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pubs.acs.org/EF

Hydrothermal Carbonization (HTC) of Lignocellulosic Biomass

S. Kent Hoekman,* Amber Broch, and Curtis Robbins
Division of Atmospheric Sciences, Desert Research Institute, 2215 Raggio Parkway, Reno, Nevada 89512, United States

ABSTRACT: Hydrothermal carbonization (HTC) of biomass involves contacting raw feedstock with hot, pressurized water.
Through a variety of hydrolysis, dehydration, and decarboxylation processes, gaseous and water-soluble products are produced, in
addition to water itself and a solid char. In this experimental effort, a 2 L Parr stirred pressure vessel was used to apply the HTC
process to a mixed wood feedstock. The effects of the reaction conditions on product compositions and yields were examined by
varying temperature over the range of 215 295 °C and varying reaction hold time over the range of 5 60 min. With increasing
temperature and time, the amounts of gaseous products and produced water increased, while the amount of HTC char decreased.
The energy density of the char increased with reaction severity. At reaction conditions of 255 °C for 30 min, the HTC char had 39%
higher energy density than the raw biomass feedstock. Aqueous solutions from HTC experiments at lower temperatures
(215 235 °C) contained significant levels of sugars. At higher temperatures (255 295 °C), greatly reduced concentrations of
sugars were observed, while concentrations of acetic acid increased. A two-step HTC process involving low- and high-temperature
regimes may be advantageous to maximize both the recovery of sugars and production of energy-dense char.

1. INTRODUCTION chemicals and making the cellulose more amenable to further

Lignocellulosic biomass is increasingly regarded as a promis-
ing, renewable feedstock for the production of heat, chemicals,
fuels, and electrical power.1 3 However, in most cases, it is
necessary to modify or pretreat the lignocellulosic material by
chemical and physical means to satisfy the requirements of
biochemical or thermochemical conversion processes. For ther-
mochemical conversion processes (e.g., gasification, pyrolysis,
and combustion), the wide diversity of physical shapes, densities,
and other handling properties among different lignocellulosic
feedstocks creates significant challenges in feeding these materi-
als into process units. To overcome these problems, it is helpful
to homogenize all feedstocks to a certain degree and, thereby,
minimize handling differences among them.
Another purpose of pretreatment prior to thermochemical
conversion of solid fuels is densification of the material in terms
of mass per volume (kg/m3) and energy content (MJ/kg). Raw
lignocellulosic material typically contains approximately 40%
oxygen (dry mass basis), which contributes nothing to the
heating value of the material. The intention of a pretreatment
process is increased carbon content and decreased oxygen
content, which together increase the energy density of biomass
materials.
An additional benefit of some pretreatment methods is
improved handling, transportation, and storage of thermochemical
feedstocks. The diversity of sources (forest thinnings, agricultural
residues, energy crops, etc.) and the seasonality of some intro-
duce challenges with logistics and reliable supply. These pro-
blems can be mitigated by pretreatment processes that convert
raw lignocellulosic material into a form that is more easily
transported and stored. In some respects, the handling logistics
of pretreated biomass then become similar to those of coal.
One form of biomass pretreatment is commonly employed as
an initial step in the production of cellulosic ethanol. Such
pretreatment is used to partially break apart the lignocellulosic
structure of the feedstock, thereby recovering sugars and other
hydrolysis and subsequent fermentation to ethanol.4 7 This is
different from our interests in investigating pretreatment pro-
cesses meant primarily to increase the energy content of the
remaining solid residue (or char) and enhance its suitability as a
feedstock for subsequent thermochemical processing.8,9
Two principal thermal approaches have been used to convert
raw lignocellulosic biomass into higher energy density chars. One
approach, called torrefaction, involves mild pyrolysis (typically
200 300 °C) conducted in an inert atmosphere.10 14 The other
approach involves treatment of biomass in a hot, pressurized,
aqueous environment. Such wet processes have been widely
studied and are known by various names, including hydrothermal
pretreatment, wet torrefaction, coalification, hot compressed
water (HCW) treatment, and hydrothermal carbonization
(HTC). In this paper, the name HTC is used, because this
appears to be the most widely accepted terminology. Early
reviews regarding HTC treatment of biomass were published
by van Krevelen15 and Bobleter.16 Several more recent reviews
on this topic have also appeared.8,17 19 Because HTC treatment
involves pressurized conditions, the process equipment may be
more complicated and costly compared to conventional torrefac-
tion. On the other hand, HTC can be carried out more quickly
than torrefaction and may more easily accommodate a broader
range of feedstocks, because the initial moisture level is not a
concern.
The solid char produced by thermal pretreatment (wet or dry)
is also known by several names, including biochar, biocoal, green
coal, and charcoal. To avoid confusion, the term HTC char is
used here when referring to the solid product produced from the
HTC process. A recent review has discussed the upgrading and
use of HTC char in several high-value applications, including
Received: December 23, 2010
Revised: March 7, 2011
Published: March 08, 2011

r 2011 American Chemical Society 1802 dx.doi.org/10.1021/ef101745n | Energy Fuels 2011, 25, 1802–1810
Energy & Fuels
Figure 1. Schematic of 2 L Parr stirred reactor system used for the HTC
process.
catalysis, surface adsorption, and energy storage.20 HTC char and
torrefied char have also been investigated as materials for soil
amendment and carbon sequestration.20 24 However, one of the
most attractive uses of HTC char is as a coal substitute in
gasification and combustion applications.
Conduct of HTC under supercritical conditions has been
shown to rapidly degrade and dissolve lignocellulosic materials,
producing noncondensable gases (H2, CO, CO2, CH4, and
others) along with a wide variety of water-soluble organic
compounds.25 27 In the present study, a milder subcritical
HTC process was conducted using a woody biomass feedstock.
Such conditions have been shown to primarily decompose
hemicellulosic material while retaining most of the cellulose
and lignin fractions and to produce a char that exhibits con-
siderable energy densification.28,29 This study focused on char-
acterizing the HTC products, defining accurate mass balances,
and determining the effects of process conditions on the
products and mass balance.
2. EXPERIMENTAL SECTION
2.1. Parr Reactor System. The HTC reactor and sampling system
used a 2 L Parr stirred pressure reactor (model 4522), as shown in
Figure 1. During the HTC process, approximately 90 g of biomass was
combined with distilled water in an 8:1 water/biomass ratio (w/w).
Prior to reaction, residual air was removed from the sealed vessel by
repeatedly pressurizing with helium and venting to vacuum. The reactor
and contents were then heated while stirring. The reaction temperature
was controlled with a National Instruments LabView data acquisition
program using two thermocouples: one installed at the outer wall of the
reactor and the other inside the reactor. During initial heating, the outer
wall temperature was set at a maximum of 380 °C. Once the internal
temperature reached the desired set point, the reactor heater was turned
off. As the internal temperature dropped below its set point, the heater
was turned back on to a lower temperature (approximately 50 °C above
the internal set-point temperature). The internal temperature was
maintained near the set point in this manner throughout the duration
of the test, as shown in Figure 2. The pressure inside the reactor (solid
line) was measured and recorded throughout the HTC process and was
compared to the saturated steam curve (dashed line), as shown in
Figure 2. This figure also indicates approximate times for each phase of
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Figure 2. Temperature and pressure profiles for HTC process. Tahoe
Mix feedstock at 255 °C. Zone A, reactor heatup; zone B, reactor hold
time; zone C, reactor cooling; and zone D, reactor venting.
the reaction, including the heating phase, the reaction hold time, the
cooling phase, and gas venting (represented by zones “A”, “B”, “C”, and
“D”, respectively).
After treatment of the biomass at the desired temperature and hold
time, the reactor vessel was immediately removed from the heated well
and placed in an ice bath to cool the contents and condense all liquids.
When the inner reactor temperature reached approximately 15 °C below
room temperature, the noncondensable gases were released to a 50 L
Tedlar bag through a heated gas line (60 °C) while measuring the flow
rate and relative humidity. Once gas flow from the reactor ceased, helium
was sparged through the chamber to liberate the trapped gases and
collect them in the Tedlar bag. The use of helium as a sparging gas makes
subsequent gas chromatography (GC) analysis more convenient. Gases
were collected until the Tedlar bag was approximately 3/4 full, which
typically resulted in a dilution ratio of approximately 5:1. The LabView
software was configured to continuously record the helium flow rate
(and total flow rate) to ensure that an accurate volume of gases collected
in the Tedlar bag was determined.
After removal of the produced gases, the reactor was opened to collect
the solid and aqueous products. The reactor contents were transferred
into a tared collection vessel, using a measured amount of rinsewater to
completely remove all products. The solid and aqueous products were
separated by vacuum filtration, and the char was rinsed (with a measured
amount of water) to remove as much of the aqueous products as
possible. The char product and aqueous solution were weighed inde-
pendently and stored (under refrigeration) until analysis.
2.2. Feedstock Preparation. The primary biomass feedstock
used for these experiments was a mix of Jeffrey Pine and White Fir
(called Tahoe Mix) obtained from the Tahoe Forest. As received, the
Tahoe Mix chip size was 1 2 in. in diameter. To promote a more
homogeneous mixture and provide effective stirring during HTC
treatment, the chip size was further reduced using a Wiley Mill with a
6 mm screen (approximately 1/4 in.). The smaller chips were separated
through a series of sieves to eliminate particles smaller than 1 mm. The 6
mm chips were then air-dried and stored in a sealed container to await
processing.
2.3. Product Characterization. 2.3.1. Gaseous Products. The
noncondensable gases collected in the Tedlar bag were analyzed using a
SRI 8610C gas chromatograph equipped with a 0.5 mL gas sampling
loop and a thermal conductivity detector (TCD). A 6 ft  1/8 in. packed
column (Haysep D) was employed, with helium as a carrier gas (flow
rate of 11 mL/min). The column temperature was increased from 40 to
200 °C at 50 °C/min and then held for 5 min. These conditions allow for
measurement of H2, N2, CO, CH4, and CO2, although N2 and CO
partially coelute. Gaseous products collected from the HTC experiments
dx.doi.org/10.1021/ef101745n |Energy Fuels 2011, 25, 1802–1810
Energy & Fuels ARTICLE

Table 1. Gradient Program for Carbohydrate Analysis by IC

time (min) 600 mM NaOH (%) water (%)

0 12 88
5 12 88
6 37 63
15 37 63
17 50 50
51 100 0
64 100 0
64.5 12 88
80 12 88

Figure 3. GC analysis of gaseous products from HTC of Tahoe Mix at

255 °C (30 min hold time).

wxere transferred from the Tedlar bags directly into the GC sample loop.
Calibration was accomplished using a custom-blended gas mixture
containing H2, CO, CO2, and CH4 in helium. A typical chromatogram
is provided in Figure 3, which shows that CO2 was the dominant gaseous
product. Although the system was purged with helium before use, trace
amounts of N2 were often seen. The GC TCD system was relatively
insensitive; thus, CH4 and H2 were usually not detectable after dilution
in the Tedlar bag, although trace amounts of each are likely formed in the
HTC process.19 A late-eluting system peak was observed when analyzing
both calibration and product mixtures, although it did not interfere with
quantification of the other constituents.
2.3.2. Aqueous Phase Products. After the aqueous and solid HTC Figure 4. Sugar analysis of aqueous products from HTC of Tahoe Mix
products were separated, the pH level and the nonvolatile residue at 215 °C (30 min hold time).
(NVR) content of the aqueous solutions were measured immediately,
while further lab analyses [total organic carbon (TOC), sugars, and
organic acids] were completed in batches after several weeks of Table 2. Gradient Program for Organic Acid Analysis by IC
refrigerated storage (in previous work, it was demonstrated that no
major degradation of the aqueous products of interest occurred during time (min) 100 mM NaOH (%) water (%)
such storage). 0.0 1 99
The pH of the liquids was measured using a Hanna Instruments HI 7.9 1 99
8424 portable pH and temperature meter. Replicate samples of the
12.9 8 92
aqueous solution were dried to determine the NVR content. Samples
were weighed into drying tins and placed in a convective oven at 105 °C 25.9 12.5 87.5
overnight (approximately 18 20 h) to obtain a constant weight. The 37.9 60 40
remaining residue represents and is reported as the NVR content of the 42.9 60 40
aqueous solution. 43.0 1 99
The TOC was determined using a Shimadzu TOC-VCSH instrument 50.0 1 99
(Columbia, MD). This instrument catalytically oxidizes all organic
compounds into CO2, which is measured by nondispersive infrared detector was used for the measurement of carbohydrate and organic acid
detection (NDIR). The nonpurgeable organic carbon (NPOC) method species (Dionex Corp., Sunnyvale, CA). For carbohydrate analysis, a
was used, in which the addition of hydrochloric acid, combined with Dionex CarboPac MA1 guard and analytical column was used with a
sparging, removes inorganic carbon (and highly volatile organic carbon) flow rate of 0.4 mL/min and a column temperature of 25 °C. A 30 μL
from the sample prior to analysis. A Shimadzu ASI-V autosampler was sample volume was loaded onto the column, and a multi-step linear
used to introduce a 25 μL sample, which was treated with 2 M HCl and gradient elution program (shown in Table 1) was used to separate the
sparged with air for 1.5 min before introduction into the catalytic carbohydrate species. Amperometric detection was performed using a
combustion chamber, held at 680 °C. The oxidation products were gold working electrode and an Ag/AgCl reference electrode with the
passed through the NDIR detector, where CO2 was quantified by standard quadruple potential waveform. Carbohydrate species concen-
comparing the sample peak areas to a three-point calibration curve trations were calculated by comparing peak area responses to those
generated from analysis of potassium hydrogen phthalate (KHP) at the generated during a multi-point calibration constructed from authentic
beginning of each run. standards. A chromatogram from analysis of sugars produced during
A set of sugars was analyzed using high-performance anion-exchange HTC of a Tahoe Mix sample is shown in Figure 4.
chromatography, with pulsed amperometric detection (HPAEC PAD A set of organic acids [including lactic acid, acetic acid, formic acid,
or simply IC method). The method used was based on similar, literature- methane sulfonic acid (MSA), glutaric acid, succinic acid, malonic acid,
reported methods.30,31 A Dionex ICS-3000 system with an ED50A maleic acid, and oxalic acid] was analyzed using ion chromatography

1804 dx.doi.org/10.1021/ef101745n |Energy Fuels 2011, 25, 1802–1810

Energy & Fuels
Figure 5. Organic acid analysis of aqueous products from HTC of
Tahoe Mix at 215 °C (30 min hold time).
(IC) following the method by Jaffrezo et al.32 A Dionex IonPac
AG11HC guard column (4  50 mm) and AS11 HC analytical column
(4  250 mm) were used. The flow rate was held at 1.5 mL/min, while
the column temperature was maintained at 25 °C. A 30 μL sample loop
delivered the sample onto the column, where a multi-step gradient
program (shown in Table 2) was used to elute the organic acid species.
After the column effluent passed through the anion self-regenerating
suppressor (ASRS 300, 4 mm) with a current of 223 mA, conductivity
was measured by a DS3 conductivity cell. Organic acid species con-
centrations were calculated by comparing peak area responses to those
generated during a multi-point calibration constructed from authentic
standards. A chromatogram from analysis of aqueous products from
HTC of a Tahoe Mix sample is shown in Figure 5.
2.3.3. HTC Char. The wet char collected from the HTC reactor was
weighed and air-dried for 48 h, with occasional stirring to promote
homogeneous drying. The moisture content of the air-dried char was
determined by oven drying (105 °C for 18 20 h). For calculation
purposes, all mass lost during both air and oven drying was assumed to
be water, although, as discussed later, small amounts of volatile organic
products may also have been lost upon drying of the char.
The calorific energy content of oven-dried HTC char was measured
with a Parr 6200 calorimeter, equipped with a Parr 6510 water handling
system. Samples were combusted in an oxygen-rich environment inside
a bomb that is contained within a water bath. The increase in
temperature of the water bath was used to determine the gross heat of
combustion (higher heating value) through a comparison to a calorific-
grade benzoic acid standard.
A ThermoElectron Flash EA 1112 automatic elemental analyzer was
used for direct measurement of C, H, N, S, and O in HTC char. The
complete analysis requires two methods, with two separate injections: one
for C, H, N, and S analysis and the other for O analysis. For C, H, N, and S
determination, the sample is weighed in a tin foil capsule and then dropped
into an oxidation/reduction (FeO and Fe) reactor kept at a temperature of
900 1000 °C. The amount of O2 necessary for complete combustion is
delivered into the reaction chamber. The exothermic reaction between the
sample and O2 temporarily raises the temperature to about 1800 °C, which
is sufficient to convert both organic and inorganic compounds into
elemental gases that are reduced and separated on a GC column using
He as the carrier gas. The produced gases (N2, CO2, H2O, and SO2) are
detected and quantified by a thermal conductivity detector (TCD). For
oxygen determination, the sample is weighed into a silver foil capsule, then
dropped into a reaction chamber containing a nickel-coated carbon catalyst,
and held at a temperature slightly above 600 °C. Under these conditions,
oxygen is converted to CO, which is routed through a water trap before
being passed to the GC column for quantification by the TCD.
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2.4. Mass Balance. A mass balance for each HTC reaction was
obtained by quantifying all materials in the gaseous, aqueous, and solid
products. All product masses were expressed relative to that of the dry
starting biomass. Gaseous products were quantified on the basis of total
gas volumes collected in Tedlar bags and GC analyses of the gas
compositions. Solid products were quantified gravimetrically, after
drying samples of the HTC char at 105 °C.
Aqueous products include NVR, volatile organics, and produced
water. The NVR content was quantified by evolving all volatiles in an
oven at 105 °C for 18 20 h (to attain a constant weight). During this
procedure, both water and volatile organics are lost. The two most
significant volatile organic compounds are formic acid and acetic acid,
which are quantified separately using the ion chromatographic method
described above. Finally, the produced water was quantified as the
difference between all water inputs and outputs. Water inputs include
moisture in the biomass feedstock, water added to the Parr reactor, and
all rinsewater. Outputs include water lost during drying of the HTC char,
along with the total aqueous solution recovered, minus the NVR content
and the volatile organics (formic and acetic acids) dissolved in the
aqueous solution.
3. RESULTS AND DISCUSSION
A series of HTC experiments was conducted to determine the
effects of the reaction temperature and hold time on the
treatment of Tahoe Mix wood chips. In one set of experiments,
a range of reaction temperatures was used, from 215 to 295 °C at
20° intervals, while the hold time was kept constant at 30 min. In
a second set of experiments, the reaction temperature was held
constant at 255 °C, while the hold time was varied from 5 to 60
min. A test at 255 °C with 30 min hold time was included in each
series of experiments to provide information about experimental
repeatability.
3.1. Mass Recovery. Despite the fact that the HTC process
has been extensively investigated, detailed mass balances have
not been widely reported.19 In this study, a total mass balance of
the HTC reaction at each temperature and hold time was carried
out by determining the mass of each recovered product fraction
and comparing the sum of all products to the total starting mass
of feedstock. The recovered products included the solid HTC
char, noncondensable gases (CO and CO2), water solubles
(NVR and volatile organics), and produced water. Mass recov-
eries for these HTC experiments are summarized in Table 3
(note that, because of a malfunction in the gas sampling system,
no gaseous products were measured from the experiment at
215 °C).
The sum of identified products in these experiments varied
from approximately 86 to 92%. The “difference” values shown in
Table 3 represent the unidentified mass needed to achieve
complete mass closure. Most of this “difference” is believed to
be water, remaining in the Parr reactor vessel and stirring
mechanism after removal of the product mixture. In subsequent
tests, tared dry towels were used to wipe out the Parr apparatus
following each HTC experiment. This showed that 5 8 g of
water was typically left behind, accounting for 6 9% of starting
dry feedstock mass. However, because this method was not used
consistently throughout the experimental matrix described here,
water left behind is categorized as the “difference”.
Another issue with respect to mass closure is the loss of volatile
organic compounds during drying of the HTC char. We have
observed in other work that the same organic materials found in
the aqueous product solutions are also adsorbed on the char. This
includes formic and acetic acids, which may be present at
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Table 3. Effect of the Reaction Temperature and Time on the HTC Mass Balancea

30 min hold time 255 °C reactor temperature

HTP product fraction 215 °C 235 °C 255 °C 275 °C 295 °C 5 min 10 min 30 min 60 min

CO2 NA 7.9 7.9 ( 0.2 10.1 11.1 5.3 5.6 7.9 ( 0.2 9.1
CO NA 0.0 0.6 ( 0.2 0.6 0.7 0.2 0.2 0.6 ( 0.2 0.4
water solubles 13.0 12.6 14.9 ( 0.6 13.0 12.3 14.0 14.1 14.9 ( 0.6 12.9
HTC char 69.1 63.7 50.3 ( 0.5 50.9 50.1 57.7 55.5 50.3 ( 0.5 52.1
produced water 3.3 3.5 12.8 ( 3.4 17.4 16.7 8.5 10.2 12.8 ( 3.4 12.5
sum (% of total) NA 87.6 86.1 ( 3.5 91.9 91.0 85.7 85.6 86.1 ( 3.5 87.0
difference NA 12.4 13.9 ( 2.0 8.1 9.0 14.3 14.4 13.9 ( 2.0 13.0
mol CO2/mol H2O NA 0.93 0.26 ( 0.08 0.24 0.27 0.26 0.22 0.26 ( 0.08 0.30
a
All results are expressed as a percentage of the starting dry feedstock mass. Results at 255 °C and 30 min are averages ( standard deviation.

significant levels but would likely be lost during drying of the
char. In future work, we plan to capture all volatiles removed
during drying of the char and quantify the volatile organic
compounds that are present.
A higher recovery of HTC char was observed at lower
temperatures, with nearly 70% of the starting dry mass recovered
at a reaction temperature of 215 °C, decreasing to approximately
50% at 295 °C. The mass of recovered char dropped dramatically
between 215 and 255 °C and then remained at approximately
50% with higher temperature treatments. These changes in char
recovery are comparable to those reported recently by Yan et al.,
who investigated a similar range of temperature conditions.28,29
As shown in Table 3, the mass recoveries of noncondensable
gases (mainly CO2) and produced water increased with an
increasing reaction temperature, while the total water solubles
remained nearly constant. Broadly speaking, these overall pro-
duct distributions are consistent with those reported in the
literature.8,19
Varying reaction hold time had a similar although smaller
effect on mass recovery to changes in the temperature. The HTC
char mass recovery was highest at short hold times and decreased
with an increasing hold time. The amounts of noncondensable
gases and produced water increased with longer hold times, while
the water solubles remained nearly constant. The relative effects
of the reaction time and temperature on the HTC process have
been investigated by others.9,19,28,29 Under the operating condi-
tions typically employed, the temperature appears to have a
stronger effect on HTC product distributions than the reaction
time.
Over the range of temperature and time conditions employed
here, approximately 50 70% of the starting feedstock mass was
recovered as char, 5 12% was recovered as gases, and 12 15%
was recovered as water-soluble products. The amount of pro-
duced water is less certain, because of handling losses and the
uncertainties inherent in measuring small increments in already
large amounts of water. However, the amount of produced water
was likely in the range of 10 20%, assuming that most of the
“difference” was actually produced water.
3.2. Noncondensable Gases. GC analysis of the nonconden-
sable gases revealed CO2 to be the dominant gaseous species,
typically responsible for about 90 95% of the total gas volume.
The remaining 5 10% was mostly CO, although trace amounts
of CH4 and H2 were likely present. CO2 formation results from
decarboxylation reactions, which, along with dehydration, repre-
sent two major processes occurring during HTC. To a first
approximation, the ratio of decarboxylation/dehydration can be
1806
defined as the mole ratio of CO2/H2O.8,19 This ratio appears to
be a function of the feedstock type but is thought to be relatively
insensitive to the reaction temperature.33 The results presented
in Table 3 show a CO2/H2O ratio between 0.2 and 0.3 for all
experiments, except at 235 °C, where analytical measurement
problems are suspected. However, if much of the “difference”
category is actually produced water (as discussed above), the true
CO2/H2O ratio is even smaller, suggesting that dehydration
dominates over decarboxylation in the HTC process.
Shortening the reaction hold time in the 255 °C experiments
noticeably reduced gas production, despite long preheat times.
This suggests that much of the decarboxylation process produ-
cing CO2 occurs during the HTC temperature hold period itself.
Also, note that, in Figure 2, the reactor pressure did not
significantly exceed the steam saturation pressure until the
temperature was above 200 °C, indicating minimal gas produc-
tion during the preheating period.
3.3. Aqueous-Phase Products. A summary of aqueous-phase
product characterizations for the two sets of HTC experiments is
presented in Table 4. Over the range of conditions that we
explored, the NVR content and the TOC levels each comprised
about 8 12% of the starting dry feedstock mass. As the reaction
severity increased (higher temperature or longer time), both
NVR and TOC slightly decreased, suggesting that organic
materials originally produced under mild conditions continue
to react under more severe conditions. This is consistent with the
observations of increased gas production (described above) and
degradation of sugars (discussed below) with increasing reaction
severity.
3.3.1. Sugars. The effects of the reaction temperature and hold
time on the production of sugar species are shown in Table 4.
“Other” sugars include minor species, such as inositol, erythritol,
xylitol, arabitol, sorbitol, trehalose, mannitol, and arabinose.
Total sugars were found to diminish rapidly with increasing
reaction temperatures, declining from approximately 1.4% at
215 °C to 0.1% at 255 °C. Several sugars were detectable only in
samples from the lowest temperature experiments, including
galactose, mannosan, trehalose, and arabinose. Glucose and
xylose (which coelute in our IC method) and levoglucosan were
present in all aqueous-phase products from HTC experiments at
temperatures of 255 °C and below. The only sugars observed
from experiments above 255 °C were the minor “other” sugars
and glycerol, all of which remained fairly constant with changes in
the temperature. Increasing the reaction hold time produced
effects similar to increasing the temperature, with higher con-
centrations of sugars present after shorter reaction hold times.
dx.doi.org/10.1021/ef101745n |Energy Fuels 2011, 25, 1802–1810
Energy & Fuels ARTICLE

Table 4. Aqueous Phase Products from HTC of Tahoe Mixa

30 min hold time 255 °C reactor temperature

product 215 °C 235 °C 255 °C 275 °C 295 °C 5 min 10 min 30 min 60 min

NVR 10.00 8.78 10.16 ( 0.39 8.36 7.52 10.09 9.88 10.16 ( 0.39 8.53
TOC 9.17 9.17 11.27 ( 1.06 8.47 7.75 11.40 12.02 11.27 ( 1.06 8.56
sugars
glucose/xylose 1.02 0.54 0.08 ( 0.03 nd nd 0.60 0.55 0.08 ( 0.03 nd
galactose 0.18 nd nd nd nd nd nd nd nd
mannosan 0.05 0.02 nd nd nd 0.02 0.01 nd nd
levoglucosan 0.07 0.06 0.01 ( 0.00 nd nd 0.08 0.07 0.01 ( 0.00 nd
glycerol 0.03 0.04 0.07 ( 0.03 0.06 0.06 0.07 0.08 0.07 ( 0.03 0.10
others 0.06 0.08 0.05 ( 0.01 0.04 0.04 0.08 0.08 0.05 ( 0.01 0.04
total sugars 1.41 0.73 0.22 ( 0.02 0.10 0.10 0.86 0.79 0.22 ( 0.02 0.14
organic acids
formic 0.83 1.02 0.89 ( 0.09 0.26 0.06 1.04 1.00 0.89 ( 0.09 0.31
acetic 2.14 2.78 3.85 ( 0.08 4.37 4.75 2.91 3.20 3.85 ( 0.08 4.08
lactic 0.21 0.34 1.47 ( 0.17 1.89 1.98 1.05 1.19 1.47 ( 0.17 1.69
others 0.15 0.19 0.21 ( 0.07 0.33 0.44 0.10 0.14 0.21 ( 0.07 0.23
total acids 3.34 4.33 6.43 ( 0.08 6.85 7.22 5.11 5.52 6.43 ( 0.08 6.31
a
All results are expressed as a percentage of starting dry feedstock mass. Results at 255 °C and 30 min are averages ( standard deviation.

The rapid degradation of sugars at elevated temperatures
is well-documented in the literature.17,18 To maximize sugar
recovery requires operation at relatively lower temperatures,
typically below 225 °C. In contrast, to maximize energy densi-
fication of the HTC char requires higher temperatures
(discussed below). This suggests that a two-step process may
be advantageous for realizing high sugar recovery in addition to
maximizing char densification.
3.3.2. Organic Acids. The effects of the reaction temperature
and hold time on the production of organic acids are also shown
in Table 4. Organic acids were present in much higher concen-
trations than were sugars; typically 3 7% of the starting dry
feedstock was recovered as organic acids, with formic, acetic, and
lactic acids being the dominant species. The remaining minor
acids lumped into “others” in Table 4 include glutaric acid,
succinic acid, MSA, malonic acid, maleic acid, and oxalic acid.
Total acids increased substantially with an increasing reaction
temperature up to 255 °C and then remained fairly constant. At
temperatures above 255 °C, formic acid levels decreased, while
acetic acid and lactic acid production increased. Increasing the
reaction hold time at 255 °C increased total acids slightly,
because of increased production of acetic and lactic acids, while
formic acid levels decreased. The acid content in the aqueous
phase products resulted in a pH level near 3.0 for all samples.
Varying the reaction temperature and hold time had little
effect on pH.
It is well-known from the literature that organic acids, parti-
cularly acetic acid, are produced by HTC processes. Our results
are consistent with the understanding that some acids are
produced from direct reaction of the starting biomass, while
additional acids are produced by further degradation of inter-
mediate products, such as sugars. Inspection of Table 4 indicates
that the sum of identified sugars and acids does not account for all
of the TOC within the aqueous phase products especially
under the lower temperature reaction conditions. On the basis of
other analyses (not reported here) and literature reports,18,19 it is
known that many other organic compounds are present in the
1807
aqueous phase. Some of the most significant include furans,
furfurals, and phenolic compounds.
3.4. HTC Char Products. Noteworthy properties of the char
samples produced in these two sets of HTC experiments are
summarized in Table 5. Figure 6 illustrates the effects of the
reaction temperature and hold time on HTC char mass recovery
and energy content. For clarity, trendlines are fit to the 30 min
hold time data for each parameter. Mass recovery is shown as a
percentage of the starting dry feedstock mass and is indicated by
square symbols (blue squares represent 30 min hold times, and
green squares represent other hold times). HTC char mass
recovery decreased dramatically with an increasing reactor
temperature from 215 to 255 °C and then remained fairly
constant up to 295 °C. A small but noticeable decrease in mass
recovery was observed with an increasing hold time at 255 °C.
The energy content of the HTC char [higher heating value
(HHV), expressed on a dry basis] is shown as circles in Figure 6
(red symbols represent 30 min hold times, and yellow symbols
represent other hold times). Increasing the reaction temperature
clearly increased the energy content of the HTC char. The
energy content of the starting dry feedstock (20.3 MJ/kg) is also
shown in Figure 6. At a reaction temperature of 255 °C (with a 30
min hold time), the resulting char had an energy content of
28.3 MJ/kg, an increase of 39% compared to the feedstock. The
char energy content continued to increase as reaction tempera-
tures exceeded 255 °C, albeit less dramatically. The HTC char
produced at 295 °C exhibited an energy content 45% higher than
the starting feedstock. A significant effect of the reaction hold
time on HTC char energy content was also observed. At a 255 °C
reaction temperature, the produced char had energy contents of
25.1 and 26.0 MJ/kg for 5 and 10 min hold times, respectively,
but increased to 29.2 MJ/kg at a 60 min hold time.
These increases in char energy density compared to raw
biomass feedstock are comparable to other reported increases.
For example, Yan et al. measured energy density increases up to
36% using loblolly pine,28,29 while Inoue et al. reported increases
of 11 73% when treating Konara (oak) wood at 250 350 °C.34
dx.doi.org/10.1021/ef101745n |Energy Fuels 2011, 25, 1802–1810
Energy & Fuels ARTICLE

Table 5. Properties of HTC Char Products from the Treatment of Tahoe Mix Feedstock

30 min hold time 255 °C reactor temperature

property feedstock 215 °C 235 °C 255 °C 275 °C 295 °C 5 min 10 min 30 min 60 min

energy content (MJ/kg) 20.32 22.58 24.27 28.26 ( 0.28 29.02 29.52 25.10 26.04 28.26 ( 0.28 29.17
mass yield (%) 69.1 63.7 50.3 ( 0.5 50.9 50.1 57.7 55.5 50.3 ( 0.5 52.1
energy densification 1.11 1.19 1.39 ( 0.01 1.43 1.45 1.23 1.28 1.39 ( 0.01 1.43
energy yield (%) 76.7 76.1 70.0 ( 0.9 72.7 72.8 71.2 71.1 70.0 ( 0.9 74.8
elemental analysis
%C 49.02 54.57 60.54 70.06 ( 0.13 70.08 73.01 62.65 62.98 70.06 ( 0.13 71.89
%H 5.93 5.89 5.66 5.19 ( 0.07 5.31 5.14 5.43 5.40 5.19 ( 0.07 5.15
%N 0.11 0.09 0.13 0.10 ( 0.06 0.16 0.14 0.05 0.04 0.10 ( 0.06 0.05
%S nd nd nd nd nd nd 0.03 nd nd nd
%O 41.26 34.89 31.59 23.42 ( 0.42 21.14 19.87 32.31 30.72 23.42 ( 0.42 22.26
atomic O/C ratio 0.63 0.48 0.39 0.25 ( 0.01 0.23 0.20 0.39 0.37 0.25 ( 0.01 0.23

Figure 6. Effects of the reaction temperature and hold time on mass
recovery and energy content of HTC char from Tahoe Mix. Hold time =
30 min, except where otherwise indicated. The mass is represented by
squares, and the energy content is represented by circles.
Energy density increases of 20 30% have been reported with
mild HTC treatment (180 °C) of wheat straw.35 Also, a similar
HTC process applied to whole microalgae was found to produce
a char having very high energy density (30 32 MJ/kg).36
Another recent study of HTC treatment of microalgae at
250 °C was reported to produce a solid product, although the
energy content was not indicated.37
It is also useful to evaluate the produced char in terms of
energy densification and energy yield. As defined by Yan et al.,28
the energy densification is the energy content of the char divided
by the energy content of the feedstock, while the energy yield is
defined as the char mass yield multiplied by the energy densifica-
tion ratio. The values for mass yield, energy densification, and
energy yield for all HTC experiments are provided in Table 5,
which reveals that energy densification increases with the reac-
tion temperature, from a low of 1.11 at 215 °C to a high of 1.45 at
295 °C. Similarly (but to a lesser extent), the energy densification
increased with an increasing hold time at 255 °C. The total
energy yield of the HTC char did not vary greatly over the sets of
experiments conducted here, ranging from 70 to 77%. Consistent
with previous reports, the highest energy yield was observed at
the lowest process temperature.28
1808
Figure 7. Van Krevelen diagram of biochar from HTC of Tahoe Mix. Hold
time =30 min, except where indicated. The temperature was at 255 °C for
indicated hold times.
The HTC process involves dehydration, condensation, and
decarboxylation reactions, resulting in a loss of some carbon,
hydrogen, and oxygen. Of these, oxygen loss is of the greatest
importance and is most desirable, because it directly increases the
energy content. The results of C, H, N, S, and O analyses carried
out on each char sample are also presented in Table 5. As the
severity of HTC increased, the carbon content of the char
increased, while the oxygen content decreased. The hydrogen
content varied only slightly with reaction severity.
A useful way to examine these changes in atomic C, H, and O
compositions is by means of a Van Krevelen diagram, as shown in
Figure 7.19,38 In this figure, typical ranges for biomass, peat,
lignite, coal, and anthracite are indicated. The starting Tahoe Mix
feedstock is shown in the upper right corner of the diagram,
within the typical biomass region. Figure 7 illustrates that, with
higher HTC process severity, the resulting char becomes in-
creasingly similar to coal. At a reaction temperature of 235 °C,
the HTC char possesses H/C and O/C ratios similar to peat,
while at 255 °C or higher, the ratios are similar to those of low-
grade coal. The beneficial impact of increasing reaction hold time
at 255 °C is also shown in this figure.
With the HTC process resulting in little change to the
hydrogen content of the char, a similar understanding of the
dx.doi.org/10.1021/ef101745n |Energy Fuels 2011, 25, 1802–1810
Energy & Fuels
relationships between HTC conditions and char characteristics
can be obtained by merely considering the atomic O/C ratios.
As shown in Table 5, this ratio decreases with increasing process
severity, going from 0.63 in the feedstock to 0.20 when treated
at 295 °C. The behavior of decreasing O/C with increasing
process severity has been discussed at length by Ruyter, who
indicated that O/C ratios of 0.2 0.3 are indicative of low-grade
coals.33
The O/C ratios observed in HTC chars are considerably lower
than in conventional, torrefied char. Yan et al. carried out both
“wet” and “dry” torrefaction processes using a loblolly pine
feedstock.28 Under HTC conditions at 260 °C, it was found that
the O/C ratio decreased from 0.65 in the feedstock to 0.24 in the
char. With dry torrefaction, an O/C ratio of only 0.54 was
obtained when carried out at 300 °C. The increased energy
densification and greater coal-like behavior of HTC char repre-
sents an important advantage of the HTC process, as compared
to conventional torrefaction, when producing fuels for combus-
tion and gasification.
4. CONCLUSIONS
HTC of lignocellulosic biomass has been shown to produce a
solid char product having considerably higher energy density
compared to the raw feedstock. As HTC reaction severity was
increased (higher temperature and longer time), the extent of
energy densification increased. Results obtained from HTC
treatment of a mixed wood feedstock obtained from the Tahoe
Forest were largely consistent with those reported in the
literature for other woody feedstocks.
Although energy densification of the HTC char was found to
increase at higher process temperatures, most of the benefit was
realized at modest temperatures. At 255 °C, a 39% increase in
energy density was achieved; this rose to 45% at 295 °C. Higher
temperature conditions also entail higher process pressures. In a
commercial application, higher pressures could require use of more
complex and costly equipment and could increase handling diffi-
culties. Although a thorough techno-economic analysis is required
for confirmation, it appears that a HTC char having desired energy
density may be most effectively produced at operating temperatures
near 255 °C and pressures near 5 MPa. Under these conditions, the
resulting char has coal-like properties and is expected to exhibit
favorable behavior with respect to combustion, gasification, and
other thermal conversion processes.
CO2 was the dominant gaseous product produced during the
HTC process, representing approximately 8% of the starting feed-
stock mass when treated at 255 °C. Various water-soluble organic
products were also produced in the HTC process, including sugars
and organic acids. Maximum sugar concentrations were observed
under low-temperature conditions (215 °C) but were degraded
considerably at higher temperatures. To achieve both maximum
sugar recovery and energy densification of the char may require a
multi-step process involving different temperature regimes. Successful
recovery and use of sugars (and other water-soluble organics) could
also improve the overall economics of this process.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: kent.hoekman@dri.edu.
1809
ARTICLE
’ ACKNOWLEDGMENT
Funding support from the U.S. Department of Energy (DOE)
under awards EE0000272 and DE-FG36-01GO11082 is gratefully
acknowledged. Laboratory analytical support was provided by
Stephanie Salke and Mark McDaniel of the Desert Research
Institute (DRI). Parr reactor experiments were conducted by Eric
Ceniceros and Keri Noack of the DRI. We also acknowledge helpful
discussions and guidance by Charles Coronella and Wei Yan of the
University of Nevada, Reno, NV, and Larry Felix of the Gas
Technology Institute.
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