Article

Cite This: Ind. Eng. Chem. Res. 2019, 58, 10698−10706 pubs.acs.org/IECR

Microwave-Assisted Organosolv Delignification: A Potential Eco-

Designed Process for Scalable Valorization of Agroindustrial Wastes
Francisco Avelino,† Francisco Marques,‡ Amanda K. L. Soares,§ Kaś sia T. Silva,∥ Renato C. Leitão,‡
Selma E. Mazzetto,∥ and Diego Lomonaco*,∥
†
Federal Institute of Education, Science and Technology of Ceará, Iguatu, Ceara 63503-790, Brazil
‡
Embrapa Agroindustria Tropical, Rua Dra. Sara Mesquita, 2270, Planalto do Pici, Fortaleza, Ceara 60511-110, Brazil
§
Department of Organic Chemistry, Institute of Chemistry, Federal University of Rio de Janeiro, 21941-909 Rio de Janeiro, Rio de
Janeiro, Brazil
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

∥
Department of Organic and Inorganic Chemistry, Federal University of Ceara, Fortaleza, Ceara 60440-900, Brazil
*
S Supporting Information
Downloaded via BUFFALO STATE on July 23, 2019 at 18:13:10 (UTC).

ABSTRACT: The extraction of high-purity technical lignins

at large scale, such as organosolv lignin, is still a challenge. The
objective of this work was to verify the environmental
feasibility of microwave-assisted organosolv delignification
(MWAOD) of sugar cane bagasse (SCB) for scalable
purposes. MWAOD studies were performed using 90% v/v
CH3COOH combined with 2.0% v/v HCl (110 °C for 30
min). The effects of the MWAOD process on the lignin
structure were evaluated. The results showed that increasing
SCB mass in the microwave reactor causes considerable
changes in neither the lignin yield and purity nor in their
interunit linkages, monolignol composition, and thermal
stability. Moreover, using recycled acetic acid spent liquor
resulted in minor differences in the process parameters and lignin structure when compared to reactions with a fresh acid liquor.
Therefore, MWAOD presents itself as a promising sustainable process for production of high-quality lignin in large scale with
high yields.

1. INTRODUCTION as the high molecular weight and polydispersity.6 These

The continuous concern about environmental pollution has led
the scientific community to focus on the development of green
materials from renewable sources that can partially or fully
replace the petroleum-based compounds. The use of green and
sustainable technological pathways to produce biobased
materials is still one of the main scientific challenges.
The lignocellulosic biomass is a renewable source that is
constituted of three main building blocks, such as lignin,
cellulose, and hemicellulose, which can be applied to the
development of biobased products.1,2 Lignin is a polymer with
a complex amorphous structure formed by the random
polymerization of three monolignols, such as p-hydroxyphenyl
(H), syringyl (S), and guaiacyl (G), through ether and
carbon−carbon linkages. Despite its complex structure, lignin
offers several possibilities of destinations due to its structure
and phenolic composition.3
However, lignin structure depends on the type of biomass
and the methods employed in its isolation.4 The most
generated technical lignin in the world is Kraft lignin, which
is a byproduct from the pulp and paper industry.5 Although it
has high availability there are some structural features that limit
its application, such as the high sulfur and ash contents, as well
features can affect the lignin reactivity compromising its use for
some applications, especially in polymer chemistry.
According to published data from the Food and Agriculture
Organization of the United Nations (FAO), the global
production of sugar cane in 2016 was 1890 × 106 t, of
which Brazil contributed 768 × 106 t, representing 40% of the
global production.7 Furthermore, the Brazilian sugar cane
harvest in the 2017−2018 season produced 657 × 106 t,8
which generated approximately 152 × 106 t of bagasse.
Considering that this bagasse contains about 22% lignin,9 it is
estimated that 38 × 106 t of lignin from bagasse can potentially
be used as a source of phenols.
The lignin derived from the sugar cane bagasse can be
extracted using a sulfur-free process, such as organosolv, in
which organic solvents (acetic or formic acids), in combination
with a mineral acid catalyst are used to extract high-quality
lignins (low carbohydrate and ash content and sulfur free
Received: March 1, 2019
Revised: May 28, 2019
Accepted: May 30, 2019
Published: May 30, 2019

© 2019 American Chemical Society 10698 DOI: 10.1021/acs.iecr.9b01168

Ind. Eng. Chem. Res. 2019, 58, 10698−10706
Industrial & Engineering Chemistry Research
lignins).3 Despite the organic solvents recycling options,
organosolv processes are energy intensive due to the high-
temperature and -pressure operating conditions combined with
the relatively long reaction times that are necessary to obtain
lignins with high yields and purities.10−13
In addition to the high energy demand and the safety risks
associated with high-pressure operating conditions, the
organosolv process tends to have long processing times,
which severely impact lignin productivity. Optimization is
required in order to maximize lignin productivity prior to
scaling up the process. Therefore, an alternative technology
that has been used for biorefinery purposes is microwave
irradiation,14−18 which, combined with the organosolv process,
promotes faster delignification reaction yielding high-quality
lignin, as shown by our previous research.19
During application of microwave irradiation (MWI), the
molecular dipoles present in the reaction medium interact with
the electric field of MWI, causing their rotation and friction
resulting in energy loss due to molecular rotation and heat
release by friction making. As a result of microwaving, more
effective productive collisions between reactants molecules are
expected and yield faster reaction times with comparable or
higher lignin yields than those of traditional organosolv
processes.20
Moreover, the microwave-assisted organosolv delignification
also offers the possibility to perform the extractions under
atmospheric pressure and mild conditions, resulting in higher
quality lignin with elevated yields than those obtained using
the traditional organosolv methodology.19,21
The laboratory-scale microwave reactors allow the utilization
of large amounts of starting material, which combined with the
mild conditions, atmospheric pressure, and short reaction
times would perfectly simulate a scalable process to be
considered to be used in pilot plants. This is perfectly possible
since larger microwave reactors designed for pilot plant
operations are available.22
However, to our knowledge, there are no studies in the
literature regarding the combination of the MWI with the
organosolv process as a potential method for lignin extraction
at large scale. This idea would be very useful for the production
of several biobased products that require a large amount of
high-quality and sulfur-free lignins,23,24 such as phenolic13,23
and epoxy resins,24−26 polyurethanes,23,27,28 biocompo-
sites,29,30 and biomaterials.31,32
According to the above discussion, the objective of this work
was to verify the environmental feasibility of the microwave-
assisted organosolv delignification as a potential method for
scale-up purposes through the use of recycled solvent. The
main process metrics (lignin yield, purity, and chemical
structure) while increasing the biomass loading were evaluated
in this study. In addition, the effect of acetosolv solution
recyclability on lignin features was also studied.
2. EXPERIMENTAL SECTION
2.1. Materials. The following solvents were used without
any pretreatments: glacial acetic acid (Synth, Brazil), HCl
(37%, Synth, Brazil), THF (HPLC-grade), and DMSO-d6
(99.5%, Sigma).
2.2. Raw Material Pretreatment. The sugar cane bagasse
(SCB) was supplied by DIAGEO (Maracanau, Brazil) and
processed as previously reported.19 The chemical composition
of sugar cane bagasse powder (SCBP) was performed
following standard procedures for determination of extractives
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(TAPPI T204 cm-97), alpha-cellulose (TAPPI T203 cm-99),
lignin (TAPPI T222 om-2), moisture, ash (TAPPI T211 om-
01), hemicellulose, and holocellulose.33 The lignocellulosic
composition of SCB is described in Table S1.
2.3. Microwave-Assisted Organosolv Delignification
Experiments (MWAOD). The microwave-assisted experi-
ments were performed in a StartSYNTH microwave reactor
(Milestone, Italy) used in an open-vessel configuration (2.45
GHz). A contactless infrared sensor was used to monitor the
temperature, with the maximum power applied being limited
to 500 W.
The reaction conditions (temperature, time, and catalyst
concentration) used in this study were previously optimized by
our group.19 The first phase of the study was the evaluation of
the MWAOD process scalability, in particular, varying the
amount of SCBP. In these experiments, different quantities of
SCBP (10, 100, 200, and 300 g) were added to a round-
bottom flask containing the acetosolv solution (acetic acid/
water solution (9/1, v/v) and 2.0% v/v HCl) in a fiber per
solution proportion of 1:10 (g/mL). The experiments were
carried out at mild conditions (110 °C during 30 min) under
reflux (atmospheric pressure) and continuous magnetic
stirring. The experiments were performed in duplicate.
The second phase of the studies included the recyclability of
the acetosolv solution. Up to three solvent recycling cycles
were evaluated. Therefore, SCBP (100 g) was mixed with
recycled acetosolv solution and 2.0% v/v HCl at the same ratio
used in the first phase. The experiments were carried out at the
same conditions described above (110 °C for 30 min) under
magnetic stirring and reflux (atmospheric pressure).
The same isolation and purification steps described
previously19 were employed in either phase. Then the lignins
in dry form were weighted, and their yields were calculated
according to eq 1
mLigIsol
η=
mLigSCB (1)
where η is the process yield (%), mLigIsol represents the dry
weight of lignin obtained in the MWAOD process (g), while
mLigSCB represents the dry weight of lignin in SCB (g) as
calculated by Klason lignin (TAPPI standards shown in Table
S1).
2.4. Structural Characterization of SCB Lignins. Purity
was reported combining the percentages of acid-soluble and
acid-insoluble (Klason lignin) lignins values of the SCB lignin
samples. Klason lignin was evaluated following a standard
procedure (TAPPI T222 om-2) with some modifications,34
and the acid-soluble lignin was evaluated by analyzing the first
filtrate obtained in Klason lignin experiments by UV−vis
spectrophotometry. Experimental details are available in the
Supporting Information.
Elemental analyses (CHN content) of SCB lignins were
carried out using a PerkinElmer 2400 (Series II CHN-S/O)
following standard procedures (Table S2).
FTIR analyses were carried out using a PerkinElmer
spectrometer (model FT-IR/NIR FRONTIER) in trans-
mission mode using KBr pellets. The spectra were recorded
in a wavenumber range from 4000 to 400 cm−1 using a
resolution of 4 cm−1 and a number of scans (NS) of 32
measurements. The relative content (RC) of functional groups
was determined according to a previous procedure reported in
the literature.35
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1
H−13C Heteronuclear single-quantum coherence (1H−13C
HSQC) experiments were carried out in a Bruker Avance DPX
300 (operating at 300 and 75 MHz for 1H and 13C nuclei,
respectively). Lignin sample (30 mg) was dissolved in 0.5 mL
of DMSO-d6, in which the residual solvent peak was used as
internal reference (DMSO δH/ δC 2.50/39.5 ppm).
Differential scanning calorimetry (DSC) analyses were
performed in a Mettler-Toledo (Schwerzenbach, Switzerland)
model DSC 823e. Lignin (10 mg) was submitted to an
annealing program (from 25 to 90 °C for 10 min and from 90
to 0 °C for 3 min) and then heated from 0 to 250 °C under N2
atmosphere with a flow rate of 50 mL min−1 and a heating rate
of 20 °C min−1. Closed Al pans with a lid centrally punctured
were employed in this experiment.
Thermogravimetric analyses (TGA) were carried out in a
Mettler-Toledo (Schwerzenbach, Switzerland) model TGA/
SDTA 851e. Lignin sample (10 mg) was submitted to a
temperature program starting from 30 to 900 °C under inert
atmosphere (N2, flow rate of 50 mL min−1) at a heating rate of
10 °C min−1.
Gel permeation chromatography (GPC) analyses were
carried out in a Shimadzu chromatograph (model LC-20AD,
Kyoto, Japan) using a setup comprised of two analytical GPC
columns (Phenogel 5 μ 50 Å and Phenogel 5 μ 103 Å, 4.6 mm
× 300 mm, Phenomenex) connected in series at 40 °C using
HPLC-grade THF as mobile phase (flow rate of 0.35 mL
min−1). A UV−vis detector (Shimadzu SPD-M20A) at 280 nm
was used to monitor the lignin samples. Sample preparation
and other experimental details are available in the SI.
3. RESULTS AND DISCUSSION
3.1. Evaluation of MWAOD Feasibility for Scale-up
Purposes. Lignin yield and purity were used to assess the
MWAOD process feasibility at different SCB loadings as
shown in Figure 1.
Figure 1. Effect of the amount of SCB used in the MWAOD process
on the lignin yield and purity.
Figure 1 shows a considerable increase in the lignin yield
when the amount of SCB was increased from 10 to 200 g. A
statistical analysis (One Way ANOVA) showed that the lignin
yield values were statistically different (α = 0.05%).
This behavior probably is due to kinetic factors involved in
the delignification process, specifically the increase in the
amount of reactants (SCB and aqueous acetic acid solution),
which probably caused a higher interaction between them and
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the microwave irradiation. Therefore, the polar compounds
present in SCB would absorb more energy, favoring cleavage of
organic molecules and disruption of complex structures,
increasing the accessibility of activated ether/ester bonds in
the substrate to the nucleophilic attack of water molecules. A
small reduction in the process yield (lignin) was observed for a
reaction load of 300 g.
On the other hand, the purity of SCB lignins did not suffer
significant changes with the increase in the amount of loaded
starting material varied in a narrow range, from 77% to 84%, as
shown by the One Way ANOVA test with a confidence of
99.5%, which considered the lignin purity values as statistically
equal. This shows the high efficiency of the MWAOD process
to promote cleavage of lignin−carbohydrate complexes
(LCC), yielding high-purity and sulfur-free lignins. However,
depending on the lignin application a higher purity level may
be required.23
There are two alternatives available to increase the lignin
purity: the first one is modification of the concentration of the
acetosolv aqueous solution by increasing the amount of water,
which probably would favor cleavage of ester bonds in LCC in
a greater extension. The second one would be purification of
the isolated lignin through some treatments, such as alkaline
hydrolysis,36 in order to obtain low residual carbohydrate
content.
It is important to highlight that most papers regarding
MWAOD report experiments performed under high pressure
and small amounts of raw material (0.2−2 g).37−40 Other
recent studies report the use of harsh conditions even under
microwave irradiation and also small amounts of starting
material (0.3−10 g).41,42
3.2. Structural Characterization of MWAOD Lignins.
3.2.1. Fourier Transform Infrared Spectroscopy (FTIR).
Identification of the characteristic functional groups in the
MWAOD lignins as well as any possible chemical modification
in their structure resulted from the extractions were monitored
by FTIR (Figure 2A). In order to help in the visualization of
such modifications, the characteristic bands in the fingerprint
region were compared by dividing their areas at a defined
wavenumber by the corresponding value of the band at 1513
cm−1,35 yielding the relative content of functional groups (RC)
(Figure 2B).
The characteristic absorption bands of MWAOD lignins
were assigned according to a previous report.43,44 Figure 2A
shows bands related to the lignin backbone that were preserved
after the extraction process: at 1604 and 1513 cm−1 (CC
stretching of the aromatic ring skeleton) and at 1465 and 1424
cm−1 (C−H deformations and aromatic skeletal deformations
coupled with C−H plane deformation). According to Figure
2B, the increase in the amount of starting material did not
influence the relative content of these groups in the obtained
lignins, except for some assigned groups at 1034 cm−1, which
were considered statistically different by One Way ANOVA
analysis with a confidence of 99.5%.
The presence of bands at 1710, 1170, and 1126 cm−1 can be
associated with the stretching of CO groups, one of the
possible assignments related to lignin−carbohydrate complexes
(LCC), whichi is indicative of residual carbohydrates in the
lignins, which were not hydrolyzed during extraction. Thus,
their intensity and their RC values can be used as an estimate
of the efficiency of the extraction process.
The RC values were quite similar for all lignins (Figure 2B),
which means that the MWAOD process was able to promote
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Figure 2. Main FTIR absorption bands of the MWAOD lignins. (A)
Fingerprint region of MWAOD lignins, and (B) relative content of
the main functional groups in their structure.
cleavage of the ester and ether bonds of LCC, independently of
the biomass loading. This can be also confirmed by the lignins
purity values (Figure 1), which is an indication that the
MWAOD process is efficient to yield high-quality lignin even
though at a larger scale.
3.2.2. Nuclear Magnetic Resonance (NMR). Evaluation of
the effects of the MWAOD process on SCB lignins structure
was studied by the 1H−13C HSQC experiment, which provides
information about how the monomers are linked to each other
(interunit linkages) as well as their types (monolignol
composition). Figures 3 and 4 show the oxygenated aliphatic
region (δH/δC 3.0−5.5/50−90) relative to the interunits
(RPIL). Figures 5 and 6 show the unsaturated/aromatic
regions of SCB lignins and their respective relative proportion
of monomers (RPM). The full 1H−13C HSQC spectra of SCB
lignins without cut off are shown in the SI (Figure S1).
RPIL and RPM values were calculated by integrating the
signal areas in the oxygenated aliphatic and aromatic regions
following the procedure reported by Rencoret et al. (2013).45
The characteristic signals present in the spectra of SCB lignins
are shown in Table S3, and their substructures are shown in
Figures 3 and 5. The assignments of the main cross-peaks were
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made according to published reports present in the
literature.46,47
Figure 3 shows that the aliphatic oxygenated region of SCB
lignins was composed of fragments linked by alkyl−aryl ether
bonds, namely,, the β-O-4 ones. This behavior was observed by
the cross-peaks related to the Cα−Hα and Cγ−Hγ correlations
of A and A’ substructures. The main difference between these
substructures is the presence of the acyl group in the γ carbon
(substituent R), which is resultant of the partial acetylation of
the aliphatic hydroxyls, due to the use of acetic acid in the
pulping process. In Figure 4 the ratio between the relative
contents of A′γ and Aγ is shown, which increased along with
the amount of starting material.
Figure 5 shows that the monolignol composition of SCB
lignins was composed of syringyl (S), guaiacyl (G), and p-
hydroxyphenyl (H) units due to the presence of cross-peaks
related to the C2,6−H2,6 (S2,6), C2−H2 (G2), C5−H5 (G5), and
C2,6−H2,6 (H2,6) correlations. In addition, there was also the
presence of cross-peaks related to the oxidized forms of S, G,
and H units, such as the ferulates (FA) and p-coumarates
(PCA).
Although these substructures are already present in native
lignins from grass and cereal lignins,6 due to the oxidizing
nature of the organosolv process, more oxidized substructures
derived from G and H units, such as ferulic and p-coumaric
acids, could be formed. Therefore, the organosolv process
could contribute to increase the amount of FA and PCA in
SCB lignins.
In general, the monolignol constituents of SCB lignins were
quite similar to other lignins from the same feedstock reported
in the literature.46,47 The presence of a cross-peak related to
ferulates (FA) in SCB lignins can be attributed to the presence
of residual carbohydrates in their structure, since they act like a
bridge between the carbohydrates and the lignin. The latter
fact correlates with the existence of absorption bands related to
LCC at 1711, 1169, and 1123 cm−1 in the FTIR spectra of
SCB lignins.
However, as shown in Figure 5, the intensities of the cross-
peaks related to FA units are relatively low, which suggests that
they were hydrolyzed during the pulping process and separated
from lignin in the acid precipitation step. This behavior is in
agreement with data reported in Figure 6A, in which low
amounts of FA are present in all lignin samples.
Another remarkable feature presented in Figure 6A and 6B is
the RPM values of SCB lignins and their S/G and H/G ratios,
which were very similar to each other. This shows that despite
the process scale increase the key lignin structural features did
not change significantly. Therefore, these results emphasize the
capability of the MWAOD process to yield high-quality lignin
with controlled modifications in its structure at larger scale,
which is very important considering its potential application in
pilot plants and industrial purposes.
3.2.3. Gel Permeation Chromatography (GPC). The
efficiency of the MWAOD process regarding the use of
different amounts of starting material was also evaluated
through the molecular weight distribution curves of SCB
lignins (Figure S2). Figure 7 shows the number-average (Mn)
and weight-average (Mw) molecular weights for those lignins,
and Table S4 summarizes their molecular weight data.
Figures S2 and 7 show that SCB lignins had very similar and
low polydispersity with Mw values within the range expected
for organosolv lignins.6 In addition, Table S4 also shows that
Mw and PDI values varied in a narrow range, in which for a
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Figure 3. Side chain region of 1H−13C HSQC spectra of SCB lignins: (A) 10, (B), 100, (C) 200, and (D) 300 g.
Figure 4. Relative proportion of interunit linkages of SCB lignins.
higher amount of raw material there was a slight increase in
those parameters.
Despite this minor difference, the most important feature is
that all obtained samples presented similar molecular weights
and, considering also their monolignol compositions, similar
reactivity. This homogeneity is a very relevant characteristic for
the process, since further chemical modifications should be
considered regarding specific applications.
3.2.4. Thermal Properties. The thermal stability and
processability of SCB lignins were evaluated through TGA
and DSC analyses. Table 1 summarizes the thermal data
obtained from these analyses, such as onset degradation
temperature (Tonset) and maximum degradation temperature
(Tmax), char yield (CY), and glass transition temperatures (Tg).
Figures S3, S4, and S5 show the TGA, DTG, and DSC curves,
respectively.
Figures S3, S4, and S5 show all SCB lignins had very similar
thermal profiles. It can be seen that those lignins had similar
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thermal stability with minor differences between their Tonset
values. However, the similarities between the Tmax and CY
suggest that the increase in the scale of the process did not
compromise the quality of the SCB lignins. This fact also
correlates with the Tg values of those lignins, which were very
similar as well. These values show that polymeric chains of
SCB lignins started to gain molecular mobility in a narrow
range of temperature. Then the Tg values show that SCB
lignins had similar processability (molecular mobility), which is
a very important feature for their further valorization, especially
in polymer chemistry.
3.3. Assessment of the Reutilization of Acetic Acid
Solution in the MWAOD Experiments. Among several
advantages of the organosolv process, one of the most
important is the possibility of solvent recycling and reuse in
the lignin extraction process. Therefore, it is crucial to verify if
the successive reutilization of the solvent generates lignins with
yields and purities comparable to those obtained using a fresh
organosolv solution. Figure 8A shows the variation of the
lignin yield and purity with the number of acetosolv solution
reutilizations in which those of fresh acetosolv solution were
used as reference (labeled as the point 0 in the graph).
Similarly, Figure 8B shows how the Mw and Mn values of SCB
lignin varied when the acetosolv solution was successively used
in its extraction. The data shown in Figure 8A and 8B are
summarized in Table 2.
Figure 8A clearly shows that the first acetosolv solution
reutilization had a lignin yield comparable to that which used a
fresh solution. However, after successive reutilization there was
observed a reduction in the lignin yield. This fact probably
occurred due to the addition of an aqueous catalyst solution to
the recuperated acetic acid, which caused its dilution since it
already had remaining water from the solvent recuperation.
Therefore, the decrease of acetic acid content in the solution
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Figure 5. Aromatic region of 1H−13C HSQC spectra of SCB lignins: (A) 10, (B), 100, (C) 200, and (D) 300 g.

Figure 7. Weight-average (Mw) and number-average (Mn) molecular

weights of SCB lignins.

Table 1. Thermal Data of SCB Lignins Obtained from TGA

and DSC Analyses
SCB loading/parameter Tonset (°C) Tmax (°C) CY (%) Tg (°C)
10 g 218 371 23.7 141
100 g 214 368 26.5 145
200 g 208 375 19.1 140
300 g 207 368 24.3 137

could hinder the solvation of lignin fragments, diminishing the

process yield.
In addition, Figure 8A also shows that the second and third
reutilizations had very similar lignin yields. This suggests that
even considering successive dilutions probably there was
Figure 6. Relative proportion of monomers of SCB lignins. reached a certain acetic acid/water proportion in which the
ability of acetic acid to solvate lignin fragments attained a limit.
However, it is shown in Figure 8A that the purity of lignins
obtained using the recuperated acetic acid was considerably
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Industrial & Engineering Chemistry Research Article

shown in Figure S8. It is possible to observe from Figures S7

and S8 that after three solvent recycles the structural features
of SCB lignins, such as monolignol composition and interunit
linkages, are still very similar to those obtained using a fresh
solution. Therefore, this suggests that even with slight
differences in lignin yield, purity, and Mw values, successive
solvent recycles can generate lignins with similar structural
features to those obtained using a fresh solution.

4. CONCLUSIONS
The present work showed that the microwave-assisted
organosolv delignification (MWAOD) process has a great
potential to be used for lignin extraction at larger scale,
generating high-purity lignin with high yield at atmospheric
pressure and mild conditions in a matter of minutes. A deep
structural characterization proved that the scaling up of
MWAOD process yielded lignins with very similar structural
features in which their backbone, interunit linkages, and
monolignol composition varied in a very narrow range values.
They also had quite similar molecular weight distribution
curves, Mw and Mn values, as well as thermal stability (Tonset)
and processability (Tg), which are important features for their
use in polymer chemistry. Moreover, it was also shown that the
MWAOD process can be performed using recycled acetic acid,
which affected the lignin yield, purity, and quality. Therefore,
the results show that the MWAOD process is an eco-friendly,
fast, safe, reliable, and feasible method to be used in pilot
plants representing an interesting alternative for extraction of
high-quality lignin in large scale for further technological
applications.

■
Figure 8. (A) Variation of the lignin yield and purity and (B) Mw and
Mn values with the number of acetosolv liquor solution recycles. ASSOCIATED CONTENT
Table 2. Variation of the Main Parameters Involved in the *
S Supporting Information

Quality of SCB Lignin Using Recycled Acetosolv Solution The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.iecr.9b01168.
no. of solvent lignin yield lignin purity Mw Mn Experimental details of the characterization of SCB
recycling (%) (%) (g mol−1) (g mol−1)
lignins; additional results (lignocellulosic composition of
0 72.2 74.8 ± 1.03 2062 1059
SCB, HSQC spectra, GPC, TGA and DSC curves of
1 76.5 91.7 ± 2.41 1336 580
SCB lignins) (PDF)

■
2 61.5 85.8 ± 1.48 1362 593
3 62.8 93.9 ± 4.02 1527 670
AUTHOR INFORMATION
higher than that of lignin extracted using a fresh solution. This Corresponding Author
probably occurred due to the increase of water content in the *E-mail: lomonaco@ufc.br. Phone: +55 85 3366 9019.
acetosolv solution as mentioned before, favoring their ORCID
nucleophilic attack to the ester linkages present in LCC, Francisco Avelino: 0000-0001-8608-7618
yielding lignins with lower carbohydrate content. Diego Lomonaco: 0000-0001-5763-4336
The behavior observed in Figure 8A can be complemented Notes
by that in Figure 8B, in which there was a decrease in the Mw The authors declare no competing financial interest.
and Mn values when the recuperated acetosolv solution was
used several times. This can also be explained by the successive
additions of aqueous catalyst solution to acetic acid. In this
■ ACKNOWLEDGMENTS
The authors acknowledge Brazilian agencies CNPq (409814/
case, the increase in the water content favored cleavage of ether 2016-4 e 407291/2018-0), CAPES, and FUNCAP for financial
bonds, since water molecules act as a nucleophile. Moreover, support and CENAUREMN (Centro Nordestino de Aplicaçaõ
the Mw and Mn values suggest that the decrease of acetic acid da Ressonância Magnética Nuclear at Fortaleza, Brazil) for
content favored the solvation of lower molecular weight NMR analyses.

fragments, which was also observed by the displacement of
their molecular weight distribution curves to lower log MW
values (Figure S6).
Figure S7 shows the 1H−13C HSQC spectrum of the SCB
lignin obtained from the third solvent recycle, while the
comparison between the RPM values of SCB lignins obtained
by using fresh and recycled (3rd reuse) acetosolv solution is
■
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