of thermodynamic equilibrium simulation in thermo-
chemical reactions such as coal gasification (van Dyk et al., 2009)
and H2 production from industrial slags (Nakano et al., 2017), it
seems to be feasible to simulate the process of sludge pyrolysis
and further discern the effects aroused by inherent minerals.
In this work, two types of sludge, i.e. raw sludge (RS) and HCl-
washing sludge (WS) were pyrolyzed in a thermogravimetric ana-
lyzer equipped with a Fourier transform infrared spectrometer cell
and a gas chromatograph coupled with a mass spectrometer (TG-
FTIR-GC/MS). The release characteristics of pyrolytic volatile prod-
ucts were determined and the derived chars were characterized.
Kinetic parameters pertaining to sewage sludge pyrolysis were
determined. Thermodynamic equilibrium simulations for RS and
WS were introduced, and the obtained results between the exper-
iment and the simulation were compared. A hypothetical sludge
sample without the presence of inherent minerals (AS) was
assumed based on the RS and simulated for pyrolysis. By these
efforts, the effects induced by internal minerals during sludge
pyrolysis were elucidated, which deepens the understanding of
sludge pyrolysis technology.
2. Materials and methods
2.1. Sewage sludge collection and handling
The sewage sludge used was obtained from a municipal wastew-
ater treatment plant in Beijing, China. After in situ mechanical
dewatering at this site, the dewatered sludge cake was transported
for final disposal. The sludge sampled was dewatered sludge (water
content of approximately 80%), and it was dried at 105 °C in a lab-
oratory oven overnight. The dried sludge was crushed, screened and
sieved to obtain the needed sample with a particle size of 0.015–
0.074 mm (designated as RS). The dilute HCl with concentration
of 5% that shows a satisfactory efficiency of demineralization
(Jiang et al., 2013) was employed to soak dewatered sludge to
obtain the sludge sample with the inherent minerals removed par-
tially. The sludge solution was magnetically stirred at room temper-
ature (25 °C) for 6 h. After that, the solution was filtered, and the
remaining was HCl-washed sludge (named as WS); deionized water
was then used to rinse the solid until the filtrate was near neutral
pH. Drying, crushing and sieving were sequentially carried out on
the WS as well as the RS. Proximate analysis, ultimate analysis
and mineral composition analysis (Tang et al., 2017) for RS and
WS were conducted, as listed in Table 1.
2.2. Sludge pyrolysis experiments
The experiments of RS and WS pyrolysis were carried out on a
TG-FTIR-GC/MS device (TGA 800-Frontier FTIR-Clarus SQ 8 GC/
MS, Perkin Elmer, USA). The device was heated from room temper-
ature to 900 °C with a constant heating rate of 30 °C/min. High pur-
ity helium (99.999%, V/V) was used as the carrier gas to flow
through the system of the TG-FTIR-GC/MS device at a flow rate
of 90 mL/min before, during and after pyrolysis. The volatiles
released from the TG furnace were directly pumped into the FTIR
cell (the scanned wavenumber range was 4000–450 cm 1 and
the scanning resolution was set at 4 cm 1). After being detected
by the FTIR cell, the flow was swept into the cell of the GC/MS. Tar-
geted m/z signals related to sludge pyrolysis were determined from
the preliminary experiment. The data of MS spectra were recorded
in real time and processed by TurboMass (Version 6.1.0, Perkin
Elmer, USA). A duplicate for RS and WS pyrolysis was performed
and the repeatability was confirmed. To avoid the condensation
 S. Tang et al. / Waste Management 80 (2018) 175–185 177

Table 1 pyrolysis (Tang et al., 2017). Based on this established method, the
Physicochemical properties of the sludge samples studied. apparent activation energy, pre-exponential factor and mechanism
Item RS WS AS function related to sludge pyrolysis were determined. By compar-
Proximate analysis (wt.%, dry basis)a ing the difference of kinetic parameters between the RS and WS,
Moisture 6.21 4.31 the effect of inherent minerals on the pyrolysis of sewage sludge
Volatile matter 53.76 58.54 in kinetics could be revealed.
Ash 27.69 19.51 0
a
Fixed carbon 12.34 17.64
2.5. Thermodynamic simulation for sludge pyrolysis
Ultimate analysis (wt.%, dry basis)b
C 35.08 38.61 48.51
H 5.77 5.90 7.98
Considering the process of sludge pyrolysis, the sludge matrix
Oc 25.01 28.26 34.59 could be separated into two fractions, i.e., organic components
N 5.38 6.78 7.44 and inherent minerals, the interaction of which resulted in the for-
S 1.07 0.94 1.48 mation and distribution pyrolytic products. Using the ultimate
Mineral composition (wt.%, dry basis)d analysis data shown in Table 1, the simplified molecular formulas
P2O5 6.60 5.11 of the RS and WS organic fraction were determined, namely,
SiO2 5.41 7.49
CH1.9738O0.5347N0.1315S0.0114 and CH1.8337O0.5490N0.1505S0.0091,
CaO 5.30 1.48
Al2O3 4.28 3.51 respectively. The mineral fraction was simulated in the form of oxi-
Fe2O3 1.78 1.30 des as listed in Table 1. To check the pyrolysis of sludge with
K2O 1.04 0.54 organic fraction only, a hypothetical sludge (AS) without minerals
MgO 0.99 0.51
based on RS was assumed, and the formula was CH1.9740O0.5348-
Na2O 0.31 0.12
TiO2 0.21 0.32
N0.1315S0.0114. Prior to simulation, the assumption that the system
ZnO 0.11 0.07 of sludge pyrolysis is under a closed environment was made. Based
MnO 0.07 0.02 on the database of FactSage software (version 7.1), the candidate
CuO 0.03 0.02 products generated from sludge pyrolysis were determined at
SrO 0.02 0.004
equilibrium (see Table S1), by resolving a serials of partial differen-
Cr2O3 0.009 0.010
tial equations derived from the Lagrangian function for those can-
a
Measured according to the Chinese Standard GB/T 17664-1999. Fixed carbon didate products under the principle of Gibbs free energy
(FC) was calculated according to the formula: FC(%) = 100% Moisture(%) Vola-
minimization. The pyrolysis process was simulated at different
tile matter (%) Ash(%).
b
Measured using an element analyzer (Flash 2000, ThermoFisher, America). pyrolysis temperatures (300, 400, 500, 600 and 700 °C in this
c
Calculated by difference (O(%) = 100% C (%) H (%) N (%) S (%) Ash(%)). study) and a constant pressure (1 atm. in this study) (Bale et al.,
d
Measured using an X-Ray Fluorescence spectrometer (ARL ADVANT XP+, 2009). Therefore, the distribution of pyrolytic products derived
ThermoFisher, America). from RS, WS and AS pyrolysis was determined. Due to the com-
plexity of the pyrolytic products predetermined using the database
of FactSage software, displaying all candidate products yields was
of volatile products released during sludge pyrolysis, the tempera-
not necessary (Sun et al., 2016). In this study, several general vola-
tures of the transfer lines between the TG and FTIR and between
tiles, particularly nitrogen- and sulfur-containing pollutants were
the FTIR and GC/MS were both maintained at 290 °C. To collect suf-
considered and presented.
ficient chars for characterization, the pyrolysis of RS and WS was
conducted on an electrical-heating horizontal furnace at 300,
400, 500, 600 and 700 °C. The furnace was heated from ambient 3. Results and discussion
temperature to the final temperature at a heating rate of
30 °C/min, and heating was stopped once the final temperature 3.1. Characterization of the RS and WS
was reached. High-purity 99.999 vol.% helium was purged into
the furnace with a flow rate of 90 mL/min before, during and after As shown in Table 1, the operation of HCl washing led to the
the heating. The recovered sludge chars were preserved in a desic- partial removal of sludge inherent minerals, by comparing ash con-
cator until later use. tent and mineral composition between the RS and WS. Sequential
measurements carried out on the RS and WS also evidenced this
result, including FTIR and N2 adsorption/desorption isotherms.
2.3. Characterization for sewage sludge and the derived chars
The FIIR spectra of the RS and WS and interpretation of the spectra
were provided in Fig. S1 and Table S2, respectively; the discrimina-
To discriminate the changes in the physicochemical properties
tion of the FTIR spectra between the RS and WS was found in the
of sewage sludge due to HCl washing, a Fourier transform infrared
wavenumber range of 3200–1200 cm 1 in which the presence of
spectrometer equipped with an attenuated total reflectance acces-
alkyl groups, aldehydes and C@O led to absorbance features, sug-
sory (FTIR ATR, Nicolet iS 50, Thermo Scientific, USA) was
gesting that the structure of the organic fraction of sewage sludge
employed for the measurement of chemical functional groups in
was partially altered after acid washing. The isotherms of N2
the wavenumber range of 4000–400 cm 1 with a resolution of
physisorption at 77 K shown in Fig. S2(a) were parallel for the RS
4 cm 1, and an accelerated surface area and porosimetry (ASAP
2020, Micromeritics, USA) was used for the measurement of sur-
face area and pore size distribution by the obtained isotherms of Table 2
N2 adsorption-desorption at 77 K. Characterizations of the chars Surface area, pore volume and pore size of the RS and WS.
derived from RS and WS pyrolysis were performed identical to Sludge sample SBET (m2/g)a Vt (cm3/g)b dp (nm)c
those for the sludge samples (RS and WS).
RS 1.22 0.0056 18.5
WS 1.77 0.0140 31.8
2.4. Kinetics of sludge pyrolysis a
Specific surface area measured using Brunauer-Emmett-Teller (BET) theory.
b
The total pore volume measured at a relative pressure equal to 0.90.
We used a method that we recently established for the determi- c
The mean pore diameter measured using Barrett-Joyner-Halenda (BJH) model
nation of the kinetic parameters pertaining to the process of sludge for the data of desorption branch.
178 S. Tang et al. / Waste Management 80 (2018) 175–185

and WS, and the derived pore size distribution of both was pre-
sented in Fig. S2(b). Table 2 shows that the specific surface areas
(SBET) of RS and WS were 1.2190 and 1.7654 m2/g, respectively,
and were not significantly discriminated, while the total pore vol-
ume (Vt) and mean pore diameter (dp) were larger for the WS than
for the RS. This result suggested that the dissolution of inherent
mineral components incorporated with the organics was ascribed
to the change of surface parameters of sewage sludge (Shao
et al., 2010). The result of the micromorphology for the RS and
WS, as illustrated in Fig. S3, also indicated a change on the sludge
surface, in that abundant pores were developed on the surface due
to the acid washing.

3.2. Volatile products characteristics

3.2.1. Overall performance of sludge pyrolysis

Fig. 1. Thermogravimetric analysis of the RS and WS at a heating rate of 30 °C/min:
solid lines denote TG curves; and dashed lines denote DTG curves. Fig. 1 shows the thermogravimetric performance of the RS and
WS heated from room temperature to 900 °C with a constant heat-

Fig. 2. FTIR spectra of volatile products generated during (a) RS pyrolysis and (b) WS pyrolysis with a heating rate of 30 °C/min.
 S. Tang et al. / Waste Management 80 (2018) 175–185
ing rate (30 °C/min), finding that the thermogravimetric (TG)
curves of the RS and WS intersected at 330 °C. Below this temper-
ature the TG curve of the RS was inferior to that of the WS, indicat-
ing that the mass of residues was greater for the WS than for the
RS, while an opposite observation appeared when temperature
was increased to over 330 °C. The weight loss rate of a sludge sam-
ple was determined by the first derivative of the TG (DTG) curve,
finding that the DTG curves of the RS and WS intersected at
230 °C. When pyrolysis temperature was lower than 230 °C, the
weight loss rate of the RS was faster than that of the WS, while
the weight loss rate of the WS was higher at temperatures, over
230–600 °C. At higher temperatures (600–900 °C) the weight loss
rate of both was close. The difference of intersection temperature
between the TG curves and DTG curves could be attributed to
the reduction in minerals due to acid washing effect (Raveendran
et al., 1995).
The profile of volatile products released during sewage sludge
pyrolysis was recorded in real time using the advanced TG-FTIR-
GC/MS technique. The chemical composition of the derived pyroly-
tic products with respect to chemical groups was investigated with
online IR spectra (Zielińska et al., 2015), as shown in Fig. 2. Charac-
teristic absorbances corresponding to particular functional groups
with respect to temperature were revealed. It can be seen that the
profile of absorbance between the RS and the WS was similar, while
the difference between both mainly focused on the absorbance
intensity. This result indicated that the partial removal of inherent
minerals via the acid washing resulted in the different releasing
rates of pyrolytic volatiles during sewage sludge pyrolysis.
To track the evolution of gaseous product composition with
respect to the functional groups between the RS and WS as the
temperature was increased, FTIR spectra corresponding to the
determined temperatures on the DTG curves were extracted from
the respective real-time FTIR spectra (see Fig. 2), as shown in
Fig. 3. These functional groups, i.e., OAH, CAH, O@C@O, C@O,
CAOAC, and CAH, were found in the volatiles due to their partic-
Fig. 3. FTIR spectra of gaseous products released during RS (black line) pyrolysis and WS (red line) pyrolysis at several determined temperatures. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)
179
ular absorbance wavenumbers (Gao et al., 2013; Wu et al., 2013),
suggesting that water, alcohols, CO2, phenols, aldehydes, carbonic
acids, aliphatic and aromatic compounds were generated during
sludge pyrolysis. The results were in agreement with a previous
study (Shao et al., 2008). The intensities of these bonds decreased
as pyrolysis temperature increased, as a consequence of the
decreased content of the organic components (Thipkhunthod
et al., 2006). The comparison of the FTIR spectra acquired at those
temperatures between the RS and WS revealed that, the partial
removal of inherent minerals indeed impacted the release rate of
volatile products during sludge pyrolysis, particularly for the
organic fragments containing CAH, O@C@O, C@O and CAOAC
bonds. This result meant that the presence of inherent minerals
caused a clumping effect during the decomposition of sludge
organic matter (Thipkhunthod et al., 2006). It should be mentioned
that absorption peaks between the RS and WS occurred at the same
wavenumbers, implying that the chemical bonds contained in
volatile products were little suffered to the changes aroused by
acid washing.
3.2.2. The release of hydrocarbons and inorganic pollutants during
sludge pyrolysis
Figs. 4 and 5 show the generation of volatile compounds includ-
ing hydrocarbons (olefins and alkanes) and nitrogen/sulfur-
containing pollutants (NH3, HCN, NO2, H2S, CH3SH, COS, SO2). By
comparing the mass spectra of the RS and WS, it was found that
the inherent minerals influenced the formation of the pyrolytic
products, which also importantly depended on pyrolysis tempera-
ture. The production of saturated and/or unsaturated hydrocar-
bons, as shown in Fig. 4, evolved with the increase in pyrolysis
temperature. The operation of acid washing affected the release
of those products, as evidenced by the difference between the RS
and WS in the release rate order. It was found that the difference
in the hydrocarbon release order occurred from 300 to 500 °C. At
this temperature range, the hydrocarbons with more than 4 carbon
180 S. Tang et al. / Waste Management 80 (2018) 175–185
Fig. 4. Release of hydrocarbons (olefins and alkanes) generated from RS and WS pyrolysis.
atoms showed an increased release rate order during WS pyrolysis,
with respect to RS; however, the hydrocarbons with 3 carbon
atoms or fewer such as CH4 and C3H6 exhibited an increased
release rate. Additionally, the temperatures corresponding to the
release peak of those hydrocarbons between the RS and WS were
very close. These results revealed that the presence of inherent
minerals to some extent benefited the production of value-added
products with short-chain hydrocarbons during sewage sludge
pyrolysis.
Additionally, the evolution of nitrogenous and sulfurous prod-
ucts generated during sewage sludge pyrolysis was tracked, as
shown in Fig. 5. For the case of nitrogen-containing volatiles, the
profiles of NH3, HCN and NO2 formation against temperature
revealed the contribution of inherent minerals to them during
sludge pyrolysis. As the precursors of NO2 formation, the promoted
production of NH3 and HCN with the aid of inherent minerals was
beneficial to the formation of NO2 during sludge pyrolysis. For
sulfur-containing volatile products, a significant reduction in the
H2S release order was observed during WS pyrolysis, indicating
that the presence of inherent minerals was responsible for the gen-
eration of H2S. The release order of CH3SH, COS, SO2 and CS2 during
RS and WS pyrolysis varied with the increase of pyrolysis temper-
ature. The difference in release order revealed that the distribution
of sulfur-containing derivatives was subjected to the presence of
inherent minerals. Therefore, achieving the control of pollutants
during sludge pyrolysis in practice should take the presence of
internal minerals and pyrolysis conditions into consideration.
3.2.3. The release of aromatic compounds during pyrolysis
The evolution of aromatic compounds that have a good con-
densability generated during sludge pyrolysis was observed as
pyrolysis temperature increased, as illustrated in Fig. 6. It was
found that most of the aromatic compounds contained nitrogen
and were abundantly released in the temperature range of 400–
700 °C. According to the substitution of nitrogen atom, those aro-
matic matters could be classified into three types, i.e., heterocyclic
(pyridine or pyrrole), nitrile and amine, which are generally
formed as the preliminary volatiles composing the vapors during
sludge pyrolysis. Due to the limitation of instrument capacity in
quantification, the signal of the ion intensity recorded was used
for comparative study. It is worthwhile to note that the ion inten-
sity of the nitrogen-containing aromatics was almost larger for the
WS than for the RS over the entire process of pyrolysis. In addition,
the initial temperature corresponding to the release of those
nitrogen-containing volatiles was lower for the WS than for the
RS. Those results confirmed that the presence of the inherent min-
erals promoted the secondary cracking of those volatiles to some
degree (Raveendran et al., 1995; Thipkhunthod et al., 2006).
3.3. Sludge-derived char characteristics
3.3.1. The yield of sludge-derived char
Fig. S4 shows the yield of sludge-derived char after pyrolysis. It
can be found that the yield of sludge char decreased with the
increase in pyrolysis temperature, which was in agreement with
 S. Tang et al. / Waste Management 80 (2018) 175–185 181

Fig. 5. Release of hydrogen, methane and common inorganic pollutants generated from RS and WS pyrolysis.

that found in previous study (Zielińska et al., 2015). This result was
attributed to the decomposition of sludge organic components
(Thipkhunthod et al., 2006). Further, the yield of sludge char
derived from the RS was larger than that for the WS when pyrolysis
temperature was increased to over 400 °C. This result revealed that
the presence of inherent minerals retarded the release of volatile
vapors and then led to the deposition of those carbonaceous vapors
(Thipkhunthod et al., 2006). It is also noticeable that the difference
in char yield between the RS and the WS was enlarged as pyrolysis
temperature was increased up to 600 °C and then was reduced
when pyrolysis temperature further increased such as at 700 °C.
This result indicated the occurrence of the deactivation of the
inherent minerals as catalysts, likely due to the accumulation of
carbonaceous agglomerates (Taarning et al., 2011).
3.3.2. Chemical functional groups of sludge-derived char
A typical chemical composition with respect to functional
groups for sludge chars generated in the pyrolysis of RS and WS
at 300, 400, 500, 600 and 700 °C, respectively, was determined
(Zielińska et al., 2015), which was presented in Fig. S5. The inter-
pretation of the FTIR spectra for those sludge chars was provided
in Table S3. With the increase of pyrolysis temperature, the spec-
tral absorbance of the derived char was reduced because of the
decomposition of the sludge organic components. When pyrolysis
temperature was increased up to 700 °C, the intensity of the absor-
bance attributed to the organic chemical bond stretching was sig-
nificantly decreased, while the detected absorbance mainly located
at lower wavenumbers was contributed by SiAO stretching
(Hossain et al., 2011), suggesting the completeness of the sludge
182 S. Tang et al. / Waste Management 80 (2018) 175–185

Fig. 6. Release of aromatic compounds generated from RS and WS pyrolysis.

component devolatilization. By comparing the absorbance intensi-
ties between the RS-derived char and WS-derived char, the organic
bond abundance (qualitatively representative of the absorbance)
was larger for the char derived from WS pyrolysis than that from
RS pyrolysis, except for the absorbance at 1010 cm 1, which was
ascribed to the SiAO stretching bond. This result demonstrated
that the inherent minerals promoted the cracking of organics in
the sewage sludge (Zielińska et al., 2015).
ysis (RS700 and WS700) were taken as examples to investigate the
effect of inherent minerals on the development of the sludge char
pore structure. The obtained nitrogen adsorption/desorption
isothermals for RS700 and WS700 and the derived pore size distri-
butions were shown in Fig. S6. Calculated structural parameters
related to the sludge-derived chars were listed in Table 3. It is
easily that both the SBET and the total pore volume (Vt) of RS700
were significantly larger than those of WS700, while the average

3.3.3. Surface area and pore structure analysis of the sludge-derived Table 3
char Surface area, pore volume and pore size of sludge-derived chars from the RS and WS.
The devolatilization of organic components during sludge
Sludge char SBET (m2/g) Vt (cm3/g) dp (nm)
pyrolysis led to the formation of pore structure and an increase
RS700 6.94 0.0306 17.6
in surface area of the sludge char (Gascó et al., 2005). Herein, the
WS700 2.27 0.0123 21.6
sludge chars generated at 700 °C during RS pyrolysis and WS pyrol-
 S. Tang et al. / Waste Management 80 (2018) 175–185 183

Table 4
The calculated kinetic parameters related to RS pyrolysis and WS pyrolysis.

Temperature region (°C) Parameter RS WS

150–240 Ea (kJ/mol) 78.56 110.53
logA 7.7912 14.0786
VC 0.0016 0.0005
Mechanism model Avrami-Erofeev equation (n = 1/3) Avrami-Erofeev equation (n = 1/3)
240–330 Ea (kJ/mol) 76.45 82.46
logA 31.4384 31.4385
VC 0.4925 0.2811
Mechanism model Avrami-Erofeev equation (n = 1/3) Avrami-Erofeev equation (n = 1/3)
330–440 Ea (kJ/mol) 86.37 86.33
logA 31.4385 31.4385
VC 1.0049 1.0053
Mechanism model Mapel power (n = 1/4) Mapel power (n = 1/4)
440–600 Ea (kJ/mol) 100.59 100.58
logA 27.1911 31.4385
VC 1.0032 1.0032
Mechanism model Mapel power (n = 1/4) Mapel power (n = 1/4)

Fig. 7. Gaseous products distribution simulated using Gibbs free energy minimization principle for sewage sludge pyrolysis.
184 S. Tang et al. / Waste Management 80 (2018) 175–185
pore diameter was smaller for RS700 than WS700. This result sug-
gested that the inherent minerals can promote the formation of
pores inside the sludge char, and then enhance the value of the
produced sludge char in practice, such that the product can be
regarded as an adsorbent for contamination remediation
(Méndez et al., 2014).
3.4. Kinetic analysis
Kinetic parameters, i.e., apparent activation energy (Ea), pre-
exponential factor (A) and the mechanism function related to the
process of sludge pyrolysis were determined using thermogravi-
metric data, as shown in Table 4 for the RS and WS. The difference
of Ea related to RS pyrolysis and WS pyrolysis showed a depen-
dence on temperature. When the temperature was under 330 °C,
the Ea of the RS was significantly smaller than that of the WS, while
the Ea of both was similar when the pyrolysis was occurring in the
temperature range of 330–600 °C. This result supported the idea
that the inherent minerals showed a catalytic effect on the decom-
position of sludge organic components at low pyrolysis tempera-
tures. On the other hand, the deactivation due to carbon
deposition (Zielińska et al., 2015) was gradually enhanced as pyrol-
ysis temperature increased, which was especially significant at
600 °C. It is also noted that the mechanism functions pertaining
to RS pyrolysis and WS pyrolysis were the same, i.e., nucleation fol-
lowed by the nuclei growth with Avrami-Erofeev equation
(n = 1/3) at 150–330 °C and nucleation following the Mapel power
law (n = 1/4) at 330–600 °C. This result confirmed the catalytic role
that internal minerals played in the process of sludge pyrolysis.
3.5. Thermodynamic analysis
Based on the principle of Gibbs free energy minimization, the
thermodynamic equilibrium simulation for the RS, WS and AS at
determined pyrolysis temperatures were simulated. The resulting
simulation for the production of concerned volatile products was
shown in Fig. 7. Since the specific contents of volatile products
detected by the instrument were not determined, the focus of
the comparison between the simulated results and the experimen-
tal results was on the trend of pyrolytic products production. For
RS and WS pyrolysis, it was found that the results of simulation
shown in Fig. 7 were well in agreement with the results shown
in Fig. 5. Thus, it can be stated that the simulation for the sewage
sludge pyrolysis was validated and that the simulation for the AS
was acceptable. The increasing production of H2 with the increase
in pyrolysis temperature indicated that the strength of hydrogen
extraction, i.e., dehydrogenation was gradually enhanced due to
external energy input into the sewage sludge system during pyrol-
ysis, which was in agreement with previous studies (Domínguez
et al., 2006; Thipkhunthod et al., 2006); the comparison of H2 pro-
duction among those three sewage sludges revealed that, inherent
minerals promoted the dehydrogenation in the process of sludge
Table 5
The total Gibbs free energy of the RS, WS and AS systems during pyrolysis at different
temperatures.
Pyrolysis temperature (°C) Total Gibbs free energy (J)a
RS WS
300 181.25 184.18
400 196.32 200.00
500 212.87 217.43
600 230.67 236.36
700 249.61 256.54
a
The mass of the sludge sample used in simulations was the same to that in
pyrolysis, so the data of total Gibbs energy were not normalized but kept as the
original when presented.
pyrolysis. Additionally, consistent trends were found in the pro-
duction of CH4, H2O and CO2 among those three sewage sludges.
The variations in CH4 production indicated an enhancement in
the demethylation of the organic components during sludge pyrol-
ysis. The same effect induced by the inherent minerals was
imposed on the dehydrogenation and decarboxylation reactions,
which was evident by the variations of the production of H2O
and CO2, respectively. The production of nitrogen-derived and
sulfur-derived products was notably of interest. For the nitrogen-
derived products, consistent trends for the production among the
RS, WS and AS were found for NH3, HCN and NO2, suggesting that
inherent minerals facilitated the formation of these nitrogenous
pollutants during the pyrolysis of sewage sludge. For the sulfur-
derived products arising from the decomposition of protein-like
matters in sewage sludge, the comparison of H2S, CH3SH, COS,
SO2 and CS2 production among those three sewage sludges demon-
strated that the presence of inherent minerals can mitigate the for-
mation of these sulfur-containing pollutants during sludge
pyrolysis, particularly when the pyrolysis process was at moderate
or high temperatures. Therefore, it was concluded that the inher-
ent minerals immobilized sludge sulfur during pyrolysis. The
effects mentioned above were ascribed to the difference of total
Gibbs free energy among the RS, WS and AS systems in the process
of pyrolysis. As shown in Table 5, the RS system during pyrolysis
had the largest total free Gibbs energy among the sludge samples,
revealing that the inherent minerals influenced the course of
sludge pyrolysis and the derived products formation by increasing
the total Gibbs energy within the sludge system.
4. Conclusions
The inherent minerals in sewage sludge influenced the attri-
butes of pyrolytic products generated during sewage sludge pyrol-
ysis, including chemical composition of volatiles and
physicochemical properties of the derived char. As revealed by
the online TG-FTIR-GC/MS technique, the hydrocarbons with less
than 3 carbon atoms showed an increased release during RS pyrol-
ysis, while the release of nitrogen-/sulfur-derived pollutants was
influenced by the presence of inherent minerals. The presence of
inherent minerals not only catalyzed the thermal cracking of
sludge organic components at the starting of sludge pyrolysis but
also accelerated the secondary decomposition of preliminarily
derived products (aromatic compounds and long-chain hydrocar-
bons) to value-added products. At the same time, the presence of
inherent minerals enhanced the derived char’s physicochemical
properties such as an increased yield, an enlarged surface area
and a well-developed pore structure. These improvements of for
the pyrolytic product attributes were achieved by the enhance-
ment of a series of thermochemical reactions such as dehydrogena-
tion, dehydration, and decarboxylation induced by inherent
minerals which increased the total Gibbs free energy of the sewage
sludge system during pyrolysis.
Acknowledgements
This study was supported by the National Science Fund for
Distinguished Young Scholars (51522401) and the National Natu-
AS
ral Science Foundation of China (51472007 and 51772141). This
184.62
work was also financially supported by Research Funding sup-
203.71
223.94
ported by the Shenzhen Science and Technology Innovation Com-
245.07 mittee (ZDSYS201602261932201, JCYJ20170412154335393, and
267.01 KQTD2016022619584022). Additional support was provided by
the Southern University of Science and Technology (Grant No.
G01296001) and Guangdong Provincial Key Laboratory of Soil
and Groundwater Pollution Control (Grant No. 2017B030301012).
 S. Tang et al. / Waste Management 80 (2018) 175–185
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.wasman.2018.09.
012.
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