Process Safety and Environmental Protection 178 (2023) 296–308

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Process Safety and Environmental Protection

journal homepage: www.journals.elsevier.com/process-safety-and-environmental-protection

Hydrothermal carbonization of food waste digestate solids: Effect of

temperature and time on products characteristic and
environmental evaluation
Mi Yan a, Feng Chen a, Tian Li b, Li Zhong c, Hongyu Feng a, Zhang Xu a, Dwi Hantoko d,
Haryo Wibowo a, *
a
Institute of Energy and Power Engineering, Zhejiang University of Technology, Hangzhou 310014, China
b
Department of Energy and Process Engineering, Norwegian University of Science and Technology, 7491 Trondheim, Norway
c
Beijing Huaneng Yangtze Environmental Technology Research Institute Co.,Ltd, Beijing 102209, China
d
Interdisciplinary Research Center for Refining & Advanced Chemicals, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia

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

Keywords: Food waste digestate solids (FWDS) is the by-product of anaerobic digestion and it contains high moisture.
Food waste digestate solids Hydrothermal carbonization (HTC) has the ability to convert wet bio-waste to hydrochar, which is a potential
Hydrothermal carbonization technology for handling FWDS. This study investigates the effect of reaction temperature and residence time on
Pyrolysis
solid and liquid products from HTC process of FWDS. The solid product was named as hydrochars, and their
Combustion
Nitrogen
physicochemical characters were tested and compared. The results showed that temperature had a more sig­
Phosphorus nificant effect on hydrochar properties, compared to residence time. The higher heating value of hydrochar was
15.46 MJ/kg and the yield was 49%, under reaction conditions of 260 ◦ C and 60 min. It was also found that
hydrochar generated at higher temperature had a more stable combustion, higher ignition temperature, higher
burnout temperature. For liquid product, the main organic matter are pyridine derivatives, pyrazine derivatives,
indole derivatives, cyclopentene derivatives and phenolic compounds. It was also discovered that the increase of
temperature can significantly reduce the concentrations of Chemical Oxygen Demand (COD) and Total Organic
Carbon (TOC) in liquid product. When reaction temperature increased from 220 ℃ to 260 ℃, the COD decreased
from 23,357 mg/L to 19,658 mg/L, TOC decreased from 9827 mg/L to 6352 mg/L, respectively. After HTC under
the conditions of 260 ◦ C and 60 min, 67% of nitrogen in solid feedstock e migrated from to liquid product, and N-
contained compounds decomposed into ammonia, while phosphorus was mainly remained in the solid phase
(>90%), which mainly existed in the form of apatite.

1. Introduction
Food waste (FW) is defined as organic municipal solid waste (MSW)
produced from the household kitchens, restaurants, and food industries.
Its generated amount is increasing drastically due to population growth
and modernization (Jin et al., 2021; Safieddin Ardebili et al., 2023). In
China, an estimated 120 million tons of FW was produced in 2019
(Wang et al., 2016). This issue calls for research into effective, efficient,
and safe disposal of FW. One of the methods being considered is
anaerobic digestion (AD), because of its good ability to treat feedstock
with high moisture and the additional benefit of producing biogas (Li
et al., 2019). However, this process produces a byproduct in the form of
food waste digestate solids (FWDS), which also contains high amounts of
moisture at around 84%. It is estimated that 0.2–0.47 tons of food waste
digestate solids are generated for each ton of food waste treated by
anaerobic digestion (Ren et al., 2018). Hence, the amount of FWDS also
increases quickly with the generation of FW. To avoid the issue of FWDS
becoming a secondary waste, various attempts have been made to treat
or dispose it. Composting has advantages such as low cost, environ­
mental sustainability, and high recycling efficiency (Liu et al., 2023).
Thus, composting is an effective method in its disposal, but the area of
agricultural land in which to use these digestate fertilizer is limited and
even decreasing. The possibility of using digestate in agriculture to
replace synthetic fertilizers is still debated. The use of highly stabilized

* Corresponding author.
E-mail address: haryowibowo83@gmail.com (H. Wibowo).

https://doi.org/10.1016/j.psep.2023.08.010
Received 29 March 2023; Received in revised form 27 July 2023; Accepted 4 August 2023
Available online 10 August 2023
0957-5820/© 2023 Institution of Chemical Engineers. Published by Elsevier Ltd. All rights reserved.
M. Yan et al.
digestate caused an increase in the portion of organic carbon in the soil,
contributing to the improvement of its quality (Zilio et al., 2022).
Excessive use of digestate fertilizer could cause the leaking of nutrients
which could pollute the surface and groundwater, resulting in eutro­
phication and hypoxia of soil (Li et al., 2020). Additionally, the utili­
zation of FWDS as fertilizer is also limited by the cost of transportation
(Kratzeisen et al., 2010). The other methods for the disposal of FWDS
(landfill and incarnation) also have drawbacks such as groundwater
contamination by leachate, bad odor emitted, or greenhouse gas emis­
sion (Zala et al., 2019). Therefore, it is essential to find more effective,
efficient, and environmentally friendly methods for the treatment of
FWDS.
Hydrothermal Carbonization (HTC) is considered a promising
method for the disposal of biomass with high moisture content (Djandja
et al., 2021). HTC is a wet thermochemical process conducted at tem­
peratures between 180 ◦ C to 300 ◦ C and autogenous pressures (3.5–5.5
MPa). The biomass feed would be converted into hydrochar through a
series reaction such as hydrolysis reaction, dehydration, and decarbox­
ylation during HTC (Mumme et al., 2011). This hydrochar has similar
characteristics with coal and could be used as clean energy carrier (Liu
et al., 2022). HTC can break down the particles and improve the dew­
aterability and hydrophobicity property of waste with high moisture
(Kambo and Dutta, 2014). As a result, hydrochar produced from HTC of
biomass is suitable for use as carbon electrodes (Dat et al., 2020),
adsorbent (Zhang et al., 2019), fuel (Aragón-Briceño et al., 2020;
Mazumder et al., 2020), soil amendment (Mariuzza et al., 2022), and
gasification feed (Akarsu et al., 2019). Studies have shown that hydro­
char from HTC have higher energy densification, shorter capillary suc­
tion time, and far higher dehydration capacity compared to untreated
food waste digestate solids (Pecchi and Baratieri, 2019). HTC could also
offer the advantages of minimizing the amount of solid residue pro­
duced, more effective utilization of resources, short operating time, and
high energy efficiency (Yan et al., 2022a; Yan et al., 2022b).
Several types of digestate have been investigated for treatment with
HTC; including food waste (Akarsu et al., 2019), plant fed (Miliotti et al.,
2020), sewage sludge (Aragón-Briceño et al., 2020), and maize silage
(Mumme et al., 2011). Most of these studies focused on making hydro­
char suitable for application as fuel (Kim et al., 2016). The heat value of
hydrochar from digestate was generally found to be between 15 and 30
MJ/kg, depending on the type of feed (Cao et al., 2021; Mumme et al.,
2011). Environmental evaluation of spent liquor from HTC is also a
significant factor for digestate disposal. HTC could decrease the Total
Organic Carbon (TOC), total N and NH+ 4 . On the other hand, it also
produces liquid phase with high phenol (Akarsu et al., 2019). Scholars
have studied the addition of phenolics to the hydrothermal carboniza­
tion of high ash sludge, and the results show that phenolic substances
increased the high calorific value of the carbonaceous solid product of
HTC (by 1.01–10.01%) and reduced the ash content (by 1.39–25.68%)
(Wang et al., 2020). It should also be noted that there was little research
on the effect of HTC on the Chemical Oxygen Demand (COD) of the
liquid product.
Previous studies have used HCl for FWDS pretreatment and incor­
porate wood chips to improve hydrochar properties (Zhu et al., 2022).
This treatment method however is costly, could incur equipment
corrosion, significantly complicate the process, and focuses on hydro­
char while ignoring liquid phase products. HTC has also been success­
fully studied for the conversion of maize silage digestate to hydrochar
and liquid phase, which was then used for fermentation to produce CH4
(Cao et al., 2020). It is worth noting that FWDS has a higher ash content
and could present a bigger challenge than maize silage digestate. While
there is little research on the comprehensive characteristics of FWDS
derived products and processes from HTC.
The nitrogen and phosphorus elements rich in biomass are also
research hotspots, such as the influence of HTC parameters on nitrogen
in sludge (Chen et al., 2023) and the use of organic acids to recover
phosphorus (Perez et al., 2022). the catalytic hydrothermal
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Process Safety and Environmental Protection 178 (2023) 296–308
carbonization to promote the removal of nitrogen from the product
Hydrochar (Zhang et al., 2023). Co-hydrothermal carbonization of
sludge and simulated food waste to explore the impact of mutual
interaction on nitrogen transformation (Wang et al., 2022). The effect of
MgCl2 on phosphorus migration. Cow manure is subjected to hydro­
thermal carbonization for phosphorus recovery (Stobernack and Malek,
2023). As a raw material rich in nitrogen and phosphorus, FWDS lacks
research on its hydrothermal carbonization. At the same time, the above
research only focuses on a single element in nitrogen or phosphorus as
the research goal, and uses additives to study its impact. There is a lack
of synchronous research on nitrogen and phosphorus, and it is unclear
whether catalysts have a positive or negative impact on phosphorus
while promoting nitrogen migration.
A large number of FWDS produced by anaerobic digestion in industry
cannot be treated, which has become a bottleneck restricting the
development of AD. This study is important when considering that the
liquid phase is organic wastewater with high pollutant contents, which
must be studied to understand its safe treatment and utilization. The
innovation of this study is the comprehensive and detailed analysis of
the three-phase products of low-grade FWDS from HTC, including their
properties as blended fuels, possible conversion paths of lignocellulose,
contamination analysis of the liquid phase, distribution of nitrogen and
phosphorus elements, and recovery potential. This study has great
practical significance for the comprehensive treatment and utilization of
FWDS.
Aiming to fill those research gaps, this paper focused on exploring
the effect of operating parameters (reaction temperature and residence
time) in HTC of FWDS and their effect on the physicochemical charac­
teristics of the product hydrochar. The evaluation included solid yield,
pyrolysis characteristic, and combustion characteristic. These values
could be used to evaluate the hydrochar’s potential for use as fuel or
activated carbon. TOC, COD, Total nitrogen (TN), NH+ 4 -N and organic
compounds in the liquid phase was also studied to provide a compre­
hensive analysis. In addition, the distribution of nitrogen and phos­
phorus in the products after hydrothermal carbonization is also analyzed
for further recovery, and it is expected that this work could provide a
deeper insight into the potential of HTC treatment for FWDS.
2. Materials and method
2.1. Materials
Food waste digestate solids were obtained from a food waste treat­
ment plant in Hangzhou, China. The average moisture content of the
FWDS was found to be 83.35%. The content of lignocellulose in FWDS is
about 25.5%. Fig. 1 shows the process for the generation and disposal of
FWDS in the waste treatment plant, to provide information about the
state.and pretreatment of the FWDS samples. The hydrochar samples
was denoted as “x + y”, in which x and y represent reaction temperature
(220 ◦ C, 240 ◦ C, 260 ◦ C) and residence time (30 min, 45 min, 60 min),
respectively.
2.2. Hydrothermal treatment
HTC experiments were conducted in a 500 mL Hastelloy batch
reactor equipped with a furnace, electric stirrer, as well as pressure and
temperature gauge. Firstly, 120 g undried FWDS (with the moisture
content of 83.35%) and 120 mL deionized water were mixed and placed
in the reactor which was sealed afterwards. In order to ensure the ma­
terials are not oxidized during the reaction and to accurately detect the
composition of the syngas after the reaction, pure N2 (99.99%) was used
to purge air from the reactor and provide N2 atmosphere for the ex­
periments. The reactor was then heated to the set temperature at a ramp
rate of 10 ◦ C/min and held at the target temperature for the pre­
determined period of time. Then, cooling water was flowed into the
reactor wall cooling system to cool the reactor to ambient conditions.
M. Yan et al.
Fig. 1. Food waste digestate solids treatment process.
The reactor was then opened and a vacuum extraction filter was used to
separate solid-liquid mixed products. The solid hydrochar was collected
and dried in a drying oven at 105 ◦ C until the total mass remained un­
changed, then ground and screened for further analysis. The obtained
liquid phase was collected and refrigerated for further analysis. Each
sample of experiments was conducted three times.
2.3. Analytical methods of HTC
The ultimate analysis of FWDS and hydrochar were carried out by an
Elemental analyzer (Dlementar vario el cube), with O content obtained
by difference. The proximate analysis, combustion characteristic, and
pyrolysis characteristic of FWDS and hydrochar were done with a
thermogravimetric analyzer (Discovery SDT 650). The higher heating
value (HHV) was determined by Automatic calorimeter (LC-CV-430).
The surface morphology of hydrochar was analyzed using scanning
electron microscope (SEM, ZEISS GeminiSEM 300, German). FT-IR of
the hydrochar was performed by a Nicolet iS20 FT-IR spectrometer
(Thermo Scientific, USA). The organic matters in liquid phase were
analyzed using GC–MS (Agilent 7890A GC-5975 C MS). The species of
nitrogen and phosphorus in the FWDS and the solid products from HTC
were detected by X-ray photoelectron spectrometer (XPS, Thermo Sci­
entific K-Alpha).
The hydrochar yield, the energy densification, and the energy yield
are regarded as main indicators for hydrochar and HTC process. They
are defined by the following Equations. The calculation formula for
higher heating value is Eq. (1), the mass of the raw material and solid
phase in Eqs. (2) and (3) are both on a dry basis.
HHV(MJ/kg) =0.349C + 1.1783H + 0.1005S − 0.1034O
(1)
− 0.0015N − 0.0221Ash
Hydrochar yield(%) =
Mass of hydrochar
× 100% (2)
Mass of feedstock
HHV of hydrochar
Energy densification(%) = × 100% (3)
HHV of feedstock
Energy yield(%) = Hydrochar yield × Energy densification (4)
2.4. Combustion and pyrolysis analysis of hydrochar
Select hydrochar would be used in combustion and pyrolysis ex­
periments to evaluate their performance as fuel. For TGA test, 10 mg of
dry FWDS/hydrochar sample was first weighed and put into an alumina
crucible, which was then placed in the TGA. The sample was then heated
under the atmosphere of air from 20 ◦ C to 950 ◦ C. The flow rate of air
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Process Safety and Environmental Protection 178 (2023) 296–308
and heating rate were set to 25 mL/min and 20 ◦ C/min, respectively.
The steps for the pyrolysis experiments were identical to the com­
bustion experiments described above, with N2 atmosphere instead of air.
The combustibility index S (%2/◦ C3⋅min2) was considered as the per­
formance for combustion characteristics of the hydrochar and was
calculated using Eq. (5):
( dw) ( dw)
S= dt max dt mean
× 100% (5)
T 2i Tb
where, (dw/dt)max and (dw/dt)mean refer to the maximum weight loss
rate and the average weight loss rate, respectively. Ti and Tb are the
ignition temperature and the burnout temperature, respectively.
2.5. Analysis of liquid product of HTC
The pH value of liquid samples was determined by a precision pH
meter. The COD concentration of liquid phases was determined by the
Dichromate method (HJ 828–2017). The TOC concentration was tested
by the TOC analyzer (Shimadzu TOC-L, Japan). Total nitrogen (TN) and
The TN and NH+ 4 -N concentrations were measured by the potassium
persulfate digestion UV spectrophotometry method (HJ 636–2012) and
Nessler’s reagent spectrophotometry (HJ 535–2009), respectively.
3. Results and discussions
3.1. Physicochemical characteristics of the hydrochar
Visual inspection of the experiment results appeared to suggest that
increase of temperature and residence time in HTC process caused the
color of hydrochar to gradually vary from brown to black, suggesting an
increase in carbonization degree. This might be caused by more residual
lignocellulosic in the feed decomposing to small compounds at higher
HTC temperatures. The internal cellular structure of FWDS appeared to
have been destroyed after HTC above 260 ◦ C, as shown by Fig. 2. In
some cases, due to the inability to directly compare with FWDS, solid
and liquid phase products produced under reaction conditions of 200 ◦ C
and 30 min were used as the reference material.
The results of ultimate analysis and proximate analysis of hydrochar
are listed in Table 1. The content of fixed carbon (FC) in hydrochar was
at 5% or less for all samples. This was because a lot of organic matter in
FW was already decomposed by microorganisms during AD to produce
methane. This was in good agreement with the finding of Reza et al.
(Reza et al., 2016) who found that there was very low FC content (as low
as 1.5%) in hydrochar. The observed increase of FC content with tem­
perature increase could be caused by the decrease of VM at high tem­
peratures (Poomsawat and Poomsawat, 2021). Additionally,
M. Yan et al. Process Safety and Environmental Protection 178 (2023) 296–308

extension of residence time. Increases in both factors decreased the

contents of hydrogen (4.68–4.19%) and nitrogen (3.53–1.57%). HTC
temperature seemed to have more significant effect on the content of the
three elements mentioned before compared to residence time.
It was also noted that the proportion of carbon increase was rela­
tively negligible (only 2.59%) compared with FWDS and hydrochar at
260 + 60. This could probably be explained by the hydrolysis of the
originally insoluble lignocellulose in the process of HTC. Previous
studies have shown that lignin hydrolyzes slowly at temperatures up to
200 ◦ C, causing the occurrence of low levels of dissolved carbon-
containing intermediates in the liquid (Zhuang et al., 2022). Most of
the products obtained from the hydrolysis reaction could continue to
undergo a series of reactions, which would finally generate hydrochar.
However, many carbon-containing intermediate products continued to
remain in the liquid phase.
Atomic ratios was used to study the degree of coalification of the
studied solid samples in this study, and the result is shown in Fig. 3 (Lin
et al., 2022). Lignite, Sub-bituminous, bituminous and Anthracite are
also shown in Fig. 3(a) as comparison to determine the degree of coal­
ification of hydrochar. The H/C and O/C atomic ratio in hydrochar was
found to decrease with the increase in temperature and residence time,
which could indicate that dehydration was the main mechanism in HTC
(Cheng et al., 2022). HTC appeared to promote significant changes in
H/C and O/C in the solid phase; with H/C atomic ratio decreasing from
1.719 to 1.426, while O/C atomic ratio decreased from 0.473 to 0.133
Fig. 2. FWDS and hydrochar after HTC with magnified views (the values in
after HTC. This places the O/C atomic ratios of most hydrochar between
figure are Temperature with ºC + Time with mins).
Lignite and Sub-bituminous coals, while their H/C atomic ratios were
significantly higher than Lignite. HTC significantly changed H/C and
dehydration and decarboxylation reactions have been reported to occur
N/C of FWDS, while temperature and time had slight effect on H/C and
during HTC and could be a contributing factor (Su et al., 2021). The
N/C of FWDS. The dehydration and decarboxylation reactions lead to a
intermediate products of HTC of lignocellulose (fructose and glucose)
decrease in the content of oxygen and hydrogen elements in hydrochar,
undergo dehydration reactions to form aldehydes and organic acids,
and the removal rate is greater than that of the demethanation reaction
such as acetic acid. Some organic acids will generate CO2 after decar­
of carbon elements.
boxylation reaction, while organic acids are dissolved in the liquid
It could also be observed that H/C and O/C atomic ratios in hydro­
phase, CO2 remains in the gas phase, and organic acids and CO2 will not
char dropped significantly with HTC temperature increase. Meanwhile,
participate in the nucleation and growth process of hydrothermal car­
H/C and O/C atomic ratios of hydrochar at 260 ◦ C only reduced slightly
bon. This results in the already low carbon content of FWDS being
with the increase residence time. This indicates that the coalification is
further reduced in the hydrothermal carbon as a product of the HTC
still slowly progressing within 30–60 min at 260 ◦ C. Changes to N/C and
reaction (Zhuang et al., 2022).
O/C atomic ratios in the hydrochar is depicted in Fig. 3(b). The N/C
The elemental compositions of hydrochar changed significantly with
atomic ratio tended to decrease as the reaction intensity increases. This
changes in HTC temperature and time. However, carbon and oxygen
could be explained by higher temperature and longer residence time
remained the main elements in all hydrochar evaluated. HTC conditions
promoting transfer of elements from solid phase to liquid phase, which
at 260 + 30 increased the carbon content in hydrochar from 32.67% to
caused the loss of N in hydrochar. A large amount of nitrogen is retained
34.65% and decreased the oxygen content from 20.60% to 8.37%
in the hydrochar produces a large amount of NOx during its combustion
compared to those in FWDS. Hydrogen and nitrogen were significantly
process (Xie et al., 2022). Low N/C atomic ratio means that the
affected by the increase of reaction temperature, and moderately by the

Table 1
Ultimate analysis, proximate analysis and fuel characteristics of FWDS and Hydrochar.
Itema FWDS 220 + 30 240 + 30 260 + 30 260 + 45 260 + 60
b
Ultimate analysis
C 32.67 33.52 34.20 34.65 35.05 35.26
H 4.68 4.43 4.46 4.34 4.27 4.19
N 3.53 1.87 1.60 1.61 1.67 1.57
S 0.34 0.27 0.29 0.23 0.52 0.29
Oc 20.60 10.75 8.60 8.37 7.48 6.26
atomic H/C 1.72 1.59 1.57 1.50 1.46 1.43
atomic O/C 0.47 0.24 0.19 0.18 0.16 0.13
atomic N/C 0.05 0.02 0.02 0.020 0.02 0.02
Proximate analysis
Moisture 1.94 1.30 1.14 1.12 1.27 1.10
Ash 38.18 49.16 50.85 50.80 51.01 52.43
VM 54.89 46.65 45.1 43.75 42.73 41.44
FC 4.99 2.89 3.50 4.33 4.99 5.03
HHV(MJ/kg) 13.97 14.74 15.20 15.24 15.42 15.46
a
The name of hydrochar “x-y” indicates the temperature is x ◦ C and residence time is y min.
b
on dry basis.
c
O= 100-(C+H+N + S+Ash).

299
M. Yan et al.
Fig. 3. Atomic H/C, N/C and O/C ratios of FWDS and hydrochar.
combustion process can minimize the generation of NOX and reduce
polluting gas emissions as much as possible.
Table 1 also shows the HHV of the hydrochar, results indicated that
proper engineering of HTC temperature and residence time could in­
crease HHV of hydrochar from 13.97 MJ/kg (FWDS) to 14.74–15.46
MJ/kg. It must be noted that compared with hydrochar from other
biomass such as avocado seed (18.6 MJ/kg (Sangaré et al., 2022)),
macadamia nut shells (19.09 MJ/kg (Samaksaman et al., 2021)) and
loblolly pine (24.5 MJ/kg (Reza et al., 2014)), the HHV of the HTC
products of FWDS is relatively low. This was probably caused by sig­
nificant amounts of organic matter having been decomposed during the
AD process, resulting in a very low content and relatively high ash
content in the FWDS. On the other hand, excessive ash content will cause
slagging and affect combustion negatively (Cao et al., 2021; Dutta et al.,
2021). Another study by Parmar et al. found very similar results, that the
hydrochar produced from vegetable, garden, and fruit waste digestate
contained low carbon content (between 27% and 32%), higher ash
content (53–59%), and a relatively low HHV of 15 MJ/kg (dry basis)
(Parmar and Ross, 2019).
3.2. Hydrochar yield and energy recovery
Fig. 4 shows trend of hydrochar production and energy yield from
HTC of FWDS under different temperatures and residence time. From
220 + 30–260 + 30, the yield of hydrochar decreased from 71.52% to
54.60%. This is in good agreement with the results that the yield of HTC
Fig. 4. Effects of HTC temperature and residence time on hydrochar yield,
energy yield and energy densification.
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Process Safety and Environmental Protection 178 (2023) 296–308
solid products decreased with the increase of temperature reported by
Martinez et al. (Mendoza Martinez et al., 2021). At fixed HTC temper­
ature of 260 ◦ C, prolonging residence time showed that the yield of
hydrochar decreased from 54.60% to 49.22%. These results suggested
that HTC temperature had significant effect on the yield of hydrochar,
while prolonging residence time above 30 min had slight effect.
In the process of HTC of FWDS, this happens through the hydrolysis
of cellulose, hemicellulose, lignin, and other organic matters in FWDS
which went undecomposed during AD. Hemicellulose and cellulose have
lower hydrolysis temperatures of 180–200 ◦ C and 220 ◦ C respectively.
While lignin begins to decompose at 250 ◦ C (Brindhadevi et al., 2021;
Zhang et al., 2021). This explains this study’s earlier finding which
showed that at HTC temperature above 260 ◦ C, the volatile matter
content in the hydrochar did not change significantly. This was because
cellulose, hemicellulose, and most of the lignin in the feedstock have
been decomposed into glucose and xylose. These compounds were then
dissolved in the liquid phase. These macromolecular compounds would
then be decomposed into liquid and gases (CO and CO2), the extent of
which increased with the increase in temperature. Under HTC at 220 ◦ C,
only some cellulose degraded. The degradation extent experienced by
the feedstock at this point was similar to that in pyrolysis. Higher tem­
perature was required for the raw material to be fully hydrolyzed and for
polycondensation reaction to occur to form hydrochar. There have been
many previous studies on the formation of hydrochar, mainly from
lignin, cellulose, and hemicellulose. Lignin depolymerizes into aromatic
oligomers, which are then hydrolyzed into benzene and phenolic com­
pounds, further nucleating to form aromatic hydrochar. Hemicellulose is
depolymerized to polysaccharides, and then undergoes hydrolysis,
dehydration, condensation to furanone derivatives and monocyclic ar­
omatics, and finally nucleated to form aromatic hydrochar (Zhuang
et al., 2022). Cellulose is hydrolyzed and decomposed into water-soluble
compounds (oligomers) with smaller molecular weights, which are
further decomposed into glucose (monomers), and glucose is partially
isomerized into fructose. The hydrolysis product then undergoes a series
of isomerization, dehydration, and cracking to produce the intermediate
5-HMF or furfural and its derivatives. The intermediate undergoes
polymerization, condensation reaction, intermolecular dehydration and
other reactions, and then undergoes aromatization to finally form
hydrochar (Wang et al., 2018b).
Fig. 4 also shows the energy densification of HHV of hydrochar
compared to the raw materials, which was calculated using Eq. (4). The
lowest energy densification was 1.055 at 220 + 30, and the highest
energy densification was 1.106 at 260 + 60. It shows that the energy
densification of hydrochar only increased very slightly, this was because
the HHV of hydrochar did not change much in HTC. Increasing HTC
M. Yan et al.
temperature and extending its residence time also was found to decrease
the energy yield slightly. This is probably caused by the high proportion
of non-combustible ash in hydrochar and the low proportion of FC.
3.3. Pyrolysis and combustion performance of hydrochar
After the characterization of hydrochar was discussed in previous
sections, the performance of hydrochar as fuel would be evaluated. This
is done by using hydrochar produced under different conditions as
feedstock for pyrolysis and combustion processes.
3.3.1. Pyrolysis performance
TG and DTG curves of FWDS and hydrochar obtained under various
reaction conditions are shown in Fig. 5. These were done under nitrogen
Fig. 5. TG and DTG curves of pyrolysis process of FWDS and hydrochars: (a) FWDS, (b) 220 + 30, (c) 240 + 30, (d) 260 + 30, (e) 260 + 45, (f) 260 + 60.
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Process Safety and Environmental Protection 178 (2023) 296–308
atmosphere, different from combustion characteristic analysis which
was done under air. The DTG curve of pyrolysis process of FWDS is
shown in Fig. 5(a), and it shows four distinct peaks in common with that
of hydrochar. These four peaks were similar to what have been reported
in a previous study (Reza et al., 2016). However, a very significant
difference between the DTG results of FWDS and hydrochar could be
observed in the 2nd and 3rd peaks. the highest peak of DTG curve of
FWDS showed up at around 325 ◦ C (2nd peak), while that of hydrochar
was found at around 450 ◦ C (3rd peak). This could be the indication of
FWDS experiencing major mass loss through the degradation of cellu­
lose, as shown by the second peak that corresponds to cellulose. While
for hydrochar, there was only little cellulose left after the anaerobic
digestion of FWDS and it only experienced little mass loss due to the
degradation of cellulose. Instead, hydrochar experienced its highest
M. Yan et al.
mass loss at 450 ◦ C with the degradation of lignin (Rodriguez Correa
et al., 2017).
As was mentioned above, cellulose does not degrade completely at
180 ◦ C. From 220 + 30–260 + 30 (Fig. 5(b)-(d)), the peak of cellulose
was seen to decrease gradually. When the temperature of HTC reached
260 ◦ C as seen in Fig. 5(d), the peak of cellulose has basically dimin­
ished. However, the peak of lignin at 450 ◦ C remained unchanged. This
indicated that lignin in hydrochar was not involved in the HTC reaction.
There is a small peak at 700–750 ◦ C which could have come from the ash
content in FWDS that contained calcium carbonate, which decomposed
at this temperature range (Funke et al., 2013). There is also a small peak
at 100 ◦ C, which might be caused by the escape of adsorbed gas in
Fig. 6. TG and DTG curves of combustion process of FWDS and hydrochars, (a) FWDS, (b) 220 + 30, (c) 240 + 30, (d) 260 + 30, (e) 260 + 45, (f) 260 + 60.
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Process Safety and Environmental Protection 178 (2023) 296–308
hydrochar, water evaporation, and VM loss.
3.3.2. Combustion performance
The TG and DTG curves of the combustion of FWDS and hydrochar
are presented in Fig. 6, with the combustion characteristic parameters
shown in Table 2. The Chinese National Standard GB/T 33304–2016 (Su
et al., 2021) was used to determine the ignition temperature (Ti),
maximum combustion rate temperature (Tm), and burnout temperature
(Tb). The (dw/dt)max, (dw/dt)mean and Tm refer to the maximum weight
loss rate, average weight loss rate and maximum combustion rate tem­
perature; respectively (Li et al., 2021). VM (range from 150◦ to 450◦ C)
and FC (range from 450◦ to 650◦ C) in Fig. 6 represent the combustion
M. Yan et al. Process Safety and Environmental Protection 178 (2023) 296–308

Table 2
Combustion parameters of FWDS and Hydrochar.
Sample Ti Tb Tm (dw/dt)max (dw/dt)mean S
(◦ C) (◦ C) (◦ C) (%/min) (%/min) (%2 /◦ C3⋅min2)
7
FWDS 235 497 300 3.1 2.3 2.84 * 10−
7
220 + 30 220 520 374 2.6 1.8 2.23 * 10−
7
240 + 30 239 580 325 1.5 1.1 1.20 * 10−
7
260 + 30 280 591 486 3.3 2.4 1.08 * 10−
7
260 + 45 270 601 489 1.5 1.0 0.97 * 10−
7
260 + 60 279 536 409 1.8 1.2 0.74 * 10−

areas of volatile matter and fixed carbon, respectively. The FWDS curve
has four obvious peaks. The two larger peaks were associated with VM
degradation and FC combustion, respectively. The curve of 220 + 30
also shows a four-peak structure ((dw/dt)max = − 2.6%), and its mass
variation rate is smaller than FWDS ((dw/dt)max= − 3.1%).
With the increase in HTC temperature and residence time, the four
peaks of FWDS changed into the three peaks of 260 + 60 curve. The
vanishing peak was the one at 325 ◦ C, indicating that the cellulose and
hemicellulose in hydrochar have undergone a complete transformation.
The products formed by transformation mainly consists of cyclo­
pentanoe derivatives, aldehyde compounds, organic acid, aromatic
structure char, etc (Zhuang et al., 2022). Ti of hydrochar fluctuated with
the change in HTC parameters, but were always higher than Ti of FWDS.
Higher ignition temperature of hydrochar meant that the storage and
transportation process of the fuel would be safer. The fluctuation phe­
nomenon might have been caused by high ash content, with the inten­
sified hydrothermal reaction at higher temperatures making the release
of VM easier. Results also suggested that the Tb of hydrochar generally
increased with the increase in HTC temperature and residence time.
However, 260 + 45 produced the maximum Tb in the study at 601 ◦ C.
Prolonging the residence time to 60 min (260 +60) produced a lower Tb
of at 536 ◦ C. The stability of compounds in the formation of hydrochar at
260 + 60 is related to lower Tb (Balmuk et al., 2023).
The average weight loss of hydrochar (dw/dt)mean decreased from
1.8% to 1.2% with increase in HTC temperature and residence time, indi
cating that high-temperature hydrochar would have longer combustion
periods. For comparison, the (dw/dt)mean of FWDS was 2.3%. The
combustibility index (S) of hydrochar was lower compared to FWDS, in
good agreement with a previous study by Su et al. (Su et al., 2021), and
with the increase of temperature from 220 ◦ C to 260 ◦ C, combustibility
index (S) showed a decreasing trend. Previous studies on HTC of maize
silage digestate has shown a trend of increasing temperature and
decreasing combustibility index (S) (Cao et al., 2020). This means that
high temperature and long residence time would reduce the compre­
hensive combustion performance of hydrochars. Considering its low
calorific value, it would be more sensible to use hydrochar as an auxil­
iary fuel.
3.4. FTIR Analysis of FWDS and hydrochars
The FTIR spectra of the raw FWDS and hydrochars generated at
different HTC temperatures and residence time are shown in Fig. 7. The
peak distribution and density of FWDS and hydrochar vary with reaction
conditions. The 3434 cm− 1 is related to O-H stretching (Soh et al.,
2023). The reduction of this band in hydrochar indicates that hydrochar
is more hydrophobic (Reza et al., 2014). The peaks of 2920 cm− 1 (C-H
tensile vibration) and 2850 cm− 1 (C-H deformation vibration) relate to
the retention of aliphatic structures after HTC (Volpe et al., 2018). The
absorption band at 1640 cm− 1 is attributed to the stretching vibration of
C–– C of lignin (Jamari and Howse, 2012). The absorption band at
1600–1100 cm− 1 is attributed to the aromatic ring skeleton and C-O
stretching (Kai et al., 2017). The broadband of around 1030 cm− 1 is
attributed to the stretching vibration of C-O-C in cellulose. When the
HTC temperature increases, the band decreases due to the degradation
of cellulose (Liang et al., 2019). The skeletal C-O stretching caused a
Fig. 7. FTIR analysis of raw biomass and hydrochars.
1
considerable fall in the relative strength of the signal peak at 600 cm−
(Nawaz and Kumar, 2023).
3.5. SEM analysis of FWDS and hydrochars
To study the surface morphology of FWDS and hydrochar generated
under different reaction conditions through SEM. As shown in Fig. 8, the
SEM image of FWDS shows a fragmented surface structure and the
surface Morphogenesis of hydrochar changed significantly. As shown in
Fig. 8(b-c), it can be observed that the surface of hydrochar is more
fragmented, with larger cracks and pores at 220 + 30 and 240 + 30,
which may be due to the release of volatile matters and gases during the
HTC process (Zhao et al., 2017). During the HTC process, volatile
components (such as CO2 and H2O) escape, leading to the formation of
many pore structures on the surface. As the HTC temperature increases,
these pore structures gradually collapse and evolve into slender cracks
(Zhao et al., 2020). In addition, on the surface of hydrochar, due to the
destruction of fiber structure, lignocellulose is hydrolyzed and carbon­
ized, ultimately aggregating to form a regular microsphere structure in
Fig. 8(e).
3.6. Environmental evaluation and key elements distribution
The liquid phase of HTC is rich in nitrogenous substances and organic
matter. Characterization of the form and content of these elements are
essential in preventing secondary pollution, as well as for efficient uti­
lization of the liquid product. The pollutant characteristics of the HTC
liquid phase are shown in Fig. 9. The pH values of the liquid phase
ranged from 7.85 to 8.4. While no trend was observed, there were small
fluctuations in pH that might be caused by the hydrolysis of some re­
sidual lipids and proteins of the feedstocks in the hydrothermal process
to generate organic acids (Ghanim et al., 2016; Hoekman et al., 2012). In
temperatures above 240 ◦ C, the decomposition of organic acids into
small molecular compounds could also contribute to the change in pH.
The intermediate product glucose, 5-HMF, or organic acids formed by
the decomposition of furfural will be further converted. Formic acid for
example, would convert further to form CO2 (Hoekman et al., 2011),
causing pH changes. However, Fig. 9 shows that this effect is miniscule.
The COD of HTC liquid phase was measured to reflect the degree of
water pollution by reducing substances, with the results shown in Fig. 9.
During HTC, the organic matters in solid phase of feedstocks would be
transferred to the liquid phase. This resulted in high COD in the liquid
phase, reaching 23,357 mg/L at 220 + 30. HTC temperature increases
from 220 ◦ C to 260 ◦ C resulted in COD change from 23,357 mg/L to
19,658 mg/L, the COD decrease ratio is 15.84%. While residence time
seemed to fluctuated the COD by about 9% compared with 260 + 30.

303
M. Yan et al.
Fig. 8. SEM images of FWDS and hydrochars: (a) FWDS, (b) 220 + 30, (c) 240 + 30, (d) 260 + 30, (e) 260 + 45, (f) 260 + 60.
Fig. 9. The contents of COD, TOC, TN, NH+
4 -N and pH in liquid fraction.
These results suggested that both temperature and residence time played
a crucial role in the COD reduction of HTC liquid phase.
The TOC of HTC liquid phase was also studied. Fig. 9 shows that TOC
in liquid phase decreased with HTC temperature increase, while resi­
dence time appeared to have very slight positive effect on TOC. TOC
decreased from 9827 mg/L to 6352 mg/L with temperature increased
from 220 ◦ C to 260 ◦ C, the TOC decrease ratio is 35.32%. At the reaction
temperature of 260 ◦ C, TOC and COD contents increased when the
residence time was 60 min, which may be related to the accelerated
depolymerization of lignin and its dissolution in the liquid phase to
produce many carbon-containing compounds. Some carbons (carbon-
containing compounds) are typically transferred from the solid feed­
stock to the liquid phase during HTC, resulting in higher content of
carbon in liquid phase.
Fig. 9 shows that the concentration of TN and NH+ 4 -N fluctuated with
the change of HTC temperature and time. The maximum concentrations
of TN and NH+ 4 -N were 4520 mg/L and 2224 mg/L, respectively. At HTC
residence time of 30 min, and the concentrations of TN and NH+ 4 -N
decreased first and then increased with the increase in temperature. The
lowest concentrations of TN and NH+ 4 -N were 2980 mg/L and 1557 mg/
L at 240 ◦ C, respectively. At HTC temperature of 260 ◦ C, the extension of
304
Process Safety and Environmental Protection 178 (2023) 296–308
time caused TN and NH+ 4 -N concentration to also decrease and then
increase. The difference is that the change of TN and NH+ 4 -N concen­
tration caused by temperature rise is greater than that caused by time
extension, which again suggested the more significant effect of HTC
temperature compared to residence time. It must be said that the con­
centration of NH+ 4 -N and TN in the liquid phase is very high, making it
potentially a good source of nitrogen fertilizer. It could be seen in Fig. 9
that when the temperature rose from 220 ◦ C to 240 ◦ C however, the
concentration of NH+ 4 -N decreased from 2126 mg/L to 1557 mg/L
(26.76% decrease). This phenomenon might be caused by the hydro­
lyzation of carbohydrates from cellulose decomposition to form
reducing sugar, which would then crack and react with NH+ 4 to form
pyrazines. Pyrrole, pyridine, and some nitrogen-containing compounds
participate in the formation of hydrochar, while on the other hand,
proteins in FWDS are still decomposing into nitrogen-containing organic
compounds and NH+ 4 -N. The above reaction processes are influenced by
temperature and time, resulting in fluctuations in the concentration of
TN and NH+ 4 -N. More in-depth research is needed on the conversion and
consumption of nitrogen during HTC.
According to the Integrated Wastewater Discharge Standard (GB
8978–1996) and the Discharge Standard of Pollutants for Municipal
Wastewater Treatment Plants (GB 18918–2002) of the People’s Re­
public of China, the COD in sewage must be less than 60 mg/L, the
ammonia nitrogen less than 15 mg/L, the TN is less than 20 mg/L, and
the TOC is not more than 20 mg/L. The pollutants in the liquid phase
obtained from the hydrothermal carbonization of FWDS far exceed the
standard, indicating that the hydrothermal waste liquid needs to be
treated by a sewage plant in order to meet the discharge standards.
3.7. The GC-MS analysis of liquid phase
The results of the hydrothermal liquid phase obtained by the hy­
drothermal carbonization of FWDS after GC-MS detection are shown in
Table S1. As various components of FWDS undergo a variety of reactions
during the HTC process, the HTC liquid phase is rich in various organic
compounds. There are pyridine derivatives, pyrazine derivatives, indole
derivatives, cyclopentene derivatives and phenolic compounds in the
liquid phase obtained under 220 + 30 reaction condition. FWDS con­
tains protein that could undergo depolymerization, hydrolysis to
M. Yan et al.
peptide substances (dipeptides, cyclic dipeptides), further dehydration
to amino acids, and amino acid reforming to produce pyrrole and pyr­
idine (Changi et al., 2015). Indole derivatives could also be derived from
amino acids, such as tryptophan. Pyrazines are also derived from amino
acids and can be obtained through the Maillard reaction. Cyclopentene
derivatives are mainly derived from polysaccharides and mono­
saccharides generated by the depolymerization and hydrolysis of
hemicellulose and cellulose (Zhuang et al., 2022). Further dehydration
and condensation of carbohydrate substances can produce cyclopentene
derivatives, furanone derivatives and monocyclic aromatics, and fur­
anone derivatives and monocyclic aromatics can further nucleate to
form hydrochar (Sevilla and Fuertes, 2009; Titirici et al., 2008). Lignin
can be depolymerized to produce aromatic oligomers, and further hy­
drolysis of intermediate products can produce phenolic compounds and
methoxybenzene compounds (Falco et al., 2011). In addition, with the
increase of reaction temperature and the extension of residence time,
some organic acids and alkanes were formed in the hydrothermal liquid
phase, such as palmitic acid produced by 260 + 30, n-pentadecanoic
acid and stearic acid produced by 260 + 60, and undecane, dodecane
and tridecane produced by 260 + 45.
3.8. Distribution of nitrogen and phosphorus in HTC products
3.8.1. N distribution in HTC products
In addition to the fuel potential of the solid hydrochar, the nitrogen
and phosphorus contained in the solid and liquid phases of the products
after the HTC of biogas residue have the value of recycling. In order to
achieve this goal, it is necessary to study the distribution and
morphology of nitrogen and phosphorus in the product.
Fig. 10 shows that the nitrogen element in the FWDS migrates to the
liquid phase during the hydrothermal process from. With the increase of
temperature (220–260 ◦ C), the proportion of nitrogen in the solid phase
shows a downward trend (38–25%), while the proportion of nitrogen in
the liquid phase shows an upward trend (53–65%). During HTC process,
- Fe, Al, Mn, etc., called unstable phosphorus, while AP refers to various
inorganic N would be transformed into NH+ 4 -N and NO3-N. While
organic N would be transformed into inorganic N, such as NH+ 4 -N (Xiao
et al., 2019). This phenomenon caused TN and NH+ 4 -N values to rise
rapidly in the liquid phase with the increase in temperature. Amino
acids were derived from the decomposition of proteins, which were
deaminated to produce ammonia gas that would later be dissolved in
liquid phase as NH+ 4 (Wang et al., 2021). The variation of residence time
had no obvious influence on the fraction of N in HTC products.
XPS analysis of N-containing compounds in solid is shown in Fig. 11.
Several N-containing compounds were observed, including inorganic-N
Fig. 10. N distribution in HTC products.
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Process Safety and Environmental Protection 178 (2023) 296–308
[(401.74 ± 0.22)eV], protein-N [(399.80 ± 0.18)eV], pyridine-N
[(399.42 ± 0.21)eV], nitrile-N [(398.83 ± 0.10)eV], NSiO2 [(402.5)
eV], Nitrate [ (>405) eV].
FWDS contains inorganic-N, protein-N and nitrile-N. After HTC, the
nitrile-N in the hydrothermal carbon obtained under the reaction con­
dition of 220 ◦ C + 30 min disappeared and NSiO2 was obtained. With
the further increase of temperature, hydrochar containing pyridine-N
can be obtained at 240 ◦ C, and some protein remains at this time. At
260 ◦ C, the protein will be completely decomposed, resulting in the
disappearance of protein in the solid phase and the generation of new
nitrates. Protein-based organic nitrogen has been reported to be very
sensitive to temperature during the hydrolysis process, this causes the
hydrolysis process to be very slow when the temperature is lower than
230 ◦ C and significantly accelerated at the temperature above 230 ◦ C
(Aragón-Briceño et al., 2021). It has been reported that nitrogen
continually transformed during HTC process. Multiple factors affect the
N transformation; such as temperature, residence time, pressure, metal
ions (Ca2+, Mg2+) in the raw materials, etc. Previous study has explained
that there are two main forms of nitrogen in biomass: inorganic nitrogen
- - -
(NH+ 4 , CN , NO3, NO2) and organic nitrogen (proteins and pyridine-N)
(Wang et al., 2018a). From the perspective of transformation path,
inorganic-N, protein-N and a small amount of nitrile-N in FWDS are
further decomposed with the rise of temperature, inorganic-N is hy­
-
drolyzed and converted into NH+ 4 and NO3, and protein is hydrolyzed to
produce intermediate products through peptide bond cleavage. These
intermediate products are further deaminated to produce NH+ 4 , and
nitrile-N is hydrolyzed and deaminated to produce NH+ 4 (Zheng et al.,
2022).
3.8.2. P distribution in HTC products
The forms of phosphorus mainly include total solid P (TSP), non-
apatite inorganic P (NAIP), apatite (AP), inorganic P (IP) and organic
P (OP)，Among them, TSP=IP+OP, IP=NAIP+AP, NAIP refers to
various forms of phosphorus combined with oxides and hydroxides of
forms of phosphorus combined with Ca2+.
After HTC, P in FWDS is transferred to the solid and liquid phases in
the product. Phosphorus in the product is mainly distributed in the solid
phase (>85%), and the phosphorus in the solid phase increases slightly
with the increase of temperature. For instance, With the increase of
temperature, the proportion of phosphorus distribution in the solid
phase increased from 88.5% to 91.3%. Fig. 12 shows the main forms of
P-compounds in FWDS and hydrochars.
P in FWDS mainly exists in the form of IP, Hydrochars produced
under different reaction conditions are also the same. The main part of
IP is AP, and with the rise of temperature, OP will convert to IP, from
53% (FWDS) to 74% (260 ◦ C), which is caused by OP hydrolysis in HTC
alkaline environment, and the main conversion product is AP.
Fig. 13 shows the XPS analysis results of some products. There are
two peaks for FWDS and all hydrochars, of which the peak of P2p3/2
orbital is about 133 eV, and the peak of P2p1/2 orbital is about 134 eV,
which indicates that the main product in the solid phase before and after
hydrothermal treatment is metal phase. Zhu et al. (Zhu et al., 2011)
revealed the main components of AP are Can/2H3− nPO4 (n = 1, 2, 3).
4. Conclusion
In this study, a comprehensive analysis was conducted on the
products of hydrothermal carbonization of food waste digestate solids
(FWDS), the main conclusions could be extracted as follows:
1) After HTC process at 260 + 60, carbon content in the solid product
increased by 8% and oxygen contents decreased by 69.6% compared
with FWDS, and the atomic ratio of H/C and O/C reached 1.46 and
0.158.
M. Yan et al.
Fig. 11. XPS analysis of N-containing compound in solid phase.
2) Hydrochar yield significantly decreased with the increase of reaction
temperature to 49.3% at 260 + 60, while prolongation of residence
time had a minor influence on the solid yield. The HHV of hydrochar
reach up to 15.46 MJ/kg at 260 + 60, considering the high ash
content and low HHV of hydrochar, it is suitable to be burned
together with coal as a blended fuel, so it is preferable to maintain a
high HHV.
3) Based on the pyrolysis and combustion testing, the hydrolysis of
cellulose and hemicellulose was almost completed during HTC at
260 + 30. The hydrochar produced from higher temperature HTC
had higher ignition temperature and stable combustion
306
Process Safety and Environmental Protection 178 (2023) 296–308
characteristics. However, the intensification of HTC can lead to a
decrease in the combustion index S.
4) The pollutants (COD, TOC, NH+ 4 -N and TN) in liquid phase decreased
significantly with HTC temperature increasing. The main organic
matter in the liquid phase is siloxane and its derivatives containing
nitrogen heterocycles and phenols, which is highly risk for envi­
ronment pollution. After HTC at 260 + 60, 67% of nitrogen in solid
feedstock e migrated from to liquid product, and N-contained com­
pounds decomposed into ammonia, while phosphorus was mainly
remained in the solid phase (>90%), which mainly existed in the
form of apatite.
M. Yan et al.
Fig. 12. Main forms of phosphorus in FWDS and solid products.
Fig. 13. XPS analysis of P-containing compound in solid phase.
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.
Acknowledgements
The authors appreciate the financial support from the National
Natural Science Foundation, China (52150410422 and 51976196). This
work was also supported by the Research Council of Norway and a
number of industrial partners through the project "Next generation
Biogas production through the Synergetic Integration of Gasification"
(Biosyngas, 319723).
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.psep.2023.08.010.
307
Process Safety and Environmental Protection 178 (2023) 296–308
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