Biomass Conversion and Biorefinery

https://doi.org/10.1007/s13399-019-00488-0

REVIEW ARTICLE

Understanding the influence of biomass particle size and reaction

medium on the formation pathways of hydrochar
Dominik Wüst 1,2 2 2 3
& Catalina Rodriguez Correa & Dennis Jung & Michael Zimmermann & Andrea Kruse & Luca Fiori
2 1

Received: 15 May 2019 / Revised: 22 July 2019 / Accepted: 24 July 2019

# Springer-Verlag GmbH Germany, part of Springer Nature 2019

Abstract
The chemical-physical processes controlling hydrothermal carbonization (HTC) are still not completely understood. This paper
focuses on two aspects: the influence on the hydrochar formation of the particle size of the feedstock and the presence of solved
compounds in the feedwater. To address these, brewer’s spent grains were crushed to < 1 mm and separated in three fractions. In
addition, residual process water (rPW) from 5-hydroxymethylfurfural (HMF) production instead of bi-distilled H2O was added in
a series of experiments for recycling. The results show a transfer limitation of hydrolysis products through pores for the particle
size fractions > 250 μm proved by HPLC analysis of liquid byproducts, particularly when rPW, containing readily condensable/
polymerizable intermediates, is added. This has a positive effect on the yield and carbon content of the hydrochars caused mainly
by an increase in its secondary char fraction. The reaction pathways involved are discussed in detail.

Keywords Hydrothermal carbonization . Waste prevention . Reaction pathways . Hydrolysis . Hydrochar

Abbreviations PW Process water

HTC Hydrothermal carbonization Cfix Fixed carbon
HC Hydrochar VM Volatile matter
HMF 5-hydroxymethylfurfural LA Levulinic acid
Ceff Carbon retention efficiency FA Formic acid
rPW Residual process water AA Acetic acid
FRU Fructose LaA Lactic acid
BSG Brewer’s spent grains GA Glycolic acid

Highlights
• Detailed understanding of the reaction pathways originated from
oligosaccharides during the hydrothermal carbonization of soft
lignocellulosic biomass
• Control of mass transfer during hydrolysis of oligosaccharides from
small biomass particle sizes through the fast condensation and
polymerization of reactive dehydration products
• Enhancement of yields and carbon retention efficiencies during
hydrothermal carbonization by recirculation of residual process water
from HMF synthesis instead of using water
Electronic supplementary material The online version of this article
(https://doi.org/10.1007/s13399-019-00488-0 ) contains supplementary
material, which is available to authorized users.

* Dominik Wüst 2
Department of Conversion Technology of Biobased Resources,
Dominik.Wust@unitn.it University of Hohenheim, Garbenstrasse 9,
70599 Stuttgart, Germany
3
1
Department of Civil, Environmental and Mechanical Engineering, Institute of Catalysis Research and Technology, Karlsruhe Institute of
University of Trento, via Messiano 77, 38123 Trento, Italy Technology, Hermann-von-Helmholtz-Platz 1,
76344 Leopoldshafen-Eggenstein, Germany
 Biomass Conv. Bioref.

MF Methylfurfural with C6 saccharides at similar conditions [7–11]. In other

FU Furfural words: once the hydrolysis yields its intermediates
DOC Dissolved organic carbon (monosacharides), the formation of HC occurs rather fast.
NDF Neutral detergent fiber, The rate limitation arising from the hydrolysis step can be
ADF Acid detergent fiber reduced by increasing the reaction temperature, which as a
ADL Acid detergent lignin drawback shifts the product distribution towards unwanted
PG Process gas transfer of carbon to the liquid and/or gaseous phase. In these
SUC Sucrose terms, a major challenge for HTC applications is to find an
GLU Glucose appropriate solution that combines efficient hydrolysis with
FRU Fructose HC formation. The most important precursor of HC is 5-
GIAD Glyceraldehyde hydroxymethylfurfural (HMF). Various pretreatment technol-
GAD Glycolaldehyde ogies for lignocellulose to produce HMF exist [12].
PA Pyruvic acid Mechanical crushing, among those, is a technology which
DHA Dihydroxyacetone can easily be applied prior to HTC but shall be kept to a
XYL Xylose minimum due to major energy consumption [13, 14]. The
ARA Arabinose effect of the particle size is therefore a parameter which needs
BDL Below detection limit to be further addressed. Another alternative to increase the HC
FAD Formaldehyde formation and carbon retention efficiency (Ceff) is the reuse of
BTO 1,2,4-benzenetriol the residual process water (rPW) obtained during the HMF
EtOH Ethanol production. When using fructose in aqueous acid-catalyzed
DHH 2,5-dioxo-6-hydroxy-hexanal solution, high HMF yields (up to 55 mol%) were reported.
ERY Erythrose The rPW that remains downstream still contains high concen-
FUA Furfuryl-alcohol trations of HMF and fructose (FRU) [15]. Since it is well
MeOH Methanol known that the conversion of C6 saccharides such as FRU to
AAD Acetaldehyde HMF and/or levulinic acid (LA) in aqueous systems suffers
MAN Mannose from the formation of up to 20 mol% yield of insoluble com-
OA Oxalic acid pounds known as humins, a recycling of its rPW within HTC
PAD Pyruvaldehyde can be a possible path to improve the Ceff of both processes.
ProA Propionic acid Concerning a commercial HTC plant, such a recycling ap-
ProeA Propenoic acid proach would reduce both the operating costs and the environ-
mental impact [16–18]. Indeed, rPW contains the key inter-
mediates involving an advantageous set of acid catalysts as
1 Introduction well as a favorable pH for HC production [19, 20]. The pur-
pose of this study is to investigate how biomass particle size
Hydrothermal carbonization (HTC) received increasing atten- and the “quality” of the reaction medium (bi-distilled water
tion in the past years due to its ability to convert wet biomasses versus rPW) affects HTC in terms of product distribution,
into valuable carbon materials. Kruse and Dahmen recently products characteristics, and Ceff.
reviewed the large amount of scientific publications in this Consequently, from the experiments conducted for the
field [1]. Those publications mostly evaluated the perfor- present work, it is expected that major fractions of HMF in
mance of a feedstock material under variation of process con- the rPW will react before the biomass is completely hydro-
ditions, mainly reaction time and temperature. The most dom- lyzed. When considering the use of rPW instead of bi-distilled
inant observation was the strong impact of temperature on water, the effect of the readily available HMF on the biomass
hydrochar (HC) yield and its properties. In this context, it is decomposition must be considered. In fact, a fast conversion
often observed that temperatures below 210 °C do not alter the of saccharides from biomass into HMF is of high interest to
properties of cellulose and lignocellulose remarkably due to allow a fast interaction between the newly created HMF and
the thermal stability of cellulose and lignin under these con- the HMF in the rPW and thus an efficient formation of sec-
ditions [2, 3]. Regarding cellulose, hydrolysis is the rate- ondary char as part of HC. Furthermore, there is limited re-
limiting step. It is known that the reaction kinetics is a search on the recirculation of process water from hydrother-
pseudo-first order, which indicates that the hydrolysis only mal conversion. Some examples included the use of process
takes place at the end of the cellulose chain [4, 5]. This is water from HTC of different biogenic residues such as loblol-
caused by hydrogen bonds within crystalline cellulose, which ly pine, poplar wood chips, miscanthus, paper as well as grape
do not break up in subcritical water [6]. This aspect becomes and orange pomace in addition to poultry litter and particular-
significant as HTC of cellulose is extremely slow compared ly not catalyzed by a Brønsted acid [18, 19, 21–24]. All
Biomass Conv. Bioref.
researchers reported an increase of HC yield by 5–10 wt.%
after the first recycle but the quality of HCs slightly decreased
in terms of carbon content and higher heating value due to
precipitation of solved salts [18].
For this study, brewer’s spent grains (BSG) as a major by-
product of brewing industry were selected because they were
proven to be convertible to C-rich chars but the average HC
yields of around 50 wt.% are low compared with other ligno-
cellulosic biomasses [25, 26]. This sugar- and protein-rich sub-
strate is mainly used in animal nutrition; however, it undergoes
microbial degradation and chemical deterioration especially in
summer due to insufficient acceptance as a commodity, which
leads to the production of greenhouse gases and other contam-
inants [27–30]. These aspects call for an alternative way of
converting BSG into valuable products, such as HC [31].
BSG is a complex biomass; hence, it can be assumed that
reducing saccharides and their degradation products react with
amines from the degradation of the protein fraction and form a
type of “tertiary char” via Maillard reactions in addition to a
“primary char” formed by a direct solid conversion (intramo-
lecular condensation) of polysaccharide fragments and lignin
and to a “secondary char” formed by aldol condensation/
addition and polymerization of dissolved intermediates [32].
Therefore, the key question is if there is a positive or per-
haps a negative interaction between intermediates from BSG
degradation with compounds present in the rPW, in view of
HC formation. The reactions involved are described in detail
by a complete reaction scheme except for the formation of
tertiary char, whose formation would require additional re-
search efforts to be fully understood.
2 Experimental section
2.1 Material and methods
2.1.1 Experimental setup
The experiments were performed in small stainless steel
(316 L; 1.4404) 13 ml batch-autoclaves filled for 70 v/v%.
BSG from the private brewery Hoepfner GmbH were careful-
ly dried (60 °C for 48 h), milled to a particle size smaller than
1 mm and then three fractions were separated by sieving: 850–
500 μm, 500–250 μm and 250–0 μm. Then, aqueous solu-
tions were prepared consisting of 10 wt.% BSG and either bi-
distilled water or the filtered (0.45 μm nylon filters) rPW from
HMF production (AVA Biochem AG, Muttenz, Switzerland).
The solutions were converted via HTC at 230 °C for 0, 30, 60,
and 120 min excluding preheating time. This means that 0 min
exactly corresponds to the preheating time. Additionally, a
series of experiments were conducted with only rPW without
BSG. The reactors were placed in an upright position in a
metal rack installed in a modified GC-Oven (Hewlett
Packard, GC-Oven 5800 Series II). After the reaction time
up to 140 min including 20 min of heating time, the autoclaves
were cooled down rapidly by blowing fresh compressed air on
them. The amounts of liquid phase (process water (PW)),
gaseous phase (process gas), and solid phase (hydrochar) were
measured by weighing the autoclaves after each separation
step. All experiments were conducted once, because it was
known from prior experiments that the overall error is around
±5% (relative) and the reproducibility is even better. The ob-
tained slurry containing the HC and the PW was separated by
centrifugation (Hermle Labortechnik GmbH, Wehingen,
Germany) and the HC was dried at 60 °C till it reached a
constant weight.
2.1.2 Physicochemical analysis
The ultimate composition of the HCs as well as of the different
fractions of BSG was determined with an Euro EA -CHNSO
Elemental Analyzer (HEKAtech GmbH, Wegberg,
Germany). The determination of ash of BSG and its particle
size fractions as well as their corresponding HCs was per-
formed according to ASTM Standard Method Number
E1755-01 at 575 (± 25) °C for 180 min. To eliminate the
carbonates and to evaluate only the organic C in HCs, an
ash determination at 1000 °C (oven temperature of
Elemental Analyser) was also performed. To calculate the
fixed carbon (Cfix), the volatile matter (VM) was determined
according to the DIN EN 15148:2009 at 900 (± 10) °C for
7 min. Additionally, the total structural composition of the
biomass was determined with the Van Soest analysis (ADF,
NDF, ADL) and the total amounts of lipids were determined
by their extraction according to VO (EG) 152/2009 III H
2009-01 and 152/2009 III C 2009-01 [33]. For the calculation
of the protein content, the nitrogen content was determined
according to Kjeldahl and multiplied by the factor 6.25, given
for cereal products (standard method ASTM D-52919). The
liquid phase was filtered (0.45-μm polypropylene filters) and
diluted 1:10 with the eluent for sample preparation for high-
performance liquid chromatography (HPLC). Subsequently,
HPLC was used to determine and quantify the substances in
the aqueous phase. The carbohydrates, organic acids, alde-
hydes, and alcohols were identified with a column from Bio-
Rad Aminex HPX-87H (300 × 7.8 mm) in a Merck Hitachi
Primade HPLC system. As eluent bi-distilled and degassed
water was diluted with sulfuric acid (4 mM). The column
was operated at 25 °C with a flow rate of 0.65 ml min−1 for
saccharides, aldehydes, furfurals, and most of organic acids
except lactic and glycolic acids which showed a successful
separation at 70 °C with flow rate of 0.65 mL min−1. The
detector was a refractive index (RI) Chromaster 5450.
Levulinic acid (LA), formic acid (FA), acetic acid (AA), lactic
acid (LaA), and glycolic acid (GA) were also calibrated via an
UV detector (1430 Diode Array Detector) at 210 nm. To

validate the results for 5-hydroxymethylfurfural (HMF),
methylfurfural (MF), and furfural (FU), another HPLC system
(Merck Hitachi, Düsseldorf, Germany) equipped with the col-
umn Lichrosper 100 RP-18 was used which was driven with
an eluent composition of water and acetonitrile (90/10) and a
flow rate of 1.4 mL min−1 at 20 °C. The total dissolved or-
ganic carbon content (DOC) of the filtrate was determined by
liquid chromatography-organic carbon detection LC-OCD
(DIMATEC Analysentechnik GmbH, Essen, Germany). The
concentrations of ammonium, nitrate, and nitrite in liquids
were measured by means of the barcode cuvette tests LCK
303, 339, and 342 in the spectral photometer DR6000 (HACH
LANGE GmbH, Düsseldorf, Germany). The DOC values
were used to create a mass-related carbon distribution. The
mineral composition was analyzed by means of inductively
coupled plasma optical emission spectrometry in an ICP-OES
Spectrometer (Agilent Technologies, Santa Clara, USA).
2.1.3 Thermogravimetric analysis
The thermal decomposition of selected HCs was analyzed in a
thermobalance (STA 449 F3 Jupiter, Netzsch, Germany).
Approximately 6 mg of HC were heated up to 105 °C and left
at this temperature for 10 min to ensure moisture release.
Subsequently, the sample was heated up to 900 °C with a
heating rate of 30 K min−1. The measurement was conducted
under constant nitrogen flow of 70 mL min−1.
2.1.4 Scanning electron microscopy
Scanning electron microscopy (SEM) of dried and pulverized
HCs was performed with a GeminiSEM 500 from Zeiss (soft-
ware: SmartSEM Version 6.01) with a thermal Schottky field
emitter cathode. The variable pressure system allowed pres-
sures up to 500 Pa that was applied in the case of non-
conductive samples. For secondary electron (SE) images, the
SEM was equipped with an inlens SE detector, an Everhart-
Thornley detector, and a variable pressure secondary electrons
(VPSE) detector.
2.2 Calculations
2.2.1 Biochemical characterization of brewer’s spent grains
For calculation of the values for hemicellulose, cellulose, and
lignin, the following equations were applied:
Hemicellulose ¼ NDF–ADF ð1Þ
Cellulose ¼ ADF–ADL ð2Þ
whereas NDF designates the neutral detergent fiber, ADF is
acid detergent fiber and ADL is acid detergent lignin.
Biomass Conv. Bioref.
2.2.2 Carbon retention efficiency related to brewer’s spent
grains
C HC  mHC
C eff ¼ x 100% ð3Þ
C BSG  mBSG
Ceff is the carbon retention efficiency related to the BSG
weighed in, CHC the carbon content of the hydrochar, mHC is
the mass of the hydrochar, CBSG is the carbon content of the
BSG, and mBSG is the initial mass of BSG (all on a dry basis).
2.2.3 Carbon retention efficiency related to residual process
water from HMF synthesis
 
cDOCPW xmPW þ mC;PG
C eff rPW ¼ 100%− x100% ð4Þ
cDOCrPW x mrPW
Ceff-rPW describes the carbon retention efficiency regarding
the HC formed from the organic compounds dissolved in the
rPW (cDOCrPW ). For this calculation the mass of C in the PW
(cDOCPW ) and process gas (PG) (mC,PG) after the HTC is re-
lated to the mass of C in the rPW (cDOCrPW times mrPW)
subtracted from 100% DOC. In other words, the DOC missing
after HTC and not transferred to PG has reacted to form HC.
2.2.4 Carbon percentage of detected reaction products
in the process water from hydrothermal carbonization
To illustrate how well the carbon balance in the process waters
after HTC of the residual process water from HMF synthesis
with and without BSG as well as after the HTC of BSG in
water could be closed, the following equation was established:
M Carbon
x cReaction Product
M Reaction Product
C% ¼ x 100% ð5Þ
cDOC
The carbon percentage of each reaction product (C%) was
calculated considering the molar percentage of carbon
(MCarbon) in the reaction product (MReaction Product) depending
on its concentration (cReaction product) related to the concentra-
tion of dissolved organic carbon (cDOC).
3 Results and discussion
Firstly, the characterization of BSG and its particle size
fractions as well as the rPW as a reaction medium alter-
native to water is reported. Secondly, the results obtained
from HTC of rPW as well as BSG in water and rPW are
presented and discussed.
Biomass Conv. Bioref.

3.1 Physicochemical analysis of feedstocks
3.1.1 Brewer’s spent grains
The contents of structural substances (biochemical characteris-
tics) as well as chemical characteristics presented in Table 1 are in
accordance with the literature [26, 34–36]. Santos et al. [37] and
Hardwick [38] reported that the chemical composition of BSG
varies with barley variety, time of harvest, malting, mashing
conditions, possible additives added, and brewing technology.
It can be proven by subtracting the ash content determined at
575 °C from the ash content determined at 1000 °C and the
content of potassium that 0.15% of 4.6% of the ash are carbon-
ates. However, this value will be neglected in calculations like for
Ceff (Figs. 4, 7, and 13) due to its low magnitude. The ash is
mainly composed of Ca2+, Mg2+, P, and S (Table 1), whereas
elements such as Na+, Ba2+, Zn2+, Mn2+, and Sr2+ occur in traces
(≤ 0.004%). Since the ash content of lignocellulosic biomass
varies from below 1% to more than 20%, BSG can be considered
as a low ash-containing biomass [21]. Its alkali and alkali earth
metal fraction could easily be leached out which has a catalyzing
effect on the formation of the secondary char fraction of HC,
affecting the secondary char particle dimension, texture, and sur-
face morphologies [39, 40].
Besides the mineral components, the saccharides in BSG
play a decisive role as precursors in the HC formation [41].
The chromatogram in Fig. S1 (Supplementary materials)
shows four relevant peaks related to oligosaccharides such
maltotriose and maltose, sucrose (SUC), glucose (GLU), and
fructose (FRU), followed by lactic acid (LaA) and glycolic
acid (GA).
Three different particle size fractions were used for further
investigation in this study. The characteristics are given in
Table 2. BSG is also composed of complex saccharides (cel-
lulose and hemicellulose), proteins, and lignin. The accessi-
bility to these components is strongly related with the particle
size as can be seen from the thermogravimetric analysis
(Fig. 1). The main degradable region for each particle size
fraction is located at 200–400 °C but their differences in struc-
tural composition are reflected in the strong decomposition
peaks present between 250 and 400 °C. These peaks corre-
spond to the decomposition of proteins and polysaccharides
such as hemicellulose, cellulose, and starch. However, the
amorphous hemicellulose decomposes at a lower temperature
compared with the crystalline cellulose [42]. Since lignin con-
sists of phenylpropanoid units interconnected by different
chemical linkages which have different binding energies, the
decomposition proceeds over the abovementioned tempera-
ture range in Fig. 1 [43].
The decomposition of the “small” (0–250 and 250–
500 μm) BSG particle size fractions shows a similar pattern.
Conversely, the sample with the largest particle size (500–
850 μm) shows faster decomposition rates between 230 and
400 °C, but slower decomposition rates at temperatures higher
than 400 °C. The reason for the different particle peaks around
300, 350, and between 400 and 500 °C in the decomposition
curve (dTG) of 500 to 850 μm may be due to a variable
structural composition of the different particle size fractions.
Bhatty [44] and Lynch et al. [27] gave hints for this hypothe-
sis. Since the smaller the particle size fraction, the higher its
content of C and H as well as its Cfix but the smaller its O and
volatile matter (VM) content (Table 2), it is likely that the
macromolecular structure of lignin and xylans from broken
barley hulls concentrated in it [45].
Consequently, the physicochemical characteristics of total
BSG fractions (≤ 1 mm), presented in Tables 1 and 2, corre-
spond to the major part of the particle size fraction 250–
500 μm with 48% followed by the fractions of 0–250 μm
and 500–850 μm with 31% and 19% respectively but also to
the minor fraction larger than 850 μm with 2%. The percent-
ages were calculated based on the mass of BSG weighed in for
the sieving procedure.

Table 1 Physico- and biochemical analysis of brewer’s spent grains on a dry basis

Biochemical characteristics [wt.%]

Crude fiber NDF[a] ADF[b] ADL[c]/ Lignin Hemicellulose[d] Cellulose[d] Crude Fat Crude Protein[e]
17.7 56.3 29.3 6.8 27.0 22.5 2.3 21.4
Chemical characteristics [wt.%]
C H N S O[d] P Ca2+ Mg2+ K+
50.8 7.4 4.1 0.4 32.7 0.51 0.41 0.15 0.05
Atomic ratios [−]
O/C H/C
0.44 1.74
Physical characteristics [wt.%]
Ash VM [f] Cfix [g]
4.6 83.3 12.1
[a]
Neutral detergent fiber. [b]Acid detergent fiber. [c]Acid detergent lignin. [d]Calculated by difference. [e]Calculated by multiplying the total nitrogen value
by a factor of 6.25. [f]Volatile matter. [g]Fixed carbon. Hemicellulose = NDF – ADF. Cellulose = ADF – ADL [33].
 Biomass Conv. Bioref.

Table 2 Ultimate and Proximate Analysis of particles of different size According to a simplified process flow sheet created by AVA
resulting from milling (< 1 mm) of softly dried Brewer’s Spent Grains
Biochem AG, the company used nitric acid (HNO3) for pH
Fraction 0–250 μm 250–500 μm 500–850 μm setting (pH = 1.0–1.5) and as a liquid catalyst for dehydration
of monosaccharides to 10–20 wt.% yield of HMF [46].
Elemental composition [wt.%] [wt.%] [wt.%] The detected organic reaction products listed in Table 3
C 49.5 49.1 47.7 correspond to those also detected by the research group of
H 7.0 6.9 6.6 Asghari [47] under acidic conditions (pH < 2).
N 4.2 3.6 2.2 Consequently, the 10 to 100% of DOC likely consists of glyc-
S 0.3 0.2 0.1 eraldehyde (GlAD), glycolaldehyde (GAD), pyruvic acid
[a]
O 34.6 35.4 38.6 (PA), and dihydroxyacetone (DHA). Nevertheless, these com-
Atomic ratios [−] [−] [−] pounds could not be unequivocally identified by the operating
H/C [−] 1.69 1.67 1.65 HPLC system.
O/C [−] 0.48 0.49 0.56 Table 4 shows the concentrations of inorganics which are
Physical characteristics [wt.%] [wt.%] [wt.%] present in rPW due to different reasons. Since ammonium and
Ash 4.4 4.8 4.8 nitrite were not found and it is well known that sugar syrup
VM[b] 81.6 82.6 83.0 does not contain any fats and proteins as precursor for com-
Cfix[c] 14.0 12.6 12.2 pounds containing organic nitrogen, it can be stated that the
[a]
total nitrogen bound in rPW is linked to nitrate and results
Calculated by difference. [b] Volatile Matter. [c] Fixed Carbon
from catalysis. The elements Al3+, Zn2+, Fe2+/3+, Cu2+, and
Mn2+ are assumed to originate from corrosion of components
3.1.2 Residual process water from HMF synthesis of the pilot-scale production plant of AVA Biochem due to the
acidic reaction medium, while Mg2+ and Ca2+ may result from
The rPW, a residual aqueous solution from HMF synthesis the sugar syrup production [48–50].
(un-concentrated sugar syrup) was used as an alternative to
water in this study. It was provided by the specialty chemicals
company AVA Biochem AG [46]. It still contains reactive 3.2 Hydrothermal carbonization of residual process
intermediate products of HTC such as HMF (47.8 C%) and water from HMF synthesis
FU (1.9 C%) as well as its precursor FRU (34.8 C%), which
makes it more attractive as a reaction medium than water [22]. As shown in Table 3, rPW from HMF synthesis is a hetero-
Table 3 presents the identified compounds in rPW and their geneous medium composed of 47.8 C% HMF, 34.8 C% FRU,
detected concentrations as well as their carbon percentages and around 17.0 C% of their degradation products (including
related to 100% DOC. the 10.0% of analytically not identifiable DOC). The presence

Fig. 1 Thermogravimetric 100 0.8

analysis of the separated particle TG 0-250 µm
size fractions of brewer’s spent TG 250-500 µm + rPW
grains (BSG) TG 500-850µm
80
dTG 0-250 µm
0.6
dTG 25-500 µm + rPW
dTG 500-850 µm
-dm/dT [% K-1]
Mass loss [%]

60

0.4

40

0.2
20

0 0.0
200 300 400 500 600 700 800
Temperature [°C]
Biomass Conv. Bioref.

Table 3 Concentrations Furthermore, the findings concerning HC formation agree

of reactions products in Parameter c [mg L−1] C% of DOC
with the concept proposed by Dinjus et al. [32] that non-
residual process water
from HMF production DOC[a] 10,241 degraded leftovers of lignocellulosic biomass, consisting of
identified by high- FRU[b] 8911 34.8 fragments of (hemi)cellulose as well as lignin, undergo a di-
performance liquid chro- FAD[c] 72 0.3 rect solid conversion (intramolecular condensation) and form
matography and their
AA[d] 72 0.2 a (poly)aromatic network. In addition to this HC fraction,
carbon percentages relat-
ed to 100% of dissolved GA[e] 372 1.1 termed primary char, secondary char results from aldol
organic carbon HMF[f] 8566 47.8 condensation/addition and polymerization of degradation
FU [g]
314 1.9 products of monosaccharides and lignin [72–74]. Because of
LA[h] 614 3.1 the similar polyol structure of GLU and xylose (XYL), their
FA[i] 323 0.8 degradation in subcritical water was proven to be similar, al-
Total 90.0 beit their dehydration products are HMF (GLU) and FU
(XYL) [72]. Arabinose (ARA) as a component of hemicellu-
[a]
Dissolved Organic Carbon. [b] Fructose. lose and its reaction pathways are not illustrated due to its low
[c]
Formaldehyde. [ d ] Acetic Acid. occurrence in biomass or rather BSG as well as its low reac-
[ e ]
Glycolic acid. [f] 5-
Hydroxymethylfurfural. [g] Furfural. tivity within short reaction times due to the occurrence of its
[h]
Levulinic acid. [i] Formic acid more stable tautomer (α-pyranose) [75].
To be precise a tertiary or even a quaternary char has actu-
of these compounds is expected to have a favorable influence ally to be described which results from Maillard reactions or
on the overall efficiency of HTC compared with water, be- the incorporation of fatty acids but focusing on it in detail is
cause these organic compounds are the precursors for the for- beyond the scope of this study [71]. As reported by Funke
mation of a carbonaceous material, known as “humins or sec- et al. [51], a process gas (PG) consisting mainly of CO2 with
ondary char” with a sphere-like geometry [11, 19, 51–55]. minor quantities of CO, CH4, and H2 as well as traces of CmHn
Furthermore, HNO3 was reported having positive effects on results from decarboxylation, decarbonylation, and oxidation
aldol condensation/addition and polymerization reactions reactions occurring during HTC.
resulting in a solid product with a higher carbon content. The reaction pathways which are accountable for the con-
The reasons are that the acidic conditions catalyze these reac- version of rPW due to its composition are highlighted in or-
tions and more reactive intermediates with a higher abundance ange color in Fig. 2. The factual identified ones are illustrated
of hydroxyl functional groups are formed by oxidation [20]. as solid lines and those that are unlikely to happen as dashed
Figure 3 and Table S1 (Supplementary Materials) display lines. The standard black lines indicate the most important
the carbon percentages related to DOC of different com- reaction pathways to primary and secondary char.
pounds in the process water after HTC. FRU cannot be de- Figure 3 and Table S1 (Supplementary Materials) shows the
tected anymore after the heating phase, and HMF is only pres- carbon percentage of the detected reaction products related to
ent at the first time point (t = 0 min). For a better understand- the DOC of the process waters after HTC. The DOC was re-
ing of the HC formation in subcritical water in a temperature duced by around 42% from 10,241 to 5,900 mg L−1 (not illus-
range from 170 to 350 °C and to explain the detected compo- trated results) during the reaction time due to carbon transfer to
nents, a scheme illustrating the decomposition pathways of the gaseous phase caused by decarboxylation, disproportion-
(ligno-)cellulosic biomass and the subsequent oligo-, di-, and ation and oxidation reactions but also due to carbon consump-
monosaccharides is presented in Fig. 2 [9, 47, 54, 56–71]. tion by aldol condensation, subsequent polymerization and aro-
matization reactions which resulted in secondary char [8, 76].
Whereas Van Dam and Bekkum [77] and Cottier and
Descotes [78] showed that aqueous and non-aqueous degra-
Table 4 Concentrations dation processes of oligo-, di-, and monosaccharides lead to
of inorganics in process Parameter c [mg L−1]
about 37 products, in this study, 13 organic compounds were
water from acid-
catalyzed conversion of NO3− 2652.7 verified in rPW by two HPLC systems and three methods, and
fructose analyzed by cu- Al3+ 0.1 hereby, up to 90.0 C% of DOC was identified. Since GLU is
vette test in a spectral Mg2+ 0.2 always below its detection limit (Fig. 3 and Table S1 -
photometer and induc-
Ca3+ 0.8 Supplementary materials), the isomerization of FRU to GLU
tively coupled plasma
optical emission spec- Fe2+/3+ 1.8 by the Lobry de Bruyn-Alberda van Ekenstein transformation
trometry in an ICP-OES Mn2+ 0.05 can be excluded in this experimental series. It mostly occurs
spectrometer under mild acidic conditions under which the weak acid anion
Zn2+ 0.2
Cu2+ 0.1 acts as a base but catalysis by dissolved metal compounds is
basically possible [77, 79–81].
 Biomass Conv. Bioref.

Maillard Reactions

Oxidation
Decarboxylation

Pyruvic acid
Amino acid Oxidation Decarboxylation

Oxalic acid Glycolic acid Methanol

Reverse aldol condensation

Hydrolysis
Oxidation
Acetic acid
Cross-Dispropotionation

Oxidation

Oxidation
Self-Dispropotionation
Formaldehyde
Dehydration +

Hydrogenation Propionic acid

Dehydration H2O-addition + Decarboxylation
Protein Rearrangement Ethanol
Lactic acid Dehydration
Dihydroxyacetone Pyruvaldehyde
Hydrolysis Degradation
Decarbonylation Propenoic acid

Isomerization
Reverse aldol
Reverse aldol condensation
Fructose condesation Acetaldehyde
Sucrose Rehydration Cross-Disproportionation
Glyceraldehyde
Rehydration
Formic acid
Dehydration Rehydration

Isomerization HMF Reverse aldol

additon
Levulinic acid
Condensation + Polymerization
Starch (Diels-Alder) Nuclei
Furfuryl Dimerization +
alcohol Degradadation
Reverse aldol 1,2,4-Benzenetriol
addition

Aromatization + Decarboxylation
Hydrolysis Hydrolysis Hydrolysis +
+ Dehydration
Electrocyclic
Rearrangement
Furfural Methylfurfural
Levuglucosan Glucose Rehydration
(Hemi-) Cellulose
Dehydration
Decarboxylation
Intramolecular
Condensation

2,5-dioxo-6-hexanal

Reverse aldol Reverse aldol condensation + Degradation

condensation +
Intramolecular
Condensation + Primary Glycoladehyde
Secondary/
Erythrose
Decarboxylation
Char Tertiary Char

Fig. 2 Decomposition pathways of relevant organic components of biomass under subcritical water conditions in a temperature range from 175 to
350 °C. The formation of gases by decarboxylation, decarbonylation, etc. are not illustrated (adapted from Ref. [9, 47, 54, 56–71])

Consecutive reactions like the dehydration to HMF and its are no clear indications that FRU, GLU, and XYL were in-
rehydration to FA and LA as well as their degradation again volved in condensation and polymerization reactions. Horvat
took place, as other research groups also proved under com- et al. [87] and Patil et al. [54] proposed that an intermediate
parable acidic process conditions [47, 82, 83]. These seem the such as 2,5-dioxo-6-hydroxy-hexanal (DHH) is firstly formed
most promoted reactions catalyzed by remaining protons from via the rehydration (ring opening mechanism) of HMF. This
HNO3 catalysis during HMF synthesis [47, 57, 83]. dimer acts as the basis for the addition of a maximum of five
Considering that furans are potentially polymerizable com- HMF molecules. As a result of this, aldol addition/
pounds, they were not detectable anymore, already after 0 min condensation nuclei are formed that further agglomerate to
of reaction time (Fig. 3 and Table S1 - Supplementary mate- secondary char (see in Fig. 5) [17, 85].
rials) [19, 53, 54]. Consecutive reactions of HMF can gener- Additionally, LA together with FA were produced from the
ally be divided into three groups, according to its functional furan ring cleavage of HMF interestingly in a molar ratio greater
groups, namely, the furan ring, formyl group (aldehyde), and than 1:1 (Figs. 2 and 3), which is in accordance with the investi-
hydroxymethyl group (alcohol). As illustrated in Fig. 2, 1,2,4- gations of Girisuta et al. [66] and Reiche et al. [20] on the decom-
benzenetriol (BTO) is the product formed by furan ring open- position of HMF into LA under acidic conditions. Flanelly et al.
ing and by closing of a cyclohexadiene or triene ring after [88] stated the dehydration of FRU, GLU, and erythrose (ERY) to
electrocyclic rearrangement and dehydration [65, 84, 85]. furfuryl-alcohol (FUA) and FU via reverse aldol condensation and
Since its carbon percentage related to the DOC keeps constant rehydration is the responsible reaction pathways for the excess of
from 60 min of reaction time on (Fig. 3 and Table S1 - FA (Fig. 2). Qi et al. [9] found that FA additionally catalyzes
Supplementary materials) and considering that BTO is less dehydration of FRU to HMF and LA molecules react with the
reactive, a common polymerization with HMF, and thus, an hydroxyl groups of secondary char, and thus, it takes part in the
implication in the formation of secondary char is unlikely [59, growth (nucleation) as building units. However, LA and FA were
86]. However, Ryu et al. [72] studied the effect of such phe- also subjected to decarboxylation and mainly ended in CO2 and
nolic compounds on the formation of HC from saccharides, H2O as well, even embedded in the structure of secondary char
demonstrating a substantial increase in carbon yield. [66, 89]. Such insights agree with the work of van Zandvoort et al.
According to the experimental and modeling studies of [17] and Cheng et al. [90] who found that secondary char origi-
Patil et al. [54], Jung et al. [40], and Dussan et al. [75], there nated from FRU consists of 60% furan rings connected via 20%
Biomass Conv. Bioref.
100%
80%
carbon percentage of DOC [C%]
60%
40%
20%
0%
0 30
reaction time [min]
Fig. 3 Carbon percentages of detected reaction products in the process waters from hydrothermal carbonization of residual process water from HMF
production in [mg L−1] (without biomass)
aliphatic linkers, decorated with oxygen-containing functional
groups, such as carboxyl, carbonyl, and hydroxyl. A decarboxyl-
ation of these carboxylic functional groups originated from LA
was confirmed by Baccile et al. [89], but according to Li et al.
[91], this reaction was rather slow at a reaction temperature of
230 °C. However, it is promoted above this temperature and
under the acidic conditions applied here. A slightly increasing
carbon content in the secondary char from 68 to 73%, which
fits to the results of Poerschmann et al. [76], and a decreasing
DOC in PW from 30 to 23% (Fig. 4), may mean decarboxyl-
ation or oxidation reactions rather than embedding of LA in
HC albeit to a minor extent. This is in accordance with van
Zandvoort et al. [17] and Reiche et al. [20]. Nevertheless, the
longer the reaction time, the higher the CeffrPW regarding the
secondary char formed from the organic compounds dis-
solved in the rPW, which yields up to 35% (Fig. 4).
Ongoing decarboxylation reactions in addition to dehydra-
tion reactions are obvious by considering the minor reductions
in O/C and H/C molar ratios, to a value comparable with hard
coal, as illustrated in the van Krevelen diagram (Fig. 9). By
1,2,4-benzenetriol
Ethanol
Formic Acid
Levulinic Acid
Methylfurfural
5-hydroxymethylfurfural
Acetic Acid
Not Detected
60 120
comparison of the dTG curves relevant to secondary char
produced from rPW (Fig. 10), to dissolved degradation prod-
ucts of digestate by Funke et al. [92] and to Kraft lignin by
Rasrendra et al. [93], all show a similar thermal decomposition
trend which starts around 250 °C and levels off at around
800 °C with highest degradation rate around 400 °C. This
insight is a strong indication of the thermal stability of this
kind of secondary char.
Figure 5 shows the indisputable relation between the
growth of carbon spheres and reaction time, which in
turn is directly related with the increase in the carbon
percentage in the HC (Fig. 4) but not with an increase
in its yield. This indicates a growth mechanism through
coalescence [40], visible especially from 30 min of
reaction time (rPW for 30 min). Finally, the results pre-
sented in this study diverge from those obtained by Qi
et al. [9], who proved a slowed growth of carbon
spheres within 6 h of reaction time due to the integra-
tion of LA in the char structure and its less reactive
functional groups.
 Biomass Conv. Bioref.

100 2 70
4 4 4

23 60
30 25 24
80

50
percentage [%]

Ceff_rPW [%]
60
40

30
40
71 72 73
68
20

20
10

0 0

reaction time [min]

C in HC C in PW C in PG Ceff_rPW
Fig. 4 Carbon distribution within the product phases after hydrothermal carbon; HC = hydrochar; PW = process water; PG = process gas;
carbonization of residual process water from HMF production at 230 °C CeffrPW = carbon retention efficiency regarding HC formed from the
for 0, 30, 60 and 120 min. The process gas is assumed as 100% CO2. C = dissolved organic compounds in the residual process water

The oxidation of LA to AA and FA, as Fang et al. [61] concentrations of FA decreased over a reaction time of 120 min
reported, could not definitely be proven, but Reiche et al. [20] is the cross-disproportionation with formaldehyde (FAD) to
confirmed the degradation of LA and FA by a decrease of pH methanol (MeOH), but it cannot be verified due to the low
down to 0 at 220 °C for 6 h. A further explanation why the concentration of FAD as reactant (Table 3 and Fig. 3) [63].

Fig. 5 Scanning electron

microscopy of hydrothermal
carbonized (reaction
temperature = 230 °C; reaction
time = 0–120 min) residual
process water from HMF
production; rPW = residual
process water from synthesis of 5-
hydroxymethylfurfural
Biomass Conv. Bioref.
Another possible reaction pathway which resulted in MeOH is
the decarboxylation of GA which includes CO2 formation and
the self-disproportionation of FAD or Cannizzaro reaction [63,
94, 95]. Since MeOH is not detectable and according to Fig. 4
up to 4% of the initial DOC converted to CO2, we conclude that
disproportionation reactions of FAD, as well as reverse aldol
condensation of FRU to GlAD, followed by the oxidation to
GA and the subsequent decarboxylation intensively took place.
Therefore, it is assumed that the sum peak #6 in Fig. S2
(Supplementary materials) corresponds to only LA probably
overlapping a peak of DHA.
On the contrary, the reaction of FRU to AA verifiably took
place under these reaction conditions (Fig. S2 –
Supplementary materials, peak #5) due to reverse aldol con-
densation and consecutive isomerization [47, 62, 96].
However, it has to be considered that AA could also have
LA and furans such as HMF and FU as educts [61]. Other
derivatives of HMF were FU due to the loss of its side group
and MF formed by dimerization and further thermal degrada-
tion as well as DHH as a nucleus for polycondensation of FU-
like compounds via their carbonyl group [54, 56, 87, 97–100].
So far, oxidation reactions of carboxylic acids and FU-
like compounds were proven under supercritical water con-
ditions or oxygen excess [58, 59, 97]. In this study, the
authors did not apply a high temperature and they exclude
an influence of the gaseous atmosphere inside the HTC
reactors, but the rPW still contains HNO3 which is able
to oxidize hydroxyl and aldehyde groups of FRU and its
degradation products [20, 101]. As a result, AA as a stable
intermediate product can be detected with a slightly in-
creasing concentration by enhancing the reaction time up
to 120 min (Fig. 3 and Table S1 - Supplementary materials)
[58]. Likely, a pH of 1.5 and increasing the reaction time
do not cause the oxidation of AA and correspondingly the
release of CO2 as observed by Fang et al. [61]. The phe-
nomenon that the pH value increased from 1.5 to 2.0 after
60 min of reaction time, as illustrated in Tab. S1
(Supplementary Materials), indicates that the dissociation
of HNO3 was pushed back by the strong presence of car-
boxylic acids such as LA, FA, and AA in PW [20, 101].
The remaining, not analytically identifiable reaction prod-
ucts of the reaction pathways from FRU to LaA via GlAD and
its keto-enol tautomers probably reacted further and this could
be the reason for the decreasing value of the ‘not detected’
species (Figs. 2 and 3). In the literature, keto-enol
tautomerization and its consecutive reactions, e.g., via LaA
by benzylic rearrangement and decarboxylation to EtOH, are
described as very fast under acidic conditions [56, 60, 82, 94,
102]. This is the reason why LaA as an intermediate product is
not verifiable at a HPLC analysis with a column temperature
of 70 °C. That means the peak #3 in Fig. S2 (Supplementary
materials) can be identified as GA but with a peak area below
its detection limit.
EtOH as a secondary product of this reaction pathway can
be verified but with a decreasing concentration till it is below
the detection limit at 120 min reaction time (Fig. S2 –
Supplementary materials, peak #7 and Fig. 3). This phenom-
enon is based on the oxidation via acetaldehyde (AAD) to AA
as well as CO2. Which of the reaction products dominate
depends on the initial O2 concentration. Since the concentra-
tion of O2 is higher than 150 mmol L−1, being already provid-
ed by HNO3− in rPW, the reaction to AAD is expected to
dominate [64, 103]. However, the carbon percentage of
EtOH is generally low which results in a not verifiable con-
centration of AAD. Whether the decarboxylation of
pyruvaldehyde (PAD) to AAD and the reverse aldol conden-
sation to FA occurred, could not be proven (Figs. 2 and 3).
Therefore, further acid-catalyzed reactions of LaA such as the
dehydration to propenoic acid and its decarbonylation to AAD
were neglected [60, 62, 85, 104]. GlAD in addition to ERY
could be formed from GLU in the open form via a reverse
aldol condensation (Fig. 2) but both are not detectable due to a
lack of isomerization to FRU. The reason why the not identi-
fiable carbon calculated on DOC is reduced by the increase of
reaction time may be related to the occurrence of decarboxyl-
ation and gas formation as well as the promotion of aldol
condensation reactions towards the formation of secondary
char (Fig. 2).
3.3 Hydrothermal carbonization of brewer’s spent
grains in water
As Table 1 illustrates, the BSG consists of 27.0% hemicellu-
lose, 22.5% cellulose, and 6.8% lignin as structural substances
[105]. As commonly known, hemicellulose is composed of
pentoses such as xylose (XYL) and ARA with few hexoses
such as GLU and mannose (MAN) in between and acts as a
connection between the fibers of cellulose and the 3-
dimensional aromatic structure of lignin [75, 106, 107]. The
recalcitrance of this hetero-matrix and the high crystallinity of
cellulose pose a major challenge to split it into its components
[108]. Additionally, the greater the particle size, the worse the
transfer of H2O in and the transfer of hydrolysis products
throughout the pores [109, 110]. The reason is that smaller
particles have a larger specific surface and thus show a larger
mass transfer resulting in a higher reactivity [111]. As Yan
et al. [112], Kim et al. [2] and Reza et al. [109] reported, within
the biomass particles, the bonds between the monomer of
hemicellulose could be easily split by releasing XYL (not
calibrated here) and crystalline cellulose began to hydrolyze
to produce anhydrosaccharides such as levuglucosan (not cal-
ibrated here) and furthermore its hydrolysis product GLU
[113, 114]. The split of the polymers led to the release of
acetyl groups connected with a pH decline till the length of
the oligomer was low enough to be solved and to be trans-
ferred through the pores of the biomass particles [115]. As

soon as there was a lack of acetyl groups the mass transfer
through the pores slowed down [14]. As a consequence, the
dehydration of released XYL from the fraction 500–850 μm
results in a carbon percentage of FU of about 19.0 C% related
to the DOC in PW, whereas that for the fraction 250–500 μm
is almost halved (10.3 C%) and that for 0–250 μm is already
around 0.5 C% after the heating time (Fig. 7). This dehydra-
tion reaction was catalyzed by the increase in carboxylic acids
such as FA till 30 min of reaction time and the resulting in-
crease of H+ protons [75].
FRU was either formed by hydrolysis of leftover SUC from
brewing or it was a product from isomerization of GLU under
the present weak acidic conditions as well as the influence of
metal compounds known as Lewis acid catalysts [77, 79–81,
116]. On the one hand, FRU and GLU were dehydrated to
HMF, with a carbon percentage of 1.9 C% in PW of the frac-
tion 0–250 μm but between 5.0 and 6.0 C% in PW of the other
fractions within heating time. On the other hand, the reverse
aldol condensation to AA, for GLU with GAD and ERY as
intermediate products, and FAD as well as GA and LaA was
initiated within heating time and with an increasing concen-
tration subsequently (Fig. 6 and Table S2 - supplementary
materials) [47, 62]. GA may also be a product from deamina-
tion of amines originated from amino acids [117, 118]. As a
consequence, when the carbon percentage of GA increases,
that of LaA decreases. As shown in Fig. 6 and Table S2
(Supplementary Materials), the reaction pathway of LaA via
decarboxylation and oxidation to AA can be verified by the
observation of firstly an increase, but after 30 min a decrease,
of the carbon percentage of EtOH and simultaneously an in-
crease in the carbon percentage of AA [119]. The increase in
carboxylic acids leads to a decrease of the pH to 3.5–4.0
outside the biomass particles and/or within the reaction medi-
um within heating time but then an increase occurs to 4.0–4.5
[105]. The reason is that under these reaction conditions, fur-
ther consecutive reactions occur. Representatives are the oxi-
dation of LA to AA as well as FA which obviously get
decarboxylated and does not react via cross-
disproportionation with FAD available at a high concentra-
tion. The formation of MeOH as second product of the last
described reaction cannot explicitly be verified because its
peak appears in the HPLC chromatograms of Fig. S3
(Supplementary materials, peak #10) at the same retention
time as LA and DHA [118].
Further sum peaks are those of PAD, GlAD and ERY (peak
#2) as well as LaA and GA (peak #3). Furthermore, there are
not specified peaks with #1 and #11. As substances for peak
#1 either extracted fragments of hemicellulose and/ or perhaps
maltotriose hydrolyzed from leftover, recalcitrant starch or
oxalic acid (OA) are possible [120]. Poerschmann et al. [76]
detected OA in the PW obtained from HTC of BSG at 200 °C
for 24 h by a HPLC system. OA can be formed either by
reduction of carbonyl groups of PAD or by oxidation of
Biomass Conv. Bioref.
hydroxyl group of GA [121]. However, the question raises if
calcium and magnesium, released from BSG (Table 1) during
hydrothermal treatment, cause the precipitation of OA as ox-
alates and affect its detectability [122–124]. Peak #11 has a
large area and is supposed to have a high impact on filling the
large gap in the DOC balance (designated as “not detected” in
Fig. 6). Surveying the chromatogram of the UV detector of
our HPLC system, peak #11 (Fig. S3 – supplementary mate-
rials) has to be a carboxylic acid [125]. According to the bul-
letin of the HPLC column provider BIO-RAD and consider-
ing the operation conditions of the system, it may be propionic
acid (ProA) in a sum peak with propenoic acid (ProeA) as
derivatives of LaA proven by Jin et al. [126]. Furthermore,
the reaction products of the keto-enol tautomerization of
GlAD but also the carbon percentage of proteins and amino
acids as well as phenols and fatty acids likely contribute to the
lack in the total ‘not detected’ species (Fig. 6 and Table S2 -
Supplementary Materials) [47]. On the one hand, the dehydra-
tion of LaA to AcA and its decarboxylation to AAD was so far
described at reaction temperatures higher than 340 °C or
strong acidic conditions [60, 62, 85, 104]. On the other hand,
it cannot be excluded at a pH of around 4(± 0.5) and with the
presence of alkali salts, which usually support the splitting of
C–C bonds. AAD showed a further reaction to AA and ace-
tone [85]. As final products of these reaction pathways, gases
like CO, CO2, CH4, and H2 were released, which was con-
firmed by HTC experiments under comparable conditions and
subsequent gas chromatography by Kruse et al. [26].
An explanation that the carbon percentages of HMF and
FU sharply decrease during HTC of particles with sizes great-
er than 250 μm within 30 min may be the fact that HMF gets
rehydrated to LA and, to a minor extent, also FA [127]. It is
obvious that they partly react via aldol condensation/addition
or Maillard reaction towards secondary or tertiary char.
However, the carbon percentage in HC is decreasing with
reaction time (Fig. 7). Since the amount of PG is increasing,
likely decarboxylation reactions of carboxylic acids dissolved
or embedded in secondary char are promoted at this stage of
hydrothermal conversion [20, 89]. This phenomenon has a
consequence for the Ceff of HTC of all particle size fractions
(Fig. 7) which firstly rises to more than 72% after 30 min, but
declines again by 2% and more, e.g. for HTC of the particle
size fraction of 0–250 μm, up to 120 min of reaction time.
The behavior of Ceff for HTC of the particle size fraction of
500–850 μm, starting from 67%, increasing to 74% after
30 min and subsequently decreasing to 71% at 120 min of
reaction time, constitutes an exception again. The reason is a
delayed mass transfer through the pores of biomass particles
affecting hydrolysis, dehydration, decarboxylation and con-
densation reactions [109, 110]. This evolution is clearly visi-
ble by a comparison of the SEM pictures of the HCs from the
“smallest” and “biggest” BSG particle size fractions in Fig. 8.
In the SEM picture “0–250 μm + H2O for 30 min,” there are
Biomass Conv. Bioref.

0.4

1,2,4-benzenetriol
Ethanol
carbon percentage of DOC [C%]

Formic Acid
Levulinic Acid
Methylfurfural

0.2 Furfural
5-hydroxymethylfurfural
Lactic Acid
Glycolic Acid
Acetic Acid
Formaldehyde
Sucrose
Glucose
Fructose

0
0 30 60 120 0 30 60 120 0 30 60 120
0-250 µm 250-500 µm 500-850 µm
reaction time [min]

Fig. 6 Carbon percentages of detected reaction products in the process waters from hydrothermal carbonization experiments with brewer’s spent grains
in distilled water in [mg L−1] for each particle size fraction related to the dissolved organic carbon (DOC)

already coagulating carbon spheres visible, whereas in the
reference picture (500–850 μm + H2O for 30 min) spheres
of different diameters can be seen. The SEM picture “0–
250 μm + H2O for 120 min” partly shows larger diameters
of spheres in the micrometer range. This insight goes along
with those of Jung et al. [40] and Sevilla and Fuertes [11] who
investigated the formation, growth mechanism, and structural
properties of carbon spheres from FRU and GLU at compa-
rable reaction conditions.
As Kruse et al. [85] stated, the formation of the phenolic
compound BTO, which is also involved in secondary char
formation, is depressed in the presence of salts originated from
biomass because other reaction mechanisms possibly domi-
nated. In the current study, the formation does not occur before
30 min of HTC of the fractions 250–500 and 500–850 μm.
For the fraction 0–250 μm, BTO may have already reacted to
form carbon spheres; however, the depression of its formation
due to its inertness can be supposed [128]. The occurrence of
further benzenediols as well as O-functionalized phenols, phe-
nolic acids (benzoic and cinnamic acid type) and
cyclopentenone is possible due to solvolysis of lignin, but it
occurs to a minor extent below 275 °C [51, 129]. As reported
by Ryu et al. [72] as well as Koch and Pein [73], these phe-
nolic compounds together with FU-like compounds are in-
volved in aldol condensation/addition reactions towards the
formation of secondary char.
Therefore, HCs obtained from HTC of BSG at 230 °C for
up to 120 min are generated as a consequence of complete
transformation of the hemicellulose rather than cellulose,
which can be assessed by thermogravimetric analysis (TGA)
of BSG and its HCs as well as by comparison of Figs. 1 and 11
[130]. The dTG curve shows that after 30 min of reaction time,
a fraction of the cellulose is still present in the HC that lowers
the overall carbon content. This means that the carbonization
is not fully completed, but strongly progressed after 120 min
[26]. A small peak between 300 and 400 °C for cellulose
 Biomass Conv. Bioref.

100 80
6 5 4
14 15 15 12 13
17 17 17
26 78
80 26 29 31
20 20
22 21 21 19
20 20 76
18
Percentage [%]

60
74

Ceff [%]
72
40
69 67 69 67
63 62 64 64 64 65 64
56 70

20
68

0 66

0-250 µm 250-500 µm 500-850 µm

reaction time [min]

C in HC C in PW C in PG Ceff

Fig. 7 Carbon distribution within the product phases after Hydrothermal PW = process water; PG = process gas; 0–250, 250–500, 500–850 μm =
Carbonization of brewer’s spent grains with water at 230 °C for 0, 30, 60 brewer’s spent grains fraction carbonized at 230 °C for 0, 30, 60 and
and 120 min. The process gas is assumed as 100% CO2. HC = hydrochar; 120 min in water; Ceff = carbon retention efficiency

supports this interpretation [1, 92]. As consequence and con-
sidering the contents of hemicellulose in comparison with
cellulose of BSG in Table 1 and the sharply declining carbon
percentages of FU towards HMF in Fig. 6 and Table S2
(Supplementary Materials), the resulting secondary char is
FU (XYL) based rather than HMF (GLU) based. However,
this insight confirms the cross-polycondensation of these
compounds as well as the self-condensation of FU, even
though Poerschmann et al. [76] reported its low reactivity.
According to van Zandvort et al. [17], this fact proves that
secondary char from XYL (FU) has a lower amount of ali-
phatic groups but more pseudo-aromatic groups and is more
chemically resistant.
BSG contains a substantial amount of proteins (21.4 wt.%,
Table 1), which are less stable in subcritical water and get
hydrolyzed to amino acids by breaking the peptide bond
[117, 131]. Nevertheless, this depolymerization was slower
than the hydrolysis of (poly-)saccharides because the peptide
bond in the protein is more stable than ß-1.4- and ß-1,6-glyco-
sidic linkages in starch and cellulose; however, it was catalyzed
under the present acidic conditions [132]. As a consequence, it
is foreseeable that reducing saccharides such as maltose origi-
nated from recalcitrant starch or glucose originated from
(hemi-)cellulose (Fig. 1), and furthermore, dehydration
products such as FU-like compounds are able to react with
the amine group of these amino acids via carbonyl groups
[133–136]. However, Wang et al. [137] found out for HTC of
food waste that enhancing the reaction temperature above
180 °C for 60 min of reaction time results in weakened
Maillard reactions due to degradation of the more reactive re-
ducing saccharides. This affects the carbon percentage in HC as
well as the Ceff negatively, as it can be seen in Fig. 7, as well as
rises the carbon percentage of “not detected” species shown in
Fig. 6 and Table S2 (Supplementary Materials). Nevertheless,
stable aromatic structures by conversion of carbon spheres into
an aromatic network and building blocks that favored N incor-
poration were formed. Additionally, amino acids got
decarboxylated to produce amines which on the one hand were
deaminated to produce carboxylic acids such as GA and am-
monia, and on the other hand underwent cyclization and con-
densation to generate pyridine-N in HC [36, 118, 137, 138].
According to Qiao et al. [139], the released ammonia catalyzed
polymerization reactions again and thus additionally promoted
the growth of carbon spheres (see in Figs. 8 and 12).
In the case of lipids, which are present in a minor amount
(2.3 wt.%, Table 1), the ester bonds were hydrolyzed into fatty
acids, such as linoleic or palmitic acid [36]. Whether these
fatty acids participated in HC formation is unclear. Instead,
Biomass Conv. Bioref.

Fig. 8 Scanning electron

microscopy of hydrothermal
carbonized (reaction
temperature = 230 °C; reaction
time = 0–120 min) brewer’s spent
grains of particle size 0–250 and
500–850 μm in water

2.0 BSG <1mm

BSG 500-850µm

BSG 250-500µm

BSG 0-250µm

1.5

1.0

0.5

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

Fig. 9 Coalification degree of hydrochars obtained from hydrothermal
carbonization of residual process water from 5-hydroxymethylfurfural
production and brewer’s spent grains as well as its mixture at 230 °C
for 0, 30, 60, and 120 min illustrated in the van Krevelen diagram by
plotting H/C atomic ratios versus O/C atomic ratios. Triangles and
squares refer to brewer’s spent grains’ particle sizes fraction 0–250 and
250–500 μm, respectively. Rhombs refer to the fractions 500–850 μm
and the cross stands for altogether (< 1 mm), each black colored. The
blue-colored shapes describe the Hydrothermal Carbonization experi-
ments with water (H2O) as reaction medium. The orange-colored shapes
describe the hydrothermal carbonization experiments with the residual
process water from 5-hydroxymethylfurfural synthesis (rPW) as reaction
medium. The orange-colored circles stand for the hydrothermal carboni-
zation of the pure residual process water 5-hydroxymethylfurfural
synthesis
 Biomass Conv. Bioref.

100 0.6
TG 0-250 µm + H2O
The H/C and the O/C atomic ratios of HCs produced from
TG 0-250 µm + rPW the particle size fractions 0–250 and 250–500 μm are reduced
TG rPW 0.5
dTG 0-250 µm till they resemble the character corresponding to bituminous-
80
dTG 0-250 µm + rPW rich brown coals. HCs from the particle size fractions 500–
dTG rPW 0.4
850 μm can be ranked as peat after the heating time, as lignin

-dm/dT [% K-1]
Mass loss [%]

after 30 and 60 min, and as low-rank brown coal after

60 0.3
120 min. Since the particle size fractions 0–250 and 250–
500 μm can be described as almost chemically equivalent
0.2
(Table 2), their HCs marginally differ in H/C and O/C atomic
40
ratios and partly appear in the van Krevelen diagram as over-
0.1
laying points.
Kruse et al. [26] and Ryu et al. [72] obtained comparable
20 0.0
200 400 600 800 results for the HTC of BSG as well as a mixture of model
Temperature [°C] substances including monosaccharides and phenolic com-
100 0.6 pounds. In summary, H/C ratios “…with H2O” and “…with
TG 0-250 µm + H2O rPW” are not significantly different from those of typical fossil
TG 0-250 µm + rPW
TG rPW 0.5 coal structures. The H/C ratios vary between 1.0 and 1.3. The
80
dTG 0-250 µm locations of the HCs produced from BSG in Fig. 9 are close to
dTG 0-250 µm + rPW
dTG rPW 0.4
those of anaerobically digested maize silage, which also rep-
resents a residual biomass from industrial processing (having
-dm/dT [% K-1]
Mass loss [%]

60
40
20
200 400 600 800
Temperature [°C]
Fig. 10 Thermogravimetric analysis of the hydrochars from the particle
size fraction 0–250 μm of BSG obtained after a reaction time of 30 min
(on the top) and 120 min (on the bottom) either by addition of distilled
water or residual process water from HMF production. BSG = brewer’s
spent grains; H2O = water; rPW = residual process water from HMF
production
they might be adsorbed on the HC surface and therefore could
be easily extracted for refining [140–144].
As can be seen in the van Krevelen diagram in Fig. 9,
reflecting also the physicochemical characteristics illustrat-
ed in Table 2, the particle size fraction 500–850 μm has a
slightly lower H/C and significantly higher O/C atomic
ratio, compared with the other particle size fractions.
Dehydration and decarboxylation along with aldol
condensation/addition and polymerization as well as aro-
matization are the dominating reactions during this coali-
fication, resulting in the release of H and O in the form of
H2O and CO2 [40, 51, 122]. However, the van Krevelen
diagram cannot display how complex the reactions are
(aldol condensation/addition, polymerization, aromatization)
on the pathway to secondary char. This emphasizes the
relevance of a more detailed liquid analysis to fully un-
derstand HC formation.
0.3
different biochemical characteristics from BSG), once carbon-
ized at 230 °C for 6 h [145]. Typical ranges for low-rank
brown coal from Germany with a VM higher than 52% are
0.2
between 0.7 and 0.9 [146]. The H/C ratios of HCs produced
from “…with rPW” decrease to typical condensed coal struc-
0.1
tures with ratios between 0.5 and 0.7. The area of anthracites
with H/C ratios below 0.5 was not achieved.
0.0
3.4 Hydrothermal carbonization of brewer’s spent
grains and residual process water
from 5-hydroxymethylfurfural synthesis
In this section, the results relevant to HTC runs with the addi-
tion of rPW to BSG instead of water are described and
discussed. This rPW consists of organic compounds reactive
towards secondary char formation such as 47.8 C% HMF,
3.1 C% LA, and 0.8 C% FA as well as 34.8 C% of their
precursor FRU (Table 3). More importantly, the supply of
H+ protons by remaining HNO3 influences mass transfer as
well as HTC reactions [47, 57, 83, 147]. H+ is expected to
promote a catalytic hydrolysis, usually achieved by the forma-
tion of AA via reverse aldol condensation or its addition as an
acid catalyst [3, 47, 62]. More precisely, it has a great catalytic
effect on acetal hydrolysis [108]. On the one hand, this can be
evaluated by comparing the thermographs of Fig. 10 taken
from HCs produced from the particle size fraction 0–
250 μm for 30 min (on the top) and 120 min (on the bottom)
in water and rPW. Since the peak between 230 and 300 °C in
the dTG disappears, hydrolysis of polysaccharides such as
hemicellulose but also hydrolysis of proteins to amino acids
by breaking peptide bonds took place [137]. Hydrolysis of
cellulose needed longer reaction time, which is confirmed by
the decreasing peak between 300 and 400 °C [148, 149].
Biomass Conv. Bioref.

0.6
Fig. 11 Dissolved organic carbon
(DOC) and concentration of
identified reaction products in the
HTC liquids of experiments with
brewer’s spent grains in residual 0.5

process water from 5-HMF pro-

duction in [mg L−1] for each par-
ticle size fraction related to the 1,2,4-benzenetriol

dissolved organic carbon (DOC) Ethanol

carbon percentage of DOC [C%]

0.4
Formic Acid
Levulinic Acid
Methylfurfural
0.3 Furfural
5-hydroxymethylfurfural
Lactic Acid
Glycolic Acid
0.2 Acetic Acid
Formaldehyde
Sucrose
Glucose
0.1 Fructose

0
0 30 60 120 0 30 60 120 0 30 60 120
0-250 µm 250-500 µm 500-850 µm
reaction time [min]

On the other hand, the results from an intensified hydro-
lysis can be retraced by comparison of carbon percentages
for SUC, FRU, and GLU in Figs. 6 and 11. However, the
difference between rPW and water as reaction medium, con-
sidering hydrolysis of (poly-)saccharides (Figs. 6 and 11),
carbon distribution (Figs. 7 and 13) as well as the carboni-
zation degree (Fig. 9) is small, which was unexpected. It
becomes apparent from Fig. 12 that the progress in reactions
towards HC up to 120 min depends on the particle size. The
reason may be that the transfer of polysaccharide fragments
through the tighter pores of larger BSG particles is limited
due to quick condensation and polymerization of HMF mol-
ecules on the BSG particles’ surface. Regions of particle
aggregates as well as films without defined structural fea-
tures, resulting from the degradation of GLU in the presence
of HNO3 (pH = 1) according to Reiche et al. [20], and as
they also appear in the SEM picture from HC “500-850 μm
+ rPW for 30 min” in Fig. 12 may be responsible for clog-
ging of pores. The consequence is that the hydrolysis of
polysaccharide fragments and di-saccharides is reduced.
Therefore, the supply of monosaccharides such as GLU
and FRU for dehydration to FU-like compounds is limited
and it has to be considered that both are also involved in the
reverse aldol condensation to AA as well as FAD and GA
[47, 62, 96].
Nevertheless, due to the addition of rPW, carbon percent-
ages for HMF and FU are still around 20.0(± 3.0) and
11.0(± 5.0) C% respectively in PW after the heating time
for HTC of all particle size fractions. This allows for
continuous accumulation of FU-like compounds (nucle-
ation), crosslinking via reactive O-containing functional
groups, appearing as oil droplets, and the subsequent poly-
merization (particle growth) towards formation of carbon
spheres (Fig. 12) [150]. Li et al. [151] and Luijkx et al.
[84] showed that phenolic compounds were also involved
by reacting with FU-like compounds. However, BTO as the
rehydration product of HMF occurs with an increasing car-
bon percentage in PW by enhancing the reaction time dur-
ing HTC of the particle size fraction 500–850 μm (Fig. 11
and Table S3 - Supplementary materials).
Taking the insights from the HTC of rPW into consider-
ation, this compound seems to react due to its concentration
and the pH of the reaction environment, because of its chem-
ical inertness [128]. Moreover, HMF is also rehydrated to LA
and FA in a molar ratio greater than 1:1 till 120 min of reaction
time, which implies an excess of FA again. Then, FA is obvi-
ously decarboxylated [20, 66, 88, 89]. Further decarboxyl-
ation reactions like that of LaA can also be verified not only
by gas formation but also by the presence of EtOH that gets
oxidized again. Since we consider peak #11 in the chromato-
grams of Fig. S3 (Supplementary materials) as ProA, its de-
hydration also takes place [126].
As it can be seen from the SEM picture of HC “0–
250 μm + rPW for 30 min” in Fig. 12, carbon spheres
of different diameters accumulate and start fusing, as also
observed by Jung et al. [40] within short reaction times.
The growth mechanism looks more advanced in compar-
ison with the results obtained from the HTC of pure rPW

Fig. 12 Scanning electron
microscopy of hydrothermal
carbonized (reaction
temperature = 230 °C; reaction
time = 0–120 min) brewer’s spent
grains with a particle size of 0–
250 and 500–850 μm in residual
process water from synthesis of 5-
hydroxymethylfurfural; rPW =
residual process water from syn-
thesis of 5-hydroxymethylfurfural
(Fig. 5) or BSG in water (Fig. 8) for the same reaction
time. However, according to Reiche et al. [20] in the case
of low pH and thus high H+ concentration, the internal
condensation was faster than the formation of carbon
spheres resulting in a distribution of shapes (Fig. 5), or
in the case of pH > 3 and at intermediate H+ concentra-
tion, the polymerization was slowed down to enable the
diffusion-controlled formation of a homogenous emulsion
of carbon spheres. In other words, the latter results in
carbon spheres of a larger diameter, which may also be
influenced by dissolved salts, but with a less extended
conjugated network. The carbon spheres shown in the
SEM picture “0–250 μm + rPW for 120 min” have a
diameter around 10 μm which was so far obtained from
hydrothermal treatment of FRU at 180 °C under neutral
conditions, GLU at 220 °C in diluted HNO3 for longer
reaction times as well as a mixture of monosaccharides
(fructose, xylose) with phenolic compounds (phenol, res-
orcinol and phloroglucinol) [20, 72, 152].
Furthermore, the acid anion concentration reduces the re-
pulsion of formed carbon spheres, and as consequence, the
coalescence proceeds faster [40]. After 120 min of reaction
time for both particle size fractions 0–250 and 500–850 μm,
Biomass Conv. Bioref.
the shapes of carbon spheres appear similar to those of HCs
produced from XYL (FU) and GLU/FRU (HMF), whereas
they are embedded in an aromatic network [109, 130, 133].
This indicates intramolecular condensation and the formation
of an aromatic network starts forming after 30 min of reaction
time, which is additionally confirmed by the constant carbon
percentages of HC illustrated in Fig. 13. However, a slight
decline in carbon percentage of HC after 30 min reaction time
is observed, which points out a limited but continuing transfer
of poly- and/ or di-saccharides through the biomass pores. As
can be seen in Fig. 11 and Table S3 (Supplementary Materials)
the release of GLU from hydrolysis fails to appear: This re-
ducing saccharide seems to react with present amino acids to
N-containing heterocycles, which enhances the tertiary char
fraction of the final HC. This becomes clear by comparison of
the “not detected” species in Figs. 6 and 11. After 120 min, the
DOC is reduced to a similar value for water and rPW variants,
which proves that the usage of rPW in the HTC process is a
suitable option with a positive impact on the HC formation.
Also, the composition of the PW is almost similar, showing
that the rPW has been successfully recycled. As shown in
Figs. 7 and 13, the carbon release as PG is even lower. The
consequence is that the Ceff for the particle size fraction 0–
Biomass Conv. Bioref.

100 3 3 120
6 4 6
12 8 11
13 14 17
17
21 19 110
17
80 26 32 32
20 19 19 17
15 14

100
Percentage [%]

60

Ceff [%]
90

40
74 75 74
68 68 68 68 69 69 69 80
65 65

20
70

0 60

0-250 µm 250-500 µm 500-850 µm

reaction time [min]

C in HC C in PW C in PG Ceff

Fig. 13 Carbon distribution within the product phases after hydrothermal HC = hydrochar; PW = process water; PG = process gas; 0–250, 250–
carbonization of brewer’s spent grains at 230 °C for 0, 30, 60 and 120 min 500, 500–850 μm = particle sizes of brewer’s spent grains carbonized at
with residual process water from the synthesis of 5- 230 °C for 0, 30, 60 and 120 min in residual process water from HMF
hydroxymethylfurfural. The process gas is assumed as 100% CO2. production; Ceff = carbon retention efficiency

250 μm is enhanced by 31% and for both other fractions by
27% up to 120 min of reaction time in comparison with HTC
in water. In total, 89 and 77% DOC of rPW is converted to
carbon in HC (Figs. 7 and 13). In addition to this, there is
another positive aspect: while in the studies of Uddin et al.
[21], Stemann et al. [22], Weiner et al. [24] and Kabadayi et al.
[23] the HC yield increased by 5–10 wt.% by PW recircula-
tion, in this study, an increase in HC yield of 15–35 wt.%
(values not illustrated) was achieved as from 30 min of reac-
tion time, albeit depending on the BSG particle size.
Additionally, the results from Kambo et al. [18], Weiner
et al. [24], and those from this study show that the quality in
terms of HC’s carbon percentage (Fig. 13) as well as its car-
bonization degree improved by PW addition (Fig. 9).
However, the PWs in the abovementioned publications were
recirculated from HTC of different biomasses. These were
loblolly pine, poplar wood chips, miscanthus, unbleached tis-
sue paper and a mixture of grape pomace, orange pomace and
poultry litter, whose PWs mainly consisted of less reactive
compounds such as short-chain carboxylic acids (AA, LA,
GA, FA). The consequence is that the research groups in-
creased the carbon contents but obtained lower mass yields
of HC due to intensified hydrolysis as well as reverse aldol
condensation reactions [24]. The reason why Kambo et al.
[18] also achieved an improvement in HC quality was the
recirculation of the PW from the HTC of miscanthus at
260 °C for 5 min which contained reactive dehydration prod-
ucts towards HC formation and provided acidic conditions
(pH = 2.68).
4 Conclusion
This publication covers two aspects, the influence of the par-
ticles size of the feedstock and the addition of rPW from HMF
production which contains reactive intermediates towards sec-
ondary char formation. Therefore, the substitution of water
with rPW may enhance the efficiency of HTC of BSG.
HTC of the smallest particle size fraction 0–250 μm of
BSG in water shows the worst results regarding its carbon
percentage in HC as well as Ceff due to a larger surface and
a greater reactivity. As a consequence, poly- and monosaccha-
rides which are relevant for Maillard reactions and thus for the
enhancement of HC yields by the formation of tertiary char are
mainly degraded to carboxylic acids. This indicates that HTC
occurs via soluble intermediates and mainly results in carbon
spheres (secondary char). The particle size fraction of BSG
(250–500 μm) with the greatest presence shows constant car-
bon percentages in HC as well as a constant Ceff up to 120 min
of reaction time, even though rPW is added. The reason is that

the transfer of polysaccharide fragments through BSG particle
pores and its hydrolysis to reducing saccharides is limited and
thus their supply is sustainable for reacting with amines. The
result is a stable structure consisting of carbon spheres (sec-
ondary char) formed by aldol condensation/addition and N-
containing heterocycles (tertiary char) resulting from Maillard
reactions embedded in an aromatic network (primary char)
formed by a direct conversion of polysaccharide fragments.
Indeed, the variation in the composition of the particle size
fractions seems negligible. Nevertheless, investigations with
additional experimental series have to be continued because
Maillard reactions as well as their influence on yields and
characteristics of HCs do not seem completely clarified (ter-
tiary char). In particular, tests with reaction time higher than
120 min could allow clarify this issue. In the case of fats,
which are considered as less reactive under subcritical water
conditions, investigations on their interactions in Maillard re-
actions become important.
As a whole, the recirculation of PW is successful when
dissolved saccharides and FU-like compounds are available
since the beginning of the upcoming HTC run. There is a
positive impact on the conversion of the larger particle sizes
concerning their structural substances, starch, and extractives
(proteins, fats), to a stable aromatic structure containing N-
heterocycles with an acceptable yield. The more DOC is re-
duced from the recirculated PW and transferred to HC, the
more efficient the HTC runs and the less problematic the
PW regarding its chemical oxygen demand for further
treatments.
Acknowledgments The authors would like to thank the
students Johannes Winkler and Markus Götz from the University of
Hohenheim for their efforts in experimentation and analytics as well as
Sonja Habicht, Hermann Köhler, and Armin Lautenbach from the
Institute of Catalysis Research and Technology of the Karlsruhe
Institute of Technology for the technical support regarding the analysis
of solid and liquid samples.
Funding information The work was financially supported by the Federal
Ministry of Education and Research within the project Humboldt
Reloaded during the winter semester 2017/2018.
Compliance with ethical standards
Conflict of interests The authors declare that they have no conflicts of
interest.
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