HTC Summary and Discussion of Chemical Mechanisms For Process Engineering

Review
Hydrothermal carbonization
of biomass: A summary and
discussion of chemical mecha-
nisms for process engineering
Axel Funke and Felix Ziegler, Technische Universität Berlin, Germany
Received October 23, 2009; revised version received November 20, 2009; accepted November 24, 2009
Published online in Wiley InterScience (www.interscience.wiley.com); DOI: 10.1002/bbb.198;
Biofuels, Bioprod. Bioref. 4:160–177 (2010)
Abstract: Hydrothermal carbonization can be defined as combined dehydration and decarboxylation of a fuel to raise
its carbon content with the aim of achieving a higher calorific value. It is realized by applying elevated temperatures
(180–220oC) to biomass in a suspension with water under saturated pressure for several hours. With this conversion
process, a lignite-like, easy to handle fuel with well-defined properties can be created from biomass residues, even
with high moisture content. Thus it may contribute to a wider application of biomass for energetic purposes. Although
hydrothermal carbonization has been known for nearly a century, it has received little attention in current biomass
conversion research. This review summarizes knowledge about the chemical nature of this process from a process
design point of view. Reaction mechanisms of hydrolysis, dehydration, decarboxylation, aromatization, and conden-
sation polymerization are discussed and evaluated to describe important operational parameters qualitatively. The
results are used to derive fundamental process design improvements. © 2010 Society of Chemical Industry and
John Wiley & Sons, Ltd
Keywords: hydrothermal carbonization, thermochemical conversion, organic waste, solid biofuel, biomass
Introduction in recent years and R&D projects have been launched to

ydrothermal carbonization is a thermochemical assess its feasibility and discover additional possibilities
H conversion process for biomass to yield a solid, coal-

like product. It has been used for almost a century in
different sciences, mainly to simulate natural coalification
for applications. To support this recent development and
to help identify areas for further research, a summary of
the published literature from nearly a century of research
in the laboratory. Due to the need for efficient biomass is provided. At first, a short discussion of possible reaction
conversion technologies, hydrothermal carbonization has mechanisms aims to approach the underlying chemistry.
attracted some interest as a possible application for biomass On this basis, process parameters and their influence on the
Correspondence to: Axel Funke, Technische Universität of Berlin, Institute of Energy Engineering, Marchstr. 18, D-10587, Berlin, Germany.
E-mail: axel.funke@mailbox.tu-berlin.de
160 © 2010 Society of Chemical Industry and John Wiley & Sons, Ltd
Review: Hydrothermal carbonization of biomass A Funke, F Ziegler
reaction network are evaluated and the most relevant prod- Moreover, it might become a viable option for the produc-
ucts presented. To conclude, fundamental process design tion of functional carbonaceous materials.
improvements are derived.
Hydrothermal carbonization is an exothermal process Research on hydrothermal carbonization
that lowers both the oxygen and hydrogen content of the Hydrothermal carbonization has been in use as a method
feed (described by the molecular O/C and H/C ratio) by for simulating natural coalification in coal petrology for
mainly dehydration and decarboxylation. This is achieved nearly a century and many experimental results have been
by applying temperatures of 180–200 o C in a suspension of published.2–31 It was introduced to this research field by
biomass and water at saturated pressure for several hours. Bergius as early as 1913 and was discussed controversially
An evaluation of experimental data to address mass and from then on.2, 4, 8, 28 Applications date back to more recent
energy balances has been summarized elsewhere.1 Table 1 years 27 and there is also a short review.19 Next to these
gives an impression of conversion characteristics and the experimental data, involved reaction mechanisms have
achievable product composition. In principle, any kind been discussed in coal petrology as well, some of which give
of biomass can be carbonized hydrothermally. Namely important indications for hydrothermal carbonization.32−48
model substances, such as cellulose and lignin, as well Closely related to artificial maturation of organic material,
as wood, plant tissue, resin and peat have been success- hydrothermal carbonization is used as a means to assess the
fully treated; the latter also on a pilot-plant scale. Even petroleum potential of oil source rocks. In organic geochem-
lignite and sub-bituminous coal have been reported to be istry it is called hydrous pyrolysis and represents one of the
hydrothermally carbonized, however, by applying higher valid methods to measure source rock potential.49–64 As that
temperatures. research is focused on oil, substantially higher temperatures
Although hydrothermal conversion processes received (300–360oC) have been applied. Some of these studies also
great attention for biomass liquefaction and gasification, a focused on the maturation (or coalification) of the organic
technical implementation of hydrothermal carbonization residues.51, 59, 60
has only been developed with comparably low effort. This Hydrolysis of plant material provides fundamental
may be due to the fact that coal as an energy carrier is infe- findings for reaction mechanisms that play a role during
rior to liquid or gaseous fuels. On the other hand, process hydrothermal carbonization. It is mainly investigated to
requirements of hydrothermal carbonization are compa- produce specific chemicals from biomass (e.g., organic
rably low while producing a fuel that is easier to handle and acids, furfural and furanoid derivatives); the solid carbona-
store because it is stable and non-toxic. Due to these facts, ceous material occurring is mostly regarded as unwanted
hydrothermal carbonization may provide some advantages byproduct. Otherwise, reaction conditions are very similar
when considering small-scale, decentralized applications. to hydrothermal carbonization except for the substantially
Table 1. Selected results from different hydrothermal carbonization experiments.

Feed Temperature Residence Time Coal Yield H/C O/C Reference
[ºC] [h] [%] [-] [-]
Cellulose 1.67 0.83
225 3 63 1.29 0.61 23
200 50 49 0.76 0.28 26
Peat Bog 1.34 0.65 15
200 10 45 1.00 0.29 15
250 0.3 36 0.87 0.23 15
Wood 1.43 0.58 29
200 72 66 0.97 0.25 29
250 72 56 0.90 0.17 29
© 2010 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 4:160–177 (2010); DOI: 10.1002/bbb 161
A Funke, F Ziegler Review: Hydrothermal carbonization of biomass
shorter residence times to prevent further degradation and • There needs to be a liquid water phase, i.e., at least satu-
polymerization. There are many literature surveys that rated pressure is necessary.2, 28, 113
cover this comprehensive research field.65–67 Closely related • The feed needs to be submerged during the whole
are hydrothermal liquefaction and gasification which aim process.113
at producing a liquid and gaseous fuel, respectively. There • The pH-value should be below 7 because alkaline condi-
are several reviews that have already covered research on tions lead to a substantially different product.13, 39, 46 Due
this subject.68–71 Although the underlying chemistry differs to byproducts, the pH value drops automatically during
from that of hydrothermal carbonization, there are some hydrothermal carbonization.
similarities that provide useful information. From a tech- • At present, the residence time cannot be limited to a
nical point of view, some of the major issues are essentially meaningful range because reaction rates are largely
the same (solid feed handling, energy recovery and heat unknown. Typical published experimental times varied
transfer, undesired precipitation). Therefore such findings between 1 and 72 h.
are extremely valuable for an evaluation of the feasibility of
Whenever the term ‘hydrothermal carbonization’ is used,
hydrothermal carbonization.
it refers to the formation of a solid residue under the above-
Technical applications for thermal dewatering of peat and
mentioned conditions. Despite these parameters, which are
lignite always incorporate some carbonization of the feed,
based on physical and chemical considerations, it appears
which was an intended effect of most applications. Thus they
unlikely that practical implementations of hydrothermal
can be regarded as hydrothermal carbonization processes, too.
carbonization operate outside a temperature range of 180–
The earliest patent can be traced back to 1850 (by Vignoles),
250°C. Many researchers use the term ‘reaction severity’,
which led to the so-called ‘wet carbonization’ of peat.72–80
which also proved useful for this survey. A higher reaction
Although realized in commercial installations, a widespread
severity refers to both increasing temperature and/or longer
application has not been achieved, mainly because peat does
residence time of the feed. With increasing reaction severity,
not represent an economic energy source in most parts of the
a product with higher carbon content is produced at a lower
world. There has also been a long history of research dedicated
theoretically possible yield. Many models exist to quantify
to hydrothermal dewatering of lignite.81−98 It is well known that
this variable, those specifically developed for hydrothermal
carbonization occurs during such treatment; depending on the
carbonization are discussed below.
process it is either prevented in order to minimize pollution of
the resulting waste stream 82 or explicitly aimed for.90
Latest research on hydrothermal carbonization focused Reaction mechanisms
on the preparation of functional carbonaceous materials
Many chemical reactions that might appear during
and achieved interesting results for a future application
hydrothermal carbonization have been mentioned
to produce even more value-added materials.99–112 Funda-
throughout the literature, but just few have been the focus
mental research, however, is still ongoing.
of detailed investigations, e.g., the hydrolysis of cellulose.
It has been realized that the process is governed in sum by
Process conditions of hydrothermal carbonization
dehydration and decarboxylation, 70 which means that it
There is no common definition of hydrothermal carboniza-
is exothermal.2, 77–80, 91 Simultaneously, functional groups
tion. Therefore, the following range of operational condi-
are being eliminated to some extent.27, 93 But the complex
tions has been defined for the sake of this literature survey:
reaction network is not known in detail, yet. So, for the
• Operation should be limited to subcritical conditions of time being, only a separate discussion of general reac-
water, due to physical and chemical reasons.47, 113 tion mechanisms that have been identified can provide
• The temperature must be above 100°C; at this range first useful information about possibilities of manipulating the
reactions have been observed.80 Substantial hydrolysis reaction. These mechanisms include hydrolysis, dehydra-
starts at a temperature of about 180°C.65 tion, decarboxylation, condensation polymerization, and
162 © 2010 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 4:160–177 (2010); DOI: 10.1002/bbb
aromatization. They do not represent consecutive reaction reaction network has been summarized elsewhere.70 Hemi-
steps but rather form a parallel network of different reac- cellulose readily hydrolyzes at around 180°C, but detailed
tion paths. It is understood that the detailed nature of these reaction pathways are less well understood. Alkaline condi-
mechanisms, as well as their relative significance during the tions give the highest reaction rates compared to acidic and
course of reaction, primarily depends on the type of feed. neutral conditions, whereas fur ther degradation reactions
Biomass components are being hydrolyzed to a vast amount of glucose are highly enhanced by acidic conditions. In a
of oligomers and monomers.4, 114–117 Extractables are being pH range from 3 to7, the rate of reaction is largely inde-
eluted simultaneously; most of them exhibit very good pendent of H+ and OH− concentration, probably because the
water solubility.118 These solved fragments and extractables hydrogen bond between cellobiose and H2O is stronger at
are subject to subsequent degradation mechanisms, such high temperatures than the influence of pH in this region.65
as dehydration and decarboxylation, while condensation Hydrothermal degradation of lignin is most likely realiz-
reactions take place. Many of the formed intermediates are able at around 200°C due to its high amount of ether bonds.
highly reactive (especially HMF from cellulose degrada- Highly reactive products with a low molecular weight are
tion and fragments from lignin). They may also represent being formed by nucleophilic reactions.122 One of them
chemicals with a high potential value.67 During the course of with potential interest is acetic acid, which is most likely
ongoing polymerization, humic acids, bitumen and insoluble formed by hydrolysis of side chains.36 Again, the amount
solids are being formed and partly precipitate to form the of different fragments being formed is very high, even by
product HTC-coal. Additionally, there might be components hydrolysis of selected components.123 Many of these frag-
of the biomass or oligomer fragments thereof that do not ments are highly reactive and quickly form precipitates by
hydrolyze under given reaction conditions (e.g., crystalline condensation reactions.
cellulose119). Interactions between the different biomass components and
More detailed reaction pathways and kinetics are largely its fragments cannot be avoided. The effect of such interac-
unknown with the exception of the hydrothermal degrada- tions on hydrolysis is largely unknown. It has been supposed
tion of glucose.70 These known degradation mechanisms do that hemicellulose fragments interact with lignin and thus
not incorporate polymerization, as this is usually considered enhance the solubility of its aromatic structures.124 This is in
as an unwanted side-reaction. The importance of hydro- agreement with the observation that lignin and hemicellulose
thermal conditions for natural coalification has been empha- form an oligomer which is usually stable under hydrothermal
sized and relevant mechanisms reviewed.120 There have also conditions.119 In case of forced convection, hydrolysis can
been efforts to describe the kinetics of lignin degradation, be completed within a few minutes and its rate is primarily
which may provide a basis for technical models.45 determined by the adjusted flow rate and not the reaction
temperature.119 It can be concluded that the rate of hydrol-
Hydrolysis
ysis of biomass is primarily determined by diff usion and
Hydrolytic reactions lead to the cleavage of mainly ester
thus limited by transport phenomena within the matrix of
and ether bonds of the biomacromolecules by addition of
biomass. This may lead to condensation of fragments within
1 mole of water. The wide range of products includes (oligo-)
the matrix of the biomass at high temperatures.105, 125, 126
saccharides of cellulose and phenolic fragments of lignin.
An impression of the complexity of the resulting reaction Dehydration
network is given by the hydrolysis of D-fructose, which is a Dehydration during hydrothermal carbonization can cover
specified substance in contrast to biomass.121 Next to other both chemical reactions and physical processes, which
degradation mechanisms mentioned below, the resulting remove water from the biomass matrix without changing its
fragments are being further hydrolyzed (e.g., 5-(hydroxyme- chemical constitution. For clarification, the latter is referred
thyl) furfural (HMF) to yield levulinic and formic acid).66 to as ‘dewatering’ in this review. Chemical dehydration
Cellulose is being hydrolyzed significantly under hydro- significantly carbonizes biomass by lowering the H/C and
thermal conditions above approximately 200°C; a detailed O/C ratios.
Early experiments with oil discovered that cellulose starts Decarboxylation

decomposing by pure dehydration according to Hydrothermal treatment causes a partial elimination of
carboxyl groups.43, 73, 79, 83, 93, 96 Detailed reaction mecha-
4(C6H10O5)n 2(C12H10O5)n+10H2O 1
nisms are largely unknown, including the effect of the
Significant decarboxylation only appears after that presence of water.70 Carboxyl and carbonyl groups rapidly
specific amount of water is formed.3 There has been no degrade above 150°C, yielding CO2 and CO, respectively.94
effort to explain the underlying chemistry, but several Early observations conclude that more CO2 is being formed
experimental results under hydrothermal conditions show than can be explained by elimination of carboxyl groups.42
that at low reaction severity, dehydration can be achieved Therefore other mechanisms must be involved.
without significant decarboxylation, too.4, 6, 23, 127 It is largely One likely source for CO2 is formic acid, which is formed
unknown to which extent biomass can be carbonized in significant amounts during the degradation of cellulose
without major decarboxylation. and decomposes under hydrothermal conditions to yield
The ratio of decarboxylation to dehydration is defined as 77 primarily CO2 and H2O.4, 130, 131 Other possible sources may
be the formation of CO2 during condensation reactions4, 43, 96
molCO2
r= 2 as well as the cleavage of intramolecular bonds.47 Another
molH 2O
assumption is that H2O acts as an oxidizing agent at elevated
temperatures (above 300°C) and that additional CO2 is
It ranges from 0.2 for cellulose to 1 for lignite and is largely
formed by the thermal destruction of such oxidized units.61
independent of temperature under subcritical conditions.128
This order of magnitude of ‘r’ is confirmed by the majority Polymerization
of the published results. During common hydrothermal Some of the fragments formed from degradation of biomac-
carbonization, the rate of dehydration appears to be much romolecules under hydrothermal conditions are highly
higher than decarboxylation. reactive; this depends on both their origin and their degree
Dehydration is generally explained by elimination of of conversion. Unsaturated compounds which polymerize
hydroxyl groups.43, 79 Isolated knowledge about more easily are being created by the elimination of carboxyl and
detailed reactions exists for the case of hydrothermal degra- hydroxyl groups.79 Condensation reactions (e.g., of aromatic
dation of glucose, e.g., the dehydration of glucose to HMF or cores 43) are often accounted for some of the formation of
1,6-anhydroglucose.129 For the case of lignin, the dehydroxi- CO2 . A theoretical evaluation of possible condensation
lation of catechol is mentioned as well as the possible forma- and cleavage reactions of relevant molecular groups can
tion of water during the cleavage of phenolic and alcohol explain experimental observations (formation and composi-
groups above 150°C and 200°C, respectively.46, 94 Another tion of gases, influence of temperature and pressure). The
source of water during hydrothermal carbonization may be same considerations conclude that the rate of carboniza-
due to the condensation of fragments, which is discussed tion is increasingly determined by steric influences with a
below. higher condensation degree of aromatics.38 It thus may be
When hydrothermal conditions are applied to biomass, the concluded that the formation of HTC-coal during hydro-
physical dewatering is linked closely to the abovementioned thermal carbonization is mainly characterized by condensa-
chemical changes. These effects have been utilized for the tion polymerization, specifically aldol condensation.129, 132
drying of lignite (‘hydrothermal dewatering’) and peat (‘wet Condensation most likely proceeds mainly with the forma-
carbonization’). Due to a lower viscosity of water, destruction of H2O. Free-radical mechanisms may appear under
tion of colloidal structures, less hydrophilic functional hydrothermal conditions, but are more likely to be
groups, and gas formation, physical dewatering is enhanced dominant at supercritical conditions and at low density.133
significantly under hydrothermal conditions. Some of these At subcritical conditions, free radicals are effectively
effects are reversible, which give rise to the idea of combined saturated by the present water and hydrogen donated by
mechanical/ thermal dewatering of lignite.97 aromatization.53, 58, 59, 69
Thus, condensation polymerization is most likely governed formation of aromatic structures.132 Aromatic structures
by step-growth polymerization,134 which is supported by exhibit a high stability under hydrothermal conditions and
the observed low rate of polymerization during experi- therefore may be considered as a basic building block of the
ments. For the case of (the highly reactive) lignin fragments, resulting HTC-coal. Cross-linking condensation of aromatic
polymerization has been reported to be completed within rings also makes up for major constituents of natural coal139
several minutes above 300°C whereas at room temperature which might explain the good agreement between natural
it continues for months.122, 135 Condensation reactions of coalification and hydrothermal carbonization. Similar
monosaccharides are even slower, especially as cross-linked chemical structure characteristics of HTC-coal and natural
polymerization competes with recondensation to oligosac- coal have been mentioned in several publications.27, 43, 79, 91
charides.66 Some degradation products of monosaccharides, On the basis of these considerations it becomes evident that
for example, HMF, show a higher reactivity. It has also been the effect of hydrothermal treatment on the carbon content
noted that fragments of hemicellulose appear to stabilize decreases with a rising number of aromatic bonds. This is
fragments of lignin, slowing condensation reactions down shown in Fig.1 for the case of lignin, which consists of a
significantly.65, 136 Results from model compounds therefore significant number of aromatic structures.
have clear limits for the extrapolation to ‘real’ biomass. Aromatization appears to be significantly dependent on
The knowledge about detailed polymerization sequences temperature. Experiments on hydrothermal dewatering of
during the course of hydrothermal carbonization is lignite and peat reported aromatization above 270°C.79, 91
essentially missing. Polymerization, which forms a solid On the other hand, conversion ‘f’ as a combination of resi-
precipitation, is widely regarded as an unwanted side reac- dence time and temperature shows a steep rise of the carbon
tion and therefore is minimized to a great extent in other content of cellulose degradation products in the range of
hydrothermal processes. It remains unknown whether the f=0.2–0.35, which can be connected to aromatization43 (Fig.
soluble fraction of HTC-coal (which has been reported 1). The reaction temperatures for these time-temperature
on2, 4, 105) represents an incompletely condensed precursor of pairs range from 200–300°C for the data points of cellulose.
the non-soluble fraction or whether these two fractions are It should be clearly pointed out that duration of neither
products of different reaction paths. Precipitation recovered heating nor cooling periods are stated in many publications
from the storage of remaining solutions has been reported of the mentioned data. Although this influence on the esti-
to be completely soluble in ammonia and alkaline lye.4 The mated residence time is significant, the impact on the uncer-
observation that the remaining insoluble fraction exhibits tainty of the calculated conversion is expected to be low due
a specific surface two orders of magnitude higher than to its definition (Eqn (4)).
the unfractionated HTC-coal 105 gives some evidence that
Other mechanisms
reaction paths might either be different or that substantial
One opinion about the chemistry underlying natural
parts of the biomass are unaffected by hydrolysis. Other
coalification promotes transformation reactions within the
experiments showed that condensing fragments within the
lignin molecule instead of a fragmentation with subsequent
biomass matrix are able to ‘block’ remaining biomacromol-
polymerization.140 The physical structure of the biomass
ecules, thus preventing water access and subsequent hydrol-
would be kept to a large extent, which has been observed in
ysis which allows for different pyrolysis reactions.125, 126
nature.36 Such transformation reactions have been proposed
Aromatization for hydrothermal carbonization as well,43 but given the high
Even though (hemi-) cellulose consists of carbohydrates, it is rate of fragmentation by degradation due to hydrolysis above
able to form aromatic structures in both non-hydrous 137 and 180°C it appears unlikely that they play a key role. There
hydrothermal 30, 138 conditions. The rise of the aromaticity are some stable compounds with a crystalline structure and
of carbon structures by hydrothermal carbonization with oligomer fragments that do not hydrolyze.70, 119 For these
increasing reaction severity has been shown with 13C-NMR compounds, transformation reactions might become impor-
measurements.27 Alkaline conditions appear to enhance the tant, though their quantitative contribution is estimated to be
Figure 1. Change of carbon content with conversion f (Eqn (4)) of hydrothermal carbonization. Experimental data from
references.2–4, 6, 13, 23, 28, 29, 31, 39, 42, 103, 104, 160
comparably low at temperatures around 200°C. Demethyla- and comparable data only allows for a qualitative evaluation
tion has been used to explain the mechanism that results in a to indicate tendencies.
phenol which becomes part of a catechol-like structure of the
coal.36 Several experimental setups measured development of Hydrous conditions
minor amounts of CH4, which seems to support this mecha- It has been observed in early experiments that biomass
nism. Pyrolytic reactions have been reported to be competing above the liquid surface does not carbonize, 2, 28 a fact that
reactions under hydrothermal conditions, too.69 In general is strongly emphasized for hydrous pyrolysis experiments
they might become significant above 200°C141 though typical as well.113 It is possible to carbonize biomass in oil as well
products from pyrolysis (e.g., CO and tars) have not been as in water, but it has been observed that the carbonization
reported to be formed in significant amounts during hydro- process is accelerated by water.3, 43, 79, 93, 115 This gives rise
thermal carbonization. Carbonization of biomacromolecules, to the question of the role of water for the mentioned reac-
which do not have contact to H2O because they have been tion mechanisms. Water is a good heat transfer and storage
blocked by precipitation of condensing fragments, has also medium which avoids local temperature peaks that might
been explained by pyrolytic reactions.125, 126 result from exothermal reactions. Water hence helps to
Fischer-Tropsch-type reactions have been observed under suppress pyrolysis.3 Moreover, the importance of hot water
hydrothermal conditions, too.130 Given the high amount of as a reactant, solvent and catalyst for organic compounds
CO2 being formed by hydrothermal carbonization, they might in natural systems has been recognized, facilitating for
play a role which has not been investigated in detail so far. example, hydrolysis, ionic condensation and cleavage.142
Many of the characterizing reactions of coalification there-
fore are enhanced by the presence of water, if not initiated. 36
Influence of process parameters Some of these effects have been described in detail, for
With the knowledge of the abovementioned reaction mecha- example, for hydrolysis.65
nisms, some of the experimentally observed influences of In subcritical conditions, the presence of water gener-
process parameters can be explained. Again, lack of systematic ally promotes ion chemistry and suppresses free radical
reactions.47, 133 This enhances bond cleavage of primarily systematically. First exothermal effects during hydrothermal
hydrogen bonds, especially hydrolysis.37, 122 On the other treatment of peat have been observed just above 100°C80 and
hand, radical polymerization is suppressed by saturation it is most likely that an onset temperature (if existent) highly
of organic compounds by donation of hydrogen ions.44, 52, depends on the feed used. Based on this proposed time-
58, 60, 62
The amount of water which is necessary to keep up temperature pair, it is suspected that above a logP = 6.5 the
these influences is very small and it has been proposed that final state of HTC-coal is reached at a carbon content of 84w%.
reaction water being formed suffices for the case of confined This has been disproven by later experiments.10, 23, 30, 146
pyrolysis.53 The previously mentioned enhancing effect Another model has been developed according to the
on condensation polymerization has been experimentally kinetic approach of Arrhenius and fitted to experimental
verified for the production of HMF. Organic solvents data.128 One of the main assumptions of this model is a
significantly suppress the formation of solid precipitation.66 constant ‘r’ (Eqn (2)), which is dependent on pressure, pH
At elevated temperatures, water solvent properties are and feed for subcritical conditions only. Complete conver-
significantly enhanced and it becomes relevant even for non- sion has been defined to be attained at an oxygen content of
polar compounds. The importance of a solvent for many of the HTC-coal of 6w% because no specific coal product can
the abovementioned reaction mechanisms is evident and be defined. It was reported that the conversion of hydro-
(temperature dependent) solubility equilibria represent thermal carbonization can be expressed as:
one major influence on the reaction network. Some of the
vast amounts of dissolved compounds present in the liquid 3500 O feed − Ot
f = 50 ⋅ t 0.2 ⋅ e − T = 4
phase from hydrothermal treatment have been identified for O feed − 6
biomass,98, 143, 144 cellulose and glucose70, 129, 145 and lignin.122
This semi-empirical model has been verified elsewhere.84
Details are discussed in the references given. The results of
On the other hand, there is concern about temperature and
these analyses are highly dependent on the different reaction
residence time being exchangeable parameters and that the
parameters used in the studies. Additionally, the amount of
achievable coal is defined primarily by the reaction tempera-
water added has an impact on the product distribution.51 As
ture.16, 43 This opinion is supported by systematic investiga-
a solvent, water also has a decisive impact on the transport
tions for the simulated maturation of organic matter which
of fragments out of the matrix of the feed which keeps these
included hydrothermal conditions.53 Although the influence
fragments from the influence of reactive centers.46, 60 Without
of temperature is dominating in the abovementioned
convection, this might become a rate-determining step.125
models, the possibility of reaching similar coals by adjusting
Temperature the residence time contradicts this opinion. A concluding
It is not surprising that the reaction rate of hydrothermal study on the possibility of exchanging time and temperature
carbonization is governed by temperature to a large extent. including a verifiable range of validity was not found within
This has been expressed by two simple kinetic models, this literature survey.
both of which define a variable that describes the reaction The influence of temperature on the partial reaction
severity. It may be questioned whether the earlier ‘rule-of- mechanisms of hydrothermal degradation of glucose is
thumb’, which proposed a doubling of a reaction rate coeffi- well known and has already been covered by an exhaustive
cient ‘P’ with a temperature rise of 10K, 3 is able to withstand review.70 As an order of magnitude, hydrolysis of glucose
a closer investigation: with subsequent dehydration may take several seconds at
270°C up to several hours at 150°C.66 The rate of polymeriza-
(T -170) tion is dependent on temperature,122 too, but a systematic
3
P =t ⋅ 2 10
influence on the reaction rate of polymerization is missing.
Some indications have already been summarized above.
By this definition, the reference temperature of hydrothermal Next to the obvious effect on the rate of reaction(s),
carbonization has been set to 170°C which has not been derived temperature has a decisive influence on the number of
biomass compounds that can be hydrolyzed. Hemicellulose From the evidence gathered, it could not be finally
is almost completely hydrolyzed around 180°C, major parts concluded which hydrothermal carbonization reaction
of lignin around 200°C and cellulose significantly not before mechanism is rate determining. Both diff usion-controlled
220°C.65 Additionally, pyrolytic reactions might become transport mechanisms during biomass decomposition and
increasingly influential at higher temperatures even in the condensation polymerization are likely to govern the overall
subcritical region.69, 141 rate of reaction.
Temperature also indirectly affects hydrothermal carboni-
Pressure
zation by changing decisive properties of water. Solvent
It is important to distinguish between the kinds of forces
properties have already been mentioned. Additionally, the
that are applied. By elevating the temperature or adding
viscosity of liquid water changes up to one order of magni-
fluids, the pressure within the reactor rises isotropically.
tude depending on temperature between 0°C and 350°C.147
Solids are distributed only on the basis of gravitational
This allows for an easier penetration of porous media which
forces and possible natural convection during heating
in consequence enhances the decomposition of biomass.
periods (for the case of an unstirred reactor). In contrast,
Residence time some experiments applied directed forces in order to simu-
Hydrothermal carbonization of biomass is a comparably late lithostatic pressure.10, 20, 22 This leads to a minimization
slow reaction. Reported residence times range from some of free volume and compaction of solids. For the purpose of
hours up to several days. In many experiments residence this survey, the former is being referred to as reaction pres-
times have been varied systematically, but its influence was sure and the latter as compaction.
not evaluated elaborately.3, 13, 23, 29, 31, 44, 73, 77, 91, 128 A longer The reaction pressure influences the reaction network
residence time generally increases reaction severity. Resi- according to the principles of LeChatelier. Reaction equi-
dence time in comparison with temperature has already librium shifts to solid and liquid phases at rising reaction
been discussed. In contradiction to the expected lower yield pressure, simultaneously to reactants with a lower number
at higher reaction severity, it has been observed that a longer of moles. It can be easily derived that both dehydration
residence time may significantly increase the yield of HTC- and decarboxylation as primary overall reactions are
coal.23, 148 This could be explained by ongoing polymeriza- being depressed at elevated reaction pressure. This effect
tion of solved fragments in the liquid phase which finally has been verified experimentally but proved to have a low
lead to precipitation of insoluble solids. impact on both hydrothermal carbonization and natural
Experiments with short residence times ranging from coalification.16, 53, 113, 139, 149, 150 The removal of extractables
some minutes up to an hour could already lead to a from biomass is generally believed to be facilitated at higher
significantly higher heating value of peat.72, 74 It is unknown reaction pressure. It is assumed that encapsulated gases are
whether the feed was subject to carbonization or whether compacted and dissolved more easily in water which allows
other effects prevailed. In case of biomass, these may a broader access of the liquid phase.118, 125
include the removal of extractable oxygen-rich compounds An early publication of experiments with a compaction of
(e.g., fragrances and oils) and/or hydrolysis of hemicellu- HTC-coal during hydrothermal carbonization reported some
lose, which have a higher heating value below the average additional rise in carbon content.2, 151 Due to a comparably
of the respective feed. Both extraction and hydrolysis take wide scatter of reaction results, this slight change is difficult
place within minutes instead of hours for the rest of carbon- to evaluate afterwards. Furthermore, it remains unclear
ization.65, 70, 118, 119, 125, 144 On the other hand, results from whether the rise in carbon content is due to the additional
some experiments with a residence time of half an hour hydrothermal treatment. The almost trivial observation that
yield an HTC-coal with a higher heating value equal to compaction leads to a simple briquetting of HTC-coal, might
or even greater than that of (‘typical’) lignin.15, 103, 104 Th is be of interest for a technical application.2, 8 Thus, compac-
cannot be achieved by sole removal of components with a tion primarily affects physical characteristics (as already
low heating value. mentioned). Condensation polymerization between solids
is facilitated as well due to an easier exchange of hydrogen the amount of TOC lost by discharging wastewater
ions which becomes significant in natural coalification in the becomes low relative to the amount of feed. This source
range of anthracite.139 But these chemical impacts of compac- of carbon loss has to be considered; organics in the water
tion are unlikely to significantly affect technical applications have been reported to reach up to 10–20% of the
of hydrothermal carbonization because polymerization of feed.15, 26, 28, 76, 77, 103, 153
solids is generally a very slow process due to low diff usivity. No publication has been found that systematically investi-
Compaction may enhance the rate of reaction indirectly by gates the abovementioned theoretic considerations experi-
allowing a higher biomass/water ratio. mentally which leaves them without further verification
until now.
Solid load
Basic considerations conclude that the ratio of biomass to pH value
water (i.e., the solid load) represents a significant parameter Many studies on hydrothermal carbonization observed a
for the hydrothermal carbonization of biomass, too. At a drop in pH during reaction. It has been proposed that a
solid load close to zero, for example, during percolation variety of organic acids are being formed and acetic, formic,
hydrolysis, biomass may be nearly completely dissolved lactic and levulinic acid have been identified as (inter-
leaving little residue.65 On the other hand, raising the mediate) products so far.4, 22, 28, 43, 66, 116, 121, 153 A neutral
solid load by evaporating water recovers large parts of the to weakly acidic environment appears to be necessary to
dissolved organic fraction as solid material.15 The fact that a achieve a simulation of natural coalification.19 Different
higher concentration of glucose at the beginning of the reac- acids and bases have been applied in experiments and a
tion leads to a larger fraction of solid precipitation during significant impact on reaction rate and product character-
hydrothermal treatment is also known for HMF produc- istics/distribution has been observed.23, 24, 93, 127 The type of
tion.66 This is easily explained by the higher concentration of acid used plays an important role; 13 small amounts of Arrhe-
monomers in the liquid phase, which generally enhances the nius acids, for example, generally catalyze dehydration.70
chance of polymerization.71 For the case of HMF produc- It should also be noted that a high pH value tends to result
tion, residence times are too short to approach equilibrium, in higher H/C ratios of the product and a coal with higher
which means that a rise of feed concentration also increases bitumen content. 13, 23, 39, 83 This effect is generally utilized
the concentration of monomers in the liquid phase. A higher for hydrothermal liquefaction. One known effect is the
biomass to water ratio to start hydrothermal carbonization enhancement of hydrolysis of cellulose under acidic condi-
is unlikely to raise the monomer concentration in the liquid tions compared to a neutral environment. Hydrolysis (side)
phase because the residence time is long enough to approach products can therefore act as autocatalysts, but their effect
solution equilibrium, 85, 95, 152 which is backed by experi- is limited at higher temperatures due to the fact that the
mental observations.153 This has also been shown for the case acidic dissociation constant decreases.65 The effect of CO2
of some inorganics.98 But as the concentration is likely to as acid catalyst (i.e., by ionization to carbonic acid) has been
rise faster at a higher solid load, polymerization would start pointed out as well.154 Effects of acidic conditions on other
earlier which would positively influence the overall resi- reaction mechanisms, such as decarboxylation and conden-
dence time. Additionally, evaporating water can shift these sation polymerization, is largely unknown. It has been
solution equilibria to form solid precipitation. The reaction reported, however, that weakly acidic conditions improve
equilibrium of condensation polymerization which proceeds the overall rate of reaction of hydrothermal carbonization.127
under formation of water is generally shifted toward poly-
mers by removing reaction water from the system. At the
Products
same time, a higher solid load might shift the reaction
network because fewer monomers are in solution relative It is not surprising that there is a vast amount of (intermediate)
to the amount of feed used. This has been observed for products involved in the course of hydrothermal carbonization
hydrothermal degradation of cellulose.145 Simultaneously, based on the diversity of the different mechanisms involved.
Many of these have been identified.65–67, 70, 122, 136 For a tech- may approach that of lignite or even sub-bituminous coal
nical application, a simple filtration to yield product groups depending on reaction severity (Fig. 3). An exception can be
appears feasible for first installations. More advanced separa- noted for the case of resin, whose H/C ratio is nearly unaf-
tion techniques to obtain specific chemicals of interest still fected. It has been observed that coal from lignin tends to
need to be developed to prove economic feasibility. Therefore have a lower hydrogen content 23 and coal from cellulose tends
product groups will be presented according to their state of to achieve a higher carbon content (Fig. 1).31
aggregation in the following sections. Complete and detailed Similar to natural coal, a fraction of HTC-coal is soluble
mass balances for hydrothermal carbonization are not avail- in different solvents, namely benzol-alcohol mixtures,
able,1 those published so far are either incomplete or based on alkaline solutions and ammonia.3, 4, 13 C-NMR spectra of
carbon only.15, 23, 77, 79, 114 The distribution of product groups, cellulose and wood have been reported to approach those of
which is illustrated in Fig. 2, should therefore be regarded as natural coal and pyrolysis yields comparable distillates.26,
27
a qualitative representation to give an overview. It does not Based on these observations, it has been concluded that
represent measured proportions although it is realistic in the the change in carbon-bridge bonding is similar to that of
order of magnitude for cellulose. Actual product distribution natural coalification and that the skeletal structure of HTC-
heavily depends on process conditions and feed. It should be coal is comparable to that of natural coal. But it has also
noted that the liquid fraction will always contain more or less been emphasized that the amount of functional groups,
significant amounts of solid particles which cannot be recov- especially oxygen-containing groups, remains higher than
ered with the applied filtration technology of choice. The use that of natural coal. It should be noted that these results are
of ‘total organic carbon’ (TOC) has been chosen to account for neutral to weakly acidic conditions only without special
for those dispersed coal particles. additives (as the case for other experiments13, 112). Although
HTC-coal still exhibits a higher amount of functional
Solids groups compared to natural bituminous coal, one impor-
The solid fraction has attracted increasing interest in the latest tant effect of hydrothermal carbonization is the elimina-
research. It will be referred to as ‘HTC-coal’ in the following tion of mainly hydroxyl and carboxyl groups resulting in a
sections. Similar to natural coal, it represents an agglomera- product which has a lower hydrophilicity than the starting
tion of different chemical substances. A first approximation material.93 This effect of decreasing the amount of func-
to characterize coal is an elementary analysis which has been tional groups is systematically utilized by hydrothermal
widely applied for characterizing HTC-coal, too. Elemental dewatering.89, 90 The behavior of inorganics during hydro-
composition reached by hydrothermal carbonization thermal carbonization is largely unknown. Major parts
remain within the HTC-coal but there is little evidence on
how this ash content is dependent on process parameters.
There are studies to evaluate a combined demineralization
and mechanical/ thermal dewatering of lignite which show
that a significant fraction is solved in the liquid phase.98 This
creates the option to produce a fuel with a lower ash content
than the original biomass.
Recent advancement in research on hydrothermal
carbonization revealed interesting results on the physical
structure of HTC-coal. It has been noted early that major
parts of it are finely dispersed in the liquid phase.28 Closer
investigations showed that HTC-coal has a small specific
surface which can be enhanced by two orders of magnitude
Figure 2. Products of hydrothermal carbonization, separated by removing extractables or by thermal treatment, thus
according to their state of aggregation. reaching a comparable specific surface to conventional
Figure 3. Behavior of different feed with increasing reaction severity during hydrothermal carbonization.
Experimental data from 7, 15, 23, 29, 31, natural maturation trends.155, 161
charcoal.104, 105 Observations on the nanostructure of HTC- of hydrothermal carbonization can be processed with
coal revealed further potential for technical applications aerobic or anaerobic treatment to lower the TOC
as functionalized carbonaceous material.101, 103, 106, 108, 111, significantly.73, 76, 81
112, 127, 148
Depending on the starting material and catalyst/ There have been no reports on a second immiscible liquid
template-assisted treatment methods, nanospheres, nanoca- phase during hydrothermal carbonization, even after treat-
bles, nanofibers, submicrocables, submicrotubes and porous ment between 300 and 360°C which is regarded as the
structures can be created with various functional groups.102 major oil generation window at hydrous pyrolysis. As reac-
tion conditions are comparable (i.e., temperature, pressure,
Liquids residence time and pH), the formation of a second liquid
Many experiments show that the amount of H2O formed oil phase must depend on the feed. Oil building poten-
during hydrothermal carbonization is significantly higher tial is highest for kerogenes from marine and lacustrine
than that of CO2 . Both products are of low economical environments.113, 155 This dependency on the feed changes
interest, whereas H2O plays a significant role as a solvent considerably when applying alkaline conditions.
and reactant. The liquid phase therefore has a high load of
inorganics and organics, many of which represent poten- Gases
tially valuable chemicals. Unless they are being recovered, The gas formed during hydrothermal carbonization mainly
these organics might become a major loss. Additionally, this consists of CO2 . Minor fractions of CO, CH4 and H2 as
highly loaded liquid phase causes problems both within the well as traces of CmHn have been reported widely, too.
process equipment and by discharging.82 Ongoing condensa- Depending on the ratio of freeboard to liquid phase in
tion polymerization and/or precipitation of solid particles the reactor, the amount of CO2 solved in water may easily
might block sensitive parts especially when accompanied be as high as the amount present in the gaseous phase.156
by high temperature differences.70, 72 These problems are The critical temperature of water can thus be significantly
comparable to other hydrothermal conversion processes for reduced, which needs to be considered in order to secure
biomass and still need further investigation. The wastewater subcritical conditions.113 Most publications did not mention
the procedure of gas measurements; a detailed comparison The residence time should generally be kept as long as
of published data therefore is unreliable. Additionally, gas possible to allow for a ‘complete’ reaction and reduce organic
measurements have been reported to scatter up to 20% losses in the wastewater. One economic way of achieving
between experimental setups with identical conditions.58, longer residence times is the recirculation of water.72, 73 With
157
Basic trends published show that the amount of gaseous this method, the energy content of the hot water can be
products increases with rising reaction temperature. Simul- recovered while keeping the consumption of fresh water low.
taneously, the fraction of CO decreases while those of CH4 Additionally, autocatalytic effects of organic acids might
and H2 increase.4, 6, 15, 28, 79, 157 give some improvement. On the other hand, starting hydro-
For an energetic use of HTC-coal it is desirable to achieve thermal carbonization in a solution that is already close to
a high heating value. The removal of oxygen from the feed its equilibrium regarding TOC and mineral content must
by decarboxylation is favorable from that point of view and have some impact on the reaction network and/or kinetics.
preferably utilized by hydrothermal liquefaction.70 On the The consequences cannot be determined yet; probable effects
other hand, it might be interesting to keep decarboxylation as are faster polymerization and higher ash content of the
low as possible in order to allow for a high carbon conversion produced HTC-coal.
from feed to HTC-coal; for example, to allow for an efficient Higher temperatures generally accelerate hydrothermal
carbon sequestration.158, 127 The target will be most likely set carbonization and might even allow for a higher achiev-
by the intended use of the HTC-coal; it should be noted at able carbon content. The downside is higher pressure with
this point that the total amount of carbon lost by CO2 is low according investment costs for pressure equipment as well as
compared to non-recoverable TOC in the wastewater. higher energy consumption generally. Therefore the required
The measurement of the amount of CO2 developed might give characteristics of the produced HTC-coal have to be considered
a technically viable control of the reaction progress because carefully according to the intended application. As concluded
decarboxylation is one of the major changes to the feed.128 for the hydrothermolysis of biomass, an elaborate temperature
profile may have significant impacts on the reaction.65 Frac-
Considerations for the design tionation of biomass components which has been achieved by
of the process these means does not necessarily need to be of importance to
hydrothermal carbonization but might give some indications
Based on the theoretical and experimental data which have
for process optimization. Moreover, the published data are not
been gathered in this review to describe reaction mecha-
sufficient to derive a desirable temperature profile.
nisms and the influence of process parameters, basic conclu-
As hydrolysis appears to be diff usion controlled and may
sions for a fundamental process design can be drawn.
represent a rate-determining step, grinding of the feed prior
The ratio of biomass to water should be kept as high as
to carbonization appears to be an advantage. However, in
possible to enhance polymerization. Less use of water is
addition to the increased energy demand and investment
generally desirable for hydrothermal processes to keep
cost necessary for such an additional processing step, it
both energetic losses and investment costs for pumps and
remains unclear whether there is any significant advantage.
heat exchangers low.70 On the other hand, it is of funda-
Carbonization also occurs within the biomass matrix105,
mental importance to ensure that the feed is submerged 125
and any additional benefit from keeping carbonization
during the whole reaction period. This could be achieved
outside this matrix cannot be quantified yet.
through compaction by mechanical means such as a press or
compressing screw. It should be noted that the bulk density
changes significantly during the whole process due to mass
Conclusions
loss of solids and new physical structures. Additionally, it Hydrothermal carbonization can produce a largely homog-
could be of advantage to remove heat by direct steam extrac- enized solid, coal-like fuel from (preferably) moist biomass.
tion. This could both decrease the amount of water in the A major side-product next to the inevitable formation
system and reduce heat exchange. of H2O and CO2 is a vast amount of organic compounds
dissolved in the liquid phase, mainly saccharides and their Acknowledgment

degradation products, organic acids and dispersed colloidal The authors would like to thank the German Federal Envi-
coal particles. Hydrolysis, dehydration, decarboxylation, ronmental Foundation for making this work possible by
aromatization, and condensation polymerization have been sponsoring it as part of its scholarship program.
recognized as relevant reaction mechanisms during hydro-
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HTC Summary and Discussion of Chemical Mechanisms For Process Engineering

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Review

Introduction in recent years and R&D projects have been launched to

H conversion process for biomass to yield a solid, coal-

Table 1. Selected results from different hydrothermal carbonization experiments.

Early experiments with oil discovered that cellulose starts Decarboxylation

dissolved in the liquid phase, mainly saccharides and their Acknowledgment

Considering the potential of some of its possible applications, 26:393–396 (1913).

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