Journal of Thermal Analysis and Calorimetry

https://doi.org/10.1007/s10973-019-09117-4

Enthalpy change during hydrothermal carbonization of biomass:

a critical review
Matteo Pecchi1   · Francesco Patuzzi1   · Daniele Basso1,2 · Marco Baratieri1 

Received: 18 June 2019 / Accepted: 26 November 2019

© Akadémiai Kiadó, Budapest, Hungary 2019

Abstract
A remarkable number of scientific papers are available in the literature about the process of hydrothermal carbonization
(HTC), also called wet or hydrous pyrolysis, applied to biomass substrates. However, the biggest share of it focuses on the
characterization of HTC products obtained from different feedstocks. Only a few works are available on the process ther-
modynamics, particularly about the determination of the enthalpy change and the related heat release or absorption during
HTC, which is a key parameter to understand the nature of the process and to evaluate the heat requirements for the design
of industrial scale HTC plants. The present review summarizes the research carried out with the aim of assessing the process
enthalpy for HTC. Two main approaches have been identified and described, and the research works are sorted into two cat-
egories: enthalpy calculation based on the direct application of the Hess’s law and enthalpy evaluation based on differential
heat measurement. The hypotheses and results obtained by the different authors are critically analysed and discussed, and
directions for further research are proposed.

Keywords  Hydrothermal carbonization (HTC) · Process enthalpy · DSC · Hess’s law

List of symbols Introduction

o
ΔHHTC Process enthalpy of HTC ( MJ kg−1)
ΔHf,x Standard enthalpy of formation of the x chemical
o
Hydrothermal carbonization (HTC), also called wet or
or phase ( MJ kg−1) hydrous pyrolysis, is a thermochemical process through
ΔHcomb Standard enthalpy of combustion ( MJ kg−1)
o
which wet biodegradable substrates are treated to obtain
t0 Start of temperature program (s) two main products: hydrochar and process water. Hydro-
tend End of temperature program (s) char is a carbonaceous material with chemical and physi-
Preaction Power curve measured during the reaction cal characteristics similar to natural peat or lignite [1–4]
( W kg−1) that has garnered the attention of both scientific and indus-
Pblank Power curve measured during the blank ( W kg−1 trial communities for its potential applications. It has been
) investigated by several authors as a possible solid renew-
able energy carrier [5–8], as a soil improver [9–11], as
a precursor of both activated carbons [12–14] and filters
[15], and for other innovative uses [16]. Depending on the
* Matteo Pecchi feedstock and on the process conditions, different chemi-
matteo.pecchi@natec.unibz.it cals can be found in the process water [17, 18]. Acetic
Francesco Patuzzi acid and phenols are the chemicals usually present in the
francesco.patuzzi@unibz.it highest concentration [2, 19]. During this process, the
Daniele Basso feedstock is heated up to temperatures ranging between
daniele.basso@unibz.it; d.basso@hbigroup.it 180 and 250 °C in a water environment, while the endog-
Marco Baratieri enous-developed pressure maintains water in its liquid
marco.baratieri@unibz.it state. Typical residence times range from several minutes
1
to some hours. The ratio between the masses of dry feed-
Faculty of Science and Technology, Free University
of Bozen - Bolzano, Bolzano, Italy stock and water is called biomass to water ratio (B/W),
2
and it typically ranges from 0.1 to 0.3 [20]. During the
HBI S.r.l, Via Volta 13/A, 39100 Bolzano, Italy

13
Vol.:(0123456789)

process, the feedstock first undergoes hydrolysis reactions,
and subsequently decarbonylation, decarboxylation, and
re-polymerization [1]. This reduces oxygen and hydrogen
quantity in the solid phase, increasing its carbon content.
Indeed, the first application of HTC aimed at improving
the fuel characteristics and dewaterability of low-quality
coals [21, 22], but nowadays this technique is seen as a
possible way to produce renewable solid fuels [3, 23] or
valuable by-products, starting from waste or biomass feed-
stocks [24, 25].
In recent years, the implementation and tuning of HTC
process have been recognized as a potential way to sustain-
ably manage wet biodegradable residues and to produce
valuable by-products [26]. However, the thermodynamic
nature of this process is not yet completely understood,
mainly because of the great variability in the physical and
chemical characteristics of the feedstocks and secondly
because of the wide range of process conditions. Indeed,
few works have dealt with the estimation of the HTC pro-
cess enthalpy, also called heat of reaction.
The determination of the exothermic or endothermic
nature of the process (characterized by positive and nega-
tive heat of reaction, respectively) and of its magnitude is
important to deeply understand the thermodynamic prin-
ciples behind the HTC process, to evaluate its heat duty,
and for the design of industrial reactors. Two different
methods to determine the enthalpy are typically applied.
In the first one, the process enthalpy change is calculated
based on the direct application of the Hess’s law, relying
on the evaluation of thermal properties of both reactants
and products. In the second one, the enthalpy value is
obtained directly by measuring the thermal power
exchanged by the system during the process. Another main
problem with this topic is the lack of a comprehensive and
critical analysis on the hypotheses and results obtained
through the two aforementioned approaches. Numerous
works review the main findings concerning the HTC pro-
cess in general, but among those papers, only few men-
tioned also the process thermodynamics. Titirici et al. [27]
described the process as spontaneous and exothermic,
reporting a value of − 5.78 MJ kg−1 glucose for the HTC
ent halpy, based on the reaction
C6 H12 O6 → C6 H4 O2 + 4H2 O . This behaviour has been
attributed to the dehydration of carbohydrates, which can
release up to one third of their energy content while water
is produced.
Two years later, a literature survey by Funke et  al.
described again the process as exothermic, asserting that
the released heat to produce coal-like materials is in the
range of 10–15% of the energy content of the feedstock
[28]. Another literature survey concerning HTC was later
published by the same authors [29]. Funke et al. attributed
13
M. Pecchi et al.
the exothermic behaviour to the dehydration and decarbox-
ylation reactions, which are responsible for both oxygen
and hydrogen decrease within the feedstock. In the fol-
lowing year, a summarizing table collecting the results of
articles dealing with the determination of the HTC process
enthalpy for coal and biomass was reported in the sup-
plementary data of a research article by the same authors
[30].
In another review paper published the same year by Libra
et al., a value of − 1.60 MJ kg−1 cellulose for the enthalpy of cel-
lulose HTC was reported [1], based on the stoichiometric
relationship given by Bergius [31]. However, Libra et al.
highlighted the limit of that relationship, since the liquid
products originated during the process were neglected. A
value of − 1.00 MJ kg−1 cellulose was also reported in Ref. [1]
based on unpublished data by Funke et al. Those values were
in the same range as the ones obtained with dry pyrolysis
(between − 0.4 and − 0.7 MJ kg−1 cellulose [32]), similar to HTC
from the chemical point of view, but performed in inert
atmosphere instead of in water environment. The review [1]
concerned also mild HTC, for which the authors supposed a
slight endothermic nature of the HTC process, based on the
similarities with mild pyrolysis, on the endothermic nature
of the hydrolysis of cellulose [33] and on the slower kinetics
of dehydration and decarboxylation reactions at mild condi-
tions. Coronella et al. [34] supported the exothermicity of
wood HTC, which exothermic intensity is proportional to the
process severity. This idea was based on the results obtained
by Funke and Ziegler [30] that used differential scanning
calorimetry (DSC) for the measurements and reported values
around − 1.00 MJ kg−1 feedstock.
The aim of this work is to summarize the research regard-
ing the evaluation of the HTC process enthalpy change and
to critically analyse the two possible approaches adopted
to fulfil this objective. Best practices in the methodologies
(direct application of the Hess’s law and calorimetric meas-
urements) are highlighted. Firstly, the theory behind these
methods is described together with the main hypotheses and
limitations, and then, the related research articles are pre-
sented, sorted according to the two categories. In the end, a
summary and discussion of the different results are given,
trying to identify the most likely range of values and provid-
ing a reference for future research.
Determination of the process enthalpy
change
Direct application of the Hess’s law
This approach is based on the direct application of the
Hess’s law, which states that the total enthalpy change of
a multi-stage chemical reaction is equal to the sum of all
Enthalpy change during hydrothermal carbonization of biomass: a critical review

the enthalpy changes occurring during each intermediate negligible compared to the specific enthalpy of formation
stage. Then, the enthalpy of a reaction can be obtained as of the chemicals itself [35].
the difference between the standard enthalpy of formation For the gas phase, the standard enthalpy of formation is
of products and reactants for a process. evaluated as the sum of the standard enthalpy of formation
Concerning HTC, this is summarized in Eq. 1, where the of the present gas species.
enthalpy change at standard conditions ( ΔHHTC o
 ) of its sim- All these data must be obtained from chemical and
plified process reaction is equal to the difference between physical analyses on the reactants and products, and thus,
the standard enthalpy of formation of the products ( ΔHf,o prod ) a big effort is required in the development of accurate
and the standard enthalpy of formation of the reactants, i.e. experimental set-up and analysis protocols.
sum of feedstock and water enthalpies of formation An important problem is the determination of the com-
( ΔHf,o feed , ΔHf,water
o
). pounds solved within the liquid phase and their concen-
( ) trations. Among the chemical species that can be found
o
ΔHHTC = ΔHf,o prod − ΔHf,feed
o o
+ ΔHf,water (1) within the liquid phase, only few have significant concen-
trations to influence the energy balance. The identification
The standard enthalpy of formation of the products con- and quantification of these components are still a complex
sists of the sum of the standard enthalpy of formation of the matter, and important species may be neglected, since the
solid hydrochar ( ΔHf,o p.sol ), of the liquid water with the rela- literature available about this topic is not so wide. As for
tive solutes ( ΔHf,o p.liq ), and gaseous products ( ΔHf,p.gas
o
): the gas phase, the literature is fairly unanimous on its com-
position, being this phase mostly composed of CO2 [1,
o
ΔHf,prod = ΔHf,o p.sol + ΔHf,o p.liq + ΔHf,o p.gas (2) 36], with only limited concentration of other compounds.
The benefit of this approach is that the measurement
This allows obtaining the final relation for the determina- of the actual heat fluxes in the reactor is not required,
tion of the process enthalpy change ΔHHTC o
: since this value is not present in the energy balance. This
( ) avoids the problems associated with the determination of
o
ΔHHTC = ΔHf,o p.sol + ΔHf,o p.liq + ΔHf,o p.gas − ΔHf,feed
o
+ ΔHof,water
the heat losses and reactor thermal inertia, or the need to
(3) carry out a blank run to measure these losses. The only
For a solid material with known composition necessary equipment is a thermocouple to evaluate the
( Ca Hb Nc Sd Oe ), the standard enthalpy of formation can be temperature of the reactor during the measurement, when
estimated applying the Hess’s law to its combustion reaction: a reactor is used. However, one drawback of this approach
∑ is the impossibility to measure the time profile of the heat
Ca Hb Nc Sd Oe + gO2 → Xi release in the reaction, since it is based on a thermody-
products
(4)
namic equilibrium balance that considers only the initial
Xi are the combustion products, and g is a stoichiometric and final state of the process. It is indeed possible to cal-
factor. The higher heating value ΔHcomb o
is associated with culate the value of the enthalpy only for single values of
the reaction, and it can be determined experimentally from residence time and temperature for each test run. Thus, the
calorimetric measurements. The standard enthalpy of forma- dependence of the process enthalpy change versus time
tion of the gaseous combustion products ( ΔHf,X o
 ) can be (when for example the process temperature is fixed) can
be evaluated only with a series of experiments of different
i
retrieved from the literature, and the standard enthalpy of
formation of molecular oxygen is equal to zero. It is then duration at the same temperature, which would require
possible to compute the standard enthalpy of formation of considerable efforts.
the initial feedstock ( ΔHf,o C H N S O  ) using the following In summary, the main advantages of the direct applica-
equation:
a b c d e
tion of the Hess’s law for the enthalpy evaluation of the
HTC process are the possibility to adopt a simplified lay-
ΔHf,o C H N S O =
∑ � o � o out of the HTC reactor, since there is no need to measure
ΔHf,X − ΔHcomb (5)
a b c d e
products i
heat fluxes and thermal losses, and to analyse specimens
with mass in the range between 0.1 and 25  kg , avoiding
For what concerns the liquid phase, its enthalpy is cal- problems linked to the biomass dis-homogeneity. The main
culated as the sum of the enthalpy of formation of water drawback is the high number of analyses to be performed
( ΔHf,water
o
 ) and of solutes in it ( ΔHf,solute
o
 ). The enthalpy of on the solid, liquid, and gaseous phase to run enthalpy
mixing relevant to the various solutes should be taken into calculations. The liquid phase requires the biggest effort,
account, but for small concentrations of acid chemicals due to the remarkable number of dissolved chemicals that
(in the range of few percentage points, as it is the case are present in significant concentration.
with HTC process liquids), its value can be considered

13

Differential calorimetry measurements
This approach relies on the direct measurement of the ther-
mal power exchanged by the system during the process.
There are mainly two apparatuses available to perform
such measurements on HTC.
The first relies on the use of high-pressure crucibles in
a standard differential scanning calorimeter (DSC). The
DSC allows to evaluate the heat of a reaction as the differ-
ence in the thermal fluxes on the sample and on a reference
blank crucible, when the two crucibles follow the same
temperature program [37, 38].
The second possibility requires the construction of a
high-pressure, relatively high-temperature reactor, where
the power consumption during the runs can be measured
using a power meter. Thermocouples and pressure gauges
are required to measure the relative parameters, while
the internal temperature is controlled by means of elec-
trical resistances. The thermal power exchanged by the
system when the process takes place is recorded during
a temperature program. The thermal power exchanged by
a similar system, during the same temperature program,
but where no reactions take place is recorded (this run
is called “blank”). Two curves of power versus time are
generated ( Preaction and Pblank for the process run and blank
case, respectively). The system used for the blank run must
be as similar as possible to the target system and must be
subjected to the same temperature program, so that the
blank case curve approximates the thermal losses of the
original system for the considered temperature program.
The process enthalpy can then be obtained subtracting
the power curve of the blank run from the one obtained
with the original system, by integral difference on the
interval between the beginning of the experiment t0 and
the end of it tend:
tend
[ ]
ΔHHTC = ∫ Preaction (t) − Pblank (t) dt (6)
t0
For the HTC process, three main possibilities are avail-
able for what concerns the blank case, as it is explained in
Fig. 1, where a simplified scheme of the possible methods
for the HTC enthalpy measurement using both high-pres-
sure DSC and an ad hoc reactor is shown.
In the first method, only available for the DSC appa-
ratus, one single run is performed, filling the reference
cell with the same amount of filler (i.e. water) used in the
sample crucible [37]. The instrument measures the differ-
ence in the thermal power exchanged by the two crucibles,
and thus, the water effect is compensated by the mass in
the reference cell. This option is not available for the ad
hoc reactor, since only one operative volume is available.
13
M. Pecchi et al.
The second method, available for both apparatuses, is the-
oretically equal to the first one, but two runs are performed
per each measurement. The blank run consists in the thermal
program applied to a crucible or a reactor filled only with
water, with the same mass that is added to the feedstock in
the process run. In the process run, the biomass is added to
the same amount of water. In this way, the heat absorbed by
the water and the thermal losses of the system are recorded
and can be subtracted from the original system power curve
to obtain the process enthalpy [37].
In the third method, the system, composed of feedstock
and water, is subjected to the same temperature program
twice [39]. The temperature program must be long enough
to complete the process. The second run allows the meas-
urement of the blank power curve, since no reaction takes
place in it [38]. The third method differs from the previous
two for theoretical reasons. When using pure water for the
blank curve determination, the difference in the heat capac-
ity between free water (in the blank specimen) and bounded
water (in the sample one) is not considered [40, 41]. A
source of error that is removed using this third method is
the difference in the position of the crucible between the run
and the blank that is unavoidable using the first and second
method [39]. In the third case, when the exhaust system is
used for the blank curve determination, the crucible is not
moved between the run and the blank, and thus, the error
related to the position is eliminated. The difference between
the heat capacity of the HTC products in the blank and of the
heat capacity of the mixture of reactants and products dur-
ing the first run must be accounted for during the enthalpy
computation [39].
These methodologies allow one to measure the time pro-
file of the enthalpy release or absorption. The use of a DSC
apparatus permits a very precise measurement of the process
enthalpy, and several tests can be performed in the same day.
The main problem is the very small dimension of the cruci-
bles in standard DSC machines. This may create problems of
dis-homogeneity in the specimens, and even if the heat flux
measurement is very precise, it may not be representative
of the real substrate. Furthermore, the very small sample
mass does not allow for chemical analysis of the products,
since sampling of the gas is not possible, and the process
yields too little quantities of liquid and solid. Some models
of DSC allow to use samples of few grams, but they do not
permit to perform all the analyses that a mass and energy
balance model would necessitate. These types of DSC also
require the use of very low heating rates to obtain the repro-
ducible results, thus being far from typical industrial prac-
tices. Another critical issue may be the entrapment of air
inside the empty part of the high-pressure crucible, since it
is not possible to fill it completely to avoid liquid to leak out
during the sealing procedure or to remain inside the screw-
like tread, as it would be lost as the endogenous pressure
Enthalpy change during hydrothermal carbonization of biomass: a critical review

Fig. 1  Schematics of the dif- High-pressure DSC Ad-hoc

ferential calorimetry method
for the determination of the Ref. cell Sample cell reactor
standard enthalpy of the HTC

1st Method
process using DSC and ad hoc
reactor Single
run

1st run

2nd Method 2nd run

1st run
3rd Method

2nd run

Water Feedstock Reacted products

develops. In this case, it is not possible to flush it out by
means of an inert gas flux, as the crucible is tightly sealed.
Possible solutions may be the use of high filling ratios to
reduce the air entrapped to a minimum (increasing the risk
of mass loss during the operation and thus of discarding the
measure) or utilizing a glove box that allows to work in an
inert atmosphere until the crucibles are sealed.
The use of a high-pressure reactor allows to perform
chemical analyses on the products. Also, air entrapment
can be avoided by flushing an inert gas inside the reactor
before its sealing. The main problem is a less precise heat
and power measurement with respect to the DSC apparatus,
due to the larger mass and to the layout, which is usually not
optimized for the power measurement.
In summary, the main advantage of the use of calorim-
etry to evaluate the enthalpy change of the HTC process
is the possibility to accurately measure the actual heat of
reaction for the whole temperature profile. On the one
hand, higher precisions and higher testing frequencies
can be achieved with high-pressure DSC with respect
to ad hoc reactors; on the other hand, the use of ad hoc
reactors allows to use higher specimen masses, avoiding
dis-homogeneity problems, as well as the possibility to
semi-continuously sample solid, liquid, and gas products
to perform further analyses. Air entrapment can also be
avoided by flushing an inert gas before the reactor sealing.
The main disadvantages are the risk of inhomogeneity and
the impossibility to analyse the products when using high-
pressure DSC, while ad hoc reactors usually incur smaller
precision and long experimental time duration (due to the
high thermal inertia).

13

Literature review of the state of the art
Direct application of the Hess’s law
The first attempt to calculate the HTC process heat for
pure cellulose was based on the enthalpy balance between
the solid feedstock and the produced char,CO2 and water
[31]. The process was run at high temperature (310 °C)
and long residence time (64 h), thus being more in the
hydrothermal liquefaction field (HTL) than in the HTC one
[42]. A value of − 1.78 MJ kgcellulose was obtained, suggest-
ing an exothermic behaviour. However, the liquid and gas-
eous products other than CO2 were neglected in the energy
calculations, as reported years later by other authors [28].
Similar results were obtained in other works, which used
peat and lignite as feedstock and obtained values of pro-
cess enthalpy in the range of 0–4.3 MJ kgfeedstock [43–46].
Almost 50 years later, a similar approach was adopted
to calculate the process enthalpy change of HTC of glu-
cose as the difference of the heating values of the products
and the reactants [47]. The temperature investigated was
between 300 and 350 °C, thus being in the HTL field.
Indeed, mostly gas and oil were produced and the solid
products, which were called char, were soluble in acetone.
The authors obtained enthalpy change values in the range
from − 1.00 to − 2.00 MJ kgfeedstock.
One year later, Hess’s law was applied to the HTC pro-
cess to evaluate its enthalpy change using loblolly pine as
feedstock [48]. Temperatures of 200, 230, and 260 °C were
investigated, and the reactor was maintained at the process
temperature for 5 min and then was rapidly quenched in an
ice bath. The liquid streams were considered in the energy
balance. The gas phase was modelled as being composed
of only CO2 since its percentage in the gas was measured
above 90%. The volatile fatty acids in the liquid were
assumed as pure acetic acid, due to its greater concen-
tration with respect to other chemicals. The precipitates
formed during the process were treated as glucose for reac-
tion temperatures up to 200 °C, or as 5-hydroxymethylfur-
fural for higher reaction temperatures.
The authors found that the reaction was slightly endo-
thermic, with endothermicity decreasing with increased
severity of the process. The enthalpy values ranged from
+0.25 to +0.56 MJ kgfeedstock  , with an uncertainty from
0.72 to 0.92 MJ kgfeedstock  . Due to the very low abso-
lute values of process enthalpy (around 2% of the initial
heating value of the feedstock) and the very high uncer-
tainty, a marked behaviour of the reaction could not be
defined. These results may have been due to the very fast
process performed. To verify this, a very similar experi-
mental design was used five years later by Cuvilas et al.
[49], but the process temperature was maintained for
13
M. Pecchi et al.
150 and 350 min. Hess’s law was directly applied to the
process, obtaining enthalpy values of − 2.53 and − 3.47
MJ kgfeedstock for 150 and 350  min, respectively. When
a 0.1  M solution of H2 SO4 was used instead of water,
enthalpy values of − 7.84 and − 8.69 MJ kgfeedstock were
obtained for 150 and 350 min, respectively.
The first prototype of an ad hoc reactor used to measure
the standard enthalpy of HTC consisted in a 25 dm3 auto-
clave for concrete absorption test, equipped with sensors
for the power consumption measurements [50]. The same
article was also published few months later in a German
version [51].
In this paper, the enthalpy of the HTC process was also
evaluated by the direct application of the Hess’s law, consid-
ering only the solid feedstock and char. The values obtained
were in the range from − 4.3 to − 5.7 MJ kgfeedstock . Those
results were compared to the ones obtained by direct meas-
ure of the heat consumption of the reactor during the HTC
of biomass, and during a reference run with only water, used
to evaluate the radiation and convection energy losses of the
reactor. The result was − 7.0 MJ kgfeedstock , but the authors
suggested the use of a continuously working and better insu-
lated autoclave to improve accuracy.
To try to improve the modelling of the energy content
of the liquid phase, its calorific value was computed as a
function of its elemental analysis and ash composition [52],
using a unified correlation for solid, liquid, and gaseous fuels
[53]. The enthalpy value was obtained by energy balance,
based on the computed higher heating value of the solid and
liquid solutes. The gas was considered as composed of only
CO2 , and the elemental composition of the solutes in the liq-
uid phase was determined by mass balance. The authors con-
sidered bulk reactions for the different feedstock, and, with
the estimated standard enthalpies for the solid and liquid
solutes, obtained a different value for the standard enthalpy
of reaction for each different substrate. The results were
negative in all the cases, so the reaction was characterized
as exothermic, ranging from − 0.68 to − 2.62 MJ kgfeedstock.
Differential calorimetry
Regarding this approach, two research works must be cited
as a reference of what has become one of the main tech-
niques for the evaluation of the standard enthalpy in pres-
surized processes.
The first one used DSC to investigate the kinetics of cel-
lulose and glucose hydrolysis and the reaction heat associ-
ated with it, in a pressurized and acid environment [33].
Even though HTC was not the objective of the research,
this article provided a useful reference for later works in the
HTC field.
The second one used DSC to investigate the energetics
of pyrolysis under pressure [32], with moisture content of
Enthalpy change during hydrothermal carbonization of biomass: a critical review
the feedstock below 26% on a mass base. Even though not
directly dealing with HTC, the main difference between this
work and later ones lays in the amount of water in the pres-
surized crucible, providing again an important reference for
later research.
The first article that used differential heat measurements
to determine the standard enthalpy of HTC obtained a value
of − 7.0 MJ kgfeedstock [50, 51]. The experimental set-up was
already described in “Direct application of the Hess’s law”
section above.
The first work dealing exactly with DSC determination of
process enthalpy for HTC was published almost two years
later [30]. Glucose, cellulose, and poplar wood were used
as feedstock and treated at 240 °C for around 200 min in
pressurized crucibles with capacity of 30 nm3 (around 4 mg
of sample). The results witnessed the exothermic behaviour
of the process in all cases, with values of standard process
enthalpy change of − 1.06, − 1.07, and − 0.76 MJ kgfeedstock
for glucose, cellulose, and wood, respectively. The stand-
ard deviation was 0.16, 0.11, and 0.27 MJ kgfeedstock  ,
respectively.
They also tested different conditions, i.e. higher tempera-
ture and acidic environment, but no significant differences
from the reference runs were found. The uncertainty related
to the DSC apparatus for long-duration experiments was dis-
cussed in a later work of the same authors [54].
Similar results were obtained with the same material
(poplar wood) at a temperature of 220 °C for 4 h [55]. The
specimens contained 4 mg of wood and 20 mg of deionized
water.
The mean process enthalpy change was − 0.5 MJ kgfeedstock
with 30% standard deviation.
Smaller sample masses were used for the evaluation of the
process enthalpy for HTC of faecal sludge, where 8 mg of
as-received sludge (with 4.3% of solid content) was hydro-
thermally carbonized inside a DSC apparatus at 160, 180,
and 200 °C for 4 h [56]. The process was exothermic with
enthalpy change of − 0.20, − 0.32, and − 0.70 MJ kgfeedstock ,
respectively (5, 9, 11% standard deviation).
To increase the dimension of the specimens, a heat flux
DSC with bigger specimen holders was adopted in another
work, using biomass from landscape management as feed-
stock [57]. The utilized model of DSC could host larger
samples volume (8.5 cm3 ), but the drawback was a very low
heating rate allowed by the machine. To avoid the problems
of too fast heating phases where the heat fluxes cannot be
measured with accuracy, the authors chose to perform the
measurement of enthalpy with a constant but low heating
rate of 1 °C min−1, in the range between 100 and 291 °C. The
stainless-steel high-pressure cell hosted a glass container
with 3.2 cm3 inner volume, filled with the samples, which
had a mass of 1.25 g. This allowed to perform elemental
analysis on the produced solid and liquid phases, which was
dried on it. The results of the DSC analysis were very pre-
cise, with a process enthalpy change of − 0.715 MJ kgfeedstock
and 2% standard deviation, once two measures with arte-
facts were removed (out of seven measures in total). Those
results were compared with the ones from the theoretical
model developed in the same article, based on the enthalpy
balance between reactants and products (Hess’s law applica-
tion). This model adopted different simplifications, and the
authors reported the results which were different from the
experimental ones, depending on the hypothesis made. The
result was − 4.45 MJ kgfeedstock when no methane production
was considered, − 2.54 MJ kgfeedstock when 23% methane was
considered in the gas phase, and − 0.922 MJ kgfeedstock when
also a fictitious molecule to account for the liquid phase
was included in the calculation. However, the percentage of
methane in the gas phases was based on the results obtained
in Ref. [58], which dealt with catalytic hydrothermal gasi-
fication, and thus, the percentage of methane for standard
HTC was probably overestimated. Another limitation in the
application of the procedure may be the model adopted for
the determination of the standard enthalpy of formation of
char and liquids. At the end of the runs, the char was left to
dry in the liquid phase, to allow the liquid solutes to remain
within it, and the elemental analysis was performed on the
obtained solid mixture. In this way, the equation accounted
for a single term for char and liquid solutes. During the water
evaporation, also the light volatiles present in the liquid may
have evaporated. The water amount was then computed by
mass difference, so the mass of light volatiles evaporated
was assimilated with the water one. The higher heating value
of this mixture was then calculated as a function of its chem-
ical composition [53], since the char mass was insufficient to
evaluate it with a calorimetric bomb. The gas quantity was
then obtained by mass balance.
A specially designed reactor for the evaluation of the
standard enthalpy of the HTC process was designed by Mer-
zari et al. [59]. The equipment consisted in a 2-dm3 batch
vessel, with four thermocouples placed at different heights,
a pressure gauge, four electrical resistances, and an electric
power meter. The reactor was also thermally insulated with
an external layer. Temperatures of 180, 220, and 250 °C were
investigated, with a constant residence time of 3 h. The bio-
mass/water ratio was chosen as 10%, with a fixed filling ratio
of the reactor of 66.67% in terms of volume. The feedstocks
were agave pulp and organic fraction of municipal solid
waste. To assess the reactor losses, the same temperature
program was applied for each reaction temperature, but only
deionized water was placed in the reactor, with the same
filling ratio of the reactor in terms of volume. The power
consumption in those tests was recorded and subtracted from
the power consumption of the experiment with also biomass
in the reactor. The results witnessed the exothermic behav-
iour of HTC in all the cases. For the agave pulp, the process
13

enthalpy change was evaluated as − 1.0, − 3.1, and − 3.9
MJ kgfeedstock,dry , for a reaction temperature of 180, 220, and
250 °C, respectively. For the organic fraction of municipal
solid waste, only one test at 220 °C was performed, yielding
an enthalpy value of − 7.3 MJ kgfeedstock,dry.
Recently, to reduce the error related to the system con-
figuration during DSC analysis, i.e. the crucible position
between run and blank, the third method described in “Dif-
ferential calorimetry measurements” section was adopted
[39]. Cellulose, wood, and digestate were used as feedstock
and heated up to 250 °C at 5 °C min−1 and kept at 250 °C
for 3 h. High-pressure crucibles with 100 μL capacity were
filled with around 8 mg of dry substrate and around 64 mg of
distilled water. The temperature program was composed of
one constant heating and one isothermal segments, and the
DSC signal was recorded during both steps. This allowed to
reduce the error related to the heating phase, which cannot
be recorded using typical isothermal analyses. The blank
curve was obtained performing a second run on the reacted
specimen without moving it. This approach led to stand-
ard deviations of 1.8, 8.0, and 3.5% for cellulose, wood,
and digestate, respectively. The difference between the heat
capacity of the reactants (and forming products) in the first
run and the one of the products in the blank was accounted
for through an iterative computation and was removed from
the uncorrected thermal flux. Values of the enthalpy change
of −0.88, −0.64, and −0.25 MJ kg−1 were found for cellu-
lose, wood, and digestate, respectively.
Critical discussion of the results
A comprehensive list of all the research works dealing with
the determination of the process enthalpy change of HTC
is shown in Table 1. The available information about the
uncertainty, the process conditions, the feedstock, the used
method, and the main critical aspects of each measure are
reported. When the same authors investigated different pro-
cess conditions, feedstock, or evaluation methods for the
process enthalpy, all the different cases are shown.
The amount of information available is not sufficient for
a comprehensive and exhaustive description of HTC ther-
modynamics, since every author utilized different feedstock
and process conditions in their experiments and adopted dif-
ferent hypotheses for their models. However, even if precise
numerical values cannot be produced, some important con-
sideration on the general trend can be given.
From the theoretical point of view, some constraints on
the upper and lower limits for the enthalpy value of bio-
mass HTC can be determined. On the one hand, the HTC
process can be described as a series of reaction taking
place in a subcritical water environment between 180 and
250 °C. These reactions are mainly hydrolysis, dehydration,
13
M. Pecchi et al.
decarboxylation, aromatization, and recondensation [1].
Hydrolysis is the reaction with the lowest activation energy
and is endothermic [1, 33], while dehydration and decar-
boxylation are exothermic and lower the oxygen and hydro-
gen content of the biomass during the process [29]. Thus,
for very low severity (temperatures below 180  °C) and
very short residence time, the process may show a slightly
endothermic behaviour. However, for the temperature range
where HTC takes place (above 180 °C), dehydration, decar-
boxylation, aromatization, and recondensation dominate
[1, 29]. The HTC process is thus exothermic. On the other
hand, the heat of decomposition of cellulose in high-pres-
sure water was theoretically derived by Rebling et al. [57],
based on the chemical composition of the products obtained
by Bergius [31]. The heat of the reaction was − 1.84
MJ kg−1 cellulose , but this value strongly depended on the char
composition and on the amount of CO2 and H2 O formed
during the process. Therefore, since the coal composition
obtained by Bergius was based on experiments performed
at extremely severe conditions (almost in the HTL field), the
obtained value could be seen as an upper bound (in absolute
value) for the enthalpy change of cellulose HTC. Similar
results, − 1.60 MJ kg−1 cellulose were proposed in another work
,
[1], based on an approximate stoichiometric HTC reaction.
Since the HHV (higher heating value) of cellulose is com-
parable to the one of the woods and greater that the one of
the residual biomasses (i.e. digestate, sludge, etc) [39], an
overall enthalpy change of the HTC process smaller than
− 1.84 MJ kg−1 cellulose should be expected (in absolute value).
Summarizing, the enthalpy change of the HTC process
applied to biomass with HHV comparable to the one of cel-
lulose should be in the exothermic range, with absolute value
below 1.84 MJ kg−1 feed.
The only positive enthalpy values that have been reported
in the literature are the ones from Yan et al. [48] and Sunner
et al. [46]. Taking into consideration the works of Coronella
et al. [34] and Funke and Ziegler [30], the HTC endothermic
behaviour evaluated can be related to the fact that the water
formation during the process was underestimated, along with
a non-precise evaluation of both liquid and gas composition.
As for the work of Yan et al., another reason may have been
the short residence time, indeed a later work adopted a simi-
lar procedure with longer residence times [49], and obtained
exothermic values of enthalpy.
Among the works that obtained enthalpy values above the
theoretical threshold of − 1.84 MJ kg−1 feed (in absolute value),
the performed estimation could be affected by the difficul-
ties—as confirmed by some of the authors—of closing the
mass balances for the enthalpy evaluation through direct
application of the Hess’s law [43–46, 50, 52]. In particular,
Ramke et al. [50] compared the value calculated by direct
application of the Hess’s law to the one calculated by dif-
ferential calorimetry obtained in the same research work,
Enthalpy change during hydrothermal carbonization of biomass: a critical review

Table 1  Summary of the scientific literature about the determination of the standard enthalpy of the HTC process
ΔHHTC/MJ kgfeed Standard T/°C Time/h Feedstock Method Simplifications and limitations References
devia-
tion/%

− 1.78 – 310 64 Cellulose Hess’s law Severe conditions (HTL), only [31]
solids considered
− 4.30 to 0.00 – – – Coal Hess’s law Only solids considered [43–46]
− 1.50 33 300–350 0.2–1 Glucose Hess’s law Severe conditions (HTL), HHV [47]
used instead of enthalpy
+0.56 129 200 0.01 Wood Hess’s law Simplified gas and liquids [48]
+0.53 142 230
+0.25 368 260
− 2.62 – 250 20 Solid waste Hess’s law Simplified gas and liquids, water [52]
formation neglected
− 1.19 Food waste
− 0.75 AD waste
− 0.68 Paper
− 1.06 15 240 10 Glucose Diff. Calorimetry Small samples, high st. dev. [30]
− 1.07 10 Cellulose
− 0.76 36 Wood
− 0.50 30 220 4 Wood Diff. Calorimetry Small samples, high st. dev. [55]
− 0.20 5 160 4 Faecal sludge Diff. Calorimetry Small samples, high st. dev. [56]
− 0.32 9 180
− 0.70 11 200
− 0.72 2 100–291 6 Biomass Diff. Calorimetry Tests at variable T [57]
− 4.45 – Rate = Hess’s law All gas is considered CO2
− 2.54 – 1 °C Hess’s law 23% of gas is considered CH4
­min−1
− 0.92 – Hess’s law Additional liquid molecule
− 2.53 – 180 2.5 Wood Hess’s law Simplified gas and liquids [49]
− 3.47 – 180 5.8 Simplified gas and liquids
− 7.84 – 180 2.5 Simplified gas and liquids, use of
acid solution instead of water
− 8.69 – 180 5.8 Simplified gas and liquids, use of
acid solution instead of water
− 7.00 – 180 18 Maize silage + beet pulp Diff. Calorimetry No uncertainty reported [50, 51]
− 5.70 to − 4.30 Hess’s law Only solids considered
− 1.00 – 180 3 Agave pulp Diff. Calorimetry Volume balance for blank run, no [59]
uncertainty reported
− 3.10 220 Agave pulp
− 3.90 250 Agave pulp
− 7.30 220 Organic waste
− 0.88 1.8 250 3 Cellulose Diff. Calorimetry Small samples [39]
− 0.64 8.0 Wood
− 0.25 3.5 Digestate

obtaining very different results. Merzari et al. [59] used an
ad hoc reactor for the determination of the process enthalpy.
The choice of using the same volume of water for the blank
case instead of the same mass with respect to the process
run may have influenced the results. The volume of water
in the blank case matched the volume of the water and the
feedstock in the process run, and thus, the mass of water in
the blank case equalled the mass of water in the process run
plus the mass of water that occupied a volume equal to the
one of the solubilized biomass. This extra mass of water
may have caused an overestimation of the endothermicity
of the blank curve, leading to overestimated exothermicity
values of the process (see Eq. 6). Another issue concerning
the use of laboratory-scale reactors is that, due to the large

13

dimensions of the reactor apparatuses, thermal inertia and
losses may have influenced the results. Unfortunately, no
uncertainty value for any of the enthalpy measures has been
reported in those two articles.
Concerning the articles that obtained values inside the
theoretical range, the majority used a DSC apparatus for the
enthalpy determination. Only three articles reported stand-
ard deviations below 5%, due to the non-homogeneity of the
biomass and the small size of the crucible and the problem
related to its positioning between run and blank. The first
result with a uncertainty around 2% used 1.5 g of feedstock
and used the second method (blank curve obtained with a
run on pure water, described in “Differential calorimetry
measurements” section) with constant heating segments
[57], while the other [39] used 8 mg of dry material using
the third method (blank curve obtained using the exhaust
specimen, described in “Differential calorimetry measure-
ments” section). Considering the articles in this category
that obtained higher values of uncertainty, the different
authors obtained the results very similar to each other and
always inside the theoretical range [30, 55, 56].
Concluding, more research is needed to properly describe
the enthalpy change during the HTC of different feedstock
types at diverse process conditions. The process is mildly
exothermic, with enthalpy change in the range between − 0.2
and − 1.1 MJ kg−1 feed depending on the biomass and on the
severity of the process. Among the method used to assess
this value, the use of a DSC apparatus with high-pressure
crucibles is the method that allowed to obtain the relatively
reproducible results within the theoretical range. Of the two
methods adopted with DSC, the subtraction of the exhaust
blank (third method described in “Differential calorimetry
measurements” section above) allowed to obtain higher
reproducibility, despite the lower sample mass, and thus, the
error related to the crucible positioning plays a very impor-
tant role in this kind of analyses. The direct application of
the Hess’s law was too dependent on the assessment of the
liquid phase composition and on the hypotheses accepted
for the modelling of the different phases, and the different
results were obtained by various authors. The use of ad hoc
reactors was probably influenced by heat losses and thermal
inertia, which magnitude was comparable with the enthalpic
effect of HTC.
Conclusions
A thorough analysis of the available literature about the
determination of the standard enthalpy change of the HTC
process applied to biomass has been performed. To the best
of the authors’ knowledge, it is the first review work that
specifically focuses on the enthalpy evaluation for the HTC
process of biomass and on the methodologies adopted for
13
M. Pecchi et al.
the purpose. The different articles have been classified based
on the method used to determine this enthalpy value. The
two possible methods, which are the direct application of
the Hess’s law and the use of differential calorimetry, have
been described in detail. The main sources of errors that
have been faced in the reviewed research papers have been
analysed.
In summary, very few works that deal with the evaluation
of the process enthalpy of HTC are available, and in these
works, very different feedstock and process conditions were
investigated. Based on theoretical considerations, the HTC
process enthalpy change is in the range between − 1.8 and 0
MJ kg−1feed , thus being in the exothermic field. The only works
that obtained the results inside this range with relatively low
standard deviations used high-pressure DSC. Three meth-
ods were used by different authors. In the first and second
ones, the blank curve that was subtracted to the DSC curve
from the experiment was obtained during a run with pure
water, while in the third method, it was obtained subtract-
ing the curve of a second run on the already reacted sample.
Despite the theoretical differences between these methods,
the results were similar and always in the range between
− 0.2 and − 1.1 MJ kg−1 feed , laying inside the theoretical limits
for the HTC enthalpy change.
Concerning the design of industrial scale HTC plant, heat
recovery from the products appears to play an importantly
greater role with respect to the small reaction exothermicity.
Acknowledgements  The authors wish to thank prof. R. Di Maggio
(University of Trento, Italy) for the very useful discussion on the vari-
ous DSC techniques and methodologies.
Funding  This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
Compliance with ethical standards 
Conflict of interest  The authors declare that they have no conflict of
interest.
References
1. Libra JA, Kyoung RS, Kammann C, Funke A, Berge ND, Neu-
bauer Y, Titirici M-M, Fühner C, Bens O, Kern J, Emmerich K-H.
Hydrothermal carbonization of biomass residuals: a comparative
review of the chemistry, processes and applications of wet and
dry pyrolysis. Biofuels. 2011;2:71–106. https​://doi.org/10.4155/
bfs.10.81.
2. Basso D, Weiss-Hortala E, Patuzzi F, Baratieri M, Fiori L. In
deep analysis on the behavior of grape marc constituents during
hydrothermal carbonization. Energies. 2018;11:1379. https​://doi.
org/10.3390/en110​61379​.
3. Basso D, Patuzzi F, Castello D, Baratieri M, Rada EC, Weiss-
Hortala E, Fiori L. Agro-industrial waste to solid biofuel through
Enthalpy change during hydrothermal carbonization of biomass: a critical review
hydrothermal carbonization. Waste Manag. 2016;47:114–21. https​
://doi.org/10.1016/j.wasma​n.2015.05.013.
4. Román S, Nabais JMV, Laginhas C, Ledesma B, González JF.
Hydrothermal carbonization as an effective way of densifying the
energy content of biomass. Fuel Process Technol. 2012;103:78–
83. https​://doi.org/10.1016/j.fupro​c.2011.11.009.
5. Zhu G, Yang L, Gao Y, Xu J, Chen H, Zhu Y, Wang Y, Liao C,
Lu C, Zhu C. Characterization and pelletization of cotton stalk
hydrochar from HTC and combustion kinetics of hydrochar pel-
lets by TGA. Fuel. 2019;244:479–91. https​://doi.org/10.1016/j.
fuel.2019.02.039.
6. Yu Y, Lei Z, Yang X, Yang X, Huang W, Shimizu K, Zhang Z.
Hydrothermal carbonization of anaerobic granular sludge: effect
of process temperature on nutrients availability and energy gain
from produced hydrochar. Appl Energy. 2018;229:88–95. https​://
doi.org/10.1016/j.apene​rgy.2018.07.088.
7. Kambo HS, Dutta A. Comparative evaluation of torrefaction and
hydrothermal carbonization of lignocellulosic biomass for the pro-
duction of solid biofuel. Energy Convers Manag. 2015;105:746–
55. https​://doi.org/10.1016/j.encon​man.2015.08.031.
8. Pradhan P, Mahajani SM, Arora A. Production and utilization
of fuel pellets from biomass: a review. Fuel Process Technol.
2018;181:215–32. https​://doi.org/10.1016/j.fupro​c.2018.09.021.
9. Basso D, Pavanetto R. Greenpeat: an innovative sustainable mate-
rial recovered from waste. Procedia Environ Sci Eng Manag.
2017;4:9–16.
10. Hitzl M, Mendez A, Owsianiak M, Renz M. Making hydro-
char suitable for agricultural soil: a thermal treatment to
remove organic phytotoxic compounds. J Environ Chem Eng.
2018;6:7029–34. https​://doi.org/10.1016/j.jece.2018.10.064.
11. Gronwald M, Vos C, Helfrich M, Don A. Stability of pyrochar and
hydrochar in agricultural soil—a new field incubation method.
Geoderma. 2016;284:85–92. https​://doi.org/10.1016/j.geode​
rma.2016.08.019.
12. Rodriguez Correa C, Bernardo M, Ribeiro RPPL, Esteves IAAC,
Kruse A. Evaluation of hydrothermal carbonization as a prelimi-
nary step for the production of functional materials from biogas
digestate. J Anal Appl Pyrolysis. 2017;124:461–74. https​://doi.
org/10.1016/j.jaap.2017.02.014.
13. Zhang X, Gao B, Fang J, Zou W, Dong L, Cao C, Zhang J, Li
Y, Wang H. Chemically activated hydrochar as an effective
adsorbent for volatile organic compounds (VOCs). Chemos-
phere. 2019;218:680–6. https​://doi.org/10.1016/j.chemo​spher​
e.2018.11.144.
14. Fan X, Shen Y, Zhang T, Li G, Tsang DCW, Wu X. Corn waste
valorization to generate activated hydrochar to recover ammo-
nium nitrogen from compost leachate by hydrothermal assisted
pretreatment. J Environ Manag. 2019;236:108–17. https​://doi.
org/10.1016/j.jenvm​an.2019.01.018.
15. Li Y, Tsend N, Li TK, Liu H, Yang R, Gai X, Wang H, Shan
S. Microwave assisted hydrothermal preparation of rice straw
hydrochars for adsorption of organics and heavy metals. Biore-
sour Technol. 2019;273:136–43. https​://doi.org/10.1016/j.biort​
ech.2018.10.056.
16. Zhang Z, Zhu Z, Shen B, Liu L. Insights into biochar and
hydrochar production and applications: a review. Energy.
2019;171:581–98. https​://doi.org/10.1016/j.energ​y.2019.01.035.
17. Köchermann J, Görsch K, Wirth B, Mühlenberg J, Klemm M.
Hydrothermal carbonization: temperature influence on hydro-
char and aqueous phase composition during process water
recirculation. J Environ Chem Eng. 2018;6:5481–7. https​://doi.
org/10.1016/j.jece.2018.07.053.
18. Reza MT, Wirth B, Lüder U, Werner M. Behavior of selected
hydrolyzed and dehydrated products during hydrothermal carboni-
zation of biomass. Bioresour Technol. 2014;169:352–61. https​://
doi.org/10.1016/j.biort​ech.2014.07.010.
19. Ding K, Le Y, Yao G, Ma Z, Jin B, Wang J, Jin F. A rapid and
efficient hydrothermal conversion of coconut husk into formic
acid and acetic acid. Process Biochem. 2018;68:131–5. https​://
doi.org/10.1016/j.procb​io.2018.02.021.
20. Volpe M, Goldfarb JL, Fiori L. Hydrothermal carbonization of
Opuntia ficus-indica cladodes: role of process parameters on
hydrochar properties. Bioresour Technol. 2018;247:310–8. https​
://doi.org/10.1016/j.biort​ech.2017.09.072.
21. Serio MA, Woo E, Charpenay S, Solomon PR, Hydrous pyrolysis
of four argonne premium coals. In: Conference 204th American
Chemical Society national meeting, Washington, DC (United
States), 23–28 Aug 1992, 1992: pp. 1681–1690.
22. Saba A, Saha P, Reza MT. Co-hydrothermal carbonization of coal-
biomass blend: influence of temperature on solid fuel properties.
Fuel Process Technol. 2017;167:711–20. https:​ //doi.org/10.1016/j.
fupro​c.2017.08.016.
23. Gao L, Volpe M, Lucian M, Fiori L, Goldfarb JL. Does hydro-
thermal carbonization as a biomass pretreatment reduce fuel seg-
regation of coal-biomass blends during oxidation? Energy Con-
vers Manag. 2019;181:93–104. https​://doi.org/10.1016/j.encon​
man.2018.12.009.
24. Wang T, Zhai Y, Zhu Y, Li C, Zeng G. A review of the hydro-
thermal carbonization of biomass waste for hydrochar formation:
process conditions, fundamentals, and physicochemical proper-
ties. Renew Sustain Energy Rev. 2018;90:223–47. https​://doi.
org/10.1016/j.rser.2018.03.071.
25. Wang L, Chang Y, Li A. Hydrothermal carbonization for energy-
efficient processing of sewage sludge: a review. Renew Sus-
tain Energy Rev. 2019;108:423–40. https​://doi.org/10.1016/j.
rser.2019.04.011.
26. Guo S, Dong X, Wu T, Zhu C. Influence of reaction condi-
tions and feedstock on hydrochar properties. Energy Convers
Manag. 2016;123:95–103. https ​ : //doi.org/10.1016/j.encon​
man.2016.06.029.
27. Titirici MM, Thomas A, Antonietti M. Back in the black: hydro-
thermal carbonization of plant material as an efficient chemical
process to treat the C
­ O2 problem? New J Chem. 2007;31:787–9.
https​://doi.org/10.1039/b6160​45j.
28. Funke A, Ziegler F. Hydrothermal carbonization of biomass: a
literature survey focussiong on its technical application and pros-
pects. Biomass. 2009;1037–50. https​://www.resea​rchga​te.net/
publi​catio​n/28160​5887_Hydro​therm​al_carbo​nizat​ion_of_bioma​
ss_A_liter​ature​_surve​y_focus​ing_on_its_techn​ical_appli​catio​
n_and_prosp​ects.
29. Funke A, Ziegler F. Hydrothermal carbonization of biomass: a
summary and discussion of chemical mechanisms for process
engineering. Biofuels Bioprod Biorefining. 2010;4:160–77. https​
://doi.org/10.1002/bbb.
30. Funke A, Ziegler F. Heat of reaction measurements for
hydrothermal carbonization of biomass. Bioresour Technol.
2011;102:7595–8. https:​ //doi.org/10.1016/j.biorte​ ch.2011.05.016.
31. Bergius F, Die Anwendung hoher Drücke bei chemischen Vorgän-
genund eine Nachbil dung des Entstehungsprozesses der Stein-
kohle 1913;41–58.
32. Mok WSL, Antal MJ, Szabo P, Varhegyi G, Zelei B. Formation of
Charcoal from Biomass in a Sealed Reactor. Ind Eng Chem Res.
1992;31:1162–6. https​://doi.org/10.1021/ie000​04a02​7.
33. Kunihisa KS, Ogawa H. Acid hydrolysis of cellulose in a differ-
ential scanning calorimeter. J Therm Anal. 1985;30:49–59. https​
://doi.org/10.1007/BF021​28114​.
34. Jin F, editor. Application of hydrothermal reactions to biomass
conversion. Green chemistry and sustainable technology. Berlin,
Heidelberg: Springer;2014. https​://doi.org/10.1007/978-3-642-
54458​-3.
13

35. Nagata I, Gotoh K, Tamura K. Association model of fluids. Phase
equilibria and excess enthalpies in acid mixtures. Fluid Phase
Equilib. 1996;124:31–54.
36. Reza MT, Lynam JG, Uddin MH, Coronella CJ. Hydrother-
mal carbonization: fate of inorganics. Biomass Bioenergy.
2013;49:86–94. https​://doi.org/10.1016/j.biomb​ioe.2012.12.004.
37. International Organization for Standardization, ISO 11357-1.
Plastics — Differential scanning calorimetry (DSC) — Part 1:
General principles. 3rd ed.; 2016. p. 33. https:​ //www.iso.org/stand​
ard/70024​.html.
38. UNI EN ISO 11357-5:2014. Materie plastiche - Calorimetria
differenziale a scansione (DSC) - Parte 5: Determinazione della
curva caratteristica temperature di reazione e tempi, entalpia di
reazione e grado di conversione; 2014.
39. Pecchi M, Patuzzi F, Benedetti V, Di Maggio R, Baratieri M.
Thermodynamics of hydrothermal carbonization assessment of
the heat release profile and process enthalpy change. Fuel Pro-
cess Technol. 2020;197:106206. https​://doi.org/10.1016/j.fupro​
c.2019.10620​6.
40. Deliiski N. Transient heat conduction in capillary porous
bodies. Convect Conduct Heat Transf. 2012. https ​ : //doi.
org/10.5772/21424​.
41. Radmanović K, Đukić I, Pervan S. Specific heat capacity of wood.
Drv Ind. 2014;65:151–7. https:​ //doi.org/10.5552/drind.​ 2014.1333.
42. Gollakota ARK, Kishore N, Gu S. A review on hydrothermal liq-
uefaction of biomass. Renew Sustain Energy Rev. 2018;81:1378–
92. https​://doi.org/10.1016/j.rser.2017.05.178.
43. Oden S, Unnerstad A. Über die Nassverkohlung des Torfes.
Brennstoff-Chemie. 1924;5:249.
44. Terres E. Über die Entwässerung und Veredlung von Rohtorf und
Rohbraunkohle. Brennstoff-Chemie. 1952;33:1–12.
45. Könnecke E, Leibnitz HG. Zur Kenntnis der Druckinkohlung
von Braunkohlen in Gegenwart von Wasser. J Für Prakt Chemie.
1955;1:200–8.
46. Sunner S, Wadsö I. Measurements on heat effects accompanying
the wet carbonization of peat in the temperature range 20 to 220
°C. Acta polytechnica Scandinavica. Vol. 297. Royal Swedish
Acad. of Engineering Sciences; 1961. p. 40. https​://books​.googl​
e.it/books?​ id=wkkRMw ​ AACAA ​ J&dq=inauth​ or:%22Stig​ +Sunne​
r%22&hl=it&sa=X&ved=0ahUK​EwiKz​fzms5​LmAhW​LGewK​
Hen8B​2oQ6A​EIKTA​A.
47. Knežević D, Van Swaaij WPM, Kersten SRA. Hydrothermal con-
version of biomass: I, glucose conversion in hot compressed water.
Ind Eng Chem Res. 2009;48:4731–43. https​://doi.org/10.1021/
ie801​387v.
48. Yan W, Hastings JT, Acharjee TC, Coronella CJ, Vásquez VR.
Mass and energy balances of wet torrefaction of lignocellulosic
biomass. Energy Fuels. 2010;24:4738–42. https:​ //doi.org/10.1021/
ef901​273n.
13
M. Pecchi et al.
49. Cuvilas CA, Kantarelis E, Yang W. The impact of a mild sub-crit-
ical hydrothermal carbonization pretreatment on Umbila wood. A
mass and energy balance perspective. Energies. 2015;8:2165–75.
https​://doi.org/10.3390/en803​2165.
50. Ramke H, Blöhse D, Lehmann H, Fettig J, Hydrothermal carboni-
zation of organic waste. In: Twelfth international waste manage-
ment and landfill symposium. 2009
51. Ramke H-G, Blöhse D, Lehmann H-J, Fettig J, Hydrothermale
Carbonisierung organischer Siedlungsabfälle. In: Bio- Und
Sekundärrohstoffverwertung V, Stofflich—Energ. 22. Kasseler
Abfall- Und Bioenergieforum, Kassel, Witzenhausen-Institut für
Abfall und Energie, Witzenhausen; 2010. pp. 141–157.
52. Berge ND, Ro KS, Mao J, Flora JRV, Chappell MA, Bae S. Hydro-
thermal carbonization of municipal waste streams. Environ Sci
Technol. 2011;45:5696–703. https​://doi.org/10.1021/es200​4528.
53. Channiwala SA, Parikh PP. A unified correlation for estimating
HHV of solid, liquid and gaseous fuels. Fuel. 2002;81:1051–63.
https​://doi.org/10.1016/S0016​-2361(01)00131​-4.
54. Funke A, Ziegler F. Propagation of uncertainties and sys-
tematic errors in the measurements of long-lasting heat flows
using differential scanning calorimetry. J Therm Anal Calorim.
2012;108:1317–24. https​://doi.org/10.1007/s1097​3-011-1352-9.
55. Stemann J, Ziegler F, Assessment of the energetic efficiency of
a continuously operating plant for hydrothermal carbonisation of
biomass. World Renew. Energy Congr. 2011—Sweden; 2011. pp.
125–132. https​://doi.org/10.3384/ecp11​05712​5.
56. Danso-Boateng E, Holdich RG, Martin SJ, Shama G, Wheatley
AD. Process energetics for the hydrothermal carbonisation of
human faecal wastes. Energy Convers Manag. 2015;105:1115–24.
https​://doi.org/10.1016/j.encon​man.2015.08.064.
57. Rebling T, Von Frieling P, Buchholz J, Greve T. Hydrothermal
carbonization: combination of heat of reaction measurements
and theoretical estimations: an experimental procedure using a
calvet differential scanning calorimeter. J Therm Anal Calorim.
2015;119:1941–53. https​://doi.org/10.1007/s1097​3-014-4361-7.
58. Waldner MH, Vogel F. Renewable production of methane from
woody biomass by catalytic hydrothermal gasification. Ind Eng
Chem Res. 2005;44:4543–51. https​://doi.org/10.1021/ie050​161h.
59. Merzari F, Lucian M, Volpe M, Andreottola G, Fiori L. Hydro-
thermal carbonization of biomass: design of a bench-Scale reactor
for evaluating the heat of reaction. Chem Eng Trans. 2018. https​
://doi.org/10.3303/cet18​65008​.
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