Waste Management 48 (2016) 383–388

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

The effect of bioleaching on sewage sludge pyrolysis

Zhihua Chen a, Mian Hu a,b,⇑, Baihui Cui c, Shiming Liu a, Dabin Guo a,b,⇑, Bo Xiao a,⇑
a
School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
b
SafeCleen Technologies Co. Ltd, Wuhan 430074, China
c
Wuhan Botanical Garden, Chinese Academy of Sciences, Wuhan 430074, China

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

Article history: The effects of bioleaching on sewage sludge pyrolysis were studied. Sewage sludge was treated by
Received 6 March 2015 bioleaching with solid concentrations of 6% (w/v), 8% (w/v), 10% (w/v). Results showed that bioleaching
Revised 22 September 2015 treatment could modify the physicochemical properties of sewage sludge and enhance the metals
Accepted 1 October 2015
removal. The optimum removal efficiencies of heavy metals were achieved with solid concentration of
Available online 21 October 2015
6% (w/v) bioleaching treatment: Cu, 73.08%; Zn, 78.67%; Pb, 24.65%; Cd, 79.46%. The characterization
results of thermogravimetric analysis (TGA) showed that the bioleached sewage sludge with a 6% (w/
Keywords:
v) solid concentration treatment was the easiest to decompose. Pyrolytic experiments of bioleached sew-
Sewage sludge
Bioleaching
age sludge were performed in a laboratory-scale fixed bed reactor. Results indicated that bioleaching
Pyrolysis treatment greatly influenced the product yields and gas composition.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction Incineration, which is effective for volume reduction, thorough sta-

With the widespread use of biological method in wastewater
treatment field, a large amount of sewage sludge (SS) is produced
as an unescapable by-product during the process of municipal
sewage (MSW) treatment (Kang et al., 2012; Zhu et al., 2013). In
China, it was reported that about 6,000,000 tons of dry sewage
sludge was generated by more than 3080 MSW treatment plants
annually (Liu et al., 2012). Moreover, numerous of sewage sludge
is expected to be generated continuously with the rapid urbaniza-
tion and stringent effluent standard implement for MSW treatment
(Gu et al., 2013). The treatments and disposals of SS are becoming
more and more severe to the environmental protection.
Nowadays, the landfill, incineration and composting are the
main methods for disposal of SS (Folgueras et al., 2013; Gasco
and Lobo, 2007). Landfill is considered as an universal solution
for sewage sludge disposal because of its low cost (Celary and
Sobik-Szoltysek, 2014). However, landfill is limited to implement
due to the shrinkage of land and leaching of toxic substances to
environment (Lin et al., 2014). Composting is a good way to con-
vert the decomposable organic materials into organic fertilizer
for farmland application. But the odor, bioaerosol emissions and
the heavy metals leaching cannot be avoided during composting.
⇑ Corresponding authors at: School of Environmental Science and Engineering,
Huazhong University of Science and Technology, Wuhan 430074, China.
E-mail addresses: mianhu_hust@126.com (M. Hu), adren840609@gmail.com
(D. Guo), xiaobo1958@126.com (B. Xiao).
bilization, sanitation and energy generation, is more and more
popular (Lin and Ma, 2012; Samolada and Zabaniotou, 2014). Nev-
ertheless, the incineration also is disadvantageous to the environ-
ment with harmful fly ash produced during burning, which
attributes to the high ash content of SS (Lin and Ma, 2012).
Bioleaching, a technologically and economically feasible pro-
cess, is considered as the most hopeful way to reduce heavy metals
in sewage sludge (Anand et al., 2006). During bioleaching process,
elemental or reduced sulfur compounds are oxidized to sulfuric
acid by a variety of acidophilic and chemoautolithotrophic bacte-
ria. The heavy metals can be dissolved from the sewage sludge as
the increase of sulfuric acid concentration (i.e. the decrease of pH
value) (Liu et al., 2008). After the bioleaching, there are still gener-
ous amount of bioleached SS ought to be further disposed. Such
bioleached SS is in low pH value and could not be treated by land-
fill or composting.
So far, pyrolysis is believed to be a considerable chemical proce-
dure to convert organic waste into valuable oils and high calorific
value combustible syngas (Bridgwater et al., 1999). Previous stud-
ies have shown that the pyrolysis behaviors of SS are greatly
affected by the components (Gasco et al., 2005; Mendez et al.,
2005). It was considered that the source of feedstock (Font et al.,
2001), inorganic constituents (Yaman, 2004), and pretreatment
methods could influence the decomposition temperature and pro-
duct distributions of pyrolysis process. In order to improve the effi-
ciency of waste resources utilization, many researchers have done
extensive investigations on the pretreatment of feedstock (Fullana

http://dx.doi.org/10.1016/j.wasman.2015.10.002
0956-053X/Ó 2015 Elsevier Ltd. All rights reserved.
384 Z. Chen et al. / Waste Management 48 (2016) 383–388
et al., 2003). The structures and chemical compositions of feed-
stock can be altered by pretreatment. Such inwardness variations
in the feedstock will lead to the change of reaction mechanism dur-
ing pyrolysis process. Bioleaching is an environmentally-friendly,
efficient and economical pretreatment method for the removal of
heavy metals from sewage sludge. The generation of acid products
and the metabolism of bacteria can remove or modify the com-
pounds of sewage sludge during bioleaching process. It seems that
the bioleaching can modify the pyrolysis behavior of sewage
sludge.
So far, to authors’ knowledge, the effects of bioleaching treat-
ment on sewage sludge compositions, pyrolytic behaviors and pyr-
olytic products received little attention. The present study aimed
to evaluate the variations in sewage sludge’s compositions, pyroly-
tic behaviors and pyrolytic products after bioleaching treatment.
2. Materials and methods
2.1. Materials
The sewage sludge (SS) used in this study was obtained from an
urban MSW treatment plant located in Wuhan, Hubei province,
China. The dehydrated SS was collected and stored in refrigerator
as the original material for bioleaching experiments. Initial pH
value of sewage sludge and moisture content of sewage sludge
was 8.6% and 80.4%, respectively. Heavy metal (Cu, Zn, Pb, and
Cd) contents of sewage sludge were measured by using an Induc-
tively Coupled Plasma Mass Spectrometry (ICP-MS) instrument
(ELAN DRC-e, PerkinElmer) after dissolved by HNO3:HClO4:HF
(3:1:1) solution. The heavy metal contents are 196.43 mg/kg
(Cu), 269.72 mg/kg (Zn), 63.21 mg/kg (Pb) and 4.82 mg/kg (Cd).
Acidithiobacillus ferrooxidans bacteria which were isolated from
sewage sludge were used to perform the bioleaching experiments.
The culture medium of 9 K broth (Xiao et al., 2013) was used for
the cultivation of At. ferrooxidans bacteria. Such 9 K broth was pre-
pared with 3 g/L (NH4)2SO4, 0.1 g/L KCl, 0.5 g/L K2HPO4, 0.5 g/L
MgSO4
7H2O, 0.01 g/L Ca(NO3)2, 44.2 g/L FeSO4
7H2O (Xiao et al.,
2013). The pH value was adjusted to 2.00 by H2SO4.
2.2. Bioleaching
Bioleaching experiments were carried out in 2.5 L flask agitated
by stirring at 200 rpm. 1 L of aqueous solution with different sew-
age sludge solid concentrations (6%, 8% and 10% (w/v)) was added
into the flasks. The solid concentration of the raw sewage sludge is
approximately 26% w/v. 10 mL medium contained microorganism
in log phase was incubated into the flask and maintained at
30 °C. 4 g FeSO4
7H2O was then fed into the flask. 150 mL distilled
water was replenished for evaporation per 48 h.
When the final pH value stabilized at 2 ± 0.1, the bioleaching
experiment was held for 4 h. Heavy metals leaching efficiency
was then investigated according to Eq. (1):
c0  c1
g ¼ 100  ð1Þ
c0
where g denotes the leaching efficiency, %; c0 (mg/kg) and c1 (mg/
kg) denote the heavy metal content of raw SS and bioleached SS,
respectively.
After the bioleaching, the flask was left standing for 2 h to sep-
arate the sediment from the liquid phase. The sediment was
washed with excessive distilled water and then was dried at
105 °C for 24 h. The dried bioleached SS was then crushed and
sieved through 2 mm size mesh. The bioleached sewage sludge
sample with 6% (w/v), 8% (w/v) and 10% (w/v) was named as SS-
6, SS-8 and SS-10, respectively. And the raw sewage sludge sample
was named as raw-SS.
2.3. Sewage sludge characterization
Sewage sludge samples were characterized according to the fol-
lowing parameters: total humic substances (THS) content, humic
acid (HA) contents, fulvic acid (FA) contents, element contents
and H/C, O/C, N/C ratios.
THS were extracted firstly with 0.1 M NaOH and thereafter with
0.1 M Na4P2O7 (pH = 10). Suspensions were centrifuged for 0.5 h
(3000 rpm). The obtained extracts were acidified with H2SO4
(pH = 1) after the supernate and coagulation were dialyzed. The
coagulated HA was re-dissolved with 0.1 M NaOH for 3 times.
The supernate was referred to fulvic acid (FA). The C contents of
THS, HA and FA were determined by the Walkley–Black method
(Nelson and Sommers, 1982).
Ultimate analysis of the sewage sludge samples was measured
by a CHNS/O analyzer (Vario Micro cube, Elementar). Such an anal-
ysis gave the weight percent of carbon, hydrogen, and nitrogen in
the samples simultaneously. The weight percent of oxygen was
determined by difference methods.
The chemical functional groups in sewage sludge samples were
investigated by using FT-IR technique. Sewage sludge samples
were ground to fine particles and mixed with KBr powder. The
mass ratio of samples to KBr powder was 1:100. The spectral res-
olution was set at 4 cm1.
2.4. Thermogravimetric analysis
Thermogravimetric analysis (TGA) is considered as a powerful
technique for pyrolysis behaviors characterization. By using TGA,
the mass loss and mass loss rate are recorded as a function of tem-
perature and time. The thermogravimetric analysis was carried out
using Pyris1 TGA instrument (Perkin Elmer Co., Ltd). TG (%) denotes
the normalized mass loss of the sample during the pyrolysis pro-
cess. DTG (%/min), which denotes the mass loss rate of the sample,
is obtained from the first derivative of TG (%) versus time (min).
3.5 ± 1.0 mg of sample was used in each experiment. Nitrogen with
a flow rate of 100 mL/min was used as carrier gas. All the samples
were heating from room temperature to 800 °C with a heating rate
of 15 °C/min.
2.5. Pyrolysis of sewage sludge samples
The pyrolysis experiments were performed according to a
laboratory-scale fixed bed pyrolysis system under atmospheric
pressure. The schematic configuration of pyrolysis experiment is
illustrated in Fig. 1. Before the experiments, nitrogen (with a con-
stant flow rate of 50 mL/min) was injected into the reactor for
20 min to maintain an inert atmosphere. Subsequently, the reactor
was heated in a heating rate of 35 °C/min to achieve the set-point
temperature (800 °C). Then, 5.0 g sewage sludge sample was put
into the stainless steel boat and placed into the middle of quartz
tubular reactor. The set-point temperature was considered as the
pyrolytic temperature which would be held for 20 min. During
the pyrolysis process, the volatile flowed out of the reactor and
was condensed. By means of such condensation process, the con-
densable volatiles (i.e. bio-oil) were captured in the collector.
And the non-condensable (combustible) gas whose volume was
measured by a gas flow meter was gathered in a Tedlar sample
bag. The main compositions of non-condensable gas (i.e. H2, CO,
CO2, CH4) were analyzed with a gas chromatography (9800T) by
using thermal conductivity detector (TCD) and TDX-01 columns.
At the end of the pyrolysis, the furnace was cooled down to room
temperature and the mass of the solid char as well as bio-oil yields
could be calculated. Each experiment was repeated two times in
order to ensure the mass balance and data reliability. The data
reported in this paper were the mean value of twice the data.
 Z. Chen et al. / Waste Management 48 (2016) 383–388
Fig. 1. Schematic diagram of sewage sludges pyrolysis apparatus. 1. Temperature control; 2. nitrogen gas cylinder; 3. rotameter; 4. thermocouple; 5. stainless steel boat; 6.
horizontal electric furnace; 7. condenser; 8. tar collection bottle; 9. cotton filter; 10. drying tube; 11. gas meter; 12. gas outlet.
3. Results and discussion
3.1. Effects of bioleaching on sewage sludge composition
During the bioleaching process, the Fe2+ is oxidized into Fe3+ by
At. ferrooxidans bacteria. The Fe3+ is leached in the liquid phase and
the sulfuric acid is generated via following chemical reactions:
At: ferrooxidans
2FeSO4 þ 0:5O2 þ H2 SO4 ƒƒƒƒƒƒƒƒƒƒ! Fe2 ðSO4 Þ3 þ H2 O
4Fe2 ðSO4 Þ3 þ 2MeS þ 4H2 O þ 2O2
! 2M2þ þ 2SO2
4 þ 8FeSO4 þ 4H2 SO4
2+
where MeS denotes the metal sulfide, and M denotes the soluble
metallic ion.
The production of sulfuric acid leads to the pH value decrease,
which is beneficial to the solubilization of sludge-borne metals.
Bioleaching process has been proven to be capable of sewage
sludge digesting, dewatering ability improvement and organic
compounds modifications.
Table 1 gives the ultimate analysis results of sewage sludge
samples. Variations in the C, H, O, N contents and H/C, O/C, N/C
ratio demonstrate that the organic matter composition of sewage
sludge has been changed by bioleaching treatment. Compared with
the raw SS (i.e. raw-SS), the H/C and N/C ratios both decrease but
the O/C ratio of sewage sludge increases after bioleaching. The
H/C ratio decreases with the solid concentrations of bioleaching
treatment, from 2.87 (raw-SS) to 2.51 (SS-10). Meanwhile, the
H/C ratio decreases from 2.77 to 2.51 as the solid concentration
increases from 6% to 10% (w/v). The phenomenon of H/C, N/C
and O/C ratios variations suggests that the bioleached sewage
sludge samples show more aromatic groups than raw-SS samples.
It could be caused by the solubilization of light organic compounds
during the bioleaching process (Gasco and Lobo, 2007). One feature
is that the SS-6 exhibited higher H/C ratio than the other SS sam-
ples. This indicates that the bioleaching with 6% (w/v) solid con-
centrations shows the optimal performance for the presence of
elevated aliphatic carbon and long chains (with CH2 groups) (Cao
et al., 2011; Gasco et al., 2005). The higher aliphatic carbon
content is beneficial to the generation of alkane gaseous or light
aromatic hydrocarbon. The N/C ratio can be used to express the
Table 1
Ultimate analysis of sewage sludge samples.
Sewage sludge C (wt%) H (wt%)
Raw-SS 12.37 ± 0.17 2.96 ± 0.09
SS-6 13.00 ± 0.12 3.01 ± 0.11
SS-8 13.68 ± 0.23 3.00 ± 0.15
SS-10 14.26 ± 0.34 2.99 ± 0.08
a
By difference.
b
Molar ratio.
385
polymerization degree of organic matter in sewage sludge. Higher
polymerized organic material contains less nitrogenous functional
groups (Gasco et al., 2005). Therefore, the higher polymerization
degree of bioleached sewage sludge at 6% (w/v) sludge solid con-
centration suggests higher dewatering capacity. As can be seen in
Table 1, the O/C ratios of SS-6, SS-8 and SS-10 are obviously higher
than those of raw-SS. The O/C ratio is not an appropriate parameter
for organic matter, indicating some oxygen can be transferred to
ðR-1Þ oxygenous function groups or oxidized during the reaction.
Table 2 lists the total humic substances (THS) content, humic
acid (HA) contents, fulvic acid (FA) contents and HA/FA ratios of
different sewage sludge samples. It can be observed that these
ðR-2Þ
parameters of sewage sludge varied significantly after bioleaching.
HA and FA are the main fractions of humic substances. FA, which is
in lower molecular weight and lower carbon content than HA, con-
tains higher oxygen in the form of functional groups (Rodriguez
et al., 2014). In addition, HA is soluble in alkali but insoluble in
acid, while the FA is soluble in both alkali and acid. After bioleach-
ing, the HA and FA contents of sewage sludge have increased. But
the HA content decreases with the increase of bioleached solid
concentrations from 0.79% (SS-6) to 0.49% (SS-10). It possibly attri-
butes to the precipitation of HA under acid condition during the
bioleaching process. Furthermore, the acidification rate of sewage
sludge decreases as the solid concentration increases (high pH),
which enhances the HA solubilization. The FA content in
bioleached sewage sludge is a little higher than that of raw-SS.
Meanwhile, the FA content decreases with the solid concentration
increasing from 2.54% (SS-6) to 2.46% (SS-10), because the hydrol-
ysis of polymerized organic matter generates more oxidized and
light molecular compounds which are similar to the FA fraction
under higher acidification rate (Gasco and Lobo, 2007). The HA/
FA ratio denotes the humic transformation degree. The HA/FA ratio
inversely relates to the N/C ratio which can be used to compare the
polymerization degree (Iakimenko et al., 1996).
Table 3 gives heavy metal contents of the raw-SS and
bioleached sewage sludge. It is obvious that the bioleaching treat-
ment can reduce the heavy metal contents in sewage sludge. For
these four heavy metals, the highest removal efficiencies (g) are
all obtained at the solid concentration of 6% (w/v) and follow the
order of Cd > Zn > Cu > Pb. Similar orders also can be found for
the 8% (w/v) and 10% (w/v) solid concentration bioleaching
Oa (wt%) N (wt%) H/Cb O/Cb N/Cb
16.89 2.79 ± 0.14 2.87 1.02 0.19
27.67 1.91 ± 0.11 2.77 1.59 0.12
26.26 2.23 ± 0.07 2.63 1.43 0.13
24.79 2.47 ± 0.18 2.51 1.30 0.14
386 Z. Chen et al. / Waste Management 48 (2016) 383–388

Table 2
Properties of sewage sludge samples.

Sewage sludge CTHS (wt%) CHA (wt%) CFA (wt%) HA/FA

Raw-SS 2.55 ± 0.09 0.25 ± 0.06 2.30 ± 0.02 0.11
SS-6 3.24 ± 0.02 0.70 ± 0.04 2.54 ± 0.08 0.28
SS-8 3.06 ± 0.10 0.59 ± 0.02 2.47 ± 0.10 0.24
SS-10 2.95 ± 0.09 0.49 ± 0.01 2.46 ± 0.03 0.20

treatments. However, the removal efficiencies of these four heavy

metals are strongly influenced by solid concentration. As can be
seen in Table 3, with solid concentration increase, the contents of
Cu, Zn, Pb and Cd in sewage sludge increase and the corresponding
removal efficiencies decrease. The phenomenon may attribute to
the final pH value of the bioleaching system. The higher solid con-
centration indicates more sewage sludge which has higher buffer-
ing capacity in the bioleaching system. And the pH value of
bioleaching also can greatly affect the solubilization efficiencies
of heavy metals during the bioleaching process (Chen and Lin,
2000; Sharifi and Renella, 2015). Another one feature is that the
removal efficiencies of Cu, Zn and Cd are significantly higher than
those of Pb at the same solid concentration. During the bioleaching
process, the lower removal efficiency of Pb is possibly due to gen-
eration of PbSO4 (Ksp = 1.62  108) which has low solubility (Chen
and Lin, 2000).
The bioleaching is also found to be efficient in heavy metals
removal at higher solid concentration than 6% (w/v). It is consid-
ered that the increase of solid concentration generally leads to a
prolonged lag period (i.e. the required time for the microorganisms
adapts to bioleaching medium), which decreases the bio-oxidation
rate and the ultimate extent of oxidation (Ahmadi et al., 2015). In
addition, the increase of sludge solid concentration can result a
decrease in metal solubilization. Moreover, once more sewage
sludge is treated, larger volume of reactor and treated time are
needed and the cost of process will also increase certainly.
FTIR spectra technique was used to qualitatively determine the
chemical structures change in bioleached sewage sludge compared
with the raw-SS. The FTIR spectra results (Fig. 2) demonstrate that
the bonds of bioleached sewage sludge (SS-6, SS-8 and SS-10) are
similar to the raw one (raw-SS). However, as for the SS-6 sample,
the OAH (stretching vibrations at 3432 cm1), C@O (stretching
vibrations at 1642 cm1), CAH (stretching vibrations at
1393 cm1) and CAO (stretching vibrations at 1038 cm1) have
been greatly enhanced compared with the other samples. It implies
that the quantities of these groups increase by breaking the macro-
molecule and release more free groups via bioleaching. As sug-
gested by Zhang et al. (2011), the OAH indicates the existence of
water, alcohol, phenol, or amine substance; C@O is compatible
with the presence of acids and aldehydes; CAH is produced by
ACH3 and ACH2 group which implies the sewage sludge contains
a lot of fat hydrocarbon organic matter. CAO corresponds to the
oxidizing substance of ether, ester, alcohol, and spenol. The FTIR
spectra results (Fig. 2) clearly show that the oxygen functional
Fig. 2. FTIR spectra profiles of sewage sludge samples.
groups of sewage sludge have increased by bioleaching. Such incre-
ment of oxygen functional groups is possibly related to a higher
content of FA, especially at 6% (w/v) solid concentration (Table 2).
FTIR spectra results demonstrate that the bioleaching treatment
leads to important changes in the characteristics organic matter of
raw-SS. Compared to the other samples, SS-6 is proven to generate
more oxygen functional groups which are conducive to the com-
bustible gases (CO, H2, CO2) formation during pyrolysis.
3.2. Thermogravimetric characterization
The thermogravimetric analysis (TGA) results (TG/DTG vs. tem-
perature profiles) are shown in Figs. 3 and 4. Fig. 3 presents the
weight loss of the sewage sludge samples. It could be observed that
the weight loss of bioleached sewage sludge samples starts at
lower temperature and finishes at higher temperature, especially
for SS-6. The TG profile of SS-6 also shows significant different
pyrolysis behaviors compared with the other bioleached SS (SS-8
and SS-10) and raw-SS. The alterations of pyrolysis behaviors attri-
bute to the differences of the ingredient in their sewage sludge
samples. As illustrated in the DTG profiles (Fig. 4), the pyrolysis
process of sewage sludge samples could be divided into four
stages. In the temperature ranges of room temperature to 120 °C,
the DTG peaks are caused by the evaporation of physically
absorbed water. For all the samples, the devolatilization stage
which is accompanied by high weight loss rate (DTG) and attribu-
ted to the volatiles volatilization occurs between 120 °C and
600 °C. The weight loss at the temperature of 600–800 °C is caused
by the decomposition of inorganic materials (mainly calcium car-
bonate) (Scott et al., 2006). However, the thermal decomposition
behaviors of the devolatilization stage (120–600 °C) are quite
complex and manifest as multiple peaks overlap. The peaks at

Table 3
Heavy metal contents (mg/kg) in sewage sludge (SS) and corresponding bioleaching efficiency (g, Eq. (1)).

Cu Zn Pb Cd
Raw SS c0 c0 c0 c0
Raw-SSa 196.43 ± 3.20 269.72 ± 1.78 63.21 ± 3.27 4.82 ± 0.84
Bioleached SS c1 g (%) c1 g (%) c1 g (%) c1 g (%)
SS-6b 52.87 ± 2.48 73.08 57.53 ± 1.49 78.67 47.63 ± 3.01 24.65 0.99 ± 0.05 79.46
SS-8b 87.42 ± 2.91 55.50 98.85 ± 0.88 63.35 51.12 ± 2.64 19.13 1.66 ± 0.04 65.56
SS-10b 105.21 ± 2.83 46.44 129.11 ± 2.72 52.13 53.52 ± 2.82 15.33 2.01 ± 0.11 58.30
a
Heavy metal contents of raw SS, c0 in Eq. (1).
b
Heavy metal contents of bioleached SS, c1 in Eq. (1).
 Z. Chen et al. / Waste Management 48 (2016) 383–388 387

Fig. 3. TG (weight loss vs. temperature) curves of sewage sludge samples.
120–395 °C denote the preliminary decomposition stage of the
organics in sewage sludge samples. In temperature range about
395–600 °C, obvious peaks also can be observed, which denotes
the secondary decomposition stage of the organics. The weight loss
rate of SS-6 in the secondary decomposition stage is higher than
the rest samples at any same temperature point. It indicates that
the organics of SS-6 is easier to decompose than the other samples.
In addition, the DTG curves of bioleached sewage sludge (SS-6, SS-8
and SS-10) are more intensive to the temperature than the raw-SS.
3.3. Pyrolysis products
alkanes and long fragment alkenes). Besides, the formed free radi-
cals can be mutually combined freely with the hydrogen atom.
Other bonds also start to break and generate more free radicals,
which induces the polymerization and cyclization reactions. There-
fore, the main primary pyrolysis products are char, small molecule
gases (CO, CO2) and macromolecular condensable volatiles. As the
temperature increases, the secondary reactions of tar cracking and
shifting, such as decarboxylation, decarbonylation, dehydrogena-
tion, cyclization, aromatization and polymerization, contribute to
the thorough reaction of the pyrolysis (Li et al., 2007). Afterward,
the light vapors underwent series reactions and are cracked to
form H2, CO, CO2, alkanes, alkenes, and aromatic hydrocarbons.
In this study, the pyrolysis experiments of sewage sludge were
carried out in the reactor at temperature of 800 °C. The results of
product distribution and gas compositions are depicted in Figs. 5
and 6. As shown in Fig. 5, the gas product yield of bioleached sew-
age sludge is larger and the char yield is less than that of the raw
sewage sludge. Meanwhile, the tar yield also changes slightly.
The variations in pyrolysis products (char, tar and gas) mainly
attribute to the changes in the characteristics of sewage sludge
after bioleaching, such as the compositions change (Tables 1 and
2) and the removal of heavy metals (Table 3). However, the gas
yield gradually decreases with the increase of solid concentration.
In addition, no remarkable change is observed for the tar yield.
60
SS-6
50 SS-8
SS-10
Raw SS
Percentage (wt.%)

40
It is believed that the organic matter in sludge mainly consisted
of fat, protein, carbohydrate, and cellulose (Kapanen et al., 2013). 30
The main functional groups of these organic compounds include
carboxylic acid, carbonyl, amide, amine, methyl and aromatic.
20
With the primary thermochemical decomposition of sewage
sludge, the instability C@O of macromolecular organic matter
begins to break and generate CO and CO2. Then, the CAC and 10
CAH bonds are ruptured to form the free radicals which are further
recombined into low molecular compounds. However, the CAC 0
bond could be easily broken since the bond energy of CAC Gas Char Tar
(346.9 kJ) is lower than that of CAH bond (413.84 kJ) (Sorum Product
et al., 2001). In general, the cleavage of alkanes which contains
more carbon atoms will form new kinds of alkanes (short fragment Fig. 5. Products percentages obtained by sewage sludge pyrolysis.

40
SS-6
SS-8
SS-10
32
raw-SS
Percentage (wt.%)

24

16

0
H2 CO CO2 CH4
Gas composition

Fig. 4. DTG curves (weight loss rate vs. temperature) of sewage sludge samples. Fig. 6. Compositions of gas derived from sewage sludge samples pyrolysis.
388 Z. Chen et al. / Waste Management 48 (2016) 383–388
Reasons may lie in that: (1) After bioleaching, the contents of fulvic
acid vary from 2.54% (SS-6) to 2.46% (SS-10) (Table 2). The fulvic
acid is rich in oxygen content and its function groups could be
easily ruptured to generate volatiles. Under different solid concen-
trations, the bioleached sewage sludge shows a gradually
decreased H/C ratio (from 2.77 (SS-6) to 2.51 (SS-10)), which
accordingly reduces the aliphatic carbon fractions. The higher ali-
phatic carbon fraction is advantageous to the generation of alkane
gaseous and light aromatic hydrocarbon. (2) Meanwhile, as can be
seen from the TG curves (Fig. 3), SS-6 sample exhibits a larger
weight loss than the other samples in the whole pyrolysis temper-
ature range. It demonstrates that the pyrolysis of SS-6 leads to a
larger volatiles volume than the rest samples (SS-8, SS-10 and
raw-SS), which may contribute to more gas production. The change
of char yield relates to heavy metals dissolution efficiency. With
the solid concentration increase, the buffering capacity of sludge
also increases. And the dissolution of heavy metals is reduced by
the pH reduction. Nonetheless, the contribution of bioleaching pre-
treatment on tar yield is inconspicuous.
Bioleaching treatment has significant influences on the compo-
nents of pyrolytic gas products. As can be seen in Fig. 6, H2 and CO
fractions in pyrolytic gas products have been improved by
bioleaching treatment, especially for the treatment with 6% (w/v)
solid concentration. The generation of CO may be resulted from
the reactions of carbonyl group cracking, oxygen function group
rupture and dehydrogenation of hydroxyl group. Such reactions
have been enhanced by bioleaching treatment. The decreasing
trend of CO2 content may be due to the fact that the fractions of
CO and CO2 are linked together according to the equilibrium of
the Boudouard reaction under the experiment conditions. CH4 con-
tent presented is slightly changed, which possibly attributes to the
variance of tar yield.
4. Conclusions
During bioleaching process, heavy metals removal efficiency,
organic compositions, pyrolytic behaviors, pyrolysis product yield
and gas components were influenced by bioleaching treatments.
Sewage sludge was treated by bioleaching with 6% (w/v), 8% (w/
v), and 10% (w/v) solid concentration. The bioleaching treatment
could improve the removal of heavy metals, especially for the 6%
(w/v) solid concentration treatment. The optimal removal efficien-
cies of Cu, Zn, Pb, Cd are 73.08%, 78.67%, 24.65% and 79.46%,
respectively. The H/C, N/C ratios of sewage sludge decreased while
the O/C ratios increased after bioleaching treatment. The humic
acid, fulvic acid and total humic contents of bioleached sewage
sludge increased compared with the raw sewage sludge. The ther-
mogravimetric analysis characterizations indicated that the organ-
ics of bioleached sewage sludge was more intensive to the
temperature than that of the raw sewage sludge. The bioleaching
of sewage sludge with 6% (w/v) solid concentration showed the
best performance on heavy metals removal, organic compositions
transformation, pyrolytic behaviors, pyrolysis product yields and
gas components.
Acknowledgments
The authors wish to acknowledge the financial supports of the
National Nature High Technology Research and Development Pro-
gram (863 Program) of China (No. 2012AA101809), National Natu-
ral Science Foundation of China (No. 21276100) and the Natural
Science Foundation of Hubei Province, China (2014CFB411). The
authors would also like to thank the Analytical and Testing Center
of Huazhong University of Science and Technology for carrying out
the analysis of the characterization of sewage sludge samples.
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