Science of the Total Environment 838 (2022) 155867

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Science of the Total Environment

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

Preparation of solid organic fertilizer by co-hydrothermal carbonization of

peanut residue and corn cob: A study on nutrient conversion
Chao-sheng Li, Rong-rong Cai
⁎
Key Laboratory of Enhanced Heat Transfer and Energy Conservation of Education Ministry, School of Chemistry and Chemical Engineering, South China University of Technology,
Guangzhou 510640, PR China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Hydrothermal treatment of agricultural

and forestry wastes to prepare fertilizers
was studied.
• Effects of thermal dynamics and material
characteristics on fertilizer effect were
evaluated.
• Co-HTC favored nutrient enrichment and
N recovery in the hydrochars.
• Possible migration and transformation
paths of nutrient elements were discussed.

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

Editor: Huu Hao Ngo With continuous recognition of green, organic and pollution-free products, the organic fertilizer plays an increasingly
important role in agricultural production. Hydrothermal carbonization (HTC) is an efficient and environmentally
Keywords: friendly biomass treatment technology that can achieve value-added utilization of solid wastes. This study evaluated
Agricultural and forestry wastes the potential of two typical agricultural and forestry wastes (corn cob and peanut residue) in preparing as solid organic
Hydrothermal carbonization
fertilizers through HTC. The effects of reaction temperature, residence time, and the raw material composition on
Hydrochar
Organic fertilizer
hydrochar yield, total nutrient content (TNC), nitrogen recovery, and nutrient elements transformation in HTC were
investigated. Corn cob was proven to be not an ideal raw material for the preparation of organic fertilizers because
of the low TNC and the high C/N ratio of its hydrochar. On the contrary, peanut residue was suitable for preparing or-
ganic fertilizers due to its high TNC and appropriate C/N ratio. The co-HTC of corn cob and peanut residue could fur-
ther improve the N recovery rate from 8.52% (for peanut residue only) to 19.51% due to the synergistic effect between
them. Under the optimal hydrothermal conditions of 240 °C, 120 min, and mixing ratio of 1:1, the hydrochar yield was
as high as 27.86%, and the C/N value (11.98) and TNC (6.331%) were both appropriate as fertilizer. Furthermore, the
potential migration and transformation paths of nutrients including N, P, K and metal elements in the co-HTC were
analyzed. The thermodynamic conditions and raw materials composition significantly affect the migration and
transformation of N, P and K between solid and liquid. N dissolved into process water (mainly ammonia) would
migrate into hydrochar and bio-oil with increasing of reaction temperature. P was fixed in hydrochar through precip-
itation and adsorption reaction with metal ions. Further, adjusting pH or adding metal salts can promote the fixation of
N and P in solid.

⁎ Corresponding author.
E-mail address: cerrcai@scut.edu.cn (R. Cai).

http://dx.doi.org/10.1016/j.scitotenv.2022.155867
Received 8 March 2022; Received in revised form 17 April 2022; Accepted 7 May 2022
Available online 12 May 2022
0048-9697/© 2022 Elsevier B.V. All rights reserved.
C. Li, R. Cai
1. Introduction
The application of chemical fertilizers significantly increases the yield
of crops and thus has played an important role in ensuring world food secu-
rity in the past few decades. (Duan et al., 2016; Ni et al., 2011; Wang et al.,
2018a) The global annual crop production exceeds 3 billion tons, requiring
187 million tons of fertilizer. (Usman et al., 2020) And this requirement is
going to cross 200 million tons by 2022. However, the extensive application
of industrial fertilizers has caused a series of ecological and environmental
problems, such as soil compaction, soil microbial environmental degrada-
tion, greenhouse gas emissions, and underground water contamination,
etc. (Smith and Siciliano, 2015; Stuart et al., 2014). Some studies have
shown that crops can take up only 30–50% of chemical fertilizers, while a
huge amount of applied N, P and K as NH3, P2O5, and K2O are lost by
40%–70%, 80%–90%, and 50%–90% through leaching, photodegradation,
chemical hydrolysis and microbial decomposition, leaving a large number
of nutrients lost in the soil (Xin et al., 2020; Tarafder et al., 2020; Mózner
et al., 2012). Therefore, many countries call for the construction of modern
ecological agriculture, which uses materials and energy efficiently, and
does not pollute the soil during the production process.
Organic fertilizer is a kind of soil-friendly fertilizer, and it is being
widely promoted as an alternative to chemical fertilizer (Fang et al.,
2021). Livestock and poultry manure, municipal solid waste, crop straw,
agricultural and sideline products, and organic waste from food processing
all have the potential to be processed into biomass organic fertilizer. Com-
pared with chemical fertilizers, biomass organic fertilizer can significantly
increase soil porosity, promote soil nutrient balance, and improve the sus-
tainable productivity of soil. Common treatments for converting agricul-
tural waste into organic fertilizers include composting and anaerobic
fermentation. They are simple and can treat a large amount of agricultural
waste. However, these technologies have drawbacks such as long prepara-
tion cycle, a large area required, easy nutrient loss and secondary pollution,
etc… These are not in conformity with the current demand for efficient and
environmentally-friendly utilization of agricultural waste. Therefore, it is
necessary to find new methods to convert agricultural waste into organic
fertilizer.
Hydrothermal carbonization (HTC) is an efficient and environmentally-
friendly processing technology for producing hydrochar from low-value
biomass wastes (such as livestock and poultry manure, sewage sludge and
agriculture waste, etc.), and the products may have the potential to be
used as organic fertilizers. HTC has the advantages of mild reaction condi-
tions, low requirements for raw material pretreatment, and almost no
harmful by-products. There are some reports on the transformation behav-
ior of elements during HTC of biomass wastes. Fei et al. (2019) found that
the risk of potentially toxic elements (Cu, Pb, Ni, Cd) contamination from
the raw sludge was efficiently reduced in hydrochar, and the nutrients (N,
P, K) content in hydrochar was lower than that in raw sludge but still far
higher than that in agricultural soil. Mau et al. (2019) found that the
recirculation of the aqueous phase in HTC of poultry litter generally
resulted in an increase in N, P, and K concentrations. After three cycles,
the concentrations of N, P, and K reached a maximum of 5400, 397, and
23,300 mg L−1, respectively. Song et al. (2020) found that the addition of
sulfuric acid (H2SO4) in HTC of pig manure can make the removal rate of
Cu and Zn in pig manure reach 55.5% and 59.0%. Xiong et al. (2019)
found that the hydrochar yield and high heating value (HHV) reached
53.2% and 15.9 MJ/kg respectively under the optimum reaction condition
(260 °C, 30 min, solid-liquid ratio of raw materials of 0.1 g/mL) during HTC
of pig manure, and the obtained hydrochar and liquid can be used as
agricultural fertilizer. The above studies only consider the effects of HTC
conditions on the contents of N, P, and K and heavy metal elements; how-
ever, no attention has been paid to the comprehensive evaluation of the
fertilizer potential of the hydrochar. In addition, the existing forms and
transformation paths of nutrients such as N and P in HTC process are
seldom studied.
Peanut residue (residue left after peanut oil extraction) and corn waste
(corn cob and corn straw) are typical agricultural and forestry wastes. Corn
2
Science of the Total Environment 838 (2022) 155867
and peanut are important crop components with large annual productions
in the world. According to statistics from the Food and Agriculture Organi-
zation (FAO), the production of corn and peanut in China are 177.54 mil-
lion tons and 15.71 million tons respectively in 2010, and reach 260.88
million tons and 18.05 million tons in 2020, respectively. (Referred to
https://www.fao.org/faostat/en/#data/QCL) A large number of peanut
residue and corn cob wastes are generated in agricultural production
every year (Nassar et al., 2022; Perea-Moreno et al., 2018; Thomas et al.,
2021). Corn cob is rich in cellulose/hemicellulose as lignocellulose bio-
mass, having a high recycling value. However, the common treatment
methods include incineration, feed, and landfill treatment in rural areas, ig-
noring the recycling value of cellulose/hemicellulose. In recent years, there
have been some studies on HTC of corn stalk (Fuertes et al., 2010; Lu et al.,
2020; Wang et al., 2021; Zhang et al., 2019), but the focus was mainly on N
removal. Peanut residue is rich in nutrients (such as protein) and thus
shows great potential to be prepared as organic fertilizers, however, there
is no research on it currently.
In this study, we investigated the effects of reaction temperature, the
mass ratio of raw materials and residence time on the yields and character-
istics of hydrochar derived from HTC of corn cob and peanut residue, and
analyzed the potential of hydrochar in the application as organic fertilizers.
Then, we explored the synergistic effect of co-HTC of corn cob and peanut
residue, and obtained the optimal thermodynamic conditions for preparing
fertilizer by co-HTC. Furthermore, we proposed the possible migration and
transformation paths of N, P and other nutrient elements in the co-HTC
process.
2. Materials and methods
2.1. Material preparation
The corn cob and peanut residue were provided by a farm in Guangdong
Province, China. The corn cob and peanut residue were milled into 80
mesh. After collection, the screened corn cob and peanut residue were
dried in an oven at 105 °C for 24 h.
2.2. Hydrothermal carbonization
As shown in Fig. 1, the HTC experiments of corn cob and peanut residue
were carried out using a 250 mL stainless steel autoclave (Model SLM250,
Beijing Shi Ji Sen Lang Experiment Instrument Co., Ltd., Beijing, China).
The maximum reaction temperature and pressure of the autoclave were
300 °C and 22.5 MPa, respectively.
Before each experiment, 10 g of raw materials (corn cob or peanut res-
idue or the mixture of them) was mixed with 100 mL of deionized water
and mechanically stirred for five minutes to ensure uniform mixing.
Then, pure nitrogen was used to purge the reactor for 5 min to remove
the air inside. The initial pressure in the reactor was maintained at 0.3
MPa. A heating rate of approximately 2 °C/min was selected in the HTC,
since a low heating rate in hydrothermal treatment is beneficial to the for-
mation of hydrochar (Zhang et al., 2008; Zhang et al., 2009; Brand et al.,
2014). It is favorable for the decomposition of biomass raw materials and
the Maillard reaction when HTC is conducted at a high temperature
(≥180 °C). However, a too high temperature (> 260 °C) will promote the
hydrothermal liquefaction reaction, decreasing the hydrochar yield and
promoting the migration of nutrients to bio-oil. Therefore, the HTC experi-
ments were performed at 180–260 °C, a reaction time of 60–240 min and at
a stirring rate of 500 rpm. After reaction, the reactor was cooled down to
the room temperature, and the gaseous products were exhausted. Then
the ethyl acetate (CH3CHOOCH2CH3) was added to the reactor to extract
liquid-phase organic matter (bio-oil). The hydrochar and liquid phase
were separated by vacuum filtration through a filter paper of 0.45 μm diam-
eter. The hydrochar was washed with deionized water, dried in an oven at
105 °C for 24 h, and milled into 80 mesh for further analysis. The remaining
liquid phase (the process water) and the bio-oil were stored at 0–4 °C for
further test. The hydrochars were designated as CC X-Y、PR X-Y and CH
C. Li, R. Cai
Fig. 1. (a) Physical map and (b) schematic diagram of HTC experiment apparatus.
X-Y for the hydrochar derived from corn cob, peanut residue, and the mix-
ture, respectively with reaction temperature of X and residence time of Y.
2.3. Analysis methods
2.3.1. Analysis of raw materials and hydrochars
The composition analysis of the raw materials for cellulose and hemicel-
lulose were measured according to the National Renewable Energy Labora-
tory (NREL) analytical methods. The contents of lignin (acid-insoluble
lignin) and crude protein were measured by Klason method and Kjeldah
method, respectively. The content of crude fats was determined according
to Soxhlet extraction method (GB5009.6–2016). According to the ASTM
D5373 standard, the ultimate analysis of the raw materials and hydrochars
for carbon (C), hydrogen (H), sulfur(S), and nitrogen (N) were carried out
using an element analyzer (Vario EL cube). Content of oxygen (O) was cal-
culated by the eq. (1):
O ð%Þ ¼ 100%  ðC þ H þ N þ SÞ%  Ash% (1)
where, O%, C%, H%, N%, S%, and Ash% refer to the content in percentage
of O, C, H, N, S, and ash, respectively.
The total nutrient content (TNC = N + P2O5 + K2O) of the raw mate-
rials and hydrochars were measured by a nutrient detector (LD-TYD). The
proximate analysis of raw materials was measured by an industrial analyzer
according to GB/T212-2008 (Lu et al., 2020). The ash and organic matter
contents of the raw materials and hydrochars were determined according
to standard ASTM D2974-14(Silva et al., 2017). The relative contents of
the elements in the ash were measured by an energy spectrometer (EDS,
EPMA-1600). The surface morphologies of raw materials and hydrochars
were observed by a scanning electron microscopy (SEM, Merlin). The sur-
face functional groups of hydrochars were analyzed using Fourier Trans-
form Infrared spectroscopy (FTIR, Nicolet IS50-Nicolet Continuum) in
wavelengths of 500–4000 cm−1 by 32 scans at 4 cm−1 resolution.
2.3.2. Analysis of liquid products
The composition of bio-oil was qualitatively tested by Agilent 8890-
7000D GC–MS spectrometer and the gas chromatographic column was
HP-INNOWax (30 m × 250 μm × 0.25 μm). The carrier gas was high-
purity helium with a flow rate of 1 mL/min. The injector temperature
was maintained at 250 °C, and the injection volume was 1.0 μL. The oven
temperature was programmed from 50 °C (hold for 3 min) to 250 °C with
a speed of 5 °C/min followed by 3 min hold at 250 °C. The temperature
3
Science of the Total Environment 838 (2022) 155867
of transfer line was set at 280 °C/min. The MS ion source was operated in
the electron ionization (EI) mode with an ionization voltage of 70 eV and
a source temperature of 230 °C. The TNC of process water was measured
by a nutrient detector (LD-TYD). The pH of process water was determined
using a pH meter (pH-100A).
2.3.3. Formula and calculation
The hydrochar yield and N recovery were calculated as follows:
Mass of hydrochar
Experimental yield ð%Þ ¼  100% (2)
Mass of raw materials
N content of hydrochar  hydrochar yield
N recovery ð%Þ ¼  100% (3)
N content of raw materials
The calculated yield and synergistic coefficient were used to analyze the
synergy effect between the corn cob and peanut residue in co-HTC, defined
as follow:
Calculated yield ð%Þ ¼ α  Experimental yield ðCC X  YÞ þ ð1  αÞ
 Experimental yield ðPR X  YÞ (4)
Experimental yield  Calculated yield
Synergistic coefficient ¼  100% (5)
Calculated yield
where α refers to the mass fraction of corn cob in the mixture.
3. Results and discussion
3.1. Hydrochar yields
Fig. 2(a) shows the effect of reaction temperature on hydrochar yields
(at 60 min). When the reaction temperature was 180 °C, the experimental
hydrochar yields obtained from corn cob and peanut residue were
51.22% and 22.50%, respectively. They decreased by 6.42% and 18.71%
with increasing reaction temperature to 220 °C, respectively; and decreased
by 26.86% and 49.60% respectively when continuing to increase to 260 °C.
It indicated that the macromolecular substances such as cellulose/hemicel-
lulose and protein in the raw materials had degraded into liquid phase.
Under the same conditions, the hydrochar yields obtain from peanut resi-
due were 22.50–11.34% lower than that of corn cob (51.22–37.46%) as
the temperature was 180–260 °C. Because the protein in peanut residue
was decomposed to form amino acids at a low temperature and dissolved
C. Li, R. Cai Science of the Total Environment 838 (2022) 155867

60
CC-derived hydrochar
PR-derived hydrochar
12.51 Calculated yield (CC:PR=1:1)
50
Experimental yield (CC:PR=1:1)
Synergistic coefficient
in liquid phase, while the cellulose and hemicellulose in the corn cob were
15 degraded to form aromatic compounds and were accumulated in the solid
phase to form hydrochar. Fig. 2(b) shows the effect of residence time on
hydrochar yields (at 240 °C) in co-HTC. The hydrochar yields were reduced
10 with the increase of residence time, but the influence of residence time on

Synergistic coefficient (%)

hydrochar yields was less significant than the reaction temperature. There
Hydrochar yield (%)

was a difference between the experimental hydrochar yield and the calcu-
5
40 lated yield under the same reaction conditions, and the experimental
hydrochar yield was greater than calculated yield with increasing of resi-
0 dence time from 60 min to 120 min and 240 min. It indicated that a syner-
30 gistic effect between corn cob and peanut residue occurred during co-HTC.
It's also seen from Fig. 2(a) that the synergistic coefficient dropped from
-3.2
-5 12.51 to −10.66 as the reaction temperature increased from 180 °C to 260
20 -6.39 °C (60 min). As listed in Table 1, cellulose (35.66%), hemicellulose
-10.66 (21.63%) are the main components of corn cob, and the protein (48.76%)
-10
is the main component of peanut residue. The Maillard reaction between
10 saccharides (decomposed from cellulose/hemicellulose) and amino acids
180 200 220 240 260 (decomposed from protein) is one of the sources of hydrochar. The forma-
Temperture (℃) tion of hydrochars were influenced by degradation of raw materials and po-
lymerization of intermediate products derived from Maillard reaction.
During the co-HTC treatment at 180 °C, a small amount of cellulose/hemi-
(a)
cellulose in the corn cob degraded to form saccharides, and the proteins in
the peanut residue decomposed to produce a large amount of amino acids.
40 The composition of CH 180–60(1:1) contains many undecomposed raw
Experimental yield (CC:PR=1:1)
9.32 materials. With increasing of reaction temperature from 180 °C to 260 °C,
Caculated yield (CC:PR=1:1)
35 7.26 8 large amounts of saccharides were formed due to the further decomposing
Synergistic coefficient
of raw materials into liquid phase. The intermediate products derived from
Synergistic coefficient (%)
Hydrochar yield (%)

30 Maillard reaction could not fully polycondensation and polymerization in a

4
short period of residence time (60 min), and retained in the liquid phase.
25 Thus, the experimental yield of hydrochar is lower than the calculated
0 yield, resulting in the decrease of the synergistic coefficient. By extend-
ing residence time from 60 min to 120 min and 240 min in co-HTC
20
(Fig. 2(b)), the synergistic coefficient of hydrochar yield increased
-4 from −6.39 reached to 9.32 and 7.26. It indicated that more intermedi-
15
ates form hydrochar through polycondensation and polymerization in a
-6.39
longer period of residence time. Furthermore, the maximum value of
10 -8 synergistic coefficient was 9.32 at 120 min. It may be the secondly de-
60 120 240
composition of hydrochar at 240 min.
Residence time (min)
A similar phenomenon occurred in the effect of corn cob addition on the
(b) synergistic coefficient. As seen in Fig. 2(c), at the conditions of 240 °C and
60 min, with the increase of corn cob content (from 1:3 to 3:1), the syner-
gistic coefficient dropped from 1.8 to −7.35. Because more saccharides
50 were produced with the increase of the corn cob content. These saccharides
Experimental yield Synergistic coefficient 4
Calculated yield
1.8 Table 1
Synergistic coefficient (%)

40 The basic analysis of raw materials.

Hydrochar yield (%)

0 Raw materials Cellulose Hemicelluloses Lignin Crude Crude

fats proteins

Composition analysis (wt%) (ad)

30 Corn cob 35.66 21.63 3.43 0.77 2.56
Peanut 16.88 3.67 19.82 1.68 48.76
-4 residue

-6.39 Ultimate analysis (wt%) (ad)

20 Raw materials C H Oa N S
-7.35
Corn cob 44.61 6.34 44.59 0.41 -c
-8 Peanut 42.68 5.04 36.07 8.93 0.44
residue
10 Proximate analysis (wt%) (ad)
CC PR 1:3 1:1 3:1 Raw materials Volatile Fixed carbonb Ashd
The mass ratio of CC and PR matterd
Corn cob 79.69 16.26 4.05
(c) Peanut 80.65 12.56 6.84
residue

Fig. 2. Hydrochar yields from (a) the HTC at varying reaction temperatures with a
Calculated by difference: O (%) = 100% − (C + H + N + S)% − Ash%.
residence time of 60 min; (b) the co-HTC at varying reaction temperatures with b
Calculated by difference: Fixed carbon% = 100% − volatile matter% − ash%.
residence time of 60 min; (C) the HTC of mixtures with varying mass ratios at c
“-” indicated no detect.
d
240 °C and 60 min. dry basis.

4
C. Li, R. Cai Science of the Total Environment 838 (2022) 155867

required more residence time (>60 min) to fully react with amino acids to 120 116.35
113.32
form hydrochar. 108.80 106.87 102.41
97.46 101.56
100
3.2. Basic properties of raw materials and hydrochar
80

C/N value
3.2.1. Ultimate analysis
The ultimate analysis of hydrochars were shown in Table 2. At reaction 60
temperatures of 180–240 °C, the S content was reduced by the HTC treat-
ment of peanut residue, and the maximum reduction was 61.36% (PR 40
220–120). The S in organic fertilizers plays an important role in plant
16.93 11.98 11.75 19.15
growth regulation. But if the S content is too high, it will inhibit the absorp- 20 9.61 15.03
12.64
7.74 9.51 12.02 10.49
tion of P by plants and affect the absorption of Fe and Mo. When the 4.78

reaction temperature and residence time were 240 °C and 60 min respec- 0

22 0
CC

C C 0- 60
C C 0- 60

24 60

)
PR

240 0
PR - 240

CH 0-60 1)
CH 40-60 1)
PR 0-60

CH R 24 0
180 0-60

CH -120 1)
CH -240 1)
CH 0-60 1)

-60 )
1)
240 (1:1
240 0(1:3
tively, the S contents of hydrochars were much lower than calculated

-6

C C 0- 12

-6

22 0(1:
(1:
(1:

(3:
(1:
1:
-
180

260

220

(
18
24
contents (0.08–0.23%) with increasing of mass fraction of corn cob during

-6

-6
CC
CC
co-HTC, and the synergistic coefficient of S content was −80.65 for CH

CC

240
240
26
2
CH

CH
240–60(1:1). It can be inferred that the corn cob has an excellent effect
on the reduction of S content in co-HTC.
As shown in the Table 1 and Table 2, with the increase of reaction tem- Fig. 3. The C/N values of raw materials and hydrochars obtained at different HTC
perature (180–260 °C) and residence time (60–240 min), the N contents of conditions.
hydrochar derived from corn cob increased by 6.82–80.49% compared
with the corn cob, and the C contents increased by 11.77–61.67%. This in-
dicated that the corn cob had an excellent fixation ability for C and N ele- the high-temperature environment formed by the decomposition of peanut
ments in HTC. Similarly, The H and O contents of hydrochar derived residue would harm the plants. The C/N ratio of hydrochar (PR 220-60)
from corn cob decreased by 4.26–18.14% and 7.76–53.04% respectively was increased to 9.51, which had a better maturity and was more suitable
because of the dehydration and decarboxylation reaction in HTC process. for fertilizer. In the process of co-HTC, the C/N ratio gradually decreased
The dominant roles of dehydration and decarboxylation reactions in the with increasing of reaction temperature. It may be caused by the fixation
HTC process can be analyzed by O/C ratio and H/C ratio. According to of the N in the hydrochar. The residence time had little effect on the C/N
Table 1, the O/C and H/C of corn cob were 0.75 and 1.71, respectively. ratio. In addition, the C/N ratio gradually increased to 19.15 with increas-
Compared with corn cob, the O/C and H/C of hydrochar derived from ing in mass fraction of corn cob in mixed raw materials from 1:3 to 3:1.
corn cob decreased by 17.33–70.67% and 14.62–49.71% respectively, indi- Therefore, the hydrochar obtain a more excellent C/N ratio and maturity
cating that decarboxylation occurs in the HTC process. during the co-HTC of corn cob and peanut residue.
The C/N ratio is an important index of organic fertilizers, indicating the
availability of N in organic fertilizers (Song et al., 2019). A C/N ratio of 12 is 3.2.2. Surface microstructure
generally accepted as indicative of a good degree of maturity (Meng et al., As shown in Fig. 4(a), the SEM image of corn cob shown a smooth,
2019). As shown in Fig. 3 and Tables 1 and 2. The corn cob and its complete, and layered surface structure. As seen in Fig. 4(c), many micro-
hydrochars had relatively low N contents and high C/N ratios, thus they spheres and porous structures were formed in the surface of CC 240-60,
were not suitable for preparing organic fertilizers. On contrary, the N con- which was entirely different from the corn cob. These microspheres were
tent in peanut residue was as high as 8.93%, and the C/N ratio was as cellulose-converted carbon spheres in the process of HTC (García-Bordejé
low as 4.78, indicating that the maturity was too high. When directly et al., 2017; Zhang et al., 2019). A fibrous surface structure of peanut resi-
using peanut residue as an organic fertilizer, the low C/N ratio caused a due was shown in Fig. 4(b). After HTC, the surface of PR 240-60 still
large amount of N loss, and inhibited the germination of seeds. Moreover, retained the original structure, and only a few microspheres were formed
(Fig. 4(d)). Particularly, as seen in Fig. 4(e), the surface of CH 240-60
(1:1) showed the structure of CC 240-60 and PR 240-60 at the same time,
Table 2
that is, the porous structure and the microspheres were both seen as the
The ultimate analysis of hydrochars obtained at different HTC conditions.
fibrous structure. It indicated that the corn cob and peanut residue (the
Sample Ultimate analysis(wt%) (ad) Atomic Ash and
mass ratio was 1:1) does not proceed sufficiently at 240 °C for 60 min
ratio Organic
matter(wt%)
during co-HTC. Increasing the temperature to 260 °C (Fig. 4(f)), or increas-
(ad) ing the residence time to 120 min (Fig. 4(g)) both accelerated the formation
C H O N S H/C O/C Ash OM
of microspheres and porous structure, and the microfiber fragmentation ap-
peared due to the destruction of the initial microstructure.
CC 180-60 49.86 6.07 41.13 0.44 –a 1.46 0.62 2.50 97.50
CC 220-60 60.50 5.68 32.65 0.52 – 1.13 0.40 0.65 99.35
CC 240-60 66.26 5.60 26.73 0.62 – 1.01 0.30 0.79 99.21 3.2.3. Surface functional groups
CC 260-60 72.12 5.19 20.94 0.74 – 0.86 0.22 1.01 98.99 Evolutions of surface functional groups of hydrochars were observed by
CC 240-120 69.64 5.40 23.65 0.68 – 0.93 0.25 0.63 99.37 FTIR analysis. Fig. 5(a) and (b) showed the effects of reaction temperature
CC 240-240 72.11 5.33 21.59 0.71 – 0.89 0.22 0.26 99.74
on the surface functional groups of hydrochar derived from corn cob and
PR 180-60 52.93 7.59 28.47 6.84 0.18 1.72 0.40 3.99 96.01
PR 220-60 54.79 6.62 22.80 5.70 0.17 1.45 0.31 9.92 90.08
peanut residue, respectively. The O\\H stretch (the peak at 3200–3700
PR 240-60 59.83 6.12 15.92 6.29 0.31 1.23 0.20 11.53 88.47 cm−1) by hydroxyl or carboxyl groups was reduced with increasing of reac-
CH 180-60(1:1) 49.11 6.48 40.94 2.90 0.01 1.58 0.63 0.56 99.44 tion temperature, indicating the occurrence of dehydration reaction during
CH 220-60(1:1) 58.31 6.26 31.17 3.88 0.05 1.29 0.40 0.33 99.67 HTC (Wang et al., 2020). The peaks of 1732 cm−1, 1251 cm−1 and 897
CH 240-60(1:1) 64.74 6.29 22.93 5.12 0.03 1.17 0.27 0.89 99.11
cm−1 were assigned C_O stretching vibrations in hemicellulose, C-OH
CH240-120(1:1) 70.08 6.47 16.53 5.85 0.08 1.11 0.18 0.99 99.01
CH240-240(1:1) 71.97 6.47 14.01 5.99 0.13 1.08 0.15 1.43 98.57 stretching in lignin and β-glycosidic bond stretching in cellulose, respec-
CH 260-60(1:1) 69.92 6.14 15.64 5.95 0.02 1.05 0.17 2.33 97.67 tively (Kojić et al., 2021; Tang et al., 2021). The intensity of these peaks de-
CH 240-60(1:3) 66.79 6.74 16.77 6.37 0.19 1.21 0.19 3.14 96.86 creased with increasing reaction temperature, indicating that a higher
CH 240-60(3:1) 69.12 6.66 20.18 3.61 – 1.16 0.22 0.43 99.57
reaction temperature promoted the degradation of hemicellulose, lignin,
a
“-” indicated no detect. and cellulose. Fig. 5(c) showed the effects of the residence time on the

5
C. Li, R. Cai Science of the Total Environment 838 (2022) 155867

Fig. 4. Representative SEM images of raw materials and hydrochars: (a)Corn cob; (b) Peanut residue; (c) CC 240-60; (d) PR 240-60; (e) CH 240-60 (1:1); (f) CH 260-60(1:1);
(g) CH 240-120(1:1).

6
C. Li, R. Cai Science of the Total Environment 838 (2022) 155867

surface functional groups of hydrochar derived from corn cob at 240 °C.
The intensity of -OH was decreased further with increasing residence
time. The peak of 2990 cm−1 is assigned to the -CH3 or -CH2- stretching vi-
bration of aliphatic groups (Kojić et al., 2021). This peak disappeared at
120 min because the aliphatic compounds gradually decreased with in-
creasing of residence time. In addition, most of the peaks basically disap-
peared at 120 min and strengthened at 240 min. The possible reason was
that the components in the hydrochar (such as phenols) undergo secondary
polymerization reactions between 120 min and 240 min.
Furthermore, the effect of reaction temperature on the hydrochar from
co-HTC (the mass ratio of corn cob and peanut residue was 1:1) was ana-
lyzed in Fig. 6. At a lower temperature, the hydrochar from co-HTC showed
the characteristic peaks of corn cob and peanut residue. The interaction be-
tween the two raw materials was not obvious at low temperatures, which
was consistent with the results of SEM analysis. The intensity of various
structural peaks of aromatic compounds increased when the reaction tem-
perature reached 260 °C, indicating that the reaction products were mainly
aromatic compounds.

3.3. Nutrient content in products

3.3.1. The nutrient content and N recovery in hydrochar

The total nutrient content of N, P2O5, and K2O (TNC) is an important
evaluation indicator of the organic fertilizers. China's agricultural organic
fertilizer standard “NY T 525-2021” (referred to http://www.moa.gov.
cn/govpublic/ncpzlaq/202107/t20210714_6371843.htm) states that the
TNC of organic fertilizer should be greater than 4%. As shown in Table 3,
the TNC of corn cob (1.614%) was far below the requirement of the stan-
dard. The corn cob and its hydrochars were both not suitable for the prep-
aration of organic fertilizers. While the TNC in peanut residue and its
hydrochars were both high. Although some of N and K in peanut pomace
was migrated from the solid to the liquid phase during HTC, the TNC of
hydrochar derived from peanut residue was still higher than the require-
ment of the standard. However, the low N recovery rate (11.33–17.23%) in-
dicated that a large amount of N migrated from the solid to the liquid phase
in the HTC process. It was not conducive to the application of peanut resi-
due in the preparation of solid organic fertilizer.
During the co-HTC process of corn cob and peanut residue (CC:PR =
1:1), the TNC was lower at lower reaction temperatures (180–220 °C).
With increase temperature to 240 °C, the TNC content exceeded the
requirements in the “NYT525–2021” standard. It was due to the migrating
of N from the water phase to the hydrochar with increasing reaction
temperature. Further, the N recovery rate of hydrochar derived from
mixed raw materials (CC:PR = 1:1) was increased by 8.52–19.51% at
180–240 °C (60 min) compared with the HTC of peanut residue. At the
reaction condition of 240 °C and 60 min, the N content and TNC of
hydrochar were decreased but the yield and N recovery of hydrochar
were improved with the increase of the corn cob mass fraction in the co-
HTC process. The N recovery rate and hydrochar yield reached 49.01%
and 34.48% respectively at CC:PR = 3:1. The effects of residence time on
N content, N recovery rate, and TNC were investigated at 240 °C and CC:
PR = 1:1. the N content, the yield and the N recovery of hydrochar were
improved with increase of residence time from 60 min to 120 min, and
those indexes were decreased at 240 min. Since the TNC of hydrochar
was relatively low at 240 °C and 60 min for CC:PR = 3:1, the recommended
optimal reaction condition for preparing organic fertilizer was 240 °C and
120 min for CC:PR = 1:1.
During the HTC process, the content of P2O5 in the hydrochar derived
from peanut residue was improved with increasing of reaction temperature.
Since the migration of P in the solid-liquid phase is affected by the pH value

Fig. 5. The FTIR of hydrochar derived from HTC: (a) the effect of reaction
temperature on surface functional groups of hydrochars derived from corn cob;
(b) the effect of reaction temperature on surface functional groups of hydrochars
derived from peanut residue; (c) the effect of residence time on surface functional
groups of hydrochar derived from corn cob.

7
C. Li, R. Cai Science of the Total Environment 838 (2022) 155867

Table 4
The pH value, EC and nutrient content in process water from co-HTC.
Sample pH EC N P2O5 K2O TNC
(mS·cm−1) (g/L) (g/L) (g/L) (g/L)

PR 180-60 4.90 9.46 6.54 1.87 3.69 12.10

PR 220-60 7.09 11.43 5.64 0.53 2.04 8.21
PR 240-60 7.70 14.71 4.95 0.53 1.97 7.45
CH 180-60(1:1) 4.14 6.61 1.56 1.45 2.40 5.41
CH 220-60(1:1) 4.77 8.51 1.53 1.02 1.40 3.95
CH 240-60(1:1) 5.10 7.82 0.81 0.88 0.54 2.23
CH 240-120(1:1) 5.15 8.06 1.39 0.45 0.54 2.38
CH 240-240(1:1) 5.39 8.11 1.36 0.22 0.42 2.00
CH 260-60(1:1) 5.38 8.02 0.74 0.82 –a 1.56
CH 240-60(1:3) 7.25 9.56 0.22 0.08 0.02 0.32
CH 240-60(3:1) 4.63 4.33 0.04 0.05 – 0.09
a
“–” indicated no detection.

Fig. 6. The FTIR of hydrochar derived from the co-HTC of CC:PR = 1:1.
of the solution and the content of some metal ions (such as Fe3+, Ca2+, etc.),
the contents of P2O5 in the hydrochars derived from co-HTC (CC:PR = 1:1)
were decreased at 180–220 °C, and increased at 240–260 °C. Meanwhile,
the K+ content in the solid phase remained low due to the higher solubility
of K+.
According to the “NYT525–2021” standard, the organic matter (OM)
content of organic fertilizer should be greater than 30%. After the co-
HTC, the ash contents of hydrochars were much lower than raw mate-
rials, and the OM contents were more than 90% (as shown in Table 2),
meeting the demand of organic fertilizer. The obtained hydrochars
only have a slightly solubility, belonging to the slightly-soluble fertilizer
or insoluble fertilizer, and it is suitable for use as a base fertilizer during
crop growth.
3.3.2. The nutrient content in process water
The effects of reaction temperature and time on the properties of pro-
cess water were shown in Table 4. During the HTC of peanut residue at
180–240 °C and 60 min, a high content of N (4.95–6.54 g/L) was detected
in the process water. After mixing corn cob and peanut residue for co-HTC
(CC:PR = 1:1), the N content in the process water decreased to 0.74–1.56
g/L, indicating that the synergistic effect between the corn cob and the pea-
nut residue caused the migration of N from the process water to the
hydrochar. Compared with 180 °C, the nutrient content of P2O5 was de-
creased by 43.45% at 260 °C. Increasing the residence time also decreased
the P content in the process water, which may be due to the migration of P
into the solid phase by means of precipitation, adsorption, etc. Moreover,
higher levels of K+ were detected in process water due to the high solubility
of K+. These results were consistent with the changes of nutrient content in
hydrochar.
The pH and conductivity of process water would gradually increase with
increasing of reaction temperature and residence time. The pH of the process
water obtained from peanut residue HTC increased to 7.70 with increasing
reaction temperature. The increase of electrical conductivity (EC) means
more salt was produced in the process water. During the co-HTC process
(CC:PR = 1:1), the pH value and EC of the process water decreased to
4.14–5.39 and 6.61–8.51 mS·cm−1, respectively. Because the organic acid
produced from the co-HTC of corn cob neutralizes the amino acids produced
by the peanut residue, and some metal ions migrate between liquid and solid.
4. Nutrient migration mechanism
4.1. Analysis of organic-N composition
Nitrogen is an important element for plant growth; thus, it is meaningful
to clarify the transformation and migration of N in the HTC process. The
major components of bio-oil product after HTC were analyzed by GC–MS
analysis. As shown in Fig. 7, the bio-oil from PR 180–60, PR 260–60, and
CH 260–60(1:1) contained N-containing heterocycles (pyrazines, pyrroles
and pyridines), phenols, aldehydes, O-containing heterocycles (including fu-
rans), N-containing organic matters (amines, amides, quaternary amines, ni-
triles, etc.), aliphatic acids and aliphatic alcohol/ethers. The formation
pathways of N-containing heterocycles included Maillard reaction between
sugars and amino acids and the dehydration of amino acids themselves to
form a ring. During HTC of peanut residue, the relative fraction of N-
containing heterocycles and N-containing organic matters in bio-oil increased
with the reaction temperature from 180 °C to 260 °C, indicating that a higher
temperature promoted more N migrating into the bio-oil. The alkaline
100
CH 260-60(1:1)
PR 260-60
PR 180-60
75
Relative content (%)

Table 3
The nutrient content and N recovery of raw materials and hydrochars.
Sample Nutrient content of hydrochar (%) N recovery (%) 50
N P2O5 K2O TNC

CC 0.41 0.156 1.048 1.614 –

PR 8.93 2.521 1.614 13.065 –
25
PR 180-60 6.84 0.108 0.444 7.392 17.23
PR 220-60 5.70 3.500 0.868 10.068 14.01
PR 240-60 6.29 4.140 0.276 10.706 11.33 0
CH 180-60(1:1) 2.90 0.092 0.029 3.021 25.75
g
ols

att g

/et tic
ocy g

de

cid
ter inin

ic m inin
n
c

ers

rs

CH 220-60(1:1) 3.88 0.030 0.064 3.974 26.63

oh lipha
en
he taini
cli

cli
hy

ca

he
ta
Ph

ta
ocy

CH 240-60(1:1) 5.12 0.201 0.628 5.949 30.84

de

ati
con

org con

A
con

Al
ter

ols

CH 240-120(1:1) 5.85 0.321 0.160 6.331 34.90

iph
O-

N-
N-

he

an

CH 240-240(1:1) 5.99 0.493 0.052 6.535 33.43

Al

alc

CH 260-60(1:1) 5.95 1.161 0.426 7.537 27.78

CH 240-60(1:3) 6.37 1.240 0.541 8.151 22.51
CH 240-60(3:1) 3.61 0.044 0.401 4.055 49.01
Fig. 7. Main components in bio-oil.

8
C. Li, R. Cai
environment promoted the combination of NH3 (formed by the decomposi-
tion of aliphatic acids) and amino acids to form amides. Therefore, the ali-
phatic acids of bio-oil were fewer at 260 °C during HTC of peanut residue.
The higher temperature was favorable for lignin degradation to produce phe-
nolic substances, so higher levels of phenols can be detected at 260 °C during
the HTC of peanut residue and co-HTC. In addition, furans and some cyclic
organic compounds would further dehydrate to form phenols.
4.2. Possible migration and transformation paths of N in co-HTC
N in the corn cob and peanut residue exists in organic N (including N-
containing heterocycles, proteins) and inorganic N (including ammonium
and nitrat/nitrite salts). After HTC process, the N-containing components
in the raw materials decomposed to form several inorganic N-containing
− − −
ions such as NH+4 , CN , NO2 and NO3 , and the N solubilized into the pro-
cess water was mainly the ammonia form. (Aragón-Briceño et al., 2020;
Ekpo et al., 2016; Sun et al., 2018; Wang et al., 2018b) Part of the N in
the raw materials was retained in the solid product through chemical
reactions, precipitation, and crystallization. According to the analysis of
the characteristics of the N-containing products in solid and liquid phases,
the possible organic-N migrate pathways occurring in the co-HTC process
were illustrated as follow (see Fig. 8):
(1) Decomposition of raw materials. The decomposition of raw mate-
rials was the beginning of organic-N migration. The protein are the main
components of peanut residue. Protein-N was dehydrated and converted
into amino-N (amino acids), and the amino acids were further converted
into imines and NH3 by decarboxylation and deamination. The pH value
of process water was higher due to the formation of NH3 during the HTC
of peanut residue, and the NH3 reduced the content of organic acids by
amination with aliphatic acids (formed by the decomposition of lipid).
The cellulose/hemicellulose and lignin were the main components of
corn cob. The cellulose and hemicellulose were dehydrated to produce sac-
charides such as glucose at 180–240 °C. These saccharides would further
form various organic acids and furfural through dehydration and Retro-
Aldol reaction. The lignin would decompose into phenols at 250 °C, a little
higher than the cellulose/hemicellulose. The decomposition products of the
corn cob would participate in the N migration process during co-HTC.
(2) Reaction of saccharides and amino acids. The Maillard reaction was
an important way to convert protein-N into N-containing heterocycles during
the co-HTC (Li et al., 2019). A large amount of organic acids and CO2 were
produced by the degradation of corn cob during co-HTC, decreasing the pH
value in process water. The decreasing of pH value would further promote
the degradation of raw materials into more saccharides, amino acids and
their decomposition products. The saccharides and amino acids (from
Fig. 8. Possible migration and transformation paths of N in co-HTC.
9
Science of the Total Environment 838 (2022) 155867
process (1)) would produce Amadori compounds through dehydration.
(Peterson et al., 2010) And the Amadori compounds would generate imine
and pyrazine derivatives through further dehydration and condensation.
These imines (including imines produced in other ways) were one of the im-
portant sources of N-containing heterocycles (such as pyrazines and pyrroles)
in co-HTC products. The N-containing heterocycles produced by the Maillard
reaction were presented in the bio-oil or polymerized into the hydrochar.
(3) Ring-forming reaction of amino acids and the feedback effect of pH.
In addition to participating in the Maillard reaction to produce N-
containing heterocycles, amino acids could also produce N-containing
heterocycles through ring-forming reactions. (Croce et al., 2017) Some of
the amino acids can ring themselves to form N-containing heterocycles
such as pyridine and pyrrole through deamination and decarboxylation.
Meanwhile, some N-containing heterocycles would also be produced by
Maillard reaction of the furans/aldehydes with the amines (derived from
degradation of saccharides and amino acids, respectively). Compared
with the HTC of corn cob, the deamination was predominant for amino
acids decomposition during co-HTC, and this could produce much NH3
and increase pH values. As a result, the migration of N was affected. The
increasing of pH values inhibits the formation of furans produced by the
decomposition of cellulose and hemicellulose. The organic acids derived
from the decomposition of saccharides would react with NH3 (produced
by the deamination of amino acids) to form amides. It was the reason
why there were lower organic acids detected in bio-oil from the co-HTC
process at 260 °C. Moreover, the phenols and benzenediols (decomposed
from lignin) could react with NH3 and promote the generation of amides.
Then the Mannich reaction of phenols with NH3 and amines increased
the content of N in hydrochar during co-HTC. (Du et al., 2014)
Therefore, the composition of the raw materials, the pH value of the so-
lution, reaction temperature, and residence time were important factors
that affect the migration of N in co-HTC process. Moreover, the solid-to-
liquid ratio of the raw materials can also affect the migration of N. In addi-
tion to the migration of organic N, the inorganic N (ammonium salt, nitrate)
in the solid will migrate to the process water during the co-HTC process,
−
mainly in the presence of NH+ 4 -N and NO3 -N. The metal ions in the raw
materials such as Ca2+, Mg2+ and PO3+ 4 can combine with N to form a
salt (NH4MgPO4·6H2O) and precipitate in the solid. (Xiao et al., 2019).
4.3. Possible migration and transformation paths of P and other nutrient elements
in co-HTC
To obtain the potential transformation pathways of P during HTC, the C
and H in the raw materials and hydrochars were removed at 550 °C and the
P and metal elements remained in the ash. The relative contents of P and
C. Li, R. Cai
other nutrient elements in the ash (expressed in oxide form) were summarized
in Fig. 9. As shown in Fig. 9(a), the ash of corn cob and peanut residue mainly
contained P and K. After HTC process, the K content in the hydrochars was
greatly reduced compared with the raw material. It means that a large amount
of K has migrated from the solid to the process water. Thus, the hydrochars of
corn cob prepared at different reaction temperatures and residence times
were not suitable as organics fertilizer due to the low contents of P and K.
Compared with the content of K, the contents of P in hydrochars from
HTC of peanut residue and co-HTC were higher. With the increase of the re-
action temperature and residence time, the proportions of P in peanut res-
idue and mixed raw materials in the hydrochar ash were increased.
Further, we found that the existence of some polyvalent metal cations
was closely related to the transformation pathway of P by analyzing the
changes in the ash content of metal elements (as shown in Fig. 9(b)-(d)).
This has been confirmed in many studies (Ghanim et al., 2018; Silva
et al., 2017; Sun et al., 2018). Metals such as Ca, Mg, Cu, and Zn can
react with P forming insoluble precipitates (phosphate salts) and adsorption
can be promoted by Fe and Al hydroxides due to their high affinity with
P (He et al., 2015; Huang et al., 2017). Ghanim et al. (2018) found that
the P is immobilized into inorganic and apatite forms, and exists in the
Fig. 9. The relatively contents of nutrient elements in ash (expressed in oxide form): (a) P2O5 and K2O; (b) SO3, MgO and CaO; (c) Na2O, ZnO, MnO and Fe2O3; (d) Al2O3,
Fe2O3, CaO and P2O5.
10
Science of the Total Environment 838 (2022) 155867
solid product during the HTC process. Ovsyannikova et al. (2019) analyzed
the HTC process of sludge after anaerobic digestion. It was found that the
organic acids and amino acids formed by the decomposition of raw mate-
rials would change the pH value of the solution, thereby affecting the
combination and decomposition of Al3+ and Ca2+ with PO3− 4 . The transfer
path of P can be simplified to the following equation:
AlPO4  2H2 O þ OH  ⇔AlðOHÞ3 þ H2 PO4 
(5)

5Ca2þ þ 3H2 PO4 þ H2 O⇔Ca5 ðPO4 Þ3 OH þ 7Hþ (6)
Fig. 10 illustrates the possible migration and transformation paths of
P in co-HTC. As seen, P was mostly precipitated and adsorbed in hydrochar,
and existed in the form of orthophosphate in the process water. Also, P can
be detected in the form of organic matter in bio-oil.
In addition, the migration and transformation of S element were
studied. After HTC treatment, the content of S in hydrochar was greatly
reduced. The organic S can be detected both in process water and bio-oil.
Therefore, it is believed that most organic S entered the process water in
the form of sulfate radicals and some formed precipitates with metal ions
C. Li, R. Cai
Fig. 10. Possible migration and transformation paths of P in co-HTC.
(such as Ca2+) and was fixed in the hydrochar; a small part of S would exist
in bio-oil in the form of organic S.
5. Conclusions
We studied the migration and transformation characteristics of nutrient
elements in HTC of typical agricultural and forestry wastes represented by
corn cob and peanut residue, and discussed their potential in the preparation
of solid organic fertilizers. The following conclusions can be concluded:
(1) After HTC treatment, the N contents of hydrochars derived from corn
cob were increased by 6.82–80.49% compared with the corn cob and
the N recovery rates of hydrochars were 54.97–67.61%, showing excel-
lent N-fixing ability. However, because the TNC of the corn cob is too
low and the C/N ratio is too large, it does not have the potential to be
prepared as organic fertilizers through HTC.
(2) Although the nutrient content of peanut residue is relatively high, it
cannot be directly used as fertilizers because of its low C/N ratio. Com-
pared with composting, the HTC treatment is a better choice for peanut
residue. The C/N ratio of hydrochar derived from peanut residue is im-
proved and becomes suitable for use as organic fertilizer.
(3) The co-HTC of corn cob and peanut residue can enhance the N recovery
rate and C/N ratio, and effectively improve the potential of peanut res-
idue in preparing solid organic fertilizer. The hydrochars obtained the
best fertilizer capacity at the reaction temperature of 240 °C, the resi-
dence time of 120 min, and the mass ratio of 1:1.
(4) The migration and transformation of nutrient elements such as N and P
in the co-HTC process are affected by the reaction temperature, resi-
dence time and raw materials composition. In the co-HTC of corn cob
and peanut residue, most of K exists in the process water in the form
of K+. The transformation of organic-N in solid-liquid phase mainly
through functional groups removal, Maillard reaction, cyclization and
polycondensation reaction. With the increase of reaction temperature,
the N dissolved into process water (mainly ammonia) would migrate
into hydrochars and bio-oils. Increasing or decreasing the pH can pro-
mote the migration of N from liquid to solid. Meanwhile, Metal ions
such as Al3+ and Fe3+ in raw materials promote the fixation of P in
hydrochars through precipitation and adsorption reaction. Thus, the
enrichment of N and P in hydrochars can be realized by adding metal
salts or adjusting the pH of solvent.
CRediT authorship contribution statement
Chao-Sheng Li: Writing - original draft, Methodology, Conceptualiza-
tion, Validation, Formal analysis.
11
Science of the Total Environment 838 (2022) 155867
Rong-Rong Cai: Supervision, Resources, Conceptualization, Writing - re-
view & editing.
Declaration of competing interest
The authors declare that they have no known competing financial inter-
ests or personal relationships that could have appeared to influence the
work reported in this paper.
Acknowledgments
We gratefully acknowledge the financial support from the Key-Area Re-
search and Development Program of Guangdong Province, China (No.
2020B1111380001), the Natural Science Foundation of China (No.
52176155), and the Natural Science Foundation of Guangdong Province,
China (No. 2019A1515010648).
References
Aragón-Briceño, C.I., Grasham, O., Ross, A.B., Dupont, V., Camargo-Valero, M.A., 2020. Hy-
drothermal carbonization of sewage digestate at wastewater treatment works: influence
of solid loading on characteristics of hydrochar, process water and plant energetics.
Renew. Energy 157, 959–973.
Brand, S., Hardi, F., Kim, J., Suh, D.J., 2014. Effect of heating rate on biomass liquefaction:
differences between subcritical water and supercritical ethanol. Energy 68, 420–427.
Croce, A., Battistel, E., Chiaberge, S., Spera, S., De Angelis, F., Reale, S., 2017. A model study
to unravel the complexity of bio-oil from organic wastes. Chemsuschem 10, 171–181.
Du, X., Li, J., Lindström, M.E., 2014. Modification of industrial softwood Kraft lignin using
Mannich reaction with and without phenolation pretreatment. Ind. Crop. Prod. 52,
729–735.
Duan, Y., Xu, M., Gao, S., Liu, H., Huang, S., Wang, B., 2016. Long-term incorporation of ma-
nure with chemical fertilizers reduced total nitrogen loss in rain-fed cropping systems.
Sci. Rep. 6, 33611.
Ekpo, U., Ross, A.B., Camargo-Valero, M.A., Fletcher, L.A., 2016. Influence of pH on hydro-
thermal treatment of swine manure: impact on extraction of nitrogen and phosphorus
in process water. Bioresour. Technol. 214, 637–644.
Fang, P., Abler, D., Lin, G., Sher, A., Quan, Q., 2021. Substituting organic fertilizer for chem-
ical fertilizer: evidence from apple growers in China. Land 10, 858.
Fei, Y.H., Zhao, D., Liu, Y., Zhang, W., Tang, Y.Y., Huang, X., Wu, Q., Wang, Y.X., Xiao, T., Liu,
C., 2019. Feasibility of sewage sludge derived hydrochars for agricultural application: nu-
trients (N, P, K) and potentially toxic elements (Zn, Cu, Pb, Ni, Cd). Chemosphere 236,
124841.
Fuertes, A.B., Arbestain, M.C., Sevilla, M., Macia-Agullo, J.A., Fiol, S., Lopez, R., Smernik, R.J.,
Aitkenhead, W.P., Arce, F., Macias, F., 2010. Chemical and structural properties of carbo-
naceous products obtained by pyrolysis and hydrothermal carbonisation of corn stover.
Aust. J. Soil Res. 48, 618–626.
García-Bordejé, E., Pires, E., Fraile, J.M., 2017. Parametric study of the hydrothermal carbon-
ization of cellulose and effect of acidic conditions. Carbon 123, 421–432.
Ghanim, B.M., Kwapinski, W., Leahy, J.J., 2018. Speciation of nutrients in hydrochar pro-
duced from hydrothermal carbonization of poultry litter under different treatment condi-
tions. ACS Sustain. Chem. Eng. 6, 11265–11272.
C. Li, R. Cai
He, C., Wang, K., Giannis, A., Yang, Y., Wang, J.Y., 2015. Products evolution during hydro-
thermal conversion of dewatered sewage sludge in sub- and near-critical water: effects
of reaction conditions and calcium oxide additive. Int. J. Hydrog. Energy 40, 5776–5787.
Huang, R., Fang, C., Lu, X., Jiang, R., Tang, Y., 2017. Transformation of phosphorus during
(hydro)thermal treatments of solid biowastes: reaction mechanisms and implications
for P reclamation and recycling. Environ. Sci. Technol. 51, 10284–10298.
Kojić, M.M., Petrović, J.T., Petrović, M.S., Stanković, S.M., Porobić, S.J., Marinović-Cincović,
M.T., Mihajlović, M.L., 2021. Hydrothermal carbonization of spent mushroom substrate:
physicochemical characterization, combustion behavior, kinetic and thermodynamic
study. J. Anal. Appl. Pyrolysis 155, 105028.
Li, Y., Liu, H., Xiao, K., Liu, X., Hu, H., Li, X., Yao, H., 2019. Correlations between the physi-
cochemical properties of hydrochar and specific components of waste lettuce: influence
of moisture, carbohydrates, proteins and lipids. Bioresour. Technol. 272, 482–488.
Lu, X., Ma, X., Chen, X., Yao, Z., Zhang, C., 2020. Co-hydrothermal carbonization of polyvinyl
chloride and corncob for clean solid fuel production. Bioresour. Technol. 301, 122763.
Mau, V., Neumann, J., Wehrli, B., Gross, A., 2019. Nutrient behavior in hydrothermal carbon-
ization aqueous phase following recirculation and reuse. Environ. Sci. Technol. 53,
10426–10434.
Meng, X., Liu, B., Zhang, H., Wu, J., Yuan, X., Cui, Z., 2019. Co-composting of the biogas res-
idues and spent mushroom substrate: physicochemical properties and maturity assess-
ment. Bioresour. Technol. 276, 281–287.
Mózner, Z., Tabi, A., Csutora, M., 2012. Modifying the yield factor based on more efficient use
of fertilizer—the environmental impacts of intensive and extensive agricultural practices.
Ecol. Indic. 16, 58–66.
Nassar, R.-U.-D., Singh, N., Varsha, S., Sai, A.R., Sufyan-Ud-Din, M., 2022. Strength, electrical
resistivity and sulfate attack resistance of blended mortars produced with agriculture
waste ashes. Case Stud. Constr. Mater. 16, e00944.
Ni, B., Liu, M., Lu, S., Xie, L., Wang, Y., 2011. Environmentally friendly slow-release nitrogen
fertilizer. J. Agric. Food Chem. 59, 10169–10175.
Ovsyannikova, E., Arauzo, P.J., Becker Gcapital Es, C., Kruse, A., 2019. Experimental and ther-
modynamic studies of phosphate behavior during the hydrothermal carbonization of
sewage sludge. Sci. Total Environ. 692, 147–156.
Perea-Moreno, M.-A., Manzano-Agugliaro, F., Hernandez-Escobedo, Q., Perea-Moreno, A.-J.,
2018. Peanut shell for energy: properties and its potential to respect the environment.
Sustainability 10, 3254.
Peterson, A.A., Lachance, R.P., Tester, J.W., 2010. Kinetic evidence of the Maillard reaction in
hydrothermal biomass processing: glucose-glycine interactions in high-temperature,
high-pressure water. Ind. Eng. Chem. Res. 49, 2107–2117.
Silva, C.C., Melo, C.A., Soares Junior, F.H., Moreira, A.B., Ferreira, O.P., Bisinoti, M.C., 2017.
Effect of the reaction medium on the immobilization of nutrients in hydrochars obtained
using sugarcane industry residues. Bioresour. Technol. 237, 213–221.
Smith, L.E.D., Siciliano, G., 2015. A comprehensive review of constraints to improved man-
agement of fertilizers in China and mitigation of diffuse water pollution from agriculture.
AgricEcosyst. Environ. 209, 15–25.
Song, C., Zheng, H., Shan, S., Wu, S., Wang, H., Christie, P., 2019. Low-temperature hydro-
thermal carbonization of fresh pig manure: effects of temperature on characteristics of
hydrochars. J. Environ. Eng. 145, 04019029.
Song, C., Yuan, W., Shan, S., Ma, Q., Zhang, H., Wang, X., Niazi, N.K., Wang, H., 2020.
Changes of nutrients and potentially toxic elements during hydrothermal carbonization
of pig manure. Chemosphere 243, 125331.
12
Science of the Total Environment 838 (2022) 155867
Stuart, D., Schewe, R.L., McDermott, M., 2014. Reducing nitrogen fertilizer application as a
climate change mitigation strategy: understanding farmer decision-making and potential
barriers to change in the US. Land Use Policy 36, 210–218.
Sun, D., Hale, L., Kar, G., Soolanayakanahally, R., Adl, S., 2018. Phosphorus recovery and
reuse by pyrolysis: applications for agriculture and environment. Chemosphere 194,
682–691.
Tang, Z., Zhao, S., Qian, Y., Jia, H., Gao, P., Kang, Y., Lichtfouse, E., 2021. Formation of per-
sistent free radicals in sludge biochar by hydrothermal carbonization. Environ. Chem.
Lett. 19, 2705–2712.
Tarafder, C., Daizy, M., Alam, M.M., Ali, M.R., Islam, M.J., Islam, R., Ahommed, M.S., Aly
Saad Aly, M., Khan, M.Z.H., 2020. Formulation of a hybrid nanofertilizer for slow and
sustainable release of micronutrients. ACS Omega 5 (37), 23960–23966.
Thomas, B.S., Yang, J., Mo, K.H., Abdalla, J.A., Hawileh, R.A., Ariyachandra, E., 2021. Bio-
mass ashes from agricultural wastes as supplementary cementitious materials or aggre-
gate replacement in cement/geopolymer concrete: a comprehensive review. J. Build.
Eng. 40, 102332.
Usman, M., Farooq, M., Wakeel, A., Nawaz, A., Cheema, S.A., Rehman, H.ur., Ashraf, I.,
Sanaullah, M., 2020. Nanotechnology in agriculture: current status, challenges and future
opportunities. Sci. Total Environ. 721.
Wang, T., Liu, Y., Liu, Q., Cummins, S., Zhao, M., 2018a. Integrative proteomic analysis re-
veals potential high-frequency alternative open reading frame-encoded peptides in
human colorectal cancer. Life Sci. 215, 182–189.
Wang, Y., Zhu, Y., Zhang, S., Wang, Y., 2018b. What could promote farmers to replace chem-
ical fertilizers with organic fertilizers? J. Clean. Prod. 199, 882–890.
Wang, T., Si, B., Gong, Z., Zhai, Y., Cao, M., Peng, C., 2020. Co-hydrothermal carbonization of
food waste-woody sawdust blend: interaction effects on the hydrochar properties and nu-
trients characteristics. Bioresour. Technol. 316, 123900.
Wang, R., Lei, H., Liu, S., Ye, X., Jia, J., Zhao, Z., 2021. The redistribution and migration
mechanism of nitrogen in the hydrothermal cocarbonization process of sewage sludge
and lignocellulosic wastes. Sci. Total Environ. 776, 145922.
Xiao, H., Zhai, Y., Xie, J., Wang, T., Wang, B., Li, S., Li, C., 2019. Speciation and transforma-
tion of nitrogen for spirulina hydrothermal carbonization. Bioresour. Technol. 286,
121385.
Xin, X., Judy, J.D., Sumerlin, B.B., He, Z., 2020. Nano-enabled agriculture: from nanoparticles
to smart nanodelivery systems. Environ. Chem. 17 (6), 413–425.
Xiong, J.B., Pan, Z.Q., Xiao, X.F., Huang, H.J., Lai, F.Y., Wang, J.X., Chen, S.W., 2019. Study
on the hydrothermal carbonization of swine manure: the effect of process parameters on
the yield/properties of hydrochar and process water. J. Anal. Appl. Pyrolysis 144,
104692.
Zhang, B., von Keitz, M., Valentas, K., 2008. Thermal effects on hydrothermal biomass lique-
faction. Appl. Biochem. Biotechnol. 147, 143–150.
Zhang, B., von Keitz, M., Valentas, K., 2009. Thermochemical liquefaction of high-diversity
grassland perennials. J. Anal. Appl. Pyrolysis 84, 18–24.
Zhang, Y., Jiang, Q., Xie, W., Wang, Y., Kang, J., 2019. Effects of temperature, time and acid-
ity of hydrothermal carbonization on the hydrochar properties and nitrogen recovery
from corn stover. Biomass Bioenergy 122, 175–182.