Article

pubs.acs.org/EF

Solid-State Nuclear Magnetic Resonance Characterization of Chars

Obtained from Hydrothermal Carbonization of Corncob and
Miscanthus
Lucia Calucci,† Daniel P. Rasse,‡ and Claudia Forte*,†
†
Istituto di Chimica dei Composti OrganoMetallici, Consiglio Nazionale delle Ricerche − CNR, Via Giuseppe Moruzzi 1, 56124 Pisa,
Italy
‡
Bioforsk, Norwegian Institute for Agricultural and Environmental Research, NO-1432 Ås, Norway

ABSTRACT: Corncob and Miscanthus feedstocks were hydrothermally carbonized at 230 °C for 6 h in an autoclave under
autogenous pressure, obtaining fine brown powders with higher carbon and lower hydrogen and oxygen contents than the
starting materials. The chemical structure of feedstocks and hydrochars was investigated by 13C cross-polarization magic angle
spinning (CP-MAS) nuclear magnetic resonance (NMR) spectroscopy complemented by Fourier transform infrared (FTIR)
spectroscopy and elemental analysis. In particular, a procedure including CP dynamics analysis and spectral deconvolution was
applied to obtain quantitative information on the composition of the analyzed materials from 13C CP-MAS spectra. Miscanthus
feedstock contained larger amounts of lignin and crystalline cellulose, which concurred to reduce cellulose exposition to hot
water during the hydrothermal carbonization (HTC) process. As a consequence, a lower furan/aromatic ratio was found for
Miscanthus versus corncob hydrochars.

■ INTRODUCTION
In recent years, hydrothermal carbonization (HTC) has
attracted much interest as a powerful method for the
conversion of biomass into highly valuable carbon materials
in a relatively cheap and sustainable way.1−17 HTC is
conducted by applying mild temperatures (180−250 °C) to
biomass in a water suspension under self-generated pressures
for several hours. The obtained carbon-rich solid (also called
hydrochar), which forms through hydrolysis, dehydration,
decarboxylation, condensation polymerization, and aromatiza-
tion reactions, possesses a core−shell structure consisting of a
hydrophobic aromatic nucleus and a hydrophilic shell
containing a high concentration of reactive oxygen functional
groups (i.e., hydroxyl/phenol, carbonyl, or carboxyl). Because
of its intrinsic properties, such as high efficiency in carbon
fixation under mild conditions, application to wet biomass, and
abundant functional groups remaining on the product surface,
HTC presents many advantages with respect to more
traditional pyrolysis techniques employed to obtain carbona-
ceous materials from biomass. Indeed, HTC looks promising
for the production of biochar for CO2 sequestration13,15,18 and
improving soil properties19−22 and for waste management.12,17
Moreover, HTC can be easily coupled to post or in situ casting
and activation procedures, thermal treatments, and functional-
ization reactions to obtain carbon materials with controlled
physical (porosity, size, crystallinity, etc.), chemical (surface
functional groups, aromaticity, etc.), and electronic properties
suitable for applications in fundamental fields, such as water
purification, gas storage, catalysis, electronics, and biomedi-
cine.2,4,6−10,15
However, until now, only simple monosaccharides and
oligosaccharides have been effectively employed for the
production of functionalized carbon materials by HTC, while
the exploitation of lignocellulosic biomass as readily accessible
and carbon-negative feedstock can at present be considered as
the next challenging step in HTC application to materials
science.15 In particular, glucose has been extensively studied,
being one of the cheapest and most abundant carbohydrates,
and the mechanism of its transformation by HTC has been
described in detail in recent publications.3,23−25 This process
includes the transformation of glucose in hydroxymethylfurfural
(HMF) and then the polymerization and polycondensation of
HMF into polyfuranic chains first and subsequently into
aromatic networks, with the proportion of polyfuranic and
condensed aromatics being dependent upon the HTC process
conditions, namely temperature and time. The same mecha-
nism has been found to govern the formation of char from
oligosaccharides and simple carbohydrates.23,26,27 On the other
hand, very recently, a fundamental difference in the formation
mechanism of hydrochar has been highlighted in the case of
cellulose, the main component of raw biomass.25,28 In fact, a
limited amount of cellulose present at the interface with water
is hydrolyzed to glucose and then transformed following the
above-described mechanism, whereas the bulk of the cellulose
is directly transformed into aromatic networks following a
mechanism similar to that of classical pyrolysis, although the
exact chemical pathways are not yet clear. General conclusions
about HTC-induced transformations of raw biomass are even
more difficult to draw because of the different cellulose,
hemicellulose, and lignin ratios and the different behavior of
these components during HTC.5,15,29−31 To the best of our
knowledge, studies on the physicochemical properties of chars
obtained by HTC of lignocellulosic biomass are still limited in
number and, furthermore, are performed on different feed-
Received: October 22, 2012
Revised: December 4, 2012
Published: December 12, 2012

© 2012 American Chemical Society 303 dx.doi.org/10.1021/ef3017128 | Energy Fuels 2013, 27, 303−309
Energy & Fuels Article

Table 1. Volatile Matter Content, Fixed Carbon, Ash Content, Elemental Composition, and H/C and O/C Atomic Ratios of
Feedstocks and HTC Chars
elemental composition (%) atomic ratio
volatile matter (%) fixed carbon (%) C N H ash Oa H/C O/C
corncob 81.1 (±0.5) 17.5 (±0.5) 48.4 (±0.3) 0.38 (±0.01) 6.5 (<0.1) 1.4 (<0.1) 43.3 1.59 0.67
Miscanthus 78.0 (±0.8) 13.5 (±0.8) 48.9 (±0.4) 0.18 (±0.01) 6.3 (<0.1) 8.5 (±0.4) 36.2 1.52 0.56
HTC corncob 67.2 (±0.1) 31.3 (±0.3) 59.8 (±1.3) 0.38 (±0.11) 5.9 (±0.1) 1.5 (±0.2) 32.4 1.18 0.41
HTC Miscanthus 61.4 (±0.9) 34.3 (±0.3) 62.9 (±0.5) 0.25 (±0.01) 5.7 (<0.1) 4.3 (±1.1) 26.9 1.07 0.32
a
Computed by difference.

stocks using quite different HTC conditions (i.e., temperature, length was 3.4 μs; the spin-lock field was 74 kHz; and the recycle delay
concentration of biomass in water, and carbonization was 6 and 2 s for feedstock and carbonized materials, respectively. 13C
time).12,13,25−27,32,33 Therefore, further work is necessary to CP-MAS NMR spectra were acquired with a contact time (tCP) of 2
better understand biomass transformations under HTC, ms and 4000 scans. The CP dynamics was investigated with variable
contact time CP-MAS experiments with tCP values ranging from 50 μs
especially as it relates to biomass composition and HTC to 80 ms, acquiring 400 scans for each experiment. The CP-MAS
conditions, and to acquire information on char structures spectra with dipolar dephasing40,41 were recorded using a tCP of 2 ms
necessary for developing applications. and a 50 μs delay prior to the contact pulse and acquiring 16 000
To this end, in the present work, a procedure for the scans. Spectral deconvolutions were performed using the SPORT-
structural characterization of hydrochar based on 13C solid-state NMR software.42 Chemical shifts are referenced to tetramethylsilane
nuclear magnetic resonance (13C SSNMR) spectroscopy is (TMS) using adamantane as an external reference.
proposed. Indeed, 13C SSNMR has proven valuable for
quantitatively detecting carbon functionality and aromaticity
of chars12,23−25,27,32,34−39 because it can be applied to both
■ RESULTS AND DISCUSSION
HTC (230 °C, 6 h) was applied to corncob and Miscanthus;
crystalline and amorphous materials and gives information on fine brown powders were obtained for both feedstocks, having a
the whole sample. The good resolution of the NMR method higher carbon content and lower hydrogen and oxygen
and the possibility of combining selective techniques enables contents with respect to the corresponding starting materials
chemical species to be identified and quantitatively determined. (Table 1). The variation in the elemental composition was
In particular, here, 1H−13C cross-polarization magic angle analyzed with the aid of a van Krevelen diagram,43 which shows
spinning (CP-MAS) experiments, recorded with different (Figure 1) that the evolution of the H/C and O/C atomic
contact time values, were analyzed with an accurate spectral
deconvolution method, obtaining the relevant CP dynamics
parameters for the different spectral signals; this enabled a
quantitative determination of the spectral contributions of the
different carbon functionality samples, which were not
isotopically enriched. This procedure is employed here for
the first time to determine the relative quantities of the different
components of feedstock materials and hydrochars. Corncob
and Miscanthus feedstocks were chosen as pilot products for
making biochar from agricultural residues and bioenergy crops,
respectively.

■ EXPERIMENTAL SECTION
Materials. Feedstocks for HTC were chaffed biomass of Miscanthus
× giganteus and corncobs from maize (Zea mays) grown in Serbia (ZP
Maize Hybrid 505) in ca. 3 cm thick cuts. Feedstock was placed into a
1 L steel autoclave (Anton Paar), immersed with deionized water, and
then heated for 6 h to 230 °C under autogenous pressure. After
cooling, the autoclave was opened and the char was removed from its
aqueous dispersion by vacuum filtration and, subsequently, dried in a
vacuum oven for 16 h at 60 °C.
Characterization. Total C, H, and N contents of feedstock and Figure 1. van Krevelen diagram of (■ and □) corncob and (● and ○)
biochar samples were determined by dry combustion using a Leco Miscanthus (□ and ○) feedstocks and (■ and ●) chars.
CHN1000 analyzer, with a charcoal standard.
The volatile matter content measurement method was according to
ASTM standard D1762-84. ratios from feedstocks to chars follows the path of a
Fourier transform infrared (FTIR) spectra of feedstock and HTC dehydration process for Miscanthus, whereas for corncob
samples were recorded with a Jasco FT/IR-6200 spectrophotometer dehydration is the main process occurring during HTC but a
using KBr pellets.
NMR experiments were carried out on a Bruker AMX-300WB
contribution of decarboxylation is also found. The H/C and O/
spectrometer working at 300.13 MHz for 1H and at 75.47 MHz for C values of our chars, which fall in the ranges reported for
13
C. 13C cross-polarization (CP) NMR spectra with magic angle lignite,44 are similar to those found for chars obtained by HTC
spinning (MAS) were recorded under proton-decoupling conditions of different biomasses12,13,26,27 and saccharides;3,28 however, it
using a 4 mm CP-MAS probehead for solid-state measurements. If not is difficult to make direct comparisons between data measured
otherwise stated, the MAS frequency was 8 kHz. The 1H 90° pulse in different studies because the carbonization conditions used
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Figure 2. FTIR spectra of (a) feedstocks and (b) HTC chars of (left) corncob and (right) Miscanthus.

(temperature, pressure, reaction time, and solid concentration) supported by the appearance of slightly more intense peaks in
are different. the 900−700 cm−1 spectral region. However, it must be
The chemical transformations that occur when corncob and pointed out that peaks at 1700, 1608, and 1514 cm−1 could also
Miscanthus are converted into carbonaceous products by means be associated to furanic structures formed from carbohydrates
of HTC were examined by FTIR and 13C SSNMR spectros- during HTC.47 Finally, bands at 1320, 1207, 1161, 1114, 1060,
copies. FTIR spectra of feedstocks and hydrochars are shown in and 1034 cm−1, narrower and more intense than in the
Figure 2. The spectra of the corncob and Miscanthus feedstocks feedstock spectra, suggest an abundance of oxygenated groups
were similar and typical of lignocellulosic materials, showing in the carbonized samples, and those between 3000 and 2800
peaks assigned to functional groups in cellulose, hemicellulose, cm−1 indicate the presence of aliphatic chains also in the
and lignin as follows:45 the strong broad band centered at hydrochars.
around 3430 cm−1 to O−H stretching vibrations in hydroxyl To better characterize the chemical structure of our
and carboxyl groups; the band between 3000 and 2800 cm−1 to materials, 13C CP-MAS spectra of feedstock and hydrochar
C−H stretching vibrations of methylene and methyl groups; samples were recorded and accurately analyzed. The spectra of
the bands at 1607, 1512, and 1265 cm−1 to CC and C−O both corncob and Miscanthus feedstocks showed signals
stretching or bending vibrations of different groups present in
characteristic of lignocellulosic materials (Figure 3).48−51 In
lignin; the bands at 1460, 1427, 1335, and 1106 cm−1 to C−H
particular, the spectral region between 60 and 110 ppm was
and C−O deformation, bending, or stretching vibrations of
dominated by cellulose signals (C-1 at 104.5 ppm, C-2, C-3,
many groups in lignin or carbohydrates; the bands at 1732,
1374, 1240, 1165, 1062, and 1035 cm−1 to CO, C−H, C− and C-5 at 72.1 and 74.6 ppm, C-4 at 83.3 and 88.1 ppm, and
O−C, and C−O deformation and stretching vibrations of C-6 at 62.2 and 64.5 ppm),52 which were superimposed to less
different groups in carbohydrates; the band at 1320 cm−1 to intense hemicellulose (C-1−C-6 carbons)48 and lignin
CH2 rocking in cellulose; the band at 898 cm−1 to C−H
deformation in cellulose; and other small bands between 900
and 700 cm−1 to C−H deformation in aromatic rings of lignin.
Corncob and Miscanthus chars showed similar FTIR spectra
(Figure 2), where many of the feedstock peaks were preserved,
as reported for other hydrochars,13,26,30 indicating that only a
partial carbonization of biomass occurs during HTC in the
conditions applied here. However, some differences could be
observed between spectra of chars and feedstocks, as expected
on the basis of the changed elemental composition. Indeed, the
band relative to O−H stretching was still present in the
hydrochar spectra but with slightly lower intensity, in
agreement with the observed dehydration. Moreover, in the
HTC spectra, the peak at 1732 cm−1, assigned to CO
stretching vibrations of the carboxyl and acetyl groups in
hemicellulose,46 was not present and the peak at 898 cm−1 had
very low intensity. This observation suggests that the HTC
process transforms hemicellulose and cellulose almost com-
pletely and partially, respectively. On the other hand, an intense
peak at 1700 cm−1 ascribable to CO vibrations of carbonyl,
quinone, ester, or carboxyl groups was observed in the char
spectra. Moreover, the peaks corresponding to aromatic skeletal
vibrations at 1608, 1514, and 1270 cm−1 were more intense in
the spectra of hydrochars than in those of feedstocks, indicating Figure 3. 13C CP-MAS spectra of (a) corncob and (b) Miscanthus
an aromatization of biomass during HTC, which is also feedstocks.

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(aliphatic side chains)53−57 signals. The splitting of the cellulose
C-4 and C-6 resonance lines is usually ascribed to the
occurrence of crystalline or internal cellulose (peaks at 88.1
and 64.5 ppm, respectively) and cellulose, which is amorphous
and/or on the surface of fibers (peaks at 83.3 and 62.2 ppm,
respectively). The shoulder at about 102 ppm could be due to
either amorphous cellulose or hemicellulose C-1. Signals from
acetate groups of hemicellulose were observed at 21.0 ppm
(methyl carbons) and 172.0 ppm (carboxyl carbons).50,52
Aromatic carbons of lignin resonated in the spectral region
between 115 and 160 ppm (115.4, 127.0, 133.0, 147.0, 152.0,
and 160.0 ppm); in particular, the peaks at 147.0, 152.0, and
160.0 ppm could be assigned to carbons bound to oxygen,
including both free phenolic groups and aromatic ethers, while
those at 115.4 and 127.0 ppm were due to protonated carbons
and that at 133.0 ppm was due to carbons bearing alkyl groups.
A small contribution to the signal at about 105 ppm is expected
from aromatic carbons of lignin syringyl units. The signal of the
methyl carbons in methoxy groups of lignin was observed at
55.8 ppm, and the signal of the carboxyl carbons was observed
at 167.2 ppm.53−57
To estimate the relative content of lignin, cellulose, and
hemicellulose from the spectra, the 1H−13C CP dynamics of
the different signals was investigated by recording 13C CP-MAS
spectra with contact time values ranging from 50 μs to 80 ms.
In these experiments, the extent of CP-enhanced 13C
magnetization observed for a given set of experimental
conditions is determined by the competing effects of 1H−13C
polarization transfer, represented by the rate constant TCH−1,
and rotating-frame proton spin−lattice relaxation, governed by
the relaxation rate T1ρH−1.58 Therefore, the evolution of the
intensity for each peak as a function of the contact time tCP is
given by eq 1
⎛ TCH ⎞
−1
⎜
M(tCP) = M *⎜1 − ⎟
⎟ (e
−tCP / T1ρH
− e−tCP/ TCH)
⎝ T1ρH ⎠ (1)
where M(tCP) is the observed magnetization and M* is the
carbon magnetization obtained under conditions of maximum
CP enhancement and infinitely long T1ρH. The signal
intensities, determined at each tCP value by applying a
deconvolution procedure,42 were employed to determine TCH,
T1ρH, and M* from eq 1 for each assigned resonance. In
particular, TCH values on the order of a few hundred
microseconds at most were found for carbohydrate peaks,
except for those of the acetate groups of hemicellulose, which
had TCH values on the order of milliseconds. On the other
hand, the lignin signals showed TCH values between 1 and 3 ms.
Proton T1ρH values of a few tens of milliseconds were found for
all signals. On the basis of the TCH and T1ρH values, it can be
observed that the aromatic lignin carbons, the methyl carbon of
hemicellulose, and the carbonyl carbons are under-represented
in the CP spectra acquired with a tCP of 2 ms shown in Figure 3.
It must be pointed out that quantitation in natural systems,
such as those investigated here, may be affected by the presence
of paramagnetic species, which could broaden carbon signals
beyond detection in the 13C NMR spectra. Indeed, electron
paramagnetic resonance (EPR) spectra recorded on corncob
and Miscanthus feedstocks and chars (data not shown)
indicated the presence of organic free radicals in all materials,
whereas no paramagnetic inorganic minerals were detected.
The radical content of chars was 2 orders of magnitude higher
than that of feedstocks (∼1018 spins/g, instead of ∼1016 spins/
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Article
g), but it was lower than those found in chars obtained from
pyrolysis (1019−1021 spins/g).38,59 Given the relatively low
radical content, the M* values determined could be safely
considered quantitatively reliable. Such values were therefore
used to obtain quantitative information on feedstock material
compositions. Following the procedure suggested by Preston et
al.,60 it was possible to estimate the overall spectral intensity
attributable to lignin and carbohydrates. To this end, the
following assignments were assumed: the signal at 55.8 ppm to
the methoxy group of guaiacyl and the two methoxy groups of
syringyl lignin moieties; the signals at 147.0 and 152.0 ppm to
carbons bound to methoxy groups in guaiacyl and syringyl
lignin moieties and to the hydroxyl group in guaiacyl units; and
the signal at 133.0 ppm to the aromatic carbon bound to the
propyl chain in guaiacyl, syringyl, and p-coumaryl units of
lignin. On the basis of these assignments, the spectral intensity
of aromatic lignin carbons was determined and used to estimate
the total signal intensity of lignin considering a basic
phenylpropane repeating unit of 9 carbons with 6 aromatic
carbons for each unit, adding the signal intensity of the
methoxy signal. The spectral intensity arising from cellulose
and hemicellulose carbons was determined by adding the M*
values of all signals ascribed to these components and
subtracting the estimated contribution from the aromatic
carbons in syringyl units at 105 ppm and that from the side-
chain carbons of all lignin units in the spectral region between
60 and 95 ppm. The spectral contribution of acetate was
evaluated as twice the M* value of the 21.0 ppm signal. The
relative spectral intensities of the different components thus
obtained are reported in Table 2. It must be pointed out that
Table 2. Relative Carbon Contributions of Lignin,
Carbohydrate, Acetate, and Other Carboxyl Groups in
Feedstocks Determined as Described in the Texta
component corncob (%) Miscanthus (%)
lignin 13.8 21.3
carbohydrate 80.0 74.3
acetate 3.2 3.1
other carboxyl 3.0 1.3
a
The estimated error is ±0.5.
these intensities are representative of the relative carbon
contents and, hence, do not directly correspond to the relative
amount of lignin, cellulose, and hemicellulose in the feedstock
materials; nonetheless, they allow a comparison between the
composition of feedstocks to be made. Indeed, we could infer
that Miscanthus feedstock has a significantly higher lignin and
lower carbohydrate content than the corncob feedstock, in
agreement with the literature.61−63 These results are also
supported by the lower H/C and O/C atomic ratios
determined from elemental analysis (Table 1) and the lower
intensities of the bands in the range of 1250−900 cm−1 ascribed
to cellulose in the FTIR spectra. In addition, cellulose
crystallinity, determined on the basis of the M* values of 13C
NMR signals at 83.3 and 88.1 ppm,64 was higher for Miscanthus
with respect to corncob (∼26%, instead of ∼14%).
The 13C CP-MAS spectra of both corncob and Miscanthus
hydrochars showed signals from residual feedstock materials
and carbonization products (Figure 4b). In particular, signals
from residual carbohydrates in the 60−100 ppm spectral region
and signals from residual lignin at about 56, 147, and 152 ppm
could easily be distinguished. Signals from carbonaceous
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Figure 4. 13C CP-MAS spectra of (left) corncob and (right) Miscanthus chars (a) with and (b) without dipolar dephasing.
Figure 5. 13C CP-MAS spectrum of Miscanthus char with spectral deconvolution.
materials were observed in the aliphatic region between 0 and
50 ppm and in the aromatic region between 110 and 160 ppm,
while a signal ascribable to ketone carbons appeared at 205
ppm, in agreement with the findings on functional groups
obtained by FTIR spectroscopy (Figure 2). As observed by
comparing the spectra in Figures 3 and 4, the proportion of
lignin with respect to carbohydrates was higher in the HTC
materials than in the corresponding feedstocks. Moreover, the
acetate peak ascribed to hemicellulose was not present in the
spectra of carbonized samples, indicating that residual
carbohydrates were essentially ascribable to cellulose.
For an unambiguous assignment of the spectra, a CP-MAS
pulse sequence with dipolar dephasing was also applied; the
resulting spectra are shown in Figure 4a. In this experiment, a
delay period, during which the 1H decoupler is turned off, is
inserted between the CP contact period and data acquisition;
during this delay, the magnetization of carbons with strong
dipolar interactions with protons is attenuated by dephasing.
Thus, 13C signal intensity persists only for non-protonated and
methyl carbons (for which 13C−1H dipolar interactions are
strongly attenuated by fast rotation around the ternary
symmetry axis), while signals of methylene and methine
carbons are significantly reduced or disappear, depending
upon the duration of the delay. Indeed, in the spectra recorded
on HTC Miscanthus using a dephasing delay of 50 μs, signals
ascribable to carbons in alkyl groups (0−40 ppm), methoxy
groups (56 ppm), non-protonated aromatic (131, 147, and 152
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ppm), and carboxyl and carbonyl groups (175 and 205 ppm,
respectively) were observed. The same signals were found in
the spectra recorded on HTC corncob together with signals of
residual carbohydrate O-alkyl and di-O-alkyl carbons, which are
most likely due to relatively mobile residues.
With the assignment made, we proceeded with the
quantitative analysis of the 13C CP spectra. Given the strong
overlap of signals and the complex structure of these systems, a
deconvolution procedure was required to unravel the
contributions to the spectral intensity in the different regions;
an example is shown in Figure 5. In this procedure, the
chemical shifts for the residual feedstock signals (cellulose and
lignin) were taken from the 13 C CP spectra of the
corresponding starting materials and the minimum number of
additional peaks, ascribed to carbonization products, was used
to obtain a satisfactory reproduction of the spectra. In
particular, in the aliphatic spectral region, signals centered at
about 15, 30, 38, and 45 ppm were considered. On the other
hand, the spectral region between 110 and 160 ppm could be
reproduced using signals at about 110, 118, 125, 133, 141, and
151 ppm, which have been assigned to aromatic and furanic
structures by Baccile et al.37 and Falco et al.24 using advanced
13
C SSNMR techniques and isotopically enriched glucose as the
starting material for HTC. Indeed, it has been shown that HTC
of cellulosic materials yields polyfuranic and condensed
aromatic structures with relative amounts which depend upon
the starting material and carbonization conditions.25 As in the
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case of feedstocks, the deconvolution procedure was also
applied to variable contact time CP spectra to perform a
quantitative determination of the relative spectral contributions
of the different components and, therefore, an evaluation of the
conversion of the biomass and a characterization of the
chemical structure of the carbonized materials. To this end, the
M* values obtained for each peak from the analysis of the CP
dynamics curves using eq 1 were used to calculate the percent
contributions reported in Table 3. The lignin contribution was
Table 3. Relative Carbon Contributions of Alkyl,
Carbohydrate, Lignin, Aromatic and Furanic, Carboxyl, and
Carbonyl Groups in Hydrochars Determined as Described in
the Texta
component corncob (%) Miscanthus (%)
alkyl 20.1 20.7
carbohydrate 26.1 15.5
lignin 23.6 36.5
aromatic and furanic 24.1 22.8
carboxyl 2.5 1.6
carbonyl 3.6 2.9
a
The estimated error is ±0.5.
determined starting from the M* values obtained for the
methoxy group by assuming that residual lignin had the same
spectrum of the original one. The obtained results indicated
that the residual feedstock material present in the chars is
mainly constituted by lignin for Miscanthus and by cellulose for
corncob, in agreement with the H/C and O/C atomic ratios
determined for the two chars (Table 1). In addition, the relative
intensities of the signals at 83.3 and 88.1 ppm indicated that
crystalline cellulose prevailed in the residual feedstocks (∼57
and ∼52% of total cellulose for Miscanthus and corncob,
respectively). Overall, the proportion of carbons in the
carbonized products was similar for the two HTC materials.
Following the procedure reported by Falco et al.,24 we
estimated the furan/arene ratio from M* values of signals at
110 ppm (fully ascribable to furan units), at 125 and 131 ppm
(fully ascribable to arene units), and at 147−152 ppm
(ascribable to both arene and furan units); the resulting values
were 0.5 and 2.2 for Miscanthus and corncob, respectively. On
the basis of these results, also taking into account the relative
amounts of carbonyl and carboxyl carbons, it can be inferred
that HTC produced more polyfuranic structures in corncob
than in Miscanthus.
The obtained results can be rationalized in terms of the quite
different behavior of cellulose, hemicellulose, and lignin under
hydrothermal conditions. Hemicellulose was found to be easily
and completely solubilized in hot compressed water, giving
monomeric sugars, while cellulose and lignin were partially
solubilized to form oligosaccharides and glucose for the former
and phenolic fragments for the latter.5,65 In particular,
crystalline cellulose was found to be resistant to swelling in
water and hydrolysis. In lignocellulosic biomass, this resistance
can be even higher because of the fact that cellulose is protected
from water by lignin and hemicellulose. The products of
solubilization and hydrolysis are usually highly reactive and
undergo dehydration, decarboxylation and condensation
polymerization reactions, with all of these reactions not being
consecutive but constituting a parallel network of different
paths.5 In particular, soluble products of lignin and hemi-
cellulose tend to react and recondense to form solid
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precipitates. When formed on the surface of cellulose, these
precipitates inhibit the access of water to cellulose, which
undergoes pyrolysis instead of dissolution and hydrolysis,66
ultimately resulting into carbonaceous materials with mainly
aromatic instead of furanic structures.25 As far as lignin is
concerned, soluble lignin fragments give fast polymerization; on
the other hand, there are some stable lignin crystalline
structures for which transformation reactions, mainly deme-
thylation and pyrolytic reactions, could occur without
fragmentation.5 As a result, lignin is not strongly modified by
the HTC process, neither chemically nor physically.67
All this considered, the disappearance of signals ascribed to
hemicellulose acetate in the FTIR and 13C NMR spectra and
the increase in the relative contribution of signals of crystalline
cellulose in the 13C NMR spectra observed for both hydrochars
are easily explained in terms of the different solubility and
hydrolyzability of hemicellulose and amorphous and crystalline
components of cellulose. The quite high proportion of
apparently unreacted lignin found in hydrochars confirmed
the low propensity of lignin to change its chemical structure
during HTC under mild conditions. The lower furan/aromatic
ratio found for Miscanthus with respect to corncob could
instead be related to the higher cellulose crystallinity and higher
lignin content in the former, with both factors concurring to the
reduction of water-exposed cellulose.
■
CONCLUSION
The application of 13C CP-MAS NMR spectroscopy to chars
obtained from HTC of corncob and Miscanthus biomass gave
valuable information on the chemical structure of the different
components present in these materials and their relative
contents. This allowed the partial preservation of cellulose and
lignin and the formation of furanic and arenic components in
chars during HTC to be highlighted and correlated to the
composition of the corresponding feedstocks, also investigated
by the same technique. Quantitative information, not directly
attainable from the spectra, was obtained by applying an
accurate procedure, including spectral deconvolution and
analysis of CP dynamics for the single resonances.
We believe that the application of this procedure to
hydrochars prepared from biomasses with different composi-
tion under systematically varied experimental conditions
(temperature, treatment duration, and autoclave loading)
could help in unravelling the mechanism of transformation of
lignocellulosic materials during HTC and in formulating
general recipes for producing chars with specific desired
properties.
■ AUTHOR INFORMATION
Corresponding Author
*Telephone: +390503152462. Fax: +390503152555. E-mail:
claudia.forte@pi.iccom.cnr.it.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
Partial funding for this research was provided by the Research
Council of Norway, Project 197531 “Advanced Techniques To
Evaluate the Long-Term Stability and Carbon Sequestration
Potential of Different Types of Biochar”. Dr. Markus Antonietti
is kindly acknowledged for preparing the hydrochar samples.
The authors are grateful to Dr. Line Tau for the elemental
dx.doi.org/10.1021/ef3017128 | Energy Fuels 2013, 27, 303−309
Energy & Fuels
analysis and Dr. Liang Wang and Dr. Morten Grønli for the
proximate analyses. Dr. Alhaji Jeng and Alice Budai are thanked
for their logistic support.
■
REFERENCES
(1) Meyer, S.; Glaser, B.; Quicker, P. Environ. Sci. Technol. 2011, 45,
9473−9483.
(2) Hu, B.; Yu, S.-H.; Wang, K.; Liu, L.; Xu, X.-W. Dalton Trans.
2008, 5414−5423.
(3) Sevilla, M.; Fuertes, A. B. Chem.Eur. J. 2009, 15, 4195−4203.
(4) White, R. J.; Budarin, V. L.; Luque, L.; Clark, J. H.; Macquarrie,
D. J. Chem. Soc. Rev. 2009, 38, 1326−1335.
(5) Funke, A.; Ziegler, F. Biofuels Bioprod. Biorefin. 2010, 4, 160−177.
(6) Titirici, M.-M.; Antonietti, M. Chem. Soc. Rev. 2010, 39, 103−116.
(7) Hu, B.; Wang, K.; Wu, L.; Yu, S.-H.; Antonietti, M.; Titirici, M.-
M. Adv. Mater. 2010, 22, 813−828.
(8) Liu, B. Z.; Zhou, X.; Qian, Y. Adv. Mater. 2010, 22, 1963−1966.
(9) Kubo, S.; Demir-Cakan, R.; Zhao, L.; White, R. J.; Titirici, M.-M.
ChemSusChem 2010, 3, 188−194.
(10) Antonietti, M.; Titirici, M.-M. C. R. Chim. 2010, 13, 167−173.
(11) Hoekman, S. K.; Broch, A.; Robbins, C. Energy Fuels 2011, 25,
1802−1810.
(12) Berge, N. D.; Ro, K. S.; Mao, J.; Flora, J. R. V.; Chappell, M. A.;
Bae, S. Environ. Sci. Technol. 2011, 45, 5696−5703.
(13) Sevilla, M.; Maciá-Agulló, J. A.; Fuertes, A. B. Biomass Bioenergy
2011, 35, 3152−3159.
(14) Glasner, C.; Deerberg, G.; Lyko, H. Chem. Ing. Tech. 2011, 83,
1890−1896.
(15) Titirici, M.-M.; White, R. J.; Falco, C.; Sevilla, M. Energy Environ.
Sci. 2012, 5, 6796−6822.
(16) Román, S.; Nabais, J. M. V.; Laginhas, C.; Ledesma, B.;
González, J. F. Fuel Process. Technol. 2012, 103, 78−83.
(17) Lu, X.; Jordan, B.; Berge, N. D. Waste Manage. 2012, 32, 1353−
1365.
(18) Titirici, M.-M.; Thomas, A.; Antonietti, M. New J. Chem. 2007,
31, 787−789.
(19) Steinbeiss, S.; Gleixner, G.; Antonietti, M. Soil Biol. Biochem.
2009, 41, 1301−1310.
(20) Rillig, M. C.; Wagner, M.; Salem, M.; Antunes, P. M.; George,
C.; Ramke, H.-G.; Titirici, M.-M.; Antonietti, M. Appl. Soil Ecol. 2010,
45, 238−242.
(21) Libra, J. A.; Ro, K. S.; Kammann, C.; Funke, A.; Berge, N. D.;
Neubauer, Y.; Titirici, M.-M.; Fuhner, C.; Bens, O.; Kern, J.;
Emmerich, K.-H. Biofuels 2011, 2, 71−106.
(22) George, C.; Wagner, M.; Kücke, M.; Rillig, M. C. Appl. Soil Ecol.
2012, 59, 68−72.
(23) Titirici, M.-M.; Antonietti, M.; Baccile, N. Green Chem. 2008,
10, 1204−1212.
(24) Falco, C.; Caballero, F. P.; Babonneau, F.; Gervais, C.; Laurent,
G.; Titirici, M.-M.; Baccile, N. Langmuir 2011, 27, 14460−14471.
(25) Falco, C.; Baccile, N.; Titirici, M.-M. Green Chem. 2011, 13,
3273−3281.
(26) Yu, L.; Falco, C.; Weber, J.; White, R. J.; Howe, J. Y.; Titirici,
M.-M. Langmuir 2012, 28, 12373−12383.
(27) Aydıncak, K.; Yumak, T.; Sınağ, A.; Esen, B. Ind. Eng. Chem. Res.
2012, 51, 9145−9152.
(28) Sevilla, M.; Fuertes, A. B. Carbon 2009, 47, 2281−2289.
(29) Karayıldırım, T.; Sınağ, A.; Kruse, A. Chem. Eng. Technol. 2008,
31, 1561−1568.
(30) Peterson, A. A.; Vogel, F.; Lachance, R. P.; Fröling, M.; Antal,
M. J., Jr.; Tester, J. W. Energy Environ. Sci. 2008, 1, 32−65.
(31) Dinjus, E.; Kruse, A.; Tröger, N. Chem. Eng. Technol. 2011, 34,
2037−2043.
(32) Cao, X.; Ro, K. S.; Chappell, M.; Li, Y.; Mao, J. Energy Fuels
2011, 25, 388−397.
(33) Kang, S.; Li, X.; Fan, J.; Chang, J. Ind. Eng. Chem. Res. 2012, 51,
9023−9031.
309
Article
(34) McBeath, A. V.; Smernik, R. J. Org. Geochem. 2009, 40, 1161−
1168.
(35) Fuertes, A. B.; Arbestain, M. C.; Sevilla, M.; Maciá-Agulló, J. A.;
Fiol, S.; López, R.; Smernik, R. J.; Aitkenhead, W. P.; Arce, F.; Macias,
F. Aust. J. Soil Res. 2010, 48, 618−626.
(36) Brewer, C. E.; Schmidt-Rohr, C.; Satrio, J. A.; Brown, R. C.
Environ. Prog. Sustainable Energy 2009, 28, 386−396.
(37) Baccile, N.; Laurent, G.; Babonneau, F.; Fayon, F.; Titirici, M.-
M.; Antonietti, M. J. Phys. Chem. C 2009, 113, 9644−9654.
(38) Bardet, M.; Hediger, S.; Gerbaud, G.; Gambarelli, S.; Jacquot, J.
F.; Foray, M. F.; Gadelle, A. Fuel 2007, 86, 1966−1976.
(39) David, K.; Pu, Y.; Foston, M.; Muzzy, J.; Ragauskas, A. Energy
Fuels 2009, 23, 498−501.
(40) Opella, S. J.; Frey, M. H. J. Am. Chem. Soc. 1979, 101, 5854−
5856.
(41) Alemany, L. B.; Grant, D. M.; Alger, T. D.; Pugmire, R. J. J. Am.
Chem. Soc. 1983, 105, 6697−6704.
(42) Geppi, M.; Forte, C. J. Magn. Reson. 1999, 137, 177−185.
(43) Schumacher, J. P.; Huntjens, F. J.; van Krevelen, D. W. Fuel
1960, 39, 223−234.
(44) Hatcher, P. G.; Breger, I. A.; Szeverenyi, N.; Maciel, G. E. Org.
Geochem. 1982, 4, 9−18.
(45) Poletto, M.; Zattera, A. J.; Santana, R. M. C. J. Appl. Polym. Sci.
2012, 126, E336−E343.
(46) Schwanninger, M.; Rodrigues, J. C.; Pereira, H.; Hinterstoisser,
B. Vib. Spectrosc. 2004, 36, 23−40.
(47) Zhang, M.; Yang, H.; Liu, Y.; Sun, X.; Zhang, D.; Xue, D.
Nanoscale Res. Lett. 2012, 7, 38.
(48) Kolodziejski, W.; Frye, J. S.; Maciel, G. E. Anal. Chem. 1982, 54,
1419−1424.
(49) Haw, J. F.; Maciel, G. E.; Schroeder, H. A. Anal. Chem. 1984, 56,
1323−1329.
(50) Bardet, M.; Emsley, L.; Vincendon, M. Solid State Nucl. Magn.
Reson. 1997, 8, 25−32.
(51) Czimczik, C. I.; Preston, C. M.; Schmidt, M. W. I.; Werner, R.
A.; Schulze, E.-D. Org. Geochem. 2002, 33, 1207−1223.
(52) Atalla, R. H.; VanderHart, D. L. Solid State Nucl. Magn. Reson.
1999, 15, 1−19.
(53) Lüdemann, H.-D.; Nimz, H. Biochem. Biophys. Res. Commun.
1973, 52, 1162−1169.
(54) Schaefer, J.; Sefcik, M. D.; Stejskal, E. O.; McKay, R. A.; Hall, P.
L. Macromolecules 1981, 14, 557−559.
(55) Hatfield, G. R.; Maciel, G. E.; Erbatur, O.; Erbatur, G. Anal.
Chem. 1987, 59, 172−179.
(56) Hatcher, P. G. Org. Geochem. 1987, 11, 31−39.
(57) Mao, J.; Holtman, K. M.; Scott, J. T.; Kadla, J. F.; Schmidt-Rohr,
K. J. Agric. Food Chem. 2006, 54, 9677−9686.
(58) Alemany, L. B.; Grant, D. M.; Pugmire, R. J.; Alger, T. D.; Zilm,
K. W. J. Am. Chem. Soc. 1983, 105, 2133−2141.
(59) Feng, J.-W.; Zheng, S.; Maciel, G. E. Energy Fuels 2004, 18,
560−568.
(60) Preston, C. M.; Trofymow, J. A.; Niu, J.; Fyfe, C. A. For. Ecol.
Manage. 1998, 11, 51−68.
(61) Kim, S. J.; Kim, M. Y.; Jeong, S. J.; Jang, M. S.; Chung, I. M. Ind.
Crops Prod. 2012, 38, 46−49.
(62) Huang, Y.; Wei, Z.; Qiu, Z.; Yin, X.; Wu, C. J. Anal. Appl.
Pyrolysis 2012, 93, 153−159.
(63) Azeez, A. M.; Meier, D.; Odermatt, J. J. Anal. Appl. Pyrolysis
2011, 90, 81−92.
(64) Samuel, R.; Pu, Y.; Foston, M.; Ragauskas, A. J. Biofuels 2010, 1,
85−90.
(65) Mok, W. S.-L.; Antal, M. J., Jr. Ind. Eng. Chem. Res. 1992, 31,
1157−1161.
(66) Hashaikeh, R.; Fang, Z.; Butler, I. S.; Hawari, J.; Kozinski, J. A.
Fuel 2007, 86, 1614−1622.
(67) Dinjus, E.; Kruse, A.; Tröger, N. Chem. Eng. Technol. 2011, 34,
2037−2043.
dx.doi.org/10.1021/ef3017128 | Energy Fuels 2013, 27, 303−309