Journal of Environmental Chemical Engineering 8 (2020) 104452

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

A new strategy for nitrogen containing compounds recovery from gaseous

products during sewage sludge pyrolysis under vacuum condition
Gaoxiang Qi a, b, c, Chao Li b, Yuanfei Mei a, c, Wei Xu a, c, Yu Shen a, b, c, *, Xu Gao a, *
a
National Research Base of Intelligent Manufacturing Service, Chongqing Technology and Business University, Chongqing 400067, China
b
College of Environment and Resources, Chongqing Technology and Business University, Chongqing 400067, China
c
Chongqing South-to-Thais Environmental Protection Technology Research Institute Co., Ltd., Chongqing 400069, China

A R T I C L E I N F O A B S T R A C T

Editor: Teik-Thye Lim Nitrogen migration from sewage sludge (SS) to gaseous products is one of the factors preventing the use of
pyrolysis technologies. A new route for nitrogen recovery by capturing NH3 using acidic gas released from SS
Keywords: pyrolysis was investigated in this study. SS was pyrolyzed from 30 to 800 ◦ C with heating rate of 10 ◦ C/min
Sewage sludge firstly, and thermogravimetry coupled to Fourier transform infrared (TG-FT-IR) analysis was conducted for
Nitrogen recovery
gaseous products characterization with different pyrolysis temperature. Then, nitrogen containing compounds
Ammonium bicarbonate
(NCCs) with the yield of 1.72 wt% was obtained from the gaseous products during SS pyrolysis at 400 ◦ C. The
Pyrolysis
Vacuum condition results of elements analysis and FT-IR characterization indicated that the NH3 in the gaseous products was
recovered in the form of NH4HCO3. The results provide valuable information and insight into pollutant com­
ponents recovery in gaseous products during SS pyrolysis, and future integration systems of SS pyrolysis and
nitrogen capture technologies may be developed for nitrogen recovery from gaseous products.

1. Introduction during pyrolysis process are closely related to second-pollution. The

Sewage sludge (SS) produced from wastewater treatment plants
(WWTPs) is a solid residue which contains predominantly biomass,
moisture, nutrients, metals, and other inorganic compounds [1]. Annual
generation of SS based on dry mass was estimated to approximate 10
million tons in European Union, 8 million tons in the United States, 4
million tons in China, and the SS production is expected to increase in
the future [2]. The large amount of SS produced annually creates severe
pollution problems, and thus needs to be treated properly. Traditional
treatment options of SS include landfill, composting, thermo-chemical
treatment, and agricultural application [3]. Among these, the
thermo-chemical treatment (pyrolysis and combustion) is an efficient
and widely studied method. Pyrolysis is a clean and efficient SS disposal
method because it can effectively reduce the SS volume, remove harmful
substances, and kill pathogenic bacteria [4]. Furthermore, gaseous and
liquid products can be used as potential chemical feedstocks and fuels,
and the solid products can be used as fuels or functional materials [5].
Biofuels production such as biogas, biooil and biochar from renewable
feedstocks such as SS can also provide a hopeful alternative for sus­
tainable fuels production [6].
However, migration behaviors of elements (epically nitrogen) in SS
nitrogen containing compounds in SS are decomposed to different
gaseous, liquid, and solid compounds. NH3 is the predominant nitrog­
enous gases under fast pyrolysis condition [7], while NH3 and HCN were
the main nitrogenous gases during microwave pyrolysis of sludge [8].
When the gases are used for providing energy by combustion, NOx will
form and be emitted which may cause serious air pollution. Therefore, it
is important to reduce the nitrogen containing compounds (NCCs) pro­
duction or develop an appropriate nitrogen recovery strategy for SS
pyrolysis. To reduce the emission of nitrogen-containing gas during SS
pyrolysis, most relevant studies focused on the following four aspects: (i)
Pretreatment technologies such as hydrothermal carbonization (HTC) or
torrefaction to fix the nitrogen in solid fraction by forming stable com­
pounds [5,9,10]. (ii) Catalytic pyrolysis by mixing SS with mineral
calcium, CaO, Ca and Na acetates, HZSM-5, etc. to fix the nitrogen in
solid fraction by intensifying N-related reactions [11–15]. (iii) Changing
the pyrolysis conditions such as atmosphere or temperature to change
the transformation routine of nitrogen during pyrolysis [16,17]. (iv)
Converting the nitrogen containing gas to N2 [18–20].
The composition of gaseous products includes acidic gas (e.g. CO2,
HCN, H2S, SO2, etc.) and basic gas (NH3) [21]. Therefore, in the present
study we demonstrate a route for nitrogen recovery by capturing the

* Corresponding authors at: No.19 Xuefu Ave., Nan’an District, Chongqing 400067, China.
E-mail addresses: shenyu@ctbu.edu.cn (Y. Shen), hughgao@outlook.com (X. Gao).

https://doi.org/10.1016/j.jece.2020.104452
Received 7 June 2020; Received in revised form 16 August 2020; Accepted 29 August 2020
Available online 6 September 2020
2213-3437/© 2020 Elsevier Ltd. All rights reserved.
G. Qi et al.
NH3 using acidic gas in the gaseous products during SS pyrolysis. The
gaseous products were characterized by FT-IR during SS pyrolysis from
30− 800 ◦ C. The element composition of raw SS, derived char and
recovered NCCs was measured. A comparative analysis of FT-IR spectra
of recovered NCCs and NH4HCO3 was conducted, and the possible re­
action routes were given. The results can provide valuable information
and insight into controlled conversion of NCCs during SS pyrolysis
process.
2. Materials and methods
2.1. Materials and reagents
SS was collected from Chongqing Sino French Water Company. The
mixture of primary and activated sludge was mixed and digested for
quantity reduction in an anaerobic digester, which were operated at
mesophilic temperature (34− 36 ◦ C). The water content of the digested
sludge was 76.96 wt%. The digested sludge was oven dried at 105 ◦ C for
24 h, and then milled in a grinder and SS with the particle size lower
than 0.18 mm was collected for pyrolysis. NH4HCO3 with 99.995 wt %
purity was purchased from Macklin (Shanghai, China).
2.2. Methods
2.2.1. SS pyrolysis
SS pyrolysis was carried out on a fixed bed reactor as shown in Fig. 1.
Volatile products pumped from the pyrolysis reactor pass through the
Y content in NCCs × mNCCs
Element recovery yield in NCCs =
Y content in raw SS × mRSS − Y content in biochar × mbiochar
nylon filter, vacuum pump, product collection bottle, and collected in a
gas bag. The pressure of the vacuum space was controlled at about -0.1
M Pa by the vacuum pump. The SS weight for pyrolysis in each exper­
iment was controlled at 100 g. The heating program of the oven was
from ambient temperature to 400 ◦ C at a rate of 10 ◦ C/min and then kept
at 400 ◦ C for 60 min. The cooling process is from 400 ◦ C to 105 ◦ C at the
rate of 1 ◦ C/min, and maintain at 105 ◦ C until taken out from the oven
chamber. Tar was eliminated by a nylon filter and recovered NCCs from
Fig. 1. Schematic diagrams of experimental system for sewage sludge pyrolysis. (1) Oven chamber, (2) Sample, (3) Heating controller, (4) Nylon filter, (5) Vacuum
pump, (6) Products collection bottle, (7) Gas collecting bag.
2
Journal of Environmental Chemical Engineering 8 (2020) 104452
the gases products were collected in the conical flask at room temper­
ature. Each experiment in this study was repeated two times.
2.2.2. Thermogravimetry coupled to Fourier transform infrared (TG-FT-IR)
analysis
To characterize the gas composition from SS pyrolysis under
different temperature, TG-FT-IR analysis was conducted by a TGA
(TGA/DSC 3+, Mettler Toledo, Switzerland) instrument coupled with a
FT-IR spectrophotometer (Vertex 70, Bruker, Germany). The mass of the
sample loaded was controlled at 19.6500 mg. Samples mass was recor­
ded every one second during pyrolysis from 30 to 800 ◦ C under the
heating rate of 10 ◦ C/min. The test was carried out under nitrogen at­
mosphere with a flow rate of 60 mL/min. The IR spectra of gaseous
products were recorded every 0.24 min at a resolution of 1.43 cm− 1 with
the wavelength range from 600 to 4000 cm− 1.
2.2.3. Elemental composition analysis
The contents of nitrogen (N), carbon (C), hydrogen (H), oxygen (O)
and sulfur (S) in raw SS, char and recovered NCCs were measured via
Vario El cube elemental analyzer (Elementar Co. Ltd, Germany). Phos­
phorus (P) in raw SS, char and recovered NCCs was analyzed by
inductively coupled plasma–optical emission spectroscopy system
(ICP–OES, Optima 8000 DV, Perkin Elmer, US). Retention rate of
element X (CHONSP) in biochar was calculated as Eq. 1, and the re­
covery rate of element Y (CHONS) in NCCs was calculated as Eq. 2.
Element retention rate in biochar =
X content in biochar × mbiochar
(1)
X content in raw SS × mRSS
(2)
where the mbiochar means the mass of biochar obtained from raw SS,
mRSS means the mass of raw SS, mNCCs means the mass of NCCs obtained
from raw SS.
G. Qi et al. Journal of Environmental Chemical Engineering 8 (2020) 104452

2.2.4. FT-IR analysis

FT-IR analysis of recovered NCCs and NH4HCO3 was performed to
identify the functional groups. To obtain the FT-IR spectra, samples were
ground and mixed with KBr and then pressed into pellets. IR spectra
were recorded in the range of 4000− 450 cm− 1 with the resolution of 32
scans and 4 cm− 1 on Shimadzu IR Prestige-21 Spectrometer.

3. Results and discussion

3.1. Analysis of gaseous products derived from SS pyrolysis

In this study, the sample was heated from 30 to 800 ◦ C at the rate of
10 ◦ C/min in nitrogen to evaluate the pyrolysis characteristics of SS. The
thermogravimetric (TG) and differential thermogravimetric (DTG)
curves during SS pyrolysis were presented in Fig. 2. Three stages of
weight loss were found in pyrolysis process. The first stage (6.02 %
weight loss) was mainly attributed to moisture evaporation and volatiles
release from ambient temperature to 185 ◦ C. The second stage is main Fig. 3. 3D FT-IR spectra of gases during sewage sludge pyrolysis at the heating
weight loss between 185 and 613 ◦ C with a sharp decrease on SS weight, rate of 10 ◦ C/min.
whereas the main organic contents degraded in this phase. 36.93 % of
the total weight was rapidly decomposed in this stage. The decomposi­
tion of SS in this the temperature range from 185− 613 ◦ C could be
divided into two stages referring to the DTG curve: (1) ~12 % weight
loss occurs at between 185 and 300 ◦ C, which is predominantly due to
decomposition of biodegradable matter, and (2) ~25 % weight loss
occurs in the temperature range from 300 to 613 ◦ C, which pertains to
the degradation of dead bacteria [3,22]. The two temperatures repre­
senting maximum decomposition are 282 and 328 ◦ C, respectively. The
last stage (613–800 ◦ C) in pyrolysis is also called stable phase, and the
mass loss rate became slow and kept stable [23]. The weight loss was
slight in this stage, and about 3.62 % of the total weight was cracked at a
lower rate. Finally, SS sample remained a solid residue (carbonaceous
residues within inorganic solid particles) equal to 53.44 % of its original
mass. The total weight loss of 46.56 % of sample weight was observed in
the pyrolysis process. Trends in mass loss rates were different from the
results previously reported by Lin et al. for SS [24]. This probably caused
by the differences in mineral and organics contents of samples used in
this study and reported literature.
The 3D FT-IR spectrum of the gases from SS pyrolysis including IR
absorbance, wavenumber and temperature were shown in Fig. 3. Several
FT-IR spectra of gases were selected at different temperature. The
characteristics of IR spectra obtained at 100 ◦ C, 200 ◦ C, 300 ◦ C, 400 ◦ C, Fig. 4. FT-IR spectra for pyrolysis gaseous products evolving from sewage
500 ◦ C, 600 ◦ C, 700 ◦ C and 800 ◦ C were shown in Fig. 4. The IR spectra sludge at different temperature with the heating rate of 10 ◦ C/min.

of the gases evolved during pyrolysis are illustrated in Fig. 5, which

including the absorption intensity of CO, CO2, CH4, hydrocarbon
(CH3CH2-), C=O, NH3, HCN, H2S and SO2 with different temperature.
As seen in Figs. 3 and 4, most of the gas was evolved between
300− 500 ◦ C, and the evolved gases of SS pyrolysis were identified by
their characteristic absorbance. In the initial pyrolysis stage (30− 185
◦
C), the peaks in the wavenumber range of 4000–3400 cm− 1, and
1900–1300 cm− 1 were attributed to the stretching and vibrations of
functional group of the groups in evolved water. With pyrolysis tem­
perature increased to 200 ◦ C, NH3 (930 and 965 cm− 1), CO2 (2358
cm− 1), benzene (670 cm− 1) were detected. As the pyrolysis temperature
reached 300 ◦ C, the absorption intensity of NH3, CO2, and benzene
increased. Moreover, the peaks at 3775, 3017, 2935, 2178, 1764, 1365
and 714 cm− 1 indicated the release of H2S, CH4, hydrocarbon (CH3CH2-
), CO, carbonyl, SO2 and HCN, respectively. When the pyrolysis tem­
perature further increases and exceeds 400 ◦ C, the absorption intensity
begins to decrease.
According to Lambert–Beer law, IR absorption intensity of a specific
gas species is linearly dependent on the gas concentration. Thus the
variation of the gas species concentration during pyrolysis can be re­
Fig. 2. TG and DTG curves for sewage sludge pyrolysis at the heating rate of 10
◦
C/min.
flected by the IR absorption intensity at a specific wavenumber. Fig. 5

3
G. Qi et al.
Fig. 5. Evolution of gaseous products with increasing temperature during sewage sludge pyrolysis.
shows the evolution of gas species with temperature increases from 30 to
800 ◦ C during SS pyrolysis. The gases evolution was mainly concen­
trated between 200 and 600 ◦ C, the release of gas species were in
agreement with the results of TG analysis. The gaseous products from SS
pyrolysis can be divided into three categories according to the elements
composition. The first category is the pyrolysis products of organic
compounds which includes CO, CO2, CH4, hydrocarbon (CH3CH2-) and
carbonyl compounds (such as acids and esters), etc,.; the second cate­
gory is the pyrolysis products were NH3 and HCN, which derived from
protein pyrolysis. The third kinds of pyrolysis products were mainly
sulfur-containing products such as H2S and SO2, which comes from the
organic sulfur-containing compounds. The evolution trends of the three
types of gases with temperature are similar.
3.2. Theoretical analysis of nitrogen recovery from gaseous products
during SS pyrolysis
The composition of gaseous products produced by SS pyrolysis has
been reported in many literatures. The main forms of carbon and
hydrogen in gaseous products are organic hydrocarbons (such as
methane) and inorganic substances (CO2, CO, H2, H2O, etc.) obtained
from the decomposition of organics in SS [25]. Carbon and hydrogen in
gaseous products in the form of CO, H2, methane, etc. can be used as
fuels, and the presence of non-combustible gases such as CO2 will reduce
the energy content value of pyrolysis gaseous products. Thus removing
the non-combustible gas can increase the calorific value of pyrolysis gas.
Nitrogen mainly exists in the form of NH3 and HCN in the gaseous
4
Journal of Environmental Chemical Engineering 8 (2020) 104452
products, which come from the amide nitrogen and nitrile nitrogen in
the SS protein, respectively, and the ratio of NH3 and HCN can be
affected by the pyrolysis conditions (temperature and atmosphere) [18].
Sulfur containing compounds (SCCs) come from both organic sulfur and
in-organics sulfate [26]. The main forms of sulfide in the pyrolysis
gaseous products include H2S, SO2, COS, CS2, and CH3SH [27].
Sulfur-containing gases were identified as the main odorants arised
during thermal treatment process of SS [27]. Therefore, removal of SCCs
such as H2S and SO2 from SS pyrolysis gas will reduce the odorants
emission. Phosphorus in SS mainly exists in the form of phosphate,
which remains stable in char during the pyrolysis process. Based on the
reported literatures, the gaseous products obtained from SS pyrolysis
can be divided into acidic gas (e.g. CO2, HCN, H2S, SO2, etc.) and basic
gas (NH3). Proposed reaction routes for NH3 capturing using acidic gas
during pyrolysis are listed as following equations (Eqs. 3–9), and stan­
dard enthalpy changes were referred to CRC Handbook of Chemistry and
Physics 84th Edition. Nitrogen in gaseous products is expected to be
recovered as ammonium salt theoretically.
NH3 (g) + CO2 (g)+H2O (l)→NH4HCO3, ΔrHø = − 99.22 kJ‧mol− 1
(3)
ø
2NH3 (g) + CO2 (g) + H2O (l)→(NH4)2CO3, ΔrH = − 170.98 kJ‧mol − 1
(4)
ø
NH3 (g) + HCN (g)→NH4CN, ΔrH = − 86.66 kJ‧mol − 1
(5)
ø
NH3 (g)+H2S (g)→NH4HS, ΔrH = − 83.66 kJ‧mol − 1
(6)
2NH3 (g)+H2S (g)→(NH4)2S, ΔrHø = − 119.32 kJ‧mol− 1
(7)
G. Qi et al. Journal of Environmental Chemical Engineering 8 (2020) 104452

NH3 (g)+SO2 (g) + H2O (l)→NH4HSO3, ΔrHø = − 130.12 kJ‧mol− 1

2NH3 (g)+SO2 (g) + H2O (l)→(NH4)2SO3, ΔrHø = − 225.88 kJ‧mol−
3.3. Composition analysis of raw SS and derived products
The experimental device as shown in Fig. 1 was designed to recover
NCCs in the SS pyrolysis gas. 400 ◦ C was chosen as the pyrolysis tem­
perature for NCCs recovery because the maximum release rate of ni­
trogen containing gases (NH3 and HCN) during SS pyrolysis was about
400 ◦ C according to results in Section 3.1. As expected, NCCs as white
crystals were obtained in the collection bottle. The raw SS, biochar,
biooil and recovered NCCs were shown in Fig. 6. To confirm the
chemical composition of recovered products, the contents of the main
inorganic non-metal elements (CHONSP) in raw SS and derived products
(8) were analyzed, and the results were listed in Table 1. The biochar yield is
64.26 wt%, which means that 35.74 wt% of mass was transferred into
1
(9) liquid and gaseous phase. By comparing the main elemental composition
of raw SS and biochar, it can be found that elements migration occurred
during pyrolysis treatment. Retention rate of C, H, O, N, S and P in
biochar was calculated as 43.35 wt%, 26.55 wt%, 9.06 wt%, 40.59 wt%,
47.12 wt% and 93.88 wt%, respectively. In other words, most of H, O,
and more than half of C, N and S transferred into liquid and gaseous
phase. Most of P was kept in biochar during pyrolysis, and the small
amount of lost P is caused by the entrainment of the pyrolysis gas during
the pyrolysis process. Gas streams will be formed during SS pyrolysis,
which making it possible for fine char particles containing P to be
entrained to the pyrolysis gas and oil.
Elemental analysis results of recovered NCCs from the pyrolysis gas
showed that the main elements were nitrogen, carbon, oxygen and
hydrogen. Combined with the proposed reaction routes in section 3.2,
the recovered white crystals with the yield of 1.72 wt% were mainly

Fig. 6. Raw sewage sludge and derived products obtained from pyrolysis process (a) Raw sewage sludge, (b) Biochar, (c) Biooil, (d) Recovered nitrogen containing
compounds from pyrolysis gas.

Table 1
Products yield and elements contents of sewage sludge and extractives.
Elements Elements content/ wt% Yield/ wt%

C H O N P S

Raw sewage sludge 28.37 4.55 23.55 5.05 2.16 1.50 /

Biochar 19.40 1.88 3.32 3.19 3.16 1.10 64.26 ± 1.32
Recovered NCCsa 15.13 4.07 60.03 17.25 N.D.b 0.11 1.72 ± 0.28
a
NCCs, nitrogen containing compounds.
b
N.D., not detected.

5
G. Qi et al. Journal of Environmental Chemical Engineering 8 (2020) 104452

Table 2
Possible reaction routes of nitrogen containing products.
Elements Inside pyrolysis Temperature/ Outside pyrolysis chamber
chamber ◦
C

H2O (bound)→
<180 H2O (gas)→H2O (liquid)
H2O (free, gas)
H
Organics→H2O
<200 H2O (gas)→H2O (liquid)
(gas)
Amides N in
>300 NH3+H2O→NH3‧H2O
protein→NH3
N
Inorganic N
<300 NH3+H2O→NH3‧H2O
(NH4+)→NH3
C Organics C→CO2 >150 CO2+NH3+H2O→NH4HCO3
H2S + NH3+H2O→NH4HS
Organic S→H2S/
S >250 SO2+NH3+H2O→NH4HSO3/
SO2
(NH4)2SO3

reactions). Due to the pyrolysis temperature was controlled at a relative

Fig. 7. FT-IR spectra of ammonium bicarbonate and recovered nitrogen con­
taining compounds from the non-condensable gas during sewage
sludge pyrolysis.
NH4HCO3, in addition to a small amount of SCCs. The low sulfur content
in recovered NCCs may be attributed to the low pyrolysis temperature
and moisture contents in SS, because the H2S concentration in gaseous
increased with pyrolysis temperature and moisture content of SS [28].
Nitrogen recovery yield in NCCs was calculated as 9.9 wt%, and sub­
sequent studies still need to optimize the nitrogen recovery yield and
evaluate the effect of experimental conditions. In order to further
confirm the speculation that NCCs is mainly NH4HCO3, FT-IR charac­
terization was conducted in section 3.4.
3.4. FT-IR analysis of NCCs
To confirm the recovered white crystals products, comparative
analysis of recovered NCCs and NH4HCO3 was conducted using FT-IR,
and the results were presented in Fig. 7. The FT-IR spectrum of recov­
ered NCCs is highly similar to that of NH4HCO3. The strong peaks at
about 3120 and 1401 cm− 1 are attributed to stretching and bending
vibration in NH+ 4 . The peaks at 2850, 2550, 1600, 1280, 830 and 700
cm− 1 are attributed to stretching and bending vibration in HCO3-. The
peak at 1675 cm− 1 is attributed to CN– stretching vibration in amides.
The peak at 1297 cm− 1 is attributed to CN– stretching vibration [29].
The peak at 2025 cm− 1 may be attributed to absorption peak of the
impurities substance in the chemicals. Based on the above analysis,
FT-IR spectra indicated the presence of NH4HCO3. This result is
consistent with the speculation of recovered NCCs structure based on the
results of elemental analysis.
3.5. Formation routes analysis of NCCs
After confirming that the NCCs were mainly NH4HCO3, the possible
formation route was analyzed according to the pathway of element
migration and conversion in the published literature. Possible reaction
routes of NCCs were listed in Table 2.
The water produced in the pyrolysis process is essential which pro­
vide the solvent of the nitrogen recovery reaction. The water mainly
came from the release of the bound water (<180 ◦ C) and the thermal
decomposition process of organic matter such as protein and fatty acid
(<200 ◦ C) [19,30]. Previous research reported that NH3 and HCN ac­
count for 80 wt% of the raw SS nitrogen in a microwave pyrolysis [20].
During the pyrolysis process, the formation of nitrogen containing
products can be attributed to reactions that include primary reactions
(such as SS decomposition) and secondary reactions (such as the re­
actions among the nitrogen-containing volatiles released from primary
low level in this study, the released NH3 mainly came from the primary
reactions including decomposition of inorganic ammonium salt and
deamination of protein [3,31]. As for sulfur, H2S, SO2 and CH3SH were
the predominant SCCs in gaseous products from SS pyrolysis at 150 −
450 ◦ C [32]. Different forms of organic sulfur require different tem­
peratures to convert into gas. mercaptan can be converted into H2S
below 300 ◦ C, while aliphatic sulfur decomposition at 300− 500 ◦ C.
Thermal decomposition of aromatic sulfur to H2S occurred at 500− 800
◦
C, and thiophene decomposition took place above 700 ◦ C. Therefore, in
this study, H2S mainly comes from the pyrolysis of mercaptan and fatty
sulfur in SS. In conventional pyrolysis, approximately 9.8 wt% of sulfur
in SS is converted to H2S at 400 ◦ C [27,33]. CO2 was mainly due to the
decarbonylation and decarboxylation reactions during SS pyrolysis [19,
34].
During the pyrolysis process, the water was released at a lower
temperature (<200 ◦ C), and liquid droplets form on the inner wall of the
collection bottle 6 (Fig. 1). NH3 dissolved in the water in the collection
bottle 6 after being pumped to form an ammonia solution. The organic
matter in SS is decomposed to generate CO2, then the CO2 and ammonia
solution in the collection bottle 6 to generate NH4HCO3. The H2S or SO2
generated by the thermal decomposition of the SS protein is pumped out
and reacts with the ammonia solution in the collection bottle 6 to
generate NH4HS, NH4HSO3 or (NH4)2SO3. It should be noted that CO2
generation last longer than the generation of NH3, so the recovered
NCCs in the collection bottle 6 was mainly NH4HCO3, rather than
(NH4)2CO3.
4. Conclusion
In this study, recovery of NCCs from SS pyrolysis gaseous products
was proved to be feasible. According to the experimental results, the
recovered NCCs were mainly NH4HCO3. In addition to nitrogen, sulfur
could also be recovered from the gaseous products during SS pyrolysis.
The results provide valuable information and insight into controlled
conversion of pollutant components in gaseous products during SS py­
rolysis. Integration systems of SS pyrolysis and nitrogen capture tech­
nologies maybe developed which would make it possible for nitrogen
recovery from gaseous products.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgements
This work was supported by National Key Research & Development
Program of China (2016YFE0205600), Chongqing Municipal Education
Commission Foundation (KJQN201900820), China Postdoctoral Sci­
ence Foundation (2019M653318), Innovation Group of New

6
G. Qi et al.
Technologies for Industrial Pollution Control of Chongqing Education
Commission (CXQT19023) and Open Funding of Chongqing Technology
and Business University (KFJJ2017072).
References
[1] A. Ronda, et al., Smouldering of different dry sewage sludges and residual
reactivity of their intermediates, Fuel 247 (2019) 148–159.
[2] H. Yesil, A. Tugtas, Removal of heavy metals from leaching effluents of sewage
sludge via supported liquid membranes, Sci. Total Environ. 693 (2019), 133608.
[3] K. Tian, et al., Investigation on the evolution of N-containing organic compounds
during pyrolysis of sewage sludge, Environ. Sci. Technol. 48 (18) (2014)
10888–10896.
[4] X.-Y. Duan, et al., Nutrient stability and sorption of sewage sludge biochar
prepared from co-pyrolysis of sewage sludge and stalks/mineral materials,
Environmental Pollutants and Bioavailability 32 (1) (2020) 12–18.
[5] T. Liu, et al., Nitrogen transformation among char, tar and gas during pyrolysis of
sewage sludge and corresponding hydrochar, J. Anal. Appl. Pyrolysis 126 (2017)
298–306.
[6] G. Qi, et al., Solvents production from cassava by co-culture of Clostridium
acetobutylicum and Saccharomyces cerevisiae, J. Environ. Chem. Eng. 6 (1) (2018)
128–133.
[7] J.-P. Cao, et al., Nitrogen transformations during fast pyrolysis of sewage sludge,
Fuel 104 (2013) 1–6.
[8] J. Zhang, et al., Key intermediates in nitrogen transformation during microwave
pyrolysis of sewage sludge: a protein model compound study, Bioresour. Technol.
132 (2013) 57–63.
[9] A. Zheng, et al., Reducing emission of NOx and SOx precursors while enhancing
char production from pyrolysis of sewage sludge by torrefaction pretreatment,
Energy 192 (2020), 116620.
[10] Y. Shen, et al., Nitrogen removal and energy recovery from sewage sludge by
combined hydrothermal pretreatment and CO2 gasification, ACS Sustain. Chem.
Eng. 6 (12) (2018) 16629–16636.
[11] H. Liu, et al., Catalytic role of conditioner CaO in nitrogen transformation during
sewage sludge pyrolysis, Fuel 134 (9) (2014) 514–520.
[12] S. Guo, et al., Effects of calcium oxide on nitrogen oxide precursor formation
during sludge protein pyrolysis, Energy 189 (2019), 116217.
[13] S. Cheng, et al., Effects of Ca and Na acetates on nitrogen transformation during
sewage sludge pyrolysis, Proc. Combust. Inst. 37 (3) (2019) 2715–2722.
[14] H. Nan, et al., Nitrogen transformation during pyrolysis of various N-containing
biowastes with participation of mineral calcium, ACS Sustain. Chem. Eng. 8 (32)
(2020) 12197–12207.
[15] K. Wang, et al., Ex-situ catalytic pyrolysis of wastewater sewage sludge–a micro-
pyrolysis study, Bioresour. Technol. 232 (2017) 229–234.
[16] F. Wei, et al., Nitrogen evolution during fast pyrolysis of sewage sludge under inert
and reductive atmospheres, Energy Fuels 31 (7) (2017) 7191–7196.
Journal of Environmental Chemical Engineering 8 (2020) 104452
[17] B. Gu, et al., Catalytic fast pyrolysis of sewage sludge over HZSM-5: a study of light
aromatics, coke and nitrogen migration under different atmospheres, Ind. Eng.
Chem. Res. (2020), https://doi.org/10.1021/acs.iecr.0c01170.
[18] J.P. Cao, et al., Catalytic reforming of volatiles and nitrogen compounds from
sewage sludge pyrolysis to clean hydrogen and synthetic gas over a nickel catalyst,
Fuel Process. Technol. 123 (2014) 34–40.
[19] B. Gu, et al., Nitrogen migration mechanism and formation of aromatics during
catalytic fast pyrolysis of sewage sludge over metal-loaded HZSM-5, Fuel 244
(2019) 151–158.
[20] H. Liu, et al., Emission control of NOx precursors during sewage sludge pyrolysis
using an integrated pretreatment of Fenton peroxidation and CaO conditioning,
Fuel 195 (2017) 208–216.
[21] A. Zaker, et al., Microwave-assisted pyrolysis of sewage sludge: a review, Fuel
Process. Technol. 187 (2019) 84–104.
[22] J. Shao, et al., Pyrolysis characteristics and kinetics of sewage sludge by
thermogravimetry Fourier transform infrared analysis, Energy Fuels 22 (1) (2008)
38–45.
[23] Y. Lin, et al., Co-pyrolysis kinetics of sewage sludge and oil shale thermal
decomposition using TGA–FTIR analysis, Energy Convers. Manage. 118 (2016)
345–352.
[24] K. Jayaraman, I. Gökalp, Pyrolysis, combustion and gasification characteristics of
miscanthus and sewage sludge, Energy Convers. Manage. 89 (2015) 83–91.
[25] M. Zhao, et al., Low-temperature alkaline pyrolysis of sewage sludge for enhanced
H2 production with in-situ carbon capture, Int. J. Hydrogen Energy 44 (16) (2019)
8020–8027.
[26] P. Gostelow, S. Parsons, R. Stuetz, Odour measurements for sewage treatment
works, Water Res. 35 (3) (2001) 579–597.
[27] S. Liu, et al., Release of organic sulfur as sulfur-containing gases during low
temperature pyrolysis of sewage sludge, Proc. Combust. Inst. 35 (3) (2015)
2767–2775.
[28] J. Zhang, et al., Release of hydrogen sulfide during microwave pyrolysis of sewage
sludge: effect of operating parameters and mechanism, J. Hazard. Mater. 331
(2017) 117–122.
[29] Y. Jin, et al., Preparation of sulfonated graphene–polyaniline nanofiber composites
by oil/water interfacial polymerization and their application for supercapacitors,
Synth. Met. 168 (2013) 58–64.
[30] E. Neyens, J. Baeyens, A review of thermal sludge pre-treatment processes to
improve dewaterability, J. Hazard. Mater. 98 (1/3) (2003) 51–67.
[31] O.S. Djandja, et al., Pyrolysis of municipal sewage sludge for biofuel production: a
review, Ind. Eng. Chem. Res. (2020), https://doi.org/10.1021/acs.iecr.0c01546.
[32] S. Cheng, et al., Effect of alkali addition on sulfur transformation during low
temperature pyrolysis of sewage sludge, Proc. Combust. Inst. 36 (2) (2017)
2253–2261.
[33] J. Zhang, et al., Sulfur transformation during microwave and conventional
pyrolysis of sewage sludge, Environ. Sci. Technol. 51 (1) (2017) 709–717.
[34] Z. Wang, et al., Study of the pyrolysis of municipal sludge in N2/CO2 atmosphere,
Appl. Therm. Eng. 128 (2018) 662–671.