Energy 200 (2020) 117398

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

Characterization and analysis of sludge char prepared from bench-

scale fluidized bed pyrolysis of sewage sludge
Yang Liu a, b, c, Chunmei Ran a, b, Azka R. Siddiqui a, b, Asif Ali Siyal a, b, Yongmeng Song a, b,
Jianjun Dai a, b, *, Polina Chtaeva a, b, Jie Fu a, b, Wenya Ao a, b, c, Zeyu Deng a, b,
Zhihui Jiang a, b, Tianhao Zhang a, b
a
College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China
b
State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing, 100029, China
c
Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China

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

Article history: Pyrolysis of sewage sludge (SS) was performed in a bench-scale fluidized bed pyrolyzer. Addition of
Received 21 December 2019 kaolin at 850
C resulted in minimum sludge char (SC) yield of 54.64 wt%. The maximum condensate
Received in revised form yield of 17.07 wt% was obtained at 650
C with Ca-bentonite addition. The H/C ratio of SC significantly
24 February 2020
decreased with increasing temperature, indicating the greater stability of high temperature SC in the soil
Accepted 13 March 2020
Available online 16 March 2020
environment. CaO obtained the largest carbon content of 12.91% in the form of carbonates, which was
related to the intensive adsorption of CO2 by CaO. Meanwhile, CaO achieved prominent retention of
sulfur in SC. CaO had a considerable ability to retain Cu and As at 850
C and all catalysts had a good
Keywords:
Fluidized bed
retention effect on As at 650
C. X-ray diffraction (XRD) analysis implied that relatively stable ZnO and
Pyrolysis SiAs2 in SC inhibited volatilization of Zn and As. The maximum energy yield (88.66%) of the condensate
Sewage sludge was obtained when kaolin was added, while the addition of CaO resulted in the highest energy yield
Char (18.27%) of non-condensable gas.
Heavy metal © 2020 Elsevier Ltd. All rights reserved.

1. Introduction
Sewage sludge (SS) is a by-product from the municipal sewage
treatment plant, which is a semi-solid with high water content. SS
contains nitrogen and phosphorus salts, various organics and in-
organics. Pathogenic microorganisms, parasitic and saprophytic
organisms, and heavy metals are also found in SS. These toxic
substances can cause serious environmental problems if they are
not treated and disposed properly. Owing to the rapid population
growth and urbanization, the production of SS increased signifi-
cantly in recent years and is expected to reach 60e90 million tons
(80% moisture content) by 2020 in China [1]. The traditional
methods for the treatment of SS are mainly landfill, incineration,
composting and land use. SS can also be used as construction ma-
terials (e.g. mold brick and lightweight concrete bone grains) [2].
Pyrolysis is an important thermochemical technology, heating SS to
a certain temperature under inert atmosphere. SS is then
* Corresponding author. College of Chemical Engineering, China.
E-mail addresses: daijianjun@hotmail.com, jjdai@mail.buct.edu.cn (J. Dai).
transformed into pyrolysis oil, non-condensable gas and char [3].
There has been growing interests in pyrolysis of complex materials
in recent years, which can provide an environmentally and
economically viable energy solution. Pyrolysis helps to improve
safety of global energy supply, and meet environmental and cli-
matic regulations on sludge treatment with reduced carbon dioxide
emissions [4].
There have been many researches on SS pyrolysis, aiming at
technical feasibility of different technologies and process funda-
mentals. Lehmann and Joseph employed pyrolysis techniques to
effectively convert SS into syngas, bio-oil and bio-char at relatively
high temperature (300e1000
C) [5]. Fonts et al. [6] investigated
the effects of solid feed rate, temperature and nitrogen flow rate on
fast pyrolysis of digested sludge. It was found that the highest oil
yield of 33 wt% was achieved at 540
C under nitrogen flow rate of
4.5 NL/min. W.D. Chanaka Udayanga et al. [7] studied the effects of
organic and inorganic constituents on the product properties dur-
ing SS pyrolysis in a vertical fixed-bed pyrolysis unit. It was found
that the additives significantly affected the yields and compositions
of non-condensable gas, tar and char. Yunxue Xia et al. [8] con-
ducted SS pyrolysis in a horizontal furnace equipped with a quartz

https://doi.org/10.1016/j.energy.2020.117398
0360-5442/© 2020 Elsevier Ltd. All rights reserved.
2 Y. Liu et al. / Energy 200 (2020) 117398
tube to investigate the enhanced phosphorus availability and heavy
metal removal by chlorination, proposing a novel method to use the
sludge biochar as potential P-fertilizer. Eilhann E. Kwon et al. [9]
demonstrated that CaCO3 reduce the content of polycyclic aromatic
hydrocarbons (PAHs) in the pyrolysis products from SS. Salman
Raza Naqvi et al. [10] investigated the thermo-kinetics of high-ash
SS using thermogravimetric analysis, the results indicated that the
SS pyrolysis may be divided into three stages.
Current SS pyrolysis research is focused on fixed bed and ther-
mogravimetric analyzer, the main research scopes are yields and
properties of pyrolysis products, concentrations and risks of heavy
metals, and pyrolysis kinetics. Furthermore, there are also some
studies on fluidized bed pyrolysis (FBP) of SS. FBP is an efficient
method for converting biomass into gas, oil and solid products due
to excellent gas-solid contact and fast reaction rate in the fluidized
bed [11]. Alejandro Jaramillo-Arangoa [12] investigated the effect of
temperature on pyrolysis of anaerobically digested SS by means of
chemical characterization of the gases, liquids and solids produced
in a fluidized bed reactor at temperature between 300 and 800
C.
The pyrolysis gas, in mass fractions, was mainly composed of CO
and CO2, while the liquid product was mostly pyrolytic water.
Antonio Soria-Verdugo [13] studied different operating conditions
to analyze the sample mass evolution with time during pyrolysis,
including bed temperature and velocity of nitrogen used as inert
gas. An increase of nitrogen velocity (e.g. from 0.8Umf to 2.5Umf)
reduced pyrolysis time and accelerated pyrolysis remarkably. A
circulating fluidized bed was used for SS pyrolysis to produce liq-
uids rich in nitrogenated heterocyclic compounds [14]. A low flu-
idized gas velocity (e.g. 1.13 m/s), high sludge feed rate (e.g.
10.78 kg/h) and large particle size (e.g. 1e2 mm) increased the yield
of heterocyclic nitrogenated compounds. Effects of temperature, SS
particle size and vapor residence time on bio-oil yield and prop-
erties, such as high heating value (HHV) and moisture content,
were evaluated by Arazo et al. [15] in a fast pyrolysis fluidized bed
reactor for SS disposal. At optimum conditions, the unit produced a
bio-oil product with HHV nearly twice as much as lignocellulosic-
derived bio-oil, and its properties were comparable to heavy fuel
oil. This FBP study focused on effects of operating conditions (e.g.
temperature and gas velocity) on the yield of pyrolysis products
and properties of liquid products.
In addition, there were some studies on the catalytic pyrolysis of
SS and CaO was known to benefit pyrolysis, for instance, CaO was
found to adsorb CO2 from non-condensable gases [16] and facilitate
the retention of sulfur [17] in the derived char during pyrolysis of
CaO conditioned sludge. However, there were limited studies
regarding the influence of aluminosilicate compounds on sludge
pyrolysis [18]. Aluminosilicate clay would act as solid acid catalyst
in the cracking reactions of the organic component of sludge and
improve the yield of volatile products. Ischia et al. [19] reported that
the release of crystalline water from clay could result in an increase
in CH4 content. Fixation of heavy metals into the derived char by
addition of clay in the sludge was also demonstrated [20]. However,
the impacts of aluminosilicate compounds (e.g. kaolin and Ca-
bentonite) on the pyrolysis product distribution and properties
have not been clearly determined. As natural ores, kaolin and Ca-
bentonite had some merits, such as good catalytic performance,
fast response and low price.
Hence, we investigated FBP of SS and the influences of pyrolysis
temperature and additives on product yields, sludge char (SC)
characteristics, and migration, existing forms and potential
ecological risks of heavy metals in SC. Based on these scenarios,
technical feasibility of FBP and immobilization of heavy metals in
SC were assessed, which is expected to be meaningful for solid
wastes treatment and disposal. We also studied the transformation
and balance of carbon element during SS pyrolysis, which were
rarely studied in previous literatures. In addition, the energy bal-
ance and energy yield of the FBP system were analyzed and the
economy of the FBP technique was also discussed.
2. Materials and characterization methods
2.1. Materials
Raw SS was obtained from a sewage treatment plant situated in
Hebei province. The SS was dried at 105
C for 12 h, then crushed
and sieved into 0.105e1.0 mm particles for the FBP experiment.
Required chemicals (analytical reagent) such as ethanol, dichloro-
methane, hydrochloric acid, nitric acid and catalysts were pur-
chased from Beijing Chemical Works.
2.2. Experimental device
Fig. 1 shows the schematics of FBP of semi-continuous opera-
tion. For more detailed descriptions, please refer to previous liter-
atures [21]. About 400 g SS was added to the feed hopper before
experiments. After reaching the preset temperature, the auger
speed was set at 5 rpm. N2 was employed as the fluidizing gas and
Ar was used as the tracer gas to assist in calculation of the flow rate
of non-condensable gases. The gas cooling and cleanup unit
including 4 cooling bottles and 4 washing bottles in the ice bath (i.e.
5, 6-ethanol, 7, 8-deionized water) were set at downstream of FBP
to remove entrained particles, separate condensates and non-
condensable gases. During the experiment, non-condensable gas
was collected every 3 min with sample bags. After the test, the inert
gas was continued to purge the FBP for more than 10 min. The
reactor was cooled to room temperature, and the SC and conden-
sates were collected and weighed. The operating temperature was
in the range of 450e950
C. Kaolin (1), Ca-bentonite (2) and CaO (3)
were used as catalysts. While SCs were represented by pyrolysis
temperatures and adopted catalysts.
2.3. Analytical methods
Proximate analyses of SS and SCs were performed based on
related standards (Proximate analysis methods for solid biofuels,
GB/28731e2012). Ultimate analysis was conducted by an elemental
analyzer (VARIO EL cube, Elementar Analysensysteme GmbH,
Germany). Meanwhile, XPS (X-ray photoelectron spectroscopy,
ESCALAB 250, Thermo Fisher Scientific Co., Ltd. USA) was employed
to analyze elemental composition and surface chemistry. Main
functional groups were exhibited by FTIR (Fourier transform
infrared spectroscopy, Bruker vector 22). Surface morphologies of
SS and SC were observed from SEM (Scanning electron microscopy,
HITACH S4700, Japan). The digestion solutions of SS and SCs were
prepared according to relevant standards (HJ 677-2013 and CJ/T
221e2005, China), which were characterized by ICP-MS (induc-
tively coupled plasma mass spectrometry, 7700 Series ICP-MS,
Agilent Technologies, USA). Crystalline structure and phase iden-
tification were analyzed by X-ray diffraction (XRD) technique (D2
PHASER, Bruker) and XRF (X-ray fluorescence, XRF-1800, SHI-
MADZU, Japan) were conducted to display chemical composition.
3. Results and discussions
3.1. Product yields at different pyrolysis conditions
3.1.1. Effects of temperature on yields of pyrolysis products
Product yields from SS pyrolysis are depicted in Fig. 2. The SC
yield declined steadily from 74.33 wt% to 58.66 wt% with increasing
pyrolysis temperature mainly due to continuous release of volatile
 Y. Liu et al. / Energy 200 (2020) 117398 3

Fig. 1. A schematic diagram of fluidized bed pyrolyser.

(a) (b) (c)

80
80 650 650-1 650-2 650-3 80 850 850-1 850-2 850-3
70
70 70
60
60 60
50
50 50
Yield (wt%)

Yield (wt%)

Yield (wt%)

Char
40 Condensate 40 40
Gas
30 30 30

20 20 20

10 10 10

0 0 0
450 550 650 750 850 950 Char Condensate Gas Char Condensate Gas
Temperature ( C)

Fig. 2. Products yields under different pyrolysis conditions: (a) with different temperatures; (b) with different additives at 650
C; (c) with different additives at 850
C (1: Kaolin; 2:
Ca-bentonite; 3: CaO; SC yield excluded the catalyst mass).

materials (Fig. 2a).
It was noticed that char yield from SS was considerably higher
than that from lignocellulosic biomass [22], due mainly to higher
ash content in SS. Meanwhile, the yield of non-condensable gas
increased from 4.08 wt% to 11.75 wt% as the temperature increased
from 450
C to 950
C, which was in agreement with the result from
previous study [23]. The secondary cracking of pyrolysis vapors at
higher temperature led to an increase in gaseous products.
Furthermore, owing to the heterogeneous reaction between char
and gaseous components (e.g. H2O), the secondary decomposition
of char at high temperatures might produce non-condensable gas.
It could be seen that the condensate yield increased with increasing
temperature and achieved the maximum of 15.83 wt% at 750
C,
owing to decomposition of organic components in SS. However, as
the temperature increased from 750
C to 950
C, the yield of
condensate gradually decreased due to secondary reactions (e.g.
4 Y. Liu et al. / Energy 200 (2020) 117398

Table 1
Proximate and ultimate analysis of SS and SC.

LHVa (MJ/kg) Ultimate analysis of SSb (wt%) Proximate analysis of SSb (wt%)

S N H C Oc Ash Volatile Fixed Carbonc

10.23 0.77 4.27 3.59 23.97 3.53 58.04 37.93 4.03

Ultimate analyses of SCb (wt%)

Sample Inert gas flow rated (m3/h) Catalysts S/% N/% H/% C/% H/Cf N/Cf

SRe SA e N Re NAe H Re HAe CRe CAe

SS e e 0.77 100.00 4.27 100.00 3.59 100.00 23.97 100.00 0.15 0.18
SC450 0.42 e 0.52 56.02 3.44 59.89 2.51 51.97 22.28 69.09 0.11 0.15
SC650 0.42 e 0.62 59.07 2.86 44.03 1.83 33.51 19.33 53.01 0.09 0.15
SC850 0.42 e 0.76 66.75 1.59 22.56 0.85 14.35 14.2 35.90 0.06 0.11
SC650-1 0.42 20 wt%kaolin 0.27 24.18 0.65 9.41 0.72 12.39 5.67 14.62 0.13 0.11
SC650-2 0.42 20 wt%Ca-bentonite 0.3 31.10 1.12 18.76 0.93 18.53 7.72 23.04 0.12 0.15
SC650-3 0.42 20 wt%CaO 0.89 96.22 0.66 11.53 1.44 29.92 9.68 30.13 0.15 0.07
SC850-1 0.42 20 wt%kaolin 1.09 95.33 0.42 5.94 0.47 7.90 5.2 13.09 0.09 0.08
SC850-2 0.42 20 wt%Ca-bentonite 0.47 47.23 0.79 12.83 0.64 12.36 6.4 18.51 0.10 0.12
SC850-3 0.42 20 wt%CaO 2.87 100.00 0.23 5.94 0.89 18.22 5.88 0.15 0.04
a
Lower heating value.
b
Oven-dry basis.
c
By difference, O (%) ¼ 100-C-H-N-S-Ash, Fixed Carbon (%) ¼ 100-Ash-Volatile.
d
The volume flow rate is measured at 20
C.
e
SR ¼ MS-SC/MSC  100, SA ¼ MS-SC/MS-SS  100 (MSC is the mass of sewage sludge char, MS-SC and MS-SS are mass of sulfur in solid products and over-dry SS; The definitions
and calculations of N, H and C are the same as S).
f
H/C ¼ HR/CR, N/C ¼ NR/CR.

cracking). Secondary reactions are known to become active at
600
C or higher [24], leading to an increase in the gas yield.
Additionally, it was found that the mass-loss percentage ranged
from 10.43 wt% to 14.71 wt% at the temperature of 450e950
C.
3.1.2. Effects of catalysts on yields of pyrolysis products
The yields of pyrolysis products using different catalysts at
650
C and 850
C are presented in Fig. 2b and c. The addition of
kaolin resulted in lower SC yields, whereas Ca-bentonite and CaO
increased SC yield. CaO captured CO2 to form CaCO3 [25], which has
larger molar mass (100.1 g/mol) than that of CaO (56.1 g/mol) [26],
leading to the mass gain of SC. The results of non-condensable gas
also illustrated this point. The CO2 yields were 7.14 wt% at 650
C
and 8.87 wt% at 850
C without addition of catalysts. When CaO
was added at mass fraction of 20 wt%, the CO2 yields decreased to
6.66 wt% at 650
C and 3.47 wt% at 850
C. The minimum yield of SC
(i.e. 54.64 wt%) was obtained when kaolin was added at 850
C. In
the presence of Ca-bentonite, the condensate yields significantly
increased because Ca-bentonite triggered release of volatiles,
consistent with results of previous study [27]. Bentonite
(AleSieOH) might effectively promote the dehydration reactions
during SS pyrolysis [28]. The maximum condensate yield of
17.07 wt% was achieved at a reaction temperature of 650
C with
Ca-bentonite addition. However, CaO decreased the condensate
yield, which might be due to secondary reactions (e.g. thermal
cracking, carbonization) of volatiles [29,30]. In addition, the release
of volatiles needed more time, thus the gas residence time
increased with CaO addition, which enhanced the secondary
cracking and decreased the condensate yield [31]. Yield of non-
condensable gas significantly increased in presence of three cata-
lysts, and kaolin significantly promoted the generation of gas.
Addition of kaolin yielded the maximum non-condensable gas
yield of 33.51 wt% at 850
C. Kaolin facilitated catalytic cracking and
hydrogenation of organic matter because of its active sites and
acidity properties [32], spontaneous decomposition, displacement,
rearrangement or polymerization of intermediates during
pyrolysis.
3.2. Proximate and ultimate analyses of SS and SC
Table 1 tabulated the elemental composition of SS and SC. SS
had higher nitrogen and sulfur contents than lignocellulosic
biomass [33]. Nitrogen was derived from the proteins fraction of
microorganisms required for wastewater purification treatments
[34]. The contents of carbon, hydrogen, nitrogen in SC decreased as
temperature increased from 450
C to 850
C, which was related to
increased devolatilization with temperature. However, the sulfur
content of SC increased with increasing pyrolysis temperature,
indicating sulfur might be present in the form of stable inorganics
[21]. The molar ratio of H/C was a major carbonization parameter
that was usually employed to describe the degree of aromaticity of
bio-char. The H/C ratio of SC was significantly reduced with
increasing temperature hence resulted in enhanced carbonization
and greater aromatic condensation [35]. Bio-char with higher
aromaticity was less likely to decompose in soil [36], indicating that
SC produced at higher temperatures was more stable in the soil
environment. The ratio of N/C in SC followed similar trend to H/C,
indicating that N-containing compounds in SC were gradually
decomposed and removed as pyrolysis temperature increased from
450
C to 850
C. When SC was incorporated into soil, organic-N
leached from the soil would be less than that from SS [37].
As abovementioned, catalysts significantly decreased the con-
tents of carbon, hydrogen and nitrogen in SC, promoting decom-
position and release of organic matter. However, for the sulfur
element, SA of SC650-3 was as high as 96.22% and SC850-3 had a SA
value of ~100%, revealing a prominent sulfur retention effect of CaO.
Meanwhile, the H/C ratio of SC increased with addition of catalysts,
the maximum H/C ratio of 0.15 was obtained with addition of CaO.
Nevertheless, these H/C ratios didn’t exceed that of SS, indicating
aromatization reactions occurred to some extent [38]. The opposite
trend was observed for N/C ratio with the exception of SC with
addition of Ca-bentonite, which indicated that kaolin and CaO
facilitated the decomposition of nitrogen-containing compounds
and Ca-bentonite did not exhibit any considerable effects. The
minimum N/C ratio of 0.04 was obtained in SC850-3, which
revealed that CaO had a strong promoting effect on the
 Y. Liu et al. / Energy 200 (2020) 117398 5

(a) (b)
16000
160000 SS wide-scan SS C1S
14000 C-OR
140000
N1s (399.73 eV) 12000
120000 O1s (532.1 eV)
C-C
10000

CPS
100000 C=O
CPS

80000 8000 COOR

C-Cl
60000 6000
C1s (284.93 eV)
40000 4000
20000 2000
0 0 Experimental line Fitting line Background
140000
SC650 wide-scan 20000 SC650 C1S
120000 18000 C-C
N1s (400.19 eV) 16000
100000
O1s (531.6 eV) 14000
C-Cl

CPS
80000
CPS

12000
C-OR
60000 10000 COOR
C1s (284.89 eV) 8000
40000 MCO3
6000
20000 4000
2000
0 Experimental line Fitting line Background
0
1200 1000 800 600 400 200 0 292 290 288 286 284 282
Binding Energy (eV) Binding Energy (eV)
(c) (d)
30000 SC650-1 C1S
C-C
25000
SC650-3
C-OR
20000
CPS

COOR
15000

10000
SC650-2
5000

0 Experimental line Fitting line Background

25000 SC650-2 C1S
C-C SC650-1
20000
CPS

15000 C-Cl
COOR
MCO3 C-OR
10000 SC650

5000

0
Experimental line Fitting line Background
30000
SC650-3 C1S SS
25000 C-C

20000
CPS

COOR
15000
MCO3
C-OR
MCO3 COOR C=O
10000

5000 C-Cl C-OR C-C

0 Experimental line Fitting line Background
292 290 288 286 284 282 0 20 40 60 80 100
Binding Energy (eV) Area ratio (%)

Fig. 3. (a) XPS wide-scan of SS and SC650; (b) C1s XPS spectra of SS and SC650; (c) C1s XPS spectra of SC650-1, SC650-2 and SC650-3; (d) Compositions and chemical states of C on
the surface of SS and SC samples.

decomposition of nitrogen-containing compounds in SS.
3.3. Carbon transformation during SS pyrolysis
3.3.1. Carbon speciation and transformation on SS and SC
Fig. 3a displays XPS wide-scan of SS and SC650. There were
visible peaks for O1s, N1s and C1s in the survey spectra of SS and
SC650. High resolution XPS spectra for C1s was performed within
280e294 eV, as shown in Fig. 3b and c. The standard values of
electron binding energy (BE) of elements in different chemical
environments were obtained from NIST X-ray Photoelectron
Spectroscopy Database [39]. Compositions and chemical states of
carbon on SS and SC surfaces are shown in Fig. 3d. For carbon on the
SS surface layer, 23.00% was attributed to CeC (e.g. hydrocarbons)
corresponding to BE ¼ 284.78 eV. Carbon was also combined with
other elements on SS surface, for instance, 55.76% CeO (e.g. ethers)
for BE ¼ 285.4 eV, 0.46% CeCl for BE ¼ 287.0 eV, 19.21% C]O (e.g.
ketones and aldehydes) for BE ¼ 287.8 eV and 1.56% COOR (esters)
for BE ¼ 288.9 eV. No MCO3 (carbonate) was observed for
BE ¼ 289.4 eV in SS. While the peaks of CeC and CeOR were
dominant in the spectra of all samples.
As shown in Fig. 3b and d, the relative contents of CeC, CeCl and
MCO3 in SC650 were higher than those in SS, showing that pyrol-
ysis increased these functional groups. Whereas the relative con-
tents of C-OR and C]O were reduced after pyrolysis, indicating
thermal instability of C-OR and C]O and the production of CO and
CO2 during pyrolysis. Metal oxides in SS might absorb CO2 pro-
duced by pyrolysis to form carbonates. As shown in Fig. 3c and d,
catalysts showed apparent effects on the carbon species on the SC
surface at 650
C. Comparing to SC650, catalysts significantly
declined the relative contents of CeC and CeCl carbon, while C-OR
and COOR increased by addition of catalysts. It was noteworthy that
6 Y. Liu et al. / Energy 200 (2020) 117398

(a) (b)
100 0% 100
5%
11% 11% 12%
17% 19%

26% 35%
80 80

36% 36%

Mass ratio (wt%)

Mass ratio (wt%)

60 47% 60
65% 51%
100%

40 40 50%
69%

53% 53%
20 20
36%
30%
23%
15%
0 0
SS 450 650 850 650 650-1 650-2 650-3
Pyrolysis condition C in gas C in condensate C in SC Pyrolysis condition

Fig. 4. Carbon distributions in SC, condensate and gas from SS pyrolysis with (a) No catalysts; (b) Catalysts (1 ¼ Kaolin, 2 ¼ Ca-bentonite, 3 ¼ CaO, Carbon in the condensate is
calculated by difference).

addition of CaO achieved the largest MCO3 carbon content of CeH and OeH bending. The absorption band at 1038 cm1 was
12.91%, which was related to the intensive adsorption of CO2 by CaO related to CeF, CeO and S]O stretching. Temperature had
[40]. considerable effects on FTIR spectra of SC, as presented in Fig. 5b. A
broad and intense band at 3421 cm1 might indicate OeH
stretching. The absorption band at 2925 cm1 was related to
3.3.2. Carbon balance during SS pyrolysis
aliphatic CeH stretching, which decreased at higher pyrolysis
Fig. 4 shows carbon distributions in SC, condensate and non-
temperature (e.g. >450
C), indicating thermal decomposition of
condensable gas from SS pyrolysis, revealing carbon balance of SS
aliphatic alcohol and alkane [41]. The peak at 1632 cm1 corre-
pyrolysis. As shown in Fig. 4a, carbon remained mainly in SC until
sponded to C]C stretching and NeH bending, which decreased
650
C and at higher temperature it was mainly in the condensates.
with increasing temperature. The band at 1454 cm1 was ascribed
The retained carbon in SC markedly decreased with increasing
to the CeH bending and the peak at 1037 cm1 might be due to CeF,
pyrolysis temperature. The carbon in SC decreased from 69 wt% to
CeO and S]O stretching. CeCl stretching and CeH bending vi-
36 wt% corresponding to pyrolysis temperature from 450
C to
brations could be found at near 778 cm1.
850
C. Meanwhile, the carbon distributions in condensates and
Fig. 5c displays the influences of catalysts on FTIR spectra of SC
non-condensable gases increased rapidly with increasing temper-
at 650
C. Addition of catalysts led to the appearance of more
ature. The decrease of carbon in SC might be due to the massive
functional groups, showing that catalysts facilitated decomposition
decomposition of C-OR and other organic substances of SS. The
of SS. At 650
C, vibration of OeH stretching around 3424 cm1
carbon released from SS was converted into organic matter in the
could be found in FTIR spectra of all SCs. In FTIR spectra of SC650-1
condensate and CO, CO2, CH4, etc. in the gas phase.
and SC650-2, a sharp peak at 1097 cm1 might be the result of CeF
Fig. 4b presents the effects of catalysts on the carbon distribu-
and CeO stretching. A broad band around 815 cm1 was related to
tions in pyrolysis products. The carbon in all SC decreased with
CeH bending. The wide band at 1630 cm1 in FTIR spectrum from
addition of catalysts at 650
C, the lowest carbon content of 15 wt%
SC650-2 suggested the presence of C]C stretching or NeH
in SC was obtained with addition of kaolin, which indicated that
bending. It was worth noting that CaO led to the appearance of
catalysts were beneficial to the release of carbon from SS. The
the most functional group species. For instance, a very sharp peak
addition of catalysts might enhance the decomposition and release
near 3642 cm1 revealed the presence of OeH stretching and the
of CeC and CeCl carbon. Among the three catalysts, CaO promoted
peak at 2514 cm1 corresponded to OeH stretching. The absorption
carbon retention in SC, which was mainly due to the increase of
band at 1796 cm1 represented CeH bending and C]O stretching
MCO3 carbon content in SC650-3. Moreover, the maximum carbon
and the band located at 1418 cm1 signified OeH bending. The
distribution in condensates (65 wt%) and maximum carbon distri-
intensity of the sharp peak at 874 cm1 of SC650-3 originated from
bution in non-condensable gases (35 wt%) were obtained with Ca-
the CeH bending. The effects of catalysts on FTIR spectra of SCs at
bentonite and kaolin additions, respectively. Correspondingly, Ca-
850
C are shown in Fig. 5d. Unlike SC650-1, the addition of kaolin
bentonite and kaolin were the most favorable additives for the
at 850
C led to OeH bending vibration around 1414 cm1 and
formation of condensates and non-condensable gases.
CeCl, CeBr, CeI stretching vibrations at 559 cm1. Compared with
SC650-2, the NeH bending vibration near 1630 cm1 disappeared
3.4. Main functional groups of SS and SC and a new vibration peak of CeCl stretching at 794 cm1 appeared
in SC850-2, which confirmed that Ca-bentonite accelerated the
FTIR spectra of the raw SS and SC produced from SS pyrolysis production of halo compound at higher temperatures. Moreover,
under different pyrolysis conditions are presented in Fig. 5. From the peak characteristics of CeF and CeO stretching at 1098 cm1
Fig. 5a, the intense band at wave number of 3700e3000 cm1 was was not observed for SC650-3. However, they were clearly visible at
classified as hydroxyl functionalities present in SS. The peak at higher temperatures.
2926 cm1 represented the OeH and CeH stretching. The observed
band between 1500 cm1 and 1800 cm1 referred to C]C
stretching and NeH bending. The peak at 1385 cm1 was caused by
 Y. Liu et al. / Energy 200 (2020) 117398 7

(a) (b)
104 SS O-H SC450 SC650 SC850
C-H C-F C-H
102 C-O C-F
O-H C=C S=O C-Cl
C-O
C-H N-H O-H C=C C-H
100 S=O
C-H
Transmittance (%)

O-H N-H

98

96
O-H

94

92

90

88

4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500
Wave number (cm-1) Wave number (cm-1)
(c) (d)
SC650-1 SC650-2 SC650-3 C-Cl
SC850-1 SC850-2 SC850-3 C=C
C-H C-H C-I
O-H C-H
O-H C=O C-Cl C-H C-Br
C=C C-H C=O
C-Cl
O-H C-H O-H O-H C=C
C=C C-F C-H O-H C-Cl
C-Cl O-H
N-H C-O C=C C=C
C-F
C-O

4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500
Wave number (cm-1) Wave number (cm-1)
Fig. 5. (a) FTIR spectrum of SS; (b) Effects of temperature on FTIR spectra of SCs; Effects of catalysts on FTIR spectra of SCs at (c) 650
C and (d) 850
C (inter gas flow rate ¼ 0.42 m3/
h, 1 ¼ Kaolin, 2 ¼ Ca-bentonite, 3 ¼ CaO).

3.5. SEM morphological structure analysis
The SC particles were dry and uniform without slagging and
fouling. SEM shows the surface morphology of SS and SC as dis-
played in Fig. 6. It was observed that there was no channels or
porous structures in raw SS. Few pores were seen on the surface of
SC450, and only nucleation and protrusions of irregular shapes
appeared. Volatiles were driven off and the crystal structure started
decomposition at relatively low temperature. Whereas some large
pores were developed on the surface of SC650, and more pores and
protrusions of different sizes and shapes appeared for SC850. More
volatiles were released and more organics were decomposed due to
higher temperature and faster heating rate at pyrolysis tempera-
ture of 650e850
C in comparison with 450
C [42]. Porous struc-
tures were generated with increasing temperature for non-catalytic
pyrolysis of SS, and interactions of pyrolysis char and pyrolysis gas
promoted pore development. Higher temperatures produced more
pyrolysis gas, which could have positive effects on SC properties.
There was an obvious disintegration and shrinkage of large
grains to small ones with CaO addition, showing loose structure
and porous characteristics. CaO promoted release of volatiles and
enhanced decomposition of organics [43], increasing surface pro-
trusions, and promoting surface morphologies and pore structures.
The cavities and void structures increased the surface area and
adsorption capacity [44], favoring further occurrence of gas-solid
reactions owing to the catalysis effects of SC.
3.6. Metallic and non-metallic contents in SS and SC
As shown in Table 2, the main non-metallic elements were Si, P
and S, which accounted for 19.31e44.10%, 2.84e8.54% and
0.74e5.21%, respectively. While the main metal elements were Al,
Fe, Ca, Mg and K, ranging from 1.06% to 31.40%. High contents of Si
and Al were observed in SS, which indicated acidic actives sites in
SS, promoting dehydrogenation and hydrocracking reactions dur-
ing SS pyrolysis [45]. It was worth noting that SS and SC had some
heavy metals, such as Zn, Cu, Cr and Ni. Increasing temperature
resulted in an increase in the contents of Si, Al, P and Mg. These
elements might exist in inorganic forms and less of them were
released into vapor phase in comparison with organics and other
elements [46]. Lower contents of Fe, Ca and Ti were observed when
temperature increased from 450
C to 850
C, owing to
8 Y. Liu et al. / Energy 200 (2020) 117398

Fig. 6. SEM images of SS and SC (3 ¼ CaO).

Table 2
Main metallic and non-metallic contents in SS and SC.

Item SS SC450 SC650 SC850 SC650-1 SC650-2 SC650-3 SC850-1 SC850-2 SC850-3

Si 23.53 23.46 27.70 27.74 44.10 33.72 19.85 34.17 32.97 19.31
Al 18.04 17.06 19.73 19.77 31.40 24.01 16.38 24.34 23.49 14.46
Fe 18.15 21.15 15.65 15.64 7.61 8.65 14.40 6.97 8.57 17.04
Ca 14.15 13.96 13.14 12.91 6.44 11.42 23.29 21.67 13.52 21.72
P 8.35 7.69 8.12 8.54 2.84 7.38 5.53 3.01 7.76 2.84
S 3.49 2.12 1.93 2.06 0.74 1.91 5.21 2.96 1.84 6.42
Mg 2.98 3.09 3.10 3.55 1.06 3.33 3.71 1.32 3.77 3.33
K 3.53 3.52 3.28 3.49 1.80 3.27 2.28 1.64 3.40 1.51
Ti 2.10 2.22 2.03 1.84 1.87 1.33 2.05 1.41 1.25 1.98
Zn 2.20 2.73 1.62 1.79 0.69 0.74 1.24 0.60 0.73 2.18
Na 0.90 0.00 1.04 0.00 0.40 0.89 0.76 0.41 0.96 0.00
Cl 0.80 0.79 0.83 0.73 0.29 0.63 1.56 0.88 0.78 1.61
Cu 0.55 0.72 0.45 0.51 0.18 0.18 0.30 0.15 0.16 0.65
Cr 0.38 0.41 0.34 0.32 0.17 0.19 0.33 0.14 0.19 0.50
Mn 0.23 0.29 0.21 0.21 0.10 0.14 0.20 0.10 0.14 0.27
Sr 0.24 0.34 0.20 0.23 0.10 0.09 0.22 0.08 0.11 0.58
Zr 0.21 0.27 0.17 0.18 0.14 0.08 0.13 0.10 0.08 0.18
Ni 0.08 0.12 0.07 0.07 0.03 0.03 0.05 0.03 0.03 0.20
Rb 0.05 0.08 0.03 0.05 0.02 0.03 0.00 0.02 0.03 0.00
Br 0.05 0.00 0.05 0.05 0.00 0.02 0.00 0.02 0.02 0.00
 Y. Liu et al. / Energy 200 (2020) 117398 9

Table 3
Heavy metals in SS and SC.

Concentration of heavy metals in SS and SC (mg/kg)

Sample Cr Ni Cu Zn As Pb

SS 416.02 40.62 290.97 1202.18 16.21 41.45

SC450 427.46 49.15 304.77 1183.20 14.68 42.58
SC650 563.66 85.31 367.51 1453.74 16.93 66.40
SC850 546.98 55.77 328.89 1623.01 20.22 51.96
SC650-1 500.19 38.36 409.81 1607.34 26.19 72.05
SC650-2 410.65 41.54 317.01 1304.58 24.20 80.46
SC650-3 272.51 25.61 205.63 865.15 22.13 28.05
SC850-1 285.78 41.79 172.11 1088.71 20.40 40.74
SC850-2 341.44 47.68 350.24 1445.60 21.38 70.98
SC850-3 404.49 46.10 472.68 1486.91 28.90 46.81
CJ/T 362e2011a 1000 200 1500 3000 75 1000

RE and RR of heavy metals in SS and SC

Heavy metal Parameter SC450 SC650 SC850 SC650-1 SC650-2 SC650-3 SC850-1 SC850-2 SC850-3

Cr RE 1.03 1.35 1.31 1.20 0.99 0.66 0.69 0.82 0.97

RR(%) 76.37 89.06 79.68 74.30 70.62 48.87 37.53 56.91 71.47
Ni RE 1.21 2.10 1.37 0.94 1.02 0.63 1.03 1.17 1.13
RR(%)b 89.93 100 83.20 58.36 73.15 47.04 56.21 81.38 83.42
Cu RE 1.05 1.26 1.13 1.41 1.09 0.71 0.59 1.20 1.62
RR(%) 77.86 83.02 68.50 87.04 77.94 52.72 32.32 83.46 100
Zn RE 0.98 1.21 1.35 1.34 1.09 0.72 0.91 1.20 1.24
RR(%) 73.16 79.48 81.81 82.63 77.63 53.69 49.48 83.38 90.92
As RE 0.91 1.04 1.25 1.62 1.49 1.37 1.26 1.32 1.78
RR(%) 67.31 68.66 75.59 99.85 100 100 68.77 91.44 100
Pb RE 1.03 1.60 1.25 1.74 1.94 0.68 0.98 1.71 1.13
RR(%)b 76.35 100 75.96 100 100 50.48 53.70 100 83.01
a
IDisposal of sludge from municipal wastewater treatment plant-Quality of sludge used in forestlandJ(CJ/T 362e2011).
b
RR is approximated to 100% in case of RR >100%.

decomposition and evaporation of organic and inorganic
compounds.
Kaolin and Ca-bentonite retained Si and Al in SC, and decreased
Fe, P, K, Ti, Zn, Cu, Cr, Mn, Ni and Br contents in SC. It was note-
worthy that the addition of CaO achieved particularly significant
retention of sulfur in SC. It might be related to some reactions be-
tween CaO and H2S (e.g. CaO þ H2 S4CaS þ H2 O, CaCO3 þ H2 S4
CaS þ H2 O þ CO2 , CaðOHÞ2 þ H2 S/CaS þ 2H2 O) [47]. Moreover, the
ions exchange might favor the retention and adsorption of sulfur in
SC during pyrolysis. It was observed that CaO seemed to be the best
candidate for immobilizing sulfur, similar to the finding of ultimate
analysis.
3.7. Analysis of heavy metals
3.7.1. Concentrations and immobilization of heavy metals in SS and
SC
From Table 3, the total contents of heavy metals in SS followed
the sequence Zn > Cr > Cu > Pb > Ni > As. The concentration of Zn
and As in SC increased significantly from 1183.20 mg/kg to
1623.01 mg/kg and from 14.68 mg/kg to 20.22 mg/kg with
increasing temperature, respectively. Simultaneously, the concen-
trations of Cr, Ni, Cu and Pb increased first, then decreased slightly
after 650
C. Nevertheless, they were still higher than those in SS.
Pyrolysis could well suppress the release of heavy metals and make
them concentrated in SC [48]. This will not cause secondary
pollution of heavy metals and is beneficial to the environment and
human health. The content of As in SS was relatively low in com-
parison with other heavy metals and it seemed that catalysts is
beneficial for retention of As. Moreover, the contents of heavy
metals in all SC met the requirements of national standards (CJ/T
362e2011, China).
In order to study the heavy metal behavior in SC and investigate
the migration characteristics, the relative enrichment (RE) factor
and residue ratio (RR) were adopted. The RE value described the
relative enrichment of heavy metals in SC, and the RR value
(0e100%) indicated the retention capacity of heavy metals. The
calculation formulas were as follows:
RE ¼ HMSC =HMSS (1)
RR ¼ HMSC =HMSS  YSC (2)
where HMSC is the content of heavy metals in SC, HMSS is the
content of heavy metals in SS, YSC is the yield of SC.
The RE and RR of heavy metals in SC are represented in Table 3.
REs of some heavy metals in SC obtained by non-catalytic pyrolysis
were greater than 1, revealing that heavy metals were enriched in
SC during SS pyrolysis without catalysts. In addition, the corre-
sponding RRs were 67.31e100% for SC450, SC650 and SC850,
indicating their good stability with no use of catalysts during FBP. It
was noteworthy that RRs of Zn and As in SC increased from 73.16%
to 81.81% and from 67.31% to 75.59% as temperature increased from
450
C to 850
C. REs of heavy metals in some SC using catalysts
were lower than those without catalysts, implied that catalysts had
a certain ability to release some heavy metals from SC. However, in
some cases, the catalysts exhibited significant retention effects on
heavy metals. For instance, the addition of CaO at 850
C increased
the RR value of Cu from 68.50% to 100%, which showed CaO had a
considerable ability to retain Cu at relatively high temperature. The
RRs of As in SC650-1, SC650-2, SC650-3, SC850-2 and SC850-3 were
higher than those in corresponding SC without catalysts, showing
that all catalysts at 650
C and Ca-bentonite and CaO at 850
C had a
good retention ability on As. The higher RRs of Pb in SC650-1,
SC650-2, SC850-2 and SC850-3 were observed in comparison
with the corresponding SC without catalysts, indicating that Ca-
bentonite could retain Pb. The retention effects of Ca-bentonite
and CaO on Zn were also observed at 850
C.
10 Y. Liu et al. / Energy 200 (2020) 117398

(a) 3 (b)7000 2
1500 6000
1 4 56 7 8 SC850
9

Intensity(counts)
Intensity(counts)
1200 5000
1,2-SiO2 3-KCuFeS2 4-Cu2O 5-LiCuFeS2
900 1,3-SiO2 2-CuCN 4-KCuFeS2 4000 2
6-ZnO 7-SiAs2 8-PbCl2 9-Cu5As2
1 5-Cu2O 6-LiCuFeS2 7-SiAs2 8-PbCl2 9-Cu5As2 1
3000 4 7 8 9 SC650
600
2000 2

300 2 7
4 5 6 8 1000
9 SS 1
3 45 6 7 8 9 SC450
0 0
10 20 30 40 50 60 70 80 90 17.8 26.7 35.6 44.5 53.4 62.3 71.2 80.1 89.0
2 2
(c)3500 (d)3710 7 1,10-Ca(OH)2 2-HCrO2 3,5-SiO2
9 1,14-Ca(OH)2 2-HCrO2 3,6-SiO2 4-Zn(CN)2
3000 5,9,17,24-CaCO3 7-As4O6 8-ZnS 8
4,7,13-CaCO3 6-ZnS 8-CaS 9-KPbO2
3180

Intensity(counts)
Intensity(counts)

10 11-Cr2O3 12-CaO
2500 12 14 16 1 12
1 20 21 23 15
5
6 8 11
15 1718 22 24 25 26 SC650-3 2650 5 9 16 20
19 SC850-3
19 6 13
2000 34 11 14 18 22 24 25 26
2120
6 10-KCuFeS 11,19-CaS 12-KPbO 13-CuSiO
2 2 3 14,24-NiO 15,26-Zn3P2 16-ZnS 17-Cu3N
1500 3 9
1590 3
2 18-Al2O3 19-NiAs 20-Ni3S4
4 7 10 25 SC650-2 2 57
8 9 10 17 SC850-2
1000 1060
15-Cr2O3 16-CaO 18-NiO 20-ZnS 21,26-Al2O3

500 22-NiAs 23-Ni3S4 25-CrClO 21-NiP2 22-CaF2 23-SiP2 25-K2ZnF4

6 530 78 9
25SC850-1
10 SC650-1 3 5 101314 15 17 21 23
3 25
13
0 0
17.8 26.7 35.6 44.5 53.4 62.3 71.2 80.1 89.0 17.8 26.7 35.6 44.5 53.4 62.3 71.2 80.1 89.0
2 2
Fig. 7. (a) XRD patterns of SS; (b) XRD patterns of SC at different temperatures; (c) XRD patterns of SC with different additives at 650
C; (d) XRD patterns of SC with different
additives at 850
C (1 ¼ Kaolin, 2 ¼ Ca-bentonite, 3 ¼ CaO).

3.7.2. Chemical compositions and immobilization mechanisms of heavy metals. CaO was effective for retaining heavy metals such as
heavy metals Cu and As. Cu2O and SiAs2 may react with CaO to generate more
Heavy metals might react with some compounds in SS, SC and stable compounds such as CuSiO3, Cu3N and NiAs, as shown in
additives to generate aluminates, aluminosilicates, silicates and Fig. 7c and d. Under higher temperature, the heavy metal chlorides
other substances, which was associated with the immobilization (i.e. PbCl2) adsorbed by Ca-bentonite could be converted into the
performance of heavy metals. In order to investigate immobiliza- acid gases such as HCl, which could react with inorganic
tion mechanisms of heavy metals in SC under different pyrolysis
conditions, the XRD analysis of heavy metals in SS and SC are
performed as epitomized in Fig. 7. Heavy metals were present in SS Table 4
and SC in various forms. For example, Cu might be present in the Potential ecological risk assessment of heavy metals in SS and SC.
forms of Cu2O and CuSiO3, Cr and Ni were mainly in the forms of
Sample Er RI Risk degree
oxides, Zn was in the form of oxides and sulfides, and Pb was
present in the form of chlorides. Heavy metal As could be combined Cr Ni Cu Zn As Pb

with other heavy metals, and other elements such as silicon and SS 0.83 1.02 0.97 0.40 2.16 0.21 5.59 Slight
oxygen. SC450 0.85 1.23 1.02 0.39 1.96 0.21 5.66 Slight
SC650 1.13 2.13 1.23 0.48 2.26 0.33 7.56 Slight
Table 3 shows that the heavy metals were enriched in SC during
SC850 1.09 1.39 1.10 0.54 2.70 0.26 7.08 Slight
SS pyrolysis without catalysts. Some salts and heavy-metal chlo- SC650-1 1.00 0.96 1.37 0.54 3.49 0.36 7.71 Slight
rides might be gradually broken down or transformed into heavy- SC650-2 0.82 1.04 1.06 0.43 3.23 0.40 6.98 Slight
metal oxides with increasing temperature, generating co-crystal SC650-3 0.55 0.64 0.69 0.29 2.95 0.14 5.25 Slight
aluminosilicates [49]. Fig. 6 shows spheres or protrusions with SC850-1 0.57 1.04 0.57 0.36 2.72 0.20 5.48 Slight
SC850-2 0.68 1.19 1.17 0.48 2.85 0.35 6.73 Slight
porous structures on SC, and may be able to enrich numerous SC850-3 0.81 1.15 1.58 0.50 3.85 0.23 8.12 Slight
inorganic elements (e.g. Si, Al, Ca, Fe) and some heavy metals (e.g.
The model parameters of potential ecological risk index
Cu, Zn). Moreover, the boiling points of heavy metals were mostly
higher than those of other components in SS, thus the volatilization Heavy metals Zn Cr Cu Pb Ni As
of these substances could wrap and protect heavy metals from Tr 1 2 5 5 5 10
leaching [50]. Relatively stable ZnO and SiAs2 in SC inhibited the Cn 3000 1000 1500 1000 200 75
volatilization of Zn and As, as shown in Fig. 7a and b. RRs of Zn and Eir Pollution degree RI Risk degree
As in SC increased significantly as temperature increased from
Eir < 40 Slight RI < 150 Slight
450
C to 850
C, indicating stability of Zn and As at relatively high
40  Eir < 80 Medium 150  RI < 300 Medium
temperature. The FBP process showed good retention of heavy
80  Eir < 160 Strong 300  RI < 600 Strong
metals in SS, immobilizing heavy metals in SC in the form of crystal
160  Eir < 320 Very strong RI  600 Very strong
structures.
Eir  320 Extremely strong
Catalysts had considerable effects on immobilization of some
 Y. Liu et al. / Energy 200 (2020) 117398 11

components, such as Al2O3, SiO2, Fe2O3 and TiO2, to form co-crystal
compounds, thereby increasing immobilization efficiency of Pb
[51]. While As was relatively easy to form stable complexes by
catalysts and achieved better immobilization.
3.7.3. Potential ecological risk assessment of heavy metals
Potential ecological risk factor (Er) and comprehensive potential
ecological risk index (RI) were adopted to assess the potential
ecological hazard of heavy metals in SS and SC, as shown in
following formulas [52,53]:
Er ¼ Tr ,Ci =Cn
X X . gas). With increasing temperature, the energy yield of SC
RI ¼ Er ¼ Tr ,Ci Cn
where Tr is the heavy metal toxic response factor, Ci is the con-
centration of individual heavy metal in SS and SC, Cn is the refer-
ence background value (CJ/T 362e2001), Tr, Ci, Cn and Er were for a
single heavy metal.
As presented in Table 4, the Er values of heavy metals in SC
obtained by non-catalytic pyrolysis showed a slight increase
compared to that in SS. While the addition of catalysts significantly
reduced the pollution degree of Cr, Ni, Zn in SC. The maximum Er
value was 3.85 for As in SC850-3, revealing a slight risk. All the Er
values were far less than 40, showing that heavy metals in SS and
SC had a slight pollution degree to environment. RI value for SS was
5.59, whereas the values of RI for SCs increased slightly with
increasing temperature. However, the RI values of SC significantly
decreased when the catalysts were added, indicating that catalysts
were beneficial to reduce the risk level of heavy metals. Remark-
ably, the RI values of SC obtained from FBP were all less than 9,
showing a very low degree of environmental risk. These results
indicated that pyrolysis in a fluidized bed was a suitable method for
safe and efficient disposal of SS.
3.8. Energy balance and energy yield
Table 5 shows the energy balance of FBP and energy yield be-
tween pyrolysis products based on their mass yields, atomic com-
positions and HHV. To the entire system, the input energy includes:
(1) electricity energy demand Qdemand, (2) SS chemical energy QSS.
The output energy includes: (1) chemical energy of condensate
Qcon, (2) chemical energy of non-condensable gas products Qgas, (3)
chemical energy of SC QSC, (4) heat loss and conversion loss in
Table 5
Energy balance for FBP and energy yield between pyrolysis products.
transform of electricity to thermal energy Qloss. The whole FBP of SS
includes drying, heating and pyrolysis. The heat demand was added
together as the total heat demand (Qtotal), that is, Qtotal ¼ Qdrying þ
Qheating þ Qpyrolysis . For the specific calculation method of Qdrying,
Qheating and Qpyrolysis, refer to related literature [54]. As the heat loss
existed, Qdemand was obtained on basis of Qtotal and heat efficiency
(70%). QSS, Qcon, Qgas and QSC were calculated on basis of HHV,
product yield and elemental composition [55].
As can be seen from Table 5, the minimum Qdemand for FBP of SS
was 2.27 MJ/kg. If the scale of experimental system was expanded
and some improvements were adopted, the energy efficiency can
(3) be improved further. Table 5 shows the distribution of energy be-
tween pyrolysis products (SC, condensate and non-condensable
(4)
decreased from 66.61% to 30.16%, while the energy yield of
condensate and non-condensable gas increased rapidly. In addition,
the addition of catalysts decreased the energy yield of SC, its energy
yields were lower than those of condensates. The maximum energy
yield (88.66%) of the condensate was obtained when kaolin was
added, while the addition of CaO resulted in the highest energy
yield (18.27%) of non-condensable gas.
4. Conclusions
The effects of temperature and catalysts on the FBP of SS were
systematically investigated. With addition of kaolin, the minimum
yield of SC (i.e. 54.64 wt%) was found at 850
C. Catalysts signifi-
cantly decreased the content of carbon, hydrogen and nitrogen in
SC. Carbon in the SS and SC surface layer was mainly present in the
forms of CeC, CeO, CeCl, C]O, COOR and MCO3. Increase in tem-
perature promoted the thermal decomposition of aliphatic alcohol,
alkane and proteinaceous compounds. Kaolin and Ca-bentonite
retained Si and Al in SC, and decreased Fe, P, K, Ti, Zn, Cu, Cr, Mn,
Ni and Br contents in SC. Heavy metals were enriched in SC during
SS pyrolysis, and all catalysts had a good retention effect on As at
650
C. CaO was suitable for retention of sulfur and heavy metals
such as Cu and As. It also, promoted decomposition of nitrogen-
containing compounds. PbCl2 adsorbed by Ca-bentonite could
form co-crystal compounds, thereby increasing immobilization of
Pb. Catalysts were beneficial to reduce the risk level of heavy metals
and RI values of SC obtained from FBP were less than 9, showing a
very low risk to the environment.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.

Parameter 450 650 850 650e1 650e2 650e3

CRediT authorship contribution statement
Energy balance for FBP of SS (MJ/kg dry SS)
Throughput (kg dry SS/h) 6 6 6 4.8 4.8 4.8
Qdrying (MJ/kg) 0.73 0.73 0.73 0.73 0.73 0.73
Yang Liu: Conceptualization, Methodology, Writing - original
Qheating (MJ/kg) 0.56 0.88 1.20 0.88 0.88 0.88 draft. Chunmei Ran: Methodology, Investigation. Azka R. Siddiqui:
Qpyrolysis (MJ/kg) 0.30 0.30 0.30 0.30 0.30 0.30 Methodology, Writing - review & editing. Asif Ali Siyal: Writing -
Qtotal (MJ/kg) 1.59 1.91 2.23 1.91 1.91 1.91 review & editing. Yongmeng Song: Methodology, Resources,
Heat efficiency (%) 70.00 70.00 70.00 70.00 70.00 70.00
Investigation. Jianjun Dai: Supervision, Writing - review & editing,
Qdemand (MJ/kg) 2.27 2.73 3.19 2.73 2.73 2.73
QSS (MJ/kg) 11.92 11.92 11.92 11.92 11.92 11.92 Funding acquisition. Polina Chtaeva: Resources, Investigation,
Qcon (MJ/kg) 5.48 7.58 9.62 10.57 10.57 7.88 Methodology. Jie Fu: Data curation. Wenya Ao: Investigation. Zeyu
Qgas (MJ/kg) 0.09 0.43 0.94 1.52 0.57 2.18 Deng: Investigation. Zhihui Jiang: Formal analysis. Tianhao
QSC (MJ/kg) 7.94 5.82 3.60 1.74 2.70 3.78 Zhang: Formal analysis.
Qloss (MJ/kg) 0.68 0.82 0.96 0.82 0.82 0.82
Energy yield between pyrolysis products of SS (%)
Condensate 45.97 63.61 80.69 88.66 88.64 66.07 Acknowledgements
Non-condensable gas 0.76 3.58 7.89 12.77 4.76 18.27
SC 66.61 48.85 30.16 14.61 22.64 31.70
Funding: This work was supported by the Ministry of Science
12 Y. Liu et al. / Energy 200 (2020) 117398
and Technology of the People’s Republic of China [grant number
2017YFE0124800].
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