Biomass Conv. Bioref.
DOI 10.1007/s13399-014-0137-3
ORIGINAL ARTICLE
Hydrothermal carbonization of various lignocellulosic biomass
Joan G. Lynam & M. Toufiq Reza & Wei Yan &
Victor R. Vásquez & Charles J. Coronella
Received: 18 March 2014 / Revised: 19 June 2014 / Accepted: 23 June 2014
# Springer-Verlag Berlin Heidelberg 2014
Abstract As a non-food, renewable energy resource, ligno-
cellulosic biomass can be used for reducing greenhouse gas
emissions. Hydrothermal carbonization (HTC) is a process to
prepare the lignocellulosic biomass for subsequent thermo-
chemical conversion. Biomass is reacted in hot compressed
water at temperatures between 200 and 275 °C and at pres-
sures sufficient to maintain liquid water. HTC was performed
on corn stover, rice hulls, Tahoe mix (Jeffrey pine and white
fir), switch grass, and Loblolly pine. These biomass sources
encompass a variety of types, including a primary agricultural
residue, a secondary agricultural residue, a forest product
removed to reduce wildfires, a primary energy crop, and a
primary forest crop. HTC reaction temperature was found to
be the process variable with the greatest effect. For the five
biomass studied, hydrochar mass yields were found to de-
crease with increasing reaction temperature, while higher
heating values increased with increasing reaction temperature.
Differences in these results among biomass sources were
found to correlate with their original hemicellulose, lignin,
aqueous soluble, and ash contents. These components ap-
peared to be observable in scanning electron microscope
images of hydrochar.
Electronic supplementary material The online version of this article
(doi:10.1007/s13399-014-0137-3) contains supplementary material,
which is available to authorized users.
J. G. Lynam : V. R. Vásquez : C. J. Coronella (*)
Chemical & Materials Engineering Department, University of
Nevada, 1664 N. Virginia St. MS 170, Reno, NV 89557, USA
e-mail: coronella@unr.edu
M. T. Reza
APECS Group, Leibniz Institute for Agricultural Engineering,
Max-Eyth-Alee-100, 14469 Potsdam, Germany
W. Yan
Gas Technology Institute, Energy Conversion Division, Des Plaines,
IL 60018, USA
Keywords Wet torrefaction . Agricultural residues .
Subcritical water . Forest products . Pretreatment . Hydrochar
1 Introduction
Biomass has the potential to reduce the world’s dependence
on fossil fuels. These are by their nature limited and often
difficult to access without risking environmental damage. The
consumption of fossil fuels increases the amount of CO2 in the
atmosphere, contributing to global warming. As a renewable
energy source, biomass uses as much CO2 in its growth as it
releases as a fuel. It is considered to be nearly carbon neutral,
with minimal contributions to global warming. In the USA
alone, over 97 million dry tonne of biomass per year is
estimated available from forested areas, while 162 million
dry tons of agricultural residue and waste per year could be
supplied by agricultural lands [1]. Although ethanol can be
made from corn and other renewable food crops, many believe
it is unethical to use food sources for the production of liquid
transportation fuels. Lignocellulosic biomass is not only a
non-food resource, but can even be a waste product, as in
the case of rice hulls or corn stover.
After mechanical size reduction, lignocellulosic biomass
can be used for direct firing or cofiring with coal for power
production [2]. Liquid biofuels can be obtained from ligno-
cellulosic biomass by either biochemical or thermochemical
conversion routes [3]. Unfortunately, diverse biomass feed-
stocks exhibit diverse handling characteristics, complicating
their general use as fuel sources. This challenge is further
compounded by the expensive logistics of seasonal availabil-
ity in the case of agricultural wastes or wide distribution in the
case of forestry. There is a need to develop pretreatment
processes that produce a uniform solid fuel from lignocellu-
losic biomass with increased higher heating value (HHV),
increased hydrophobicity for better storage, and

homogeneous handling characteristics. Increased HHV means
that less biomass can be transported to generate the same
amount of power. Hydrothermal carbonization (HTC), also
known as wet torrefaction, or dry torrefaction can be used for
this purpose [4]. The objective of this study is to characterize
the hydrochar produced by HTC, looking at different types of
biomass, and to investigate the effect of process conditions on
hydrochar properties.
An alternative, dry torrefaction (mild pyrolysis) is typically
performed in an inert atmosphere at 0.1 MPa between 225 and
300 °C using reaction times which vary between 30 min and
several hours [4, 5]. Dry torrefaction produces a lower HHV
solid product compared to HTC when performed at similar
temperatures and for similar reaction times [4]. Another dis-
advantage of dry torrefaction is the energy needed to dry the
feedstock prior to reaction, considered to outweigh the energy
released by dry torrefaction if the feedstock has more than
30 % water [6]. Since HTC’s solid product is more hydropho-
bic, less energy is required to dry it than to dry raw biomass
[7]. However, advantages of dry torrefaction include low
pressure operation and the fact that it requires no water
recycling system [5].
Hydrothermal carbonization (HTC) is also known as hy-
drothermal pretreatment or wet torrefaction. HTC is usually
performed at temperatures higher than 180 °C, at pressures
high enough to ensure liquid water, and under an inert atmo-
sphere, which prevents wet oxidation of lignin [8]. The HTC
reaction time has been reported to be 1 min to several hours,
although most of the reactions that remove mass from the
biomass seem to occur within the first 20 min after bringing
the reactor to temperature [9–12]. Additional reactions in the
liquid phase occur subsequently [8]. Additives, such as acids
or bases, can affect the formed products [9]. Adding acid to
the reactants can increase the HHV of the solid product, as
well as reduce the mass yield [13]. Water, acting as both
reactant and solvent, shows different physical and chemical
properties depending on the operating conditions [14]. At
temperatures between 227 and 327 °C, water may act as both
a base and an acid because its ionic product is maximized. In
addition, water’s dielectric constant is decreased at these tem-
peratures so that it acts more like a non-polar solvent [15].
During HTC, hemicelluloses and cellulose are hydrolyzed to
oligomers and monomers, while lignin is mostly unaffected at
temperatures below 275 °C [9, 16–20]. The solid product,
hydrochar, which is also known as biochar or biocoal, has
reduced equilibrium moisture content, which favors long-term
storage [7]. The hydrochar is quite friable and is readily made
into durable pellets to facilitate handling [21].
The present work investigates the importance of tempera-
ture, time, water to biomass ratio, and biomass particle size on
one representative biomass. The effect of HTC on mass yield
and increase in fuel value for four other biomass is also
studied.
Biomass Conv. Bioref.
2 Experimental
2.1 Materials
Biomass feedstocks acquired for testing include Loblolly pine
(Alabama, USA), pelletized corn stover (Pennsylvania, USA),
Tahoe mix (a mixture of Jeffrey pine and white fir from the
Tahoe forest), switch grass (Nevada, USA), and rice hulls
(California, USA). HHVs are 19.5, 15.6, 20.3, 15.3, and
20.3 MJ/kg for loblolly pine, corn stover, Tahoe mix, switch
grass, and rice hulls, respectively.
2.2 Hydrothermal carbonization
HTC of lignocellulosic biomass was performed in a 100 mL
Parr bench-top reactor (Moline, IL) at temperatures ranging
from 200 to 280 °C. The temperature of the reactor was
controlled using a Single Display Proportional-Integral-
Derivative (PID) Controller (Winona, MN). The reactor pres-
sure was autogenic and was indicated by a pressure gauge
ranging from 1.4 to 6.9 MPa. In other words, the reactor
pressure was approximately that of the vapor pressure of water
under the same conditions. For each run, a mixture of biomass
feedstock and water was loaded into the reaction vessel. The
water to biomass mass ratio was either 5:1 or 10:1. Prior to the
reaction, the biomass was stirred manually to ensure complete
wetting. Nitrogen was passed through the reactor for 10 min
prior to each run to purge oxygen from the reactor. Heating of
the reactor required 15–30 min, after which the reaction was
maintained at the desired temperature for either 5 or 20 min.
Next, the reactor was cooled at room temperature rapidly by
immersion into an ice bath. The gaseous product was released
without further evaluation. The liquid and solid products were
separated by vacuum filtration using a 0.6 μm Whatman filter.
All reactions were performed at least twice, and the average
reported. Mass yield measurements had uncertainties of ±5 %.
2.3 Heat of combustion
Heats of combustion of solid samples were measured in a Parr
1241 adiabatic oxygen bomb calorimeter (Moline, IL). Solid
samples (0.5–1.0 g) were dried at 105 °C for 24 h prior to
analysis. The uncertainty of measurements is ±0.5 MJ/kg.
2.4 Fiber analysis
The van Soest method of NDF-ADF-ADL (neutral detergent
fiber, acid detergent fiber, and acid detergent lignin) dissolu-
tion was used to determine the percentage of aqueous solu-
bles, hemicellulose, cellulose, and lignin components in bio-
mass samples [22]. In untreated biomass, hemicellulose is the
fraction present in NDF but not in ADF, while cellulose is the
fraction present in ADF but not in ADL. Mass removed by
Biomass Conv. Bioref.
neutral detergent is considered to be soluble in water (aqueous
solubles). Klason lignin content was found by subtracting ash
content from the ADL. Ash was determined by (NREL/TP-
510-42622) [23]. Fiber analysis measurements made with this
method are generally accurate to ±5 % [13]. Application of
this fiber analysis technique to HTC-treated lignocellulosic
biomass is problematic, since the solid products of HTC likely
contains fractions with solubility properties distinct from
those present in untreated biomass, as discussed further in
Sections 3.2 and 3.3.
2.5 Scanning electron microscopy
An FE-SEM Hitachi scanning electron microscope (SEM)
model S-4700 was used to visualize pretreated loblolly pine.
Loblolly pine samples (0.5-mm mesh size) either raw or
pretreated at 200, 230, and 260 °C were used for SEM images.
The samples were maintained on special studs and platinum
coated with polaran coater tar 5,000, under an argon atmo-
sphere for a coating thickness of approximately 1,000 Å. The
samples were dried in a 105 °C oven for 24 h prior to analysis.
A voltage of 15–20 kV with a magnification of 250–1,000
times was used for the images
2.6 Proximate analysis
Hydrochar samples were analyzed with a Perkin Elmer TGA-
7 Thermogravimetric Analyzer (Waltham, MA) to determine
the contents of moisture, volatile matter, and fixed carbon
[24]. Thermogravimetric analysis was carried out under a
nitrogen purge at a constant rate of 50 mL min−1 to prevent
oxidation of samples. Samples were first heated up to 105 °C
at the rate of 10 °C min−1, maintained at 105 °C for 10 min,
then rapidly increased to 900 °C at the rate of 50 °C min−1, and
held at that temperature for 60 min. Mass evaporating at
105 °C was considered to be moisture. Mass evaporating at
temperatures between 105 and 900 °C was referred to as
volatiles. All mass remaining after heating to 900 °C consisted
of fixed carbon and ash [24].
2.7 Experimental design
The following variables were initially investigated using lob-
lolly pine as a representative biomass: HTC temperature (T),
time of HTC reaction at temperature (t), mass ratio of water to
loblolly pine (R), and mesh size of biomass (S). Each variable
was set at either a low or high level, as indicated in Table 1.
Experimental order was randomized with duplicates of each
condition and the average reported. A half factorial design was
used to provide level IV resolution, such that no main effect
was aliased with any other main effect or two-way interaction.
This type of experimental design gives valuable information
about which variables or interaction of variables produce the
largest effect with the least number of experiments.
3 Results and discussion
3.1 Effects of reaction temperature, holding time, water
to biomass ratio, and particle size
Important dependent variables for HTC include mass yield,
energy densification, and energy yield. Mass yield is defined
as the mass ratio of dried hydrochar to dried reactant biomass.
Energy densification is the ratio of the higher heating value
(HHV) of the dried hydrochar to that of the original dried
biomass and are both reported on an ash-free basis. The
energy yield is defined as the mass yield times the energy
densification and describes how the total fuel value of the
hydrochar relates to the fuel value of the original biomass.
Reaction temperature (T), HTC holding time (t), water to
biomass ratio (R), and biomass particle size (S) are considered
to be the important process variables for HTC [25]. Loblolly
pine was selected as a representative lignocellulosic biomass
to investigate these parameters. In any reaction, temperature
and time influence the products generated. Initial concentra-
tion of the biomass reactant (the inverse of the water to
biomass ratio) has been reported to be a significant parameter
for HTC [26]. The mesh size of the loblolly pine was also
varied to investigate the possible mass transfer limitations.
Table 1 indicates a trend toward lower mass yield with in-
creasing holding time. Mass yield was only 42.0 % at the
higher reaction temperature with lower biomass concentration
(higher water to biomass ratio). It is possible that reduced
particle size also reduces mass yield, which would be expect-
ed if any mass transfer limitations occur. However, the most
important product changes occur with temperature change. A
reaction temperature increase from 200 to 260 °C causes a
large decrease in mass yield and a large increase in energy
densification (Table 1). For example, mass yield for the runs at
200 °C and 5 min (Table 1) is near 86.1 %, while mass yields
for runs at 260 °C and 5 min are near 55 %, which is a
substantial decrease with increasing temperature. Energy yield
also decreases with increasing reaction temperature; it goes
from near 95 % to close to 70 % for the same runs. Since
energy yield is the product of mass yield and energy densifi-
cation, this decrease is due to the large decrease in mass yield.
Energy densifications for all the 200 °C runs were near 1.1,
while the 260 °C runs had energy densifications near 1.4. This
means that the higher reaction temperature runs (260 °C)
produced hydrochar with fuel values 40 % higher than that
of raw loblolly pine, while the lower reaction temperature runs
(200 °C) gave hydrochar with fuel values 10 % higher than the
raw loblolly pine. A statistical analysis (ANOVA) of the

Table 1 Effect of HTC reaction temperature (T), holding time (t), water biomass ratio (R), and particle size (S) on mass yield, energy densification, and
energy yield for Loblolly pine
T (°C) t (min) R (g water/g pine) S(mm)
200 5 5 0.16
200 5 10 0.24
200 20 5 0.24
200 20 10 0.16
260 5 5 0.24
260 5 10 0.16
260 20 5 0.16
260 20 10 0.24
results shows that at 95 % confidence, only reaction temper-
ature significantly affects the mass yield and energy densifi-
cation. Other variables (holding time, water to biomass ratio,
and biomass feedstock size) were shown to have statistically
insignificant effects on the measured variables. The statistical
analysis also shows that the interactions among the four
variables were not significant. Therefore, manipulation of
these variables can be done independently within the variable
range of the experiments.
The literature shows temperature to be a significant factor
in HTC, with other process variables less consequential. The
influence of holding time and water to biomass ratio varies
with biomass feedstock. Gao et al. (2013) found times less
than 4 h to give similar hydrochar properties when water
hyacinth was the feedstock, and Heilmann et al. (2010) found
time was not a significant variable when HTC was applied to
microalgae [27, 28]. However, when applied to distiller’s
grain as a feedstock, Heilmann et al. (2011) reported that time
was a significant factor, with increased carbonization when
time was increased from 0.5 to 2 h [29]. For microalgae and
distiller’s grain, higher water to biomass ratio (19:1) gave
lower mass yield than a lower one (3:1) [28, 29]. Rogalinski
et al. (2008), when using rye straw, found particle size and
biomass concentration to have no effect on mass yield [30].
Clearly, biomass type plays an important role in determining
the effects of process variables. Optimization for each feed-
stock needs to be considered independently.
3.2 Change in biomass and temperature effects on mass yield,
energy densification, and energy yield
Due to the significant effect of reaction temperature, hydro-
thermal carbonization (HTC) of various types of biomass was
performed at temperatures of 200, 230, and 260 °C, using
water to biomass ratio of 5:1 and a holding time of 5 min.
Figure 1 shows the mass yield, energy densification, and
energy yield results for rice hulls, corn stover, Tahoe mix,
switch grass, and Loblolly pine. Mass yield ranged from 30 to
94 % and definitely decreases with increasing HTC reaction
Biomass Conv. Bioref.
Mass yield (%) Energy densification Energy yield (%)
86.1 1.11 95.5
87.2 1.07 93.5
85.7 1.15 98.4
79.0 1.12 88.1
57.0 1.44 81.8
53.6 1.24 66.3
50.0 1.42 71.0
42.0 1.48 61.9
temperature for all biomass. Such a decrease would be ex-
pected, since the rate of mass loss during HTC follows an
Arrhenius form [20].
A closer look at the makeup of the biomass can help to
understand these results. Lignocellulosic biomass is consid-
ered here to consist of five fractions: hemicelluloses, cellulose,
lignin, aqueous solubles, and ash. Table 2a shows fiber anal-
ysis data for each of these raw biomass sources. Biomass with
greater content of hemicellulose and aqueous solubles results
in lower mass yield of hydrochar after HTC, particularly at
260 °C. For example, switch grass and corn stover have more
hemicellulose and aqueous solubles compared to the other
biomass tested and exhibited a lower mass yield at 260 °C.
The softwood biomass, Tahoe mix and Loblolly pine, have
lower amounts of hemicellulose and aqueous solubles, and
exhibit higher mass yield at 260 °C. These results suggest that
hemicellulose and aqueous solubles react easily in the hydro-
thermal carbonization (HTC) process [4]. Other published
work supports this conclusion [31–34]. Reza et al. (2013)
found the rate constant for hemicellulose hydrolysis to be
4.5 times that of cellulose at 260 °C for HTC and claimed
that the aqueous solubles reaction rate is nearly instantaneous
[20].
Ash tends to be inert in the HTC process, particularly at
lower temperatures. For this reason, biomass with higher ash
content, such as corn stover and rice hulls, shows higher mass
yields for a 200 °C HTC reaction temperature. However,
when HTC causes biomass removal from the lignocellulosic
matrix, the ash incorporated in the matrix may be released
simultaneously [35]. This would explain a decreased mass
yield for corn stover and switch grass at higher HTC reaction
temperatures. Rice hulls, with their peculiar silicon coating
and extraordinarily high ash content, retain ash during HTC,
thus maintaining a higher mass yield than the other grass-like
biomass, despite their relatively high aqueous solubles content
[36].
It is possible to determine a fiber analysis on the HTC
biochar, but the results must be interpreted with care, as the
components in the char may have quite different solubility and
Biomass Conv. Bioref.

Fig. 1 Effect of temperature on a

a) mass yield (%), b) energy 95
densification, and c) energy yield
(%) for rice hulls, pelletized corn 85
stover, Tahoe mix (a mixture of 75
Jeffrey pine and white fir from the Mass rice hulls
65
Tahoe forest), switch grass, and Yield corn stover
Loblolly pine (%) 55 Tahoe mix
45 switch grass
35 Loblolly pine
25
180 200 220 240 260 280
HTC Temperature (°C)
b 1.45
1.40
1.35
1.30
Energy 1.25 rice hulls
Densi- corn stover
1.20
ficaon Tahoe mix
1.15
1.10 switch grass
1.05 Loblolly Pine
1.00
180 200 220 240 260 280
HTC Temperature (°C)

c
95

85

Energy 75 rice hulls

Yield 65 corn stover
(%) Tahoe mix
55
switch grass
45
Loblolly pine
35
180 200 220 240 260 280
HTC Temperature (°C)

Table 2 Fiber analysis of (a) raw biomasses and (b) Loblolly pine raw and HTC pretreated at 200 °C and 260 °C

Hemicellulose (%) Cellulose (%) Lignin (%) Aqueous solubles (%) Ash (%)

(a) Biomass
Rice hulls 14.9 39.8 11.3 12.9 21.1
Corn stover 26.3 29.7 11.3 26.3 6.5
Tahoe mix 18.2 50.7 23.8 6.1 1.3
Switch Grass 28.1 37.1 5.6 21.8 7.4
Loblolly pine 11.5 55.4 30.0 2.7 0.4
(b) Loblolly pine
Raw 11.5 2.7 0.4
200 °C HTC 1.1 15.2 0.5
260 °C HTC 0.7 18.1 0.8

reactivity characteristics than native biomass. The content of
hemicellulose is determined by the difference in NDF and
ADF. The presence of compounds in the NDF not in the ADF
could include compounds other than hemicellulose. However,
it is safe to conclude that when the difference between the
NDF and the ADF in a treated biochar is less than that in the
raw biomass, then the hemicellulose is no longer present in the
solid. The results of this limited fiber analysis are shown in
Table 2b. The experimental conditions of the treatment at
200 °C used a water to biomass ratio of 5:1, a holding time
of 5 min, and a particle size of 0.16 mm, and those for the
260 °C run were the same except that particle size was
0.24 mm. The mass yield for 200 °C was 86.1 % and for
260 °C was 57.0 %, indicating that the higher temperature
removed more of the biomass material from the hydrochar. At
200 and 260 °C, most of the loblolly pine’s hemicellulose is
apparently extracted, and likely hydrolyzed to monosaccha-
rides, such as xylose, arabinose, galactose, and mannose [34,
37]. A preliminary analysis of the liquid products by HPLC,
not shown here, showed the presence of various sugars (xy-
lose, glucose, arabinose, galactose, and mannose), consistent
with other investigations [37–39]. While soluble in water,
these sugars are likely to precipitate into the pores of the
hydrochar, accounting for increased aqueous solubles found
in the hydrochars, as shown in Table 2b.
For all the biomass investigated, energy densification in-
creased with HTC reaction temperature, as shown in Fig. 1b.
Hemicellulose and cellulose have a lower HHV compared to
lignin [40]. When they are removed, a higher proportion of
lignin must remain, causing an increased HHV. In addition,
cellulose that undergoes HTC may form oligomers, which
polymerize into a lignin-like substance [41]. This may explain
why Loblolly pine, which has both the highest cellulose
(55.4 %) and the highest lignin (30.0 %) concentrations, has
the highest energy densifications (up to 1.43) at all HTC
temperatures for the biomass investigated (Fig. 1b).
After cellulose hydrolysis to glucose, glucose can isomer-
ize in the presence of acid, which is produced in the
Fig. 2 Mass yield versus 100
reactivity index (ratio of reactive 90
to inert biomass components) for
the five biomass types 80
70
60
Mass
50
yield (%)
40
30
20
10
0
0 1
Biomass Conv. Bioref.
reaction scheme, to fructose, which dehydrates to 5-
hydroxymethylfurfural (5-HMF) [42]. This 5-HMF may pre-
cipitate into the pores of the solid product and then be
accounted for as aqueous solubles in the dried biochar [15,
37]. Compared to cellulose or glucose, 5-HMF has a greater
HHV, and therefore its increased presence may also partially
account for the greater energy densification found in Loblolly
pine [43].
Both Loblolly pine and Tahoe mix are softwoods. The
Tahoe mix is a mix of two species and is made from whole
trees, while the Loblolly pine, a commercial timber, is
debarked and relatively clean. Both biomass follow similar
trends in HTC, except for the energy densification, shown in
Fig. 1b, where we see a much greater increase for Loblolly,
compared to the Tahoe mix. An explanation for this observa-
tion is not readily apparent, but there are several possibilities.
Just from the fiber analysis, we find that the Tahoe mix has a
reactive index value of 0.97, twice that of the loblolly (0.47),
as discussed below. The difference in ash composition may
catalyze or inhibit some reactions. The composition of the
soluble fraction is likely to be quite different between the two,
and the characteristics of the cellulose fraction are likely to be
quite different. Further study of the differences in aqueous
solubles, as well as lignin and cellulose, of softwood biomass
could prove useful in determining factors that influence ener-
gy densification.
Switch grass and corn stover have more hemicellulose
compared to the other biomass tested. Hemicellulose is bond-
ed to cellulose by lignin “glue”, shielding and preventing it
from decomposing [44]. When the hemicellulose removed is a
large portion of the biomass structure, the cellulose is then
more accessible for reactions, such as solubilization, hydroly-
sis, and polymerization [30; 34]. As hemicellulose and some
of the cellulose are solubilized to monomeric forms, a higher
proportion of lignin must remain in the biochar. A portion of
the cellulose may also polymerize under these conditions,
producing higher molecular weight products. This may ac-
count for the increased HHV and thus the increased energy
200 °C
230 °C
260 °C
2 3 4 5
Reacvity index
Biomass Conv. Bioref.
densification that switch grass and corn stover show (Fig. 1b).
Rice hulls, which have intermediate aqueous solubles, hemi-
cellulose, cellulose, and lignin values, were found to have
intermediate energy densification.
In light of the results discussed above and presented in
Table 2 and in Fig. 1, we have attempted to identify an index
of reactivity to predict the mass yield in HTC reactions. The
most successful index identified from this work is one defined
as the ratio of “reactive components” in the raw biomass:
Reactive Components H 0 þ S0
IR ¼ ¼
Inert components L0 þ A0
Here, H0, S0, L0, and A0 refer to fiber fractions of hemicel-
lulose, solubles, lignin, and ash, as reported in Table 2. By this
index, the biomass tested, in order of reactivity are switch
grass > corn stover > tahoe mix > rice hulls > Loblolly pine,
Fig. 2 shows the mass yield as a function of this reactivity
index at three temperatures, along with a line fitted to the data
taken at 260 °C. The dependence on this index of reactivity is
apparent and becomes obvious with increasing temperature.
Energy yield is an important practical consideration for
conversion of biomass to hydrochar by HTC. As shown in
Fig. 1c, at 260 °C, softwood biomass gave a higher energy
yield hydrochar than the grass-type biomass, except for rice
hulls, which have a high ash content that increases their mass
Fig. 3 Scanning electron microscope images of raw Loblolly pine and
loblolly pine HTC pretreated at 200 °C. a raw Loblolly pine at 250×, b
200 °C hydrochar at 250×
yield. At lower HTC reaction temperatures, energy yields
were similar for the different biomass types. Thus, a higher
HTC reaction temperature may be optimal for softwood bio-
mass, but a lower one may be preferable for grass-type
biomass.
3.3 Increased aqueous solubles and friability
Increased pore area likely occurred due to the removal of
cellulose and hemicellulose in the solid product [45]. Since
more surface area is available for precipitation, more sugars
and other chemicals can adhere to the accessible pores. Mono-
mers of cellulose and hemicellulose and organic acids are
produced by the HTC reactions [37]. These non-volatiles
can adhere to the surface area in the pretreated biomass unless
extensive washing is performed. Likely for these reasons,
aqueous solubles increased with higher HTC temperature, as
shown in Table 2b. The mass fraction of aqueous solubles
compounds increases with extent of reaction, from 2.7 % for
raw biomass, to 15.3 % for biomass pretreated at 200 °C, to
18.1 % for biomass pretreated at 260 °C. When the solid is
dried at 105 °C, water and volatiles evaporate. Non-volatile
substances precipitate on the extensive biomass surface area,
rather than on the container surfaces. These precipitates are
part of the hydrochar, but are quantified as aqueous solubles
by fiber analysis, since they are soluble in water. With vigor-
ous washing, these compounds might be more correctly char-
acterized as dissolved chemicals, including sugars. The empty
spaces left in the solid product are also likely the cause of the
higher friability observed in the hydrochar.
3.4 Scanning electron microscope images
Figure 3 shows SEM images of raw Loblolly pine and Lob-
lolly pine hydrochar from a 200 °C HTC reaction temperature
using a water to biomass ratio of 5:1 and a holding time of
5 min. In general, cellulose can be described as colinear
crystalline bundles of microfibrils in the raw lignocellulosic
biomass, while hemicellulose covers the cellulose, and lignin
is the strata between microfibrils that also connect the hemi-
cellulose and microfibrils to each other [44]. Aqueous solu-
bles can be found as a thin layer over the whole configuration.
Figure 3a is a ×250 magnification of the raw Loblolly pine.
Table 3 Proximate analysis of Loblolly pine raw and HTC pretreated at
200 and 260 °C
Loblolly pine Moisture (%) Volatiles (%) Fixed carbon (%)
Raw 3.6 83.7 12.3
200 °C HTC 1.3 86.0 12.2
260 °C HTC 1.3 72.2 25.7

The lignocellulosic structure is not clear. The lignocellulosic
biomass shown likely has starches, proteins, and other soluble
compounds filling the spaces between microfibrils. In the
image of biochar pretreated at 200 °C in Fig. 3b, it is possible
that biopolymers such as lignin wrapping microfibril cellulose
bundles are observable. This idea suggests that at 200 °C all
the aqueous solubles are completely removed and that much
of the hemicellulose is decomposed, so that lignin is detached
from cellulose microfibrils. Kobayashi et al. (2009) reported
that below 200 °C fibrous materials are observed, which
suggests that the decomposition of woody biomass begins
above 200 °C [46]. Additional SEM images of hydrochar
pretreated at 230 and 260 °C are available in Online Resource
1 (“230 °C and 260 °C Hydrochar SEM images”).
3.5 Recycling of liquid product
Reusing the liquid product of HTC to treat fresh biomass
would reduce the quantity of wastewater needing treatment
in an industrial plant. Replicated experiments using recycled
liquid product were performed with Loblolly pine, one at
200 °C and the other at 260 °C. At 200 °C, the mass yield
and energy densification were relatively constant when the
liquid product was reused instead of pure water, but at 260 °C,
there were some distinct changes. The mass yield increased
from 57.0 to 65.6 %, and the energy densification ratio de-
creased from 1.44 to 1.31. Uddin et al. (2013) reported similar
results for mass yield and energy densification for hydrochar
when liquid product was recycled in HTC pretreatment [47].
When Stemann et al. (2013) performed HTC at 220 °C for 4 h
on poplar wood chips and process water was recycled, they
reported increased concentration of organic acids leading to
polymerization reactions and higher energetic yield for the
solid product [48].
For these shorter time and higher reaction temperature
experiments, HTC chemistry is apparently inhibited by com-
pounds produced at 260 °C that are water soluble, possibly
because equilibrium reactions occur in the reaction scheme.
Lynam et al. (2011) reported similar reductions in acetic acid
formation when acetic acid was added to initial reactants in
hydrothermal carbonization (HTC), which is indicative of
concentration-shifts due to relative amounts of reactants and
products in equilibrium reactions (i.e., Le Chatelier’s
principle) [13].
3.6 Proximate analysis
Table 3 shows that the proximate analysis of raw Loblolly
pine had similar volatiles, fixed carbon, and ash values as
those for Loblolly pine undergoing HTC at 200 °C. Moisture
content is higher for raw Loblolly pine compared to the
hydrochars, suggesting that hydrochar is more hydrophobic
than its feedstock [7]. For 260 °C HTC hydrochar, volatile
Biomass Conv. Bioref.
content decreased and fixed carbon content increased com-
pared to 200 °C HTC hydrochar. Oxygenated compounds in
biomass, including polysaccharides, are preferentially degrad-
ed during HTC, and the HTC char has a higher elemental
carbon content than the originating biomass [6, 34, 37]. Dur-
ing HTC, it is known that cellulose fragments undergo poly-
merization and these carbonaceous polymers are expected to
have relatively low volatiles content due to cross linking [34;
37]. Thus, the increased fixed carbon in biochar produced at
temperatures that cause cellulose to react is expected.
4 Conclusion
HTC is a method for producing a hydrophobic, friable solid
fuel for subsequent thermochemical conversion from diverse
lignocellulosic biomass feedstocks, without the need for initial
drying. Energy densification of biomass was found to increase
by up to 43 %. Reaction temperature was the main process
variable significantly affecting mass yield and energy densi-
fication. For an HTC reaction temperature of 260 °C, the solid
product hydrochar had increased fixed carbon and decreased
volatiles. Fiber analysis suggested that hemicellulose hydro-
lyzes readily at temperatures between 200 and 260 °C. When
subjected to HTC at 260 °C, grass-like biomass feedstocks of
higher hemicellulose content produced low mass yield, while
softwood biomass of low hemicellulose content produced
high mass yield, so that softwood biomass hydrochar pro-
duced a higher energy yield. A reactivity index is defined as
the ratio of relatively reactive compounds (extractives and
hemicellulose) to relatively inert compounds (lignin and
ash), which was used to correlate HTC reactivity of various
biomass feedstocks.
Acknowledgments The authors gratefully acknowledge the support by
Department of Energy (Contract Number: DE-FG36-01GO11082). The
authors acknowledge meaningful conversations with project partners,
including Larry Felix of the Gas Technology Institute, and Craig Einfeldt
of Changing World Technologies. Experimental work of Mr. Tapas
Acharjee and Mr. Jason Hastings is gratefully acknowledged.
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