Research Article

Cite This: ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX pubs.acs.org/journal/ascecg

Relating Structural and Microstructural Evolution to the Reactivity

of Cellulose and Lignin during Alkaline Thermal Treatment with
Ca(OH)2 for Sustainable Energy Production Integrated with CO2
Capture
Hassnain Asgar,† Sohaib Mohammed,† Ivan Kuzmenko,‡ and Greeshma Gadikota*,†
†
Department of Civil and Environmental Engineering and Grainger Institute for Engineering, University of WisconsinMadison,
2228 Engineering Hall, 1415 Engineering Drive, Madison, Wisconsin 53706, United States
‡
X-Ray Science Division, Advanced Photon Source, Argonne National Laboratory, Building 433A, 9700 Cass Avenue, Lemont,
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Illinois 60439, United States

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*
S Supporting Information

ABSTRACT: The transition toward a low carbon economy

necessitates the implementation of a wide range of negative
emissions technologies, including bioenergy integrated with
CO2 capture and storage. Advancing large-scale or modular
technologies for bioenergy with carbon capture and storage
requires a fundamental understanding of chemo-morpholog-
ical coupling in these material systems. In this context,
integrated chemical pathways such as alkaline thermal
treatment (ATT) of biomass which involves the production
of bio-H2 while converting and storing CO2 as solid
carbonates provides promising potential for integrating
bioenergy with carbon capture and storage. In this study, we
elucidate the structural and morphological changes when
biomass feedstocks such as cellulose and lignin are reacted with calcium hydroxide to capture, convert, and store CO2 as calcium
carbonate while producing energy carrier such as H2. These structural and morphological changes were monitored using
synchrotron based in operando multiscale X-ray scattering measurements. Enhanced CO2 capture at temperatures above 375 °C
was evident from the significant growth of the calcium carbonate phase at these conditions. Increase in the surface area and
porosity of cellulose was noted compared to lignin due to the relatively fast decomposition of cellulose. Pore−solid interfaces in
Ca(OH)2 + cellulose system became smoother in the temperature range of 500−700 °C compared to Ca(OH)2 + lignin
system, where the interfaces became rougher. Enhanced roughness of the pore−solid interfaces in the presence of lignin is
attributed to the simultaneous slow decomposition of lignin and formation of calcium carbonate.
KEYWORDS: biomass, cellulose, lignin, X-ray scattering, carbon capture, calcium carbonate, alkaline thermal treatment

■ INTRODUCTION
One of the grand challenges in sustainable energy production
is the need to develop energy generating processes with in-
built environmental controls. In this context, the increasing
need to deploy negative emission technologies to rapidly
transition toward a low carbon economy1 necessitates the
advancement of fundamental science associated with bioenergy
production with CO 2 capture and storage (BECCS)
technologies. While several studies assessed the large-scale
potential of integrating conventional carbon capture and
storage technologies (CCS) with bioenergy production,2−5
few studies explored alternative chemical pathways which
involve simultaneously upcycling biomass conversion to
produce clean fuels such as H2 while converting and storing
CO2 as solid carbonates.6−9 Conventional approaches of
recovering energy from biomass have included pyrolysis in
the temperature range of 375−525 °C which yield liquid oils,
solid charcoal, and gaseous compounds.10−13 H2 gas can be
produced from the pyrolysis of biomass in a controlled
environment as shown by the following reaction:
Cx HyOz + heat → H 2 + CO + CH4 + hydrocarbons
(1)
Methane and hydrocarbons produced via the reaction shown
above can be reformed by steam to yield additional H2 via the
water−gas shift reaction shown below.14
hydrocarbons + CH4 + H 2O → CO + H 2 (2)
Received: December 15, 2018
Revised: January 16, 2019
Published: January 30, 2019

© XXXX American Chemical Society A DOI: 10.1021/acssuschemeng.8b06584

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CO + H 2O → CO2 + H 2 (3)
While energy production from biomass pyrolysis is
considered CO2 neutral because this CO2 has origins in the
atmosphere before it is converted to biomass via photosyn-
thesis,15 capturing the produced CO2 adds the carbon-negative
component to bioenergy production. The potential to capture
CO2 emitted from burning coal using calcium oxide (CaO)
and calcium hydroxide (Ca(OH)2) as sorbents were reported
by Curran and coworkers16 and Wang and coworkers,17
respectively. The conversion and storage of CO2 in the form of
calcium and magnesium carbonates has been investigated in
the context of carbon mineralization.18−27 Further, the
integration of calcium carbonate chemistry in the context of
calcium or chemical looping combustion has been re-
ported.28,29 However, the approach of integrating alkaline
sorbents including calcium, magnesium and sodium hydroxide
for CO2 capture and storage with bioenergy production, also
known as alkaline thermal treatment (ATT),7−9 is a highly
promising route for integrating sustainable energy production
with integrated CO2 capture. The general reaction pathway
associated with the ATT of biomass is shown by the following
reaction:
Cx HyOz + Ca(OH)2 + H 2O → H 2 + CaCO3
(4)
However, it is not certain if the reacting sorbent is CaO or
Ca(OH)2 because the following sequence of reactions can
occur in the presence of CO2 with increasing temperature to
produce calcium carbonate (CaCO3).30
Ca(OH)2 → CaO + H 2O (5)
CaO + CO2 → CaCO3 (6)
Ca(OH)2 + CO2 → CaCO3 + H 2O (7)
Different studies have reported the gaseous products formed
during the pyrolysis of biomass. The major products of
cellulose and lignin pyrolysis are H2, CO, CH4, and CO2 with
some minor quantities of C2H4 and C2H6, as reported by Yang
and coworkers.10 Higher H2 yield from lignin pyrolysis (20.84
mmol/g) was noted compared to cellulose (5.48 mmol/g),
while the CO2 emissions from both cellulose and lignin were
6.58 and 7.81 mmol/g, respectively. Conversion of biomass to
H2-rich fuel gas integrated with CO2 capture by using CaO as a
sorbent was reported by Guoxin et al.6 High yields of H2
production with significant suppression of CO2 during the
ATT of cellulosic biomass was reported by Stonor et al.7
Group I and II hydroxides were shown to facilitate the ATT
process by sequestering CO2 to produce solid carbonates.7
Additionally, a 10% Ni/ZrO2 catalyst was reported to increase
the overall yield of H2 gas produced. For example, improve-
ments in H2 yield from 0.4% (without catalyst) to 16.1% (with
catalyst) and 1.2% (without catalyst) to 31.4% (with catalyst)
were noted on reacting Mg(OH)2 and Ca(OH)2 with
cellulose, respectively. Recent studies on the ATT of cellulose
have demonstrated the promise of using this process to
produce higher yields of H2. However, it was mentioned earlier
that the pyrolysis of lignin produces higher yield of H2 as
compared to cellulose. Therefore, with the increasing interest
in sustainably utilizing lignin-bearing biomass feedstocks for
bioenergy production31−34, the effectiveness of the ATT
process for lignin valorization needs to be evaluated.
B DOI: 10.1021/acssuschemeng.8b06584
Research Article
Additionally, the nature of products evolving during the
pyrolysis of different biomass is well-known,1011 but there is a
limited understanding of the temperatures that correspond to
CO2 capture and the formation of carbonates. The evolution of
gaseous products greatly depends upon the biomass feed and
the temperature. For example, in a packed bed pyrolysis
analysis, it was found that H2 was released at temperatures
higher than 400 °C, and its release was enhanced by increasing
the temperature up to 600 °C or higher.10 The temperature
ranges that correspond to the high production of H2 in
cellulose and lignin are 700−800 and 600−700 °C,
respectively.10 In the case of cellulose and lignin, significant
quantities of CO2 were released at 400−600 °C.10 Therefore, it
is essential to evaluate the temperature transitions that
correspond to the uptake of CO2 to produce carbonate phases
for optimizing and enhancing the efficiency of the ATT
process.
Therefore, the precise tuning of the temperature conditions
for the ATT process necessitates addressing the following
research questions: (1) What are the detailed phase transitions
that occur during the ATT of cellulose and lignin? (2) What
are the corresponding morphological changes that occur
during these phase transitions? (3) How do these phase and
morphological transitions vary with lignin and cellulose? To
address these questions, we utilized multiscale in operando X-
ray scattering measurements to elucidate the changes in the
reactant and product phases with the corresponding textural
changes in the materials. The wide angle X-ray scattering
(WAXS) measurements provide detailed insights into the
evolution of the solid reactant and product phases, while the
ultrasmall/small angle X-ray scattering (USAXS/SAXS)
measurements show the evolution of textural changes with
reaction progress35−42 (Figure 1). The cross-scale evolution in
Figure 1. Schematic of the experimental setup for determining the
structural and morphological features during the alkaline thermal
treatment of biomass using in operando USAXS/SAXS/WAXS
measurements.
the structure and morphology of the solid products during
bioenergy production integrated with carbon capture,
utilization, and storage starting from cellulose and lignin
reacted with Ca(OH)2 can be effectively probed using in
operando USAXS/SAXS/WAXS measurements. Further, ther-
mogravimetric analyses (TGA) were performed to relate
weight changes to the temperature transitions. The evolution
in the surface area and porosity were determined using BET
analyses. These analyses were combined to develop a
comprehensive understanding of chemo-morphological cou-
pling during alkaline thermal treatment process for sustainable
bioenergy production integrated with carbon capture and
storage.
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■ MATERIALS AND METHODS

Lignin and cellulose powders were purchased from Sigma-Aldrich,
whereas calcium hydroxide (Ca(OH)2) was provided by HiMedia
Laboratories Pvt. Ltd. All the powders were used in the study as
received.
The in operando USAXS/SAXS/WAXS measurements were
performed to determine the cross-scale evolution in the structure
and morphology of the solid products during bioenergy production
integrated with carbon capture, utilization, and storage. These
measurements were performed at Sector 9-ID at Advanced Photon
Source (APS) in Argonne National Laboratory (ANL), Argonne, IL.
The biomass (lignin and cellulose) and Ca(OH)2 powders were
mixed in 50 wt % ratio for the measurements. The temperature ramp
rate was set at 3.3 °C/min, and the samples were reacted at
temperatures up to 750 °C. A schematic of the experimental setup is
shown in Figure 1.
The USAXS/SAXS instruments use multiple dispersive reflections Figure 2. Identification of the functional groups in cellulose, lignin,
from perfect crystals to reach a region of scattering vector q, where q = and calcium hydroxide using FTIR spectroscopy measurements.
(4π/λ)sin θ, λ is the wavelength of the X-ray used, and 2θ is the
scattering angle. These instruments are based on the original Bonse−
Hart double-crystal configuration.43 The total X-ray flux, wavelength, Table 1. Functional Groups Present on Cellulose, Lignin,
and corresponding energy during the measurements were 10−13 and Ca(OH)2 Powders
photon s−1, 0.59 Å, and 21.0 keV, respectively. Silver behenate and wavenumber
the NIST standard reference material, SRM 640d (Si), were used to sample (cm−1) functional groups
perform the calibrations. Finally, the Irena44 and Nika45 software
Ca(OH)2 3639 O−H stretching mode
packages embedded in IgorPro software (Wavemetrics, Lake Oswego,
OR) were used to reduce and analyze the data. 1420.29, 874.44 C−O from CO3−
The variations in the mass with temperature were recorded via 3330.83 O−H stretching mode
thermogravimetric (TG) measurements, performed up to 750 °C with 2893.91 C−H symmetrical stretch
a ramp rate of 2.5 °C/min in an N2 environment (purged at 25 mL/ 1427.23 HCH and OCH in-plane bending
min) using a Thermogravimetric Analyzer (TGA, TA Instruments, vibration
Q550, New Castle, DE). TGA was also coupled with an online gas 1314.57 CH2 rocking vibration
chromatography instrument (Micro GC Fusion Gas Analyzer, Inficon, cellulose 1201.73 C−O−C symmetrical stretching and O−
Bad Ragaz, Switzerland) to monitor the evolution of CO2 gas during H plane deformation
the ATT process. To evaluate changes in the chemical bonding of the 1159.99 C−O−C symmetrical stretching
reactants, infrared (IR) spectra were acquired in attenuated total 1052.83, 1028.07 C−C, C−OH, C−H ring and side groups
reflection (ATR) mode using a fourier transform infrared-attenuated vibrations
total reflection spectrometer (FTIR-ATR, Nicolet iS 10, Waltham, 661.71 C−OH out-of-plane bending
MA). The spectra were collected in the range of 4000−650 cm−1, 3249.16 O−H stretching from phenolic/aliphatic
both before and after the TGA measurements. The changes in the groups
porosity and specific surface area of the powders because of the 2934.98 C−H stretching in aromatic methoxyl
reaction of biomass and Ca(OH)2 were determined using the 1593.05. 1511.27, aromatic skeleton vibrations
Brunauer−Emmett−Teller technique (BET, Quantachrome NOVA- 1424.24
touch Analyzer, Boynton Beach, FL). These measurements coupled lignin 1450.66 C−H deformation and aromatic ring
with the X-ray scattering data provided detailed insights into the vibrations
structural and morphological evolution of the reactants and products 1265.01 C = O stretch in Guaiacyl (G) unit
over the course of the reaction. 1123.71 C−H in-plane deformation

■
RESULTS AND DISCUSSION
Characterization of Powders. The surface area of
cellulose, lignin, and Ca(OH)2 were found to be 1.02, 3.93,
and 3.55 m2/g, respectively. Detailed infrared spectroscopy
analyses were performed to evaluate the chemical composition
of the reactants. The infrared spectra of cellulose, lignin, and
Ca(OH)2 are presented in Figure 2. The typical functional
groups are labeled in Figure 2 and listed in Table 1. In the
spectrum of Ca(OH) 2 , the sharp peak at 3639 cm −1
corresponds to the O−H stretching in Ca(OH)2 crystals.46
Additionally, two peaks at 1420.29 and 874.44 cm−1 were
observed corresponding to the out-of-plane bending of CO32−
in CaCO3, which implies slight carbonation of Ca(OH)2 in the
air.46−48 The typical functional groups in cellulose were
identified as O−H stretching, C−H symmetrical stretch, CH2
rocking vibrations, and C−O−C symmetrical stretching groups
at 3330.83, 2893.91, 1314.57, and 1159.99 cm−1, respectively.
A comparison of the spectra of cellulose and lignin showed
different oxygen-containing functional groups.10,49,50 For
C DOI: 10.1021/acssuschemeng.8b06584
853.82, 814.48 C−H out of plane vibration in G-unit
example, aromatic vibrations, guaiacyl (G) units, and methoxyl
(−O−CH3) groups were noted in lignin in the range of
1593.05−814.48 cm−1, which were characteristically absent in
cellulose.
Phase Evolution in the Biomass Feedstocks and
Calcium Hydroxide Due to Integrated CO2 Capture. To
evaluate the phase transitions in the alkaline sorbent, which is
Ca(OH)2 in this case, the changes in the wide-angle X-ray
scattering patterns were carefully evaluated as a function of
temperature. The changes in the characteristic reflections of
Ca(OH)2 from (101) and (110) planes corresponding to d =
2.617 and 1.790 Å, respectively, when Ca(OH)2 is reacted with
cellulose and lignin are presented in Figure 3 and Figure 4,
respectively. Significant changes in the peak intensities of
Ca(OH)2 were noted at reaction temperatures above 350 °C
(Figure 3 (a-2 and b-2) and Figure 4 (a-2 and b-2)). The
decomposition of Ca(OH)2 was noted at temperatures
between 300−400 °C with complete decomposition achieved
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Figure 3. Changes in the characteristic Ca(OH)2 peaks where panels a-1 and b-1 represent hkl reflections of (101) (q = 2.40 Å−1, d = 2.617 Å) and
(110) (q = 3.51 Å−1, d = 1.790 Å), respectively, during reaction with cellulose. The integrated peak intensities normalized with respect to the
maximum values are shown in panels a-2 and b-2.

Figure 4. Changes in the characteristic Ca(OH)2 peaks where panels a-1 and b-1 represent hkl reflections of (101) (q = 2.40 Å−1, d = 2.617 Å) and
(110) (q = 3.51 Å−1, d = 1.790 Å), respectively, during reaction with lignin. The integrated peak intensities normalized with respect to the
maximum values are shown in panels a-2 and b-2.

D DOI: 10.1021/acssuschemeng.8b06584
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Figure 5. Changes in the weight of cellulose (a-1) and lignin (b-1) with and without calcium hydroxide. The corresponding first derivative of
weight changes is shown in panels a-2 and b-2 for comparison.

Figure 6. Changes in the characteristic CaCO3 peaks where panels a-1 and b-1 represent hkl reflections of (104) (q = 2.06 Å−1, d = 3.05 Å) and
(113) (q = 2.76 Å−1, d = 2.27 Å), respectively, during reaction with cellulose. The integrated peak intensities normalized with respect to the
maximum values are shown in panels a-2 and b-2.

E DOI: 10.1021/acssuschemeng.8b06584
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ACS Sustainable Chemistry & Engineering Research Article

Figure 7. Changes in the characteristic CaCO3 peaks where panels a-1 and b-1 represent hkl reflections of (104) (q = 2.06 Å−1, d = 3.05 Å) and
(113) (q = 2.76 Å−1, d = 2.27 Å), respectively, during reaction with lignin. The integrated peak intensities normalized with respect to the maximum
values are shown in panels a-2 and b-2.

Figure 8. Changes in the characteristic CaO peaks where panels a-1 and b-1 represent hkl reflections of (202) (q = 3.687 Å−1, d = 1.704 Å) and
(200) (q = 2.607 Å−1, d = 2.41 Å), respectively, during the reaction with cellulose. The hkl reflection for Ca(OH)2 at (111) (q = 3.727 Å−1, d =
1.685 Å) is shown in panel a-1. The integrated peak intensities normalized with respect to the maximum values are shown in panels a-2 and b-2.

at 500 °C in both cases with cellulose and lignin.30,51,52 The with temperature is associated with the thermal expansion of
increase in the d-spacing of (110) and (101) planes of calcite the solids on heating. The phase transitions of Ca(OH)2
F DOI: 10.1021/acssuschemeng.8b06584
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ACS Sustainable Chemistry & Engineering Research Article

Figure 9. Changes in the characteristic CaO peaks where panels a-1 and b-1 represent hkl reflections of (202) (q = 3.687 Å−1, d = 1.704 Å) and
(200) (q = 2.607 Å−1, d = 2.41 Å), respectively, during the reaction with lignin. The hkl reflection for Ca(OH)2 at (111) (q = 3.727 Å−1, d = 1.685
Å) is shown in panel a-1. The integrated peak intensities normalized with respect to the maximum values are shown in panels a-2 and b-2.

corresponded to the thermogravimetric analyses representing
the weight loss at temperatures above 300 °C (Figure 5),
associated with the dehydroxylation of Ca(OH)2. These data
suggest that calcium initially present in the hydroxide state is
either converted to calcium oxide or calcium carbonate. To
probe the fate of calcium, the evolution of characteristic peaks
of CaCO3 and CaO was determined.
Because the overarching objective of the ATT process is to
enhance the capture of CO2 using alkaline sorbents such as
CaO while producing H2 (as shown in eq 4), it is important to
evaluate the temperature corresponding to the onset and
growth of CaCO3. The characteristic reflections from (104)
and (113) planes of calcite (CaCO3) during the reaction of
cellulose and lignin with Ca(OH)2 corresponding to the d-
spacing of 3.022 and 2.273 Å are presented in Figure 6 and
Figure 7, respectively. The emergence of calcite phases is
evident at 300 °C with a slow growth until 400 °C, as indicated
by a small increase in the integrated peak intensities (Figure 6
(a-2, and b-2) and Figure 7 (a-2, and b-2)). At temperatures
above 400 °C, the peak intensities for calcite increase
significantly. These data suggest that between the temperature
range of 300−400 °C, Ca(OH)2 initially reacts with CO2 to
form CaCO3. In the presence of water vapor, eq 4 which
represents the evolution of H2 through the ATT process may
be dominant. However, at temperatures higher than 400 °C,
the formation of CaCO3 is governed by the carbonation of
CaO according to eq 6. To test these hypotheses, the changes
in the characteristic peaks of CaO were determined.
The changes in the characteristic CaO reflections at (200)
and (202) planes, and (111) plane of Ca(OH)2 is presented in
Figure 8 and Figure 9. Tracking the peak intensities for CaO
(200) and (202) planes provided detailed insights into the
changes in the structure of CaO. In cellulose and lignin, the
G DOI: 10.1021/acssuschemeng.8b06584
integrated intensities of the characteristic CaO peaks increase
around 450 °C and continued to increase until 500 °C, which
corresponds to the temperature of complete dehydroxylation
of Ca(OH)2 (Figure 8 (a-2) and Figure 9 (a-2)). Further, the
integrated intensities corresponding to the CaO peaks
continued to decrease until 700 °C, which corresponded to
the consumption of CaO to produce CaCO3. The subsequent
increase in the peak intensity of CaO on heating above 700 °C
corresponded to the decomposition of CaCO3 to produce
CaO53 (Figure 8 (a-2, b-2) and Figure 9 (a-2, b-2)).
Detailed insights from the in operando phase changes in the
calcium-bearing species are intended to complement the
previous studies reporting the gas-phase compositions of the
ATT processes. For example, the gas phase compositions
comprising H2, CO, CH4, and CO2 resulting from the pyrolysis
of cellulose, hemicellulose, and lignin varied in the temperature
range of 150−900 °C.10 Higher yields of CO were noted from
cellulose pyrolysis as opposed to H2 and CH4 from lignin.10
ATT of cellulose with Group I and II hydroxides yielded
similar gaseous products.7−9 Substantial suppression of gaseous
CO2 production owing to its capture by alkali or alkaline metal
conversion to the carbonate products resulted in higher H2
yields. To describe the changes in the solid-state chemistry that
correspond to the studies focused on gas-phase analyses,7−10
the evolution of various phases of calcium was related to the
temperatures corresponding to CO2 production during
biomass pyrolysis (Figure 10 (a-1) and (a-2)). The major
product during the pyrolysis for both cellulose and lignin is
CO2 and is readily available in the temperature range of 300−
600 °C. The onset of CaCO3 formation and dehydroxylation
of calcium hydroxide was noted at 300 °C. At temperatures in
the range of 500−700 °C, the conversion of CaO to CaCO3
was noted. Increase in temperature above 700 °C resulted in
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Figure 10. Comparison of the evolution of Ca(OH)2, CaO, and CaCO3 phases in cellulose (a-1) and lignin (b-1). Changes in the release of CO2
from cellulose (a-2) and lignin (b-2) with and without Ca(OH)2. The shaded region indicates the presence of CO2 during the reaction of cellulose
and lignin with calcium hydroxide.7−10
the calcination of CaCO3 to produce CaO. To confirm this,
the evolution of CO2 being released during the pyrolysis of
biomass and the reaction with Ca(OH)2 was monitored. The
results of gas chromatography for cellulose and lignin with and
without Ca(OH)2 are presented in Figure 10 (a-2) and (b-2),
respectively. The vol % of the released CO2 was normalized
with the initial mass of biomass used in all cases. For cellulose,
maximum CO2 released was in the temperature range of 300−
450 °C, followed by the fractional release up to 750 °C.
However, in case of lignin, relatively large amount of CO2 was
released over the broad temperature range of 300−700 °C.
During reaction with Ca(OH)2, the amount of CO2 released
from cellulose was decreased from 7 × 10−3 vol %/mg of
cellulose to 4.7 × 10−3 vol %/mg of cellulose. Additionally, a
peak for CO 2 released right after 600 °C emerged,
corresponding to the calcination of CaCO3 at higher
temperatures (>600 °C). Whereas, for lignin, almost all of
the CO2 released was captured during the ATT process.
Moreover, similar to the case of cellulose + Ca(OH)2, CO2
peak from the calcination of CaCO3 was noted. In case of
lignin + Ca(OH)2, however, the CO2 peak at higher
temperatures (>600 °C) also contains some of the CO2
released from the secondary pyrolysis of lignin due to the
degradation of complex aromatic groups.54,55
To understand the temperature transitions in greater detail,
thermogravimetric analyses were performed (Figure 5). The
onset of degradation temperatures and percent residual weight
is presented in Table S1. Additionally, the results from the gas
chromatography experiments were superimposed with the
H DOI: 10.1021/acssuschemeng.8b06584
Research Article
results of TGA to relate the CO2 evolution with the change in
weight % and are presented in Figure S1. Pyrolysis of cellulose
resulted in the most significant weight loss with only 8% of
retained weight after 750 °C, with the highest conversion of
cellulose to CO2 at temperatures ∼300 °C (Figure S1(a-1)).
This was attributed to the fast pyrolysis and ease of
degradation of cellulosic constituents.10 Lignin exhibited a
different trend compared to cellulose. The decomposition of
lignin to CO2 was relatively slower owing to its complex
structure and occurred over a wider temperature range of
200−750 °C (Figure S1 (b-1)). The initial decomposition
temperature (onset) for lignin was observed at 268 °C,
followed by secondary decompositions at 360 and 685 °C.
Weight loss in the range 250−500 °C is attributed to the
decomposition of carbohydrate components in lignin evolving
as volatile gases such as CO2 and CH4. The weight loss at
temperatures greater than 500 °C is attributed to the
decomposition of the aromatic skeleton in lignin.54,55 More-
over, the weight retained by lignin was 39.5 wt % compared to
8 wt % in the case of cellulose.
ATT of cellulose and lignin with Ca(OH)2 was also studied
using thermogravimetric analyses (Figures 5(a) and (b)). The
onset of Ca(OH)2 decomposition occurred at 374 °C, which
corresponded to the dehydroxylation of Ca(OH)2 to produce
CaO and H2O.30 Postdehydroxylation of Ca(OH)2, the
residual weight % was ∼77%. Further, different trends in the
decomposition behavior of Ca(OH)2 + cellulose and Ca(OH)2
+ lignin mixtures were observed. In the Ca(OH)2 and cellulose
system, two separate decomposition regimes were noted: the
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first onset occurred ∼316 °C, which corresponded to the
decomposition of cellulose to produce CO2 (Figure S1), and
the second ∼382 °C was associated with the dehydroxylation
of Ca(OH)2. In the Ca(OH)2 and lignin system, decom-
position temperatures of both Ca(OH)2 and lignin overlapped
with an onset ∼328 °C. The lower mass of lignin and calcium
hydroxide mixture compared to cellulose and calcium
hydroxide suggests that the solid decomposition of lignin in
calcium hydroxide is higher compared to that of cellulose and
calcium hydroxide.
To further understand the changes in the composition and
structures of powders during the reaction, the infrared spectra
were recorded before and after performing thermogravimetric
analyses (Figure S2). The spectra of cellulose and lignin, after
thermal decomposition, clearly indicate the removal of oxygen-
containing functional groups. In the case of Ca(OH)2 and
cellulose, almost all the oxygen-containing functional groups
were decomposed, and obvious carbonate peaks were observed
at 1420.08 and 896.20 cm−1. Similarly, the carbonate peaks in
Ca(OH)2 and lignin material systems were present at 1410.04
and 865.66 cm−1. Additionally, in both cases, O−H stretching
vibrational bands were observed ∼3640 cm−1, which was
associated with the physical adsorption of H2O by CaO when
exposed to air. Increased surface area and porosity of the
postpyrolysis products of a mixture of biomass and calcium
oxide suggests an enhanced affinity for water56−58 (Table 2).
Table 2. Surface Area of Samples before and after TGA
cumulative pore volume
surface area (m2/g) (cc/g)
sample before TGA after TGA before TGA after TGA
Ca(OH)2 3.55 31.60 0.007 0.046
cellulose + Ca(OH)2 4.22 98.67 0.006 0.126
cellulose 1.02 55.19 0.002 0.065
lignin + Ca(OH)2 2.70 11.74 0.005 0.014
lignin 3.93 5.87 0.008 0.008
Morphological Changes in the Biomass Feedstocks
and Calcium Hydroxide Due to Integrated CO2 Capture.
With increasing interest in utilizing the residues post energy
recovery, understanding the morphologies of these materials is
essential. On the basis of the phase changes reported in the
previous section, significant changes in the morphologies of
cellulose or lignin as they are reacted with Ca(OH)2 were
expected. The changes in the porosity, surface area, and the
pore−solid interface were probed in this study. The cumulative
pore volume (cc/g) and pore volume distribution (cc/nm/g)
trends as a function of pore diameter (nm) for the samples
under study are presented in Figure 11. The quantitative
information about the surface area (m2/g) and cumulative pore
volume (cc/g) are also reported in Table 2.
As a result of alkaline thermal treatment, the cumulative
pore volume of Ca(OH)2 + cellulose and Ca(OH)2 + lignin
systems increased from 0.006 to 0.13 cc/g and 0.005 to 0.01
cc/g, respectively. Corresponding increases in the surface areas
of Ca(OH)2 + cellulose and Ca(OH)2 + lignin systems from
4.22 to 98.67 m2/g and 2.70 to 11.74 m2/g were noted. The
magnitude of the morphological changes with cellulose bearing
systems was higher compared to lignin due to the greater ease
of decomposing cellulose as opposed to lignin.
To understand the origin of the changes in the surface areas
and the porosities, pure Ca(OH)2, cellulose, and lignin were
I DOI: 10.1021/acssuschemeng.8b06584
Research Article
treated at similar experimental conditions as the mixtures of
Ca(OH)2 and biomass (e.g., cellulose and lignin). The surface
areas and the cumulative porosities of these materials
postreaction were significantly higher compared to the
materials prereaction. This suggests that the increase in the
surface area and porosities arising from the decomposition of
the solid reactants dominates the formation of denser phases
such as CaCO3.
Furthermore, the changes in the basal planes and the pore−
solid interface were effectively captured by USAXS and SAXS
measurements, as shown in Figure 12. In the SAXS regime for
both cases, the characteristic reflections from the (001) basal
plane of Ca(OH)2 were observed at q = 1.30 Å −1,
corresponding to the d-spacing of 4.83 Å.59 The peak shifts
of the (001) plane to smaller q values (larger d-spacing) with
an increase in temperature is attributed to thermal expansion.
In case of Ca(OH)2 + cellulose, the last (001) reflection
appeared with a very low intensity at 500 °C. While, for
Ca(OH)2 + lignin, the (001) peak diminished before 500 °C
with a very low-intensity peak appearing at 475 °C. These
findings were in agreement with the changes in the other
phases of calcium hydroxide as shown in Figures 3 and 4.
In addition to providing insights into the changes in the
basal spacing of Ca(OH)2, detailed insights into the changes in
the pore−solid interface from the Porod slope were obtained
using USAXS/SAXS data.35−38,60−62 The Porod slope provides
information about the “fractal dimensions” of the scattering
objects. In this work, the Porod slope was calculated for the q
values in the range 0.02−0.2 Å−1 and the fractality of local
structure was investigated. The Porod slope was calculated
using the following equations:
A
I (Q ) = +B
Qn (8)
log10[I(Q ) − B] = log10 A − n log10 Q (9)
In the above equations, I(Q) is the scattering intensity, and n
is the slope. The values of Porod slopes provide useful insights
into the morphology of scattering objects. Porod slopes
between 3 and 4 represent scattering from rough interfaces
with a fractal dimension, D, where n = 6 − D represents a
surface fractal. Porod slopes of 4 represent scattering from
smooth surfaces, while a Porod slope of 1 represents scattering
from rigid rods. Porod slope between 2 and 3 is indicative of
scattering from branched systems or networks also known as
mass fractals.
The Porod slopes of Ca(OH)2 + cellulose increased from
3.2 to 3.5 as the reaction proceeded from 100 to 400 °C, which
suggested a smoothening of the pore−solid interface (Figure
12 (a-2)). Further heating to 450 and 475 °C, which
corresponds to the dehydroxylation of Ca(OH)2 and rapid
formation of CaCO3, enhanced the roughness of the pore−
solid interface. Progressive growth of CaCO3 enabled the
formation of smoother surfaces in Ca(OH)2 + cellulose
system. In the case of lignin, however, the pore−solid
interfaces became increasingly rougher with higher conversion
to CaCO3 in the temperature range of 500−750 °C. Insights
into the differences in the evolution of the pore−solid interface
in the case of cellulose and lignin with increasing carbon
mineralization behavior were obtained from thermogravimetric
analyses (Figure 5 (a-1) and (a-2)). For example, cellulose
decomposition occurs quickly, and significant changes in the
weight do not occur at temperatures above 300 °C. In the case
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ACS Sustainable Chemistry & Engineering Research Article

Figure 11. Changes in the cumulative pore volume and pore volume distributions in cellulose (a-1), (a-2) and lignin (b-1), (b-2), respectively.

Figure 12. Changes in the combined slit-smeared UXAS/SAXS data for cases with Ca(OH)2 and cellulose (a-1) and Ca(OH)2 and lignin (b-1).
The reflections from Ca(OH)2 (001) plane corresponding to q = 1.30 Å−1 and d = 4.83 Å are evident in panels a-1 and b-1. Panels a-2 and b-2
represent the changes in the Porod slopes for q in the range of 0.02−0.2 Å−1 for Ca(OH)2 and cellulose and Ca(OH)2 and lignin, respectively.

of lignin, however, decomposition occurs over a wider contributing factor for producing fewer rough pore−solid
temperature range (Figure 5 (b-2)) and simultaneous interfaces in cellulose. The simultaneous decomposition of
CaCO3 formation and lignin decomposition were noted. The lignin and formation of CaCO3 contributes to the formation of
formation of well-defined CaCO3 phases is the dominant rougher pore−solid interfaces as the reaction temperature
J DOI: 10.1021/acssuschemeng.8b06584
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering
increases above 500 °C. These morphological insights are
useful when considering the reuse of the products postpyr-
olysis.
■ CONCLUSION
In this study, we elucidated the evolution of the structural and
morphological features of Ca(OH) 2 during bioenergy
production from cellulose and lignin when integrated with
CO2 capture. Significant onset of calcium carbonate growth
was only noted at temperatures above 375 °C, suggesting that
CO2 capture was enhanced at these conditions. Enhanced
formation of CaCO3 phases corresponded to the decom-
position of Ca(OH)2 to produce CaO. Although lignin
decomposed slowly compared to cellulose, the onset of carbon
mineralization and the temperature ranges for CO2 capture did
not change. However, higher amount of CO2 was captured
during ATT of lignin as compared to the ATT of cellulose.
Increase in the surface area and porosity of cellulose system as
opposed to the lignin system was attributed to the relatively
fast decomposition of cellulose. Pore−solid interfaces in
Ca(OH)2 + cellulose system became smoother in the
temperature range of 500−700 °C compared to Ca(OH)2 +
lignin system, where the interfaces became rougher. The
roughness in the Ca(OH)2 + lignin system was attributed to
the simultaneous decomposition of lignin and formation of
CaCO3. These structural and morphological insights are useful
in advancing our fundamental understanding of alkaline
thermal treatment of biomass.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.8b06584.
Changes in the compositions of CO2 in cellulose
without (a-1) and with (a-2) calcium hydroxide and in
lignin without (b-1) and with (b-2) calcium hydroxide
using thermogravimetric analysis coupled with online
microgas chromatography measurements; changes in the
characteristic functional groups in (a) cellulose and (b)
lignin systems before and after thermogravimetric
analyses from ATR-FTIR spectra; and identification of
the onset temperature for significant weight change and
the residual weight % based on thermogravimetric
analyses (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*Phone: +1 608-262-0365; E-mail: gadikota@wisc.edu.
ORCID
Sohaib Mohammed: 0000-0002-0262-9481
Greeshma Gadikota: 0000-0002-6527-8316
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors would like to acknowledge the experimental
support provided by Dr. Jan Ilavsky at the USAXS facility, X-
ray Science Division, Argonne National Laboratory. The use of
the Advanced Photon Source, an Office of the Science User
Facility operated for the U.S. Department of Energy (DOE)
K DOI: 10.1021/acssuschemeng.8b06584
Research Article
Office of Science by Argonne National Laboratory, is
supported by the U.S. DOE under Contract DE-AC02-
06CH11357. Wisconsin Alumni Research Foundation and
the College of Engineering at the University of Wisconsin,
Madison provided the financial support for this research.
■
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M DOI: 10.1021/acssuschemeng.8b06584
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX