Ultrasonics - Sonochemistry 51 (2019) 332–339

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Ultrasonics - Sonochemistry
journal homepage: www.elsevier.com/locate/ultson

Furfural production from lignocellulosic biomass by ultrasound-assisted acid T

hydrolysis
⁎
Cezar A. Bizzi , Daniel Santos, Tainara C. Sieben, Gustavo V. Motta, Paola A. Mello,
Erico M.M. Flores
Departamento de Química, Universidade Federal de Santa Maria, 97105-900 Santa Maria, RS, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: Furanic platforms (e.g. furfural, furfuryl alcohol and hydroxymethylfurfural) can be obtained from biomass,
Furfural production being considered as a green alternative to petrochemical products such as fuels, and solvents. In this work, the
Lignocellulosic materials use of ultrasound energy was investigated for the conversion of several lignocellulosic materials into furfural.
Ultrasound-assisted acid hydrolysis The following parameters were evaluated: reaction time (30 to 120 min), ultrasound amplitude (20 to 70%) and
Process intensification
feedstock amount (100 to 500 mg). The ultrasound-assisted acid hydrolysis (UAAH) process was applied to
Fine chemicals
Building blocks
several lignocellulosic materials (sugar cane straw, rice husk, yerba-mate waste, grass and wood waste) aiming
an investigation about the effects when working with real and complex feedstock. Better furfural yields
(72.4 ± 4.3 mg g−1) were obtained from 0.1 g of grass, employing an ultrasound cup horn system operating at
20 kHz, 20 mL of 4 mol L−1 HNO3, at 30 °C, 50% amplitude, and 60 min of sonication. Under the same reaction
conditions, the results were compared with those obtained at silent condition (mechanical stirring,
100 to 500 rpm), which demonstrate the ultrasound effects for furfural synthesis. Therefore, the proposed UAAH
process can be considered as a suitable alternative for biomass conversion to furfural, because it does not need
previous step of lignin removal and might be performed in a single step.

1. Introduction compounds are industrially produced by dehydration of sugars. When

Nowadays, special attention is being paid to the biomass conversion
into fine chemicals such as fuels, solvents and plastics [1]. The interest
in the biomass conversion can be justified due to two global issues: the
necessity of using renewable carbon sources for compensating the ex-
pected decrease of petroleum reservoirs and the need of decreasing
greenhouse gas emissions [2,3]. During the last decade the main focus
of biomass conversion from lignocellulosic materials has been related to
the production of intermediary molecules used as chemical platforms
[4,5]. These molecules are considered building blocks for the devel-
opment of alternative routes to sustainable production of fuels, plastics
and solvents [5].
Furanic platforms (e.g. furfural, furfuryl alcohol and hydro-
xymethylfurfural) might be produced from biomass, which can be
considered as a greener alternative to petrochemical products [6].
Furfural is mainly used as a solvent for the refining of lubricating oils
and diesel fuels, for the production of plastics, and agrochemicals, as
well as a chemical intermediate in the production of solvents such
tetrahydrofuran and methyl tetrahydrofuran [7]. In general, furanic
this process follows a conventional route, it generally comprises a
number of side reactions, the use of toxic reagents and long reaction
time [8]. In this sense, the development of alternative processes for
obtaining such class of compounds under milder reaction conditions is
of primary importance [6,8].
Among the technologies that contributes for process intensification
[9–11], ultrasound energy has been considered a promising alternative
[12–18]. The main effects observed when a reaction medium is soni-
cated are associated to increase the convection and acoustic cavitation
[19,20]. While the former effect contributes for enhancing the mass
transfer, the latter leads to the production of highly reactive radicals
inside the reaction medium [19,20].
Some studies reported that ultrasound presents synergic effects to
several chemicals processes. In the context of biomass treatment, most
of them are devoted to the pretreatment [21–23]. Ultrasound-assisted
lignin removal from lignocellulosic biomass was demonstrated leading
to a drastic time reduction in the pretreatment, as well as the high
lignin removal (68%) and good recovery of total solid and fermentable
sugars [21].

⁎
Corresponding author.
E-mail address: cezar.bizzi@gmail.com (C.A. Bizzi).

https://doi.org/10.1016/j.ultsonch.2018.09.011
Received 31 May 2018; Received in revised form 7 September 2018; Accepted 7 September 2018
Available online 27 September 2018
1350-4177/ © 2018 Elsevier B.V. All rights reserved.
C.A. Bizzi et al.
Only a few reports were found in the literature focusing on the use
of ultrasound energy for obtaining fine chemicals from lignocellulosic
biomass [23]. The feedstock heterogeneity can impair the biomass
conversion. Taking into account that lignin, flavonoids and organic
acids may interfere in the synthesis leading to the formation of side
products, a careful evaluation must be performed in order to investigate
the process suitability [5,7]. As an example, ultrasound was associated
with ionic liquids to the conversion of glucose, cellulose and bamboo to
5-hydroxymethylfurfural [24]. Several ionic liquids were used to dis-
solve biomass, allowing hydroxymethylfurfural yields of about 43, 31
and 13% (from glucose, cellulose and bamboo, respectively), in less
than 10 min [24]. Similarly, ultrasound energy was used for furfural
production from microcrystalline cellulose. This process, based on acid
hydrolysis, was demonstrated as a model concept for microcrystalline
cellulose. In this case, furfural was obtained at reduced reaction time
(60 min), at room temperature, only by using ultrasound and diluted
acid solution, which means a condition of energy and reagents saving
[15].
In the present work the application of ultrasound energy for lig-
nocellulosic biomass conversion to furfural by acid hydrolysis was
evaluated. Microcrystalline cellulose and several lignocellulosic mate-
rials (sugar cane straw, rice husk, yerba-mate waste, grass and wood
waste) were used as feedstocks. For evaluating the better furfural pro-
duction in the proposed ultrasound-assisted acid hydrolysis (UAAH), a
range of reaction conditions using ultrasound (reaction time, amplitude
and feedstock amount) were investigated. For this study, ultrasound
energy was delivered in reaction medium using a cup horn system
operating at 20 kHz. The obtained results using UAAH proposed process
were compared with those under silent conditions.
2. Materials and methods
2.1. Instrumentation
The UAAH was performed using a 20 kHz and 750 W (nominal
power) ultrasonic system (VC 750, Sonics and Materials Inc., Newtown,
USA) coupled to a cup horn system (76 mm diameter, 165 mm long).
Products were identified by electrospray ionization with high-re-
solution time-of-flight mass spectrometry (ESI-ToF-MS, Xevo G2 Q-ToF,
Waters, USA). Mass spectra were acquired from 50 to 1000 Da and ESI-
ToF-MS detection was performed in positive ion mode with a capillary
voltage of 2.00 kV, cone voltage of 40 V, and an extractor cone voltage
of 2.10 V. Desolvation gas and cone gas flow rates were 400 L h−1 and
10 L h−1, respectively. The desolvation temperature was set to 400 °C
and the source temperature was 150 °C. System control and data ac-
quisition were performed using MassLynx V 4.1 software. Mass in-
strument was calibrated in order to enhance the accuracy and precision.
Chromatographic analyses were performed using a gas chromato-
graph (Varian CP 3800, CA, USA) equipped with a flame ionization
detection (GC-FID). A polyethylene glycol capillary column was used
(30 m × 0.25 mm i.d. ×0.25 µm film thickness, Agilent Technologies).
Helium was used as carrier gas with split/splitless injection mode with
a purge time of 0.75 min and split of 1:20. The flame ionization detector
was supplied with synthetic air (60 mL min−1) and hydrogen
(40 mL min−1). The injection volume was 1 μL. The injector and de-
tector temperatures were 150 °C and 280 °C, respectively. The tem-
perature program was performed as the following: the temperature was
initially set to 120 °C and held for 1 min, then increased to 180 °C (rate
of 10 °C min-1) and held for 1 min, and finally increased to 210 °C (rate
of 20 °C min-1) and held at this temperature for 1.54 min, for a total
analysis time of 10 min.
The results obtained by GC-FID were compared with those obtained
by ultra-performance liquid chromatograph coupled to high-resolution
time-of-flight mass spectrometry equipped with an electrospray ioni-
zation source (UPLC-ToF-MS, Acquity™ UPLC system, Waters Corp.,
Milford, USA). Separation was performed in a BEH C18 column
333
Ultrasonics - Sonochemistry 51 (2019) 332–339
(2.1 × 50 mm, 1.7 µm, Waters) coupled to a mass spectrometer (Xevo
G2 Q-ToF, Waters), equipped with an electrospray ionization (ESI)
source. Injection volume was 10 µL and autosampler temperature was
maintained at 25 °C. Binary solvent pump was operated isocratically
with water and acetonitrile as mobile phases (96:04, v/v), both solu-
tions containing 0.1% formic acid, at a flow rate of 0.2 mL min−1.
The obtained products were confirmed using 13C and 1H nuclear
magnetic resonance (NMR). Spectra were recorded on a Bruker
Advance III NMR spectrometer with 32 scans, which were processed
using Bruker-Topspin software. The NMR spectra were acquired by 13C
and 1H, using 150.92 and 600.13 MHz, respectively.
Feedstocks and residues after UAAH were analyzed by scanning
electron microscopy (SEM, microscope model Sigma 300 VP Carl Zeiss,
Germany) with a field emission filament of Schotky type (filament
tungsten coated with zirconium oxide), equipped with a Gemini
Column (Zeiss, Germany). Additionally, the major functional groups in
each feedstock were identified by Fourier transform infrared spectro-
scopy (FTIR, spectrometer model Spectrum One® FTIR, USA). All the
obtained spectra ranged between wave numbers 4000 and 400 cm−1
and the baseline was corrected and vector normalized. Spectral re-
solution was set at 4 cm−1.
2.2. Materials and chemicals
For this study, microcrystalline cellulose was obtained from Sigma-
Aldrich (purity of 99%, Germany). Five other types of lignocellulosic
biomass were used: rice husk, sugar cane straw, yerba-mate waste, grass
and wood waste, which were purchased in a local farm. All feedstocks
were dried at 105 °C up to a constant weight. These materials were then
kept in sealed bags until use.
Water was purified using a Milli-Q system (Millipore Corp., USA)
and it was used to prepare all the reagents and standard solutions.
Nitric acid (65%) and chloroform were of analytical grade (Merck,
Germany). Furfural standard (purity of 99%, Sigma-Aldrich, Germany)
was used. Nitrogen, argon, helium, synthetic air and hydrogen (purity
of 99.999, 99.5, 99.9999, 99.999 and 99.999% respectively, White
Martins, Brazil) were used for analytical techniques. Acetonitrile and
methanol used in ESI-ToF-MS were of LC-MS grade (purity of 99.9%,
Fluka, Germany, and Tedia, USA, respectively).
2.3. Methods
The UAAH process was carried out in a glass cylindrical reactor with
5 cm of internal diameter and 12 cm height. Temperature was con-
trolled using a circulating water bath (model MCT 110 Plus, Servylab
Ltda., Brazil). Feedstocks (0.5 g) were transferred to the reactor with
20 mL of acid solution. Further, this reaction mixture was subjected to
UAAH using a cup horn system (20 kHz/750 W).
Preliminary experiments were performed using microcrystalline
cellulose as model feedstock. Reaction temperature (30 °C), HNO3
concentration (4 mol L−1) and ultrasound system (cup horn) were se-
lected according previous literature [15]. The following parameters
were evaluated: reaction time (30 to 120 min), the ultrasound ampli-
tude (20 to 70%) and the cellulose amount (100 to 500 mg).
Results obtained with UAAH were compared with those by hydro-
lysis at silent condition (without ultrasound), which was performed
using mechanical stirring (100 to 500 rpm) at 30 °C and 60 min. After
choosing the process parameters, the UAAH process was applied to
several lignocellulosic biomass (rice husk, sugar cane straw, yerba-mate
waste, grass and wood waste).
The energy input in the UAAH process was determined by calori-
metry, according to previous works [25,26]. This evaluation was per-
formed with 0.1 g of all lignocellulosic biomass and 20 mL of 2 mol L−1
HNO3, which was sonicated for 20 min (50% amplitude). Temperature
was monitored using a digital thermometer and the determined power
was related to the sonication time, to give the power (W) transferred to
C.A. Bizzi et al.
the solution.
Previously to the characterization by ESI-ToF-MS, extracts were
passed through a polytetrafluoroethylene membrane filter (0.22 µm),
and then diluted with methanol or water (1:10, v/v). For furfural
analysis by GC-FID, UPLC-ToF-MS and NMR a final step was applied
using liquid-liquid extraction with chloroform, followed by solvent
evaporation at reduced pressure. In GC-FID and UPLC-ToF-MS the
conditions were selected according to Eurachem Guide recommenda-
tions [27]. Additionally, the residues after UAAH were evaluated by
FTIR and SEM. In both cases the residues were dried up to a constant
weight at 105 °C. These materials were then kept in sealed bags until
any further use.
For SEM, the residual feedstock from UAAH was cut into sections of
10 × 10 mm and further positioned on the specimen stub. Metal
overlay was not necessary and the images were obtained using the
energy dispersive detector (EDS) with an accelerating voltage at 8 kV.
For FTIR analysis each sample was previously weighed before
spectrum acquisition (about 25 ± 5 mg of powder sample) and placed
onto the ATR crystal. Crystal was cleaned with acetone between each
analysis. For each sample, spectra were obtained in triplicate with 16
scans, 4 cm−1 resolution and normalized.
3. Results and discussion
3.1. Characterization of lignocellulosic materials
The characterization of lignocellulosic materials is a required in-
formation for bioprocess development aiming industrial scale. Some
problems, such as pipe clogging, corrosion and reduction of reaction
yield can be avoided with the knowledge of the main characteristics of
the feedstock. Thus, before UAAH treatment, ash, moisture and metals
content were determined. Additionally, a complementary information
about the main functional groups was obtained from FTIR. Both in-
formation are present in Appendix A. Part I: Characterization of lig-
nocellulosic materials. From this characterization it was possible to see
how challenging can be the use of different feedstocks, presenting so
diverse composition. Such information, which demonstrates structural
feedstock complexity, must be taken into account before applying the
conversion process.
3.2. Optimization of conversion to furfural
The hydrolysis conditions are important parameters for the opti-
mization of cellulose conversion. Depending on the reaction time
(30 to 120 min), amplitude (20 to 70%) or feedstock amount (100
to 500 mg) used, high or low furfural production were achieved. In the
evaluated reaction time, 20 mL of diluted acid (4 mol L−1 HNO3) and
0.5 g of microcrystalline cellulose were subjected to UAAH. Ultrasound
amplitude was set at 50% and it was applied for 30, 60 and 120 min at
30 °C. The obtained results are presented in Fig. 1a.
After 30 min of sonication furfural production reached about
Fig. 1. Effect of (a) reaction time, (b) ultrasound amplitude and (c) feedstock amount in the UAAH process (20 mL of 4 mol L−1 HNO3; 30 °C; error bars are the
standard deviation, n = 3).
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Ultrasonics - Sonochemistry 51 (2019) 332–339
12 mg g−1. When sonication time was increased up to 60 or 120 min, 42
and 56 mg g−1 of furfural were produced, respectively. Despite the in-
crease in furfural production using 120 min, this longer reaction time
was considered unsuitable, because the yield was not considerably
improved. Based on this result, 60 min of reaction time was selected for
further evaluations. It is important to highlight that the time for furfural
production was significantly reduced when it was compared with data
found in the literature, which were usually higher than 3 h (without
sonication) [7].
The optimization of ultrasound parameters for allowing optimal
experimental conditions for the proposed UAAH also included the
amplitude evaluation. To optimize this parameter, experiments were
performed at amplitude ranging from 20 up to 70% (60 min of soni-
cation). In these experiments, 0.5 g of microcrystalline cellulose and
20 mL of 4 mol L−1 HNO3 were sonicated at 30 °C. The effect of am-
plitude values on furfural production are shown in Fig. 1b.
Lower amplitude values (20, 30 and 40%) resulted in low produc-
tion of furfural (10, 20 and 40 mg g−1, respectively). When 50% am-
plitude was applied, furfural production was about 60 mg g−1, which
remained practically constant for higher ultrasound amplitude (60 and
70%). An important aspect to be pointed when choosing the optimal
ultrasound amplitude is the energy consumption. By increasing the
amplitude from 20 to 70% the average ultrasonic power delivered to
the probe was increased from 21.5 kJ to 265.4 kJ (energy values pro-
vided by the ultrasonic controller at the end of each experiment). In this
sense, the amplitude has been chosen based on the relationship between
energy saving condition and furfural yields. Thus, considering that no
increase in the furfural production was observed using ultrasound
amplitude higher than 50%, this condition was chosen for further ex-
periments.
Concerning the influence of feedstock amount, the furfural pro-
duction was investigated using 0.1 to 0.5 g of sample. These experi-
ments were performed using 20 mL of 4 mol L−1 HNO3, 50% amplitude,
and 60 min at 30 °C as reaction conditions (Fig. 1c).
As expected, the use of lower feedstock amount increased the effi-
ciency of furfural production. According to the results presented in
Fig. 1c, the increase in the feedstock amount resulted in a reduction of
furfural production from 224 to 46 mg g−1. The increase in furfural
yield observed when 100 mg of feedstock amount was used can be at-
tributed to the amount of reagents (maintained always equal while
feedstock amount changed) and to the physical effects caused by ul-
trasound energy, which contributed for disorganization of crystalline
structure of cellulose, contributing for a better conversion with good
selectivity. Increasing the feedstock amount the disorganization of
crystalline structure of cellulose may be impaired, which certainly
contributed for reducing the furfural yield. Once the selectivity of fur-
fural production was not impaired when increasing the sample mass
(only yields), when considering a process at bigger scale this must be
circumvented by the suitable design of reactors (not evaluated in this
study). Finally, considering furfural yields and compromise condition
between energy and production, the optimized condition was 0.1 g of
C.A. Bizzi et al. Ultrasonics - Sonochemistry 51 (2019) 332–339

Table 1 According to the results presented in Table 1, the furfural produc-

Furfural production from several feedstocks in the UAAH process (0.1 g of tion was about 36.4 to 72.4 mg g−1. The lower conversion was observed
feedstock, 20 mL of 4 mol L−1 HNO3, 50% of amplitude at 30 °C and 60 min; for rice husk (36.4 ± 7.9 mg g−1) while the best condition for con-
average ± standard deviation, n = 3). version of lignocellulosic biomass to furfural by UAAH was obtained
Feedstock Furfural production, mg g−1 Furfural yield, % when reaction was driven using grass as feedstock
(72.4 ± 4.3 mg g−1). The different yield observed for these feedstocks
Rice husk 36.4 ± 7.9 3.64
can be justified by the particular lignin composition and ash content.
Sugar cane straw 49.9 ± 5.1 4.99
Yerba-mate waste 62.1 ± 2.0 6.21
The high ash content reduces the amount of available carbon, impairing
Grass 72.4 ± 4.3 7.24 the furfural production efficiency. For lignin a more difficult reaction
Wood waste 60.8 ± 9.0 6.08 between the cellulosic fraction and the H+ occurs. In these conditions,
the production of 2,3 unsaturated aldehyde intermediate is impaired
and the reaction route is interrupted. A possible oxidative route to
feedstock, 4 mol L−1 HNO3, at 30 °C, 50% of amplitude and 60 min of furfural synthesis from lignocellulosic materials (cellulose and hemi-
sonication. cellulose) can be seen in Fig. 2.
During the experiments for UAAH conversion of lignocellulosic
3.3. UAAH conversion of several feedstock to furfural materials a remaining solid residue was observed for all conditions.
This non-solubilized material was visually similar to the starting ma-
The conversion of biomass can be hindered by many factors, such as terial. In order to better elucidate the contribution of ultrasound for
cellulose molecular weight, the available surface area of the substrate, biomass conversion, a morphological evaluation was performed by
hemicellulose content, feedstock particle size, porosity, cell wall SEM. Images obtained for lignocellulosic materials, before and after
thickness and the lignin barrier (content and distribution). Thus, the UAAH treatment are shown in Fig. 3.
UAAH process was optimized for sugar cane straw, rice husk, yerba- The SEM images present a clear evidence that ultrasound energy
mate waste, grass and wood waste. The selected experimental condi- resulted in substantial modification on the lignocellulosic structure
tions were: 0.1 g of substrate, which was sonicated for 60 min (50% after UAAH. SEM images obtained at high magnifications showed that
amplitude) using 20 mL of 4 mol L−1 HNO3 at 30 °C. The obtained re- the initial feedstocks are originally characterized by particles with well-
sults are presented in Table 1. organized and lamellar structures, normally associated to

Fig. 2. Possible oxidative route to furfural synthesis from lignocellulosic materials (cellulose and hemicellulose). Adapted from references [8,15].

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Fig. 3. SEM images obtained for (a) rice husk, (b) rice husk after UAAH, (c) sugar cane straw, (d) sugar cane straw after UAAH, (e) yerba-mate waste, (f) yerba-mate
waste after UAAH, (g) grass, (h) grass after UAAH, (i) wood waste and (j) wood waste after UAAH (optimized UAAH conditions: 60 min of ultrasound treatment using
4 mol L−1 HNO3, at 30 °C, 50% amplitude, for 0.1 g of feedstock). Red circles indicate standards related to the original organization of biomass, while yellow arrows
indicate structural changes in biomass after UAAH treatment.

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Fig. 4. Chromatograms and spectra for (a) experiment under optimized UAAH conditions (60 min of ultrasound treatment using 4 mol L−1 HNO3, at 30 °C, 50%
amplitude, for 0.1 g of grass) and (b) experiment under silent conditions (250 rpm, 30 °C, 60 min and 0.1 g of grass).

lignocellulosic materials. After UAAH these structures were dis-
organized and some microfibrils were exposed. For the lignocellulosic
hydrolysis, biomass rupture and acid hydrolysis can be improved by
ultrasound energy. Based on the obtained results, as conversion was
improved and lignocellulosic biomass was physically modified
according to the SEM images, it is possible to assume that ultrasound
plays an important role, helping for the hydrolysis of biomass for fur-
fural production, even using milder reaction conditions (diluted HNO3
solution, room temperature and atmospheric pressure). It is worthy to
mention that a previous step of lignin removal was not required for the

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Table 2
. Comparison between the proposed UAAH process with other ultrasound-assisted processes.
Reference Feedstocks Ultrasound system Time Temperature Objective Solution Yields, %

This work Rice husk Cup horn 60 min 30 °C Furfural synthesis (single step) diluted HNO3solution 3.64
Sugar cane straw 4.99
Yerba-mate waste 6.21
Grass 7.24
Wood waste 6.08
[15] Microcrystalline cellulose Probe, bath and cup horn 60 min 30 °C Furfural synthesis (single step) diluted H2SO4, HCl and HNO3 22.6
solution
[24] Glucose Probe 10 min 60–120 °C Hydroxymethylfurfural ionic liquids 43
Cellulose 31
Local bamboo 13
*
[21] Areca nut husk Probe 180 min 35 °C Delignification alkaline solution
Bon bogari
moj
*
[22] Groundnut shells Probe 70 min 80 °C Delignification alkaline solutiom
Coconut coir
Pistachio shells

* Not informed; references 21 and 23 were not dedicated to the synthesis of fine chemicals.

proposed UAAH process, being a feasible alternative for saving reagents
and time.
3.4. Influence of ultrasound for furfural production
In order to evaluate the effects of ultrasound in furfural production,
silent experiments with mechanical stirring were carried out. The ex-
perimental conditions chosen in this case were those previously opti-
mized for UAAH process (0.1 g of substrate, 4 mol L−1 HNO3, at 30 °C
and 60 min), but using mechanical stirring (100, 250 or 500 rpm) in-
stead of ultrasound energy. Comparative results for acid hydrolysis
using grass as feedstock can be seen in Fig. 4, where the chromato-
grams, mass spectrum and NMR spectrum obtained using UAAH
(Fig. 4a) and using mechanical stirring (Fig. 4b) are presented. When
mechanical stirring was used for biomass hydrolysis it was not possible
to obtain NMR information due to furfural absence. Chromatograms
and spectra for the other feedstocks are presented in Supplementary
Material (Appendix A - Part II: Influence of ultrasound for furfural
production).
According to the results obtained using mechanical stirring, furfural
production was not detected (≤3.4 µg g−1). The absence of furfural
production can be associated to the low energy that the reaction mix-
ture was exposed when reaction medium was mechanically stirred.
Using 100, 250 or 500 rpm, the experimental conditions (acid con-
centration, temperature and reaction time) were not enough to furfural
production. This result (silent condition), combined with the study
where amplitude was evaluated (furfural production showed de-
pendency on the US amplitude), were considered for assuming that US
has a beneficial effect when looking for furfural production. Furfural
was only produced when reaction medium was sonicated, which de-
livered enough energy for starting carbohydrate hydrolysis. The ultra-
sound energy generates micro mixing regions that increases reaction
rate and mass transfer when compared to silent conditions. Moreover,
some physical and chemical mechanisms, via shear forces, surface
erosion and radical production have been attributed to ultrasound in
the conversion of lignocellulosic materials [5,7,15]. These aspects,
mainly observed when reaction medium was sonicated, generate high
disorganization degree and increase the feedstock contact surface, fas-
tening the biomass conversion. In addition, furfural was produced only
when biomass was sonicated. The acoustic wave contributed for over-
coming the lignin barrier and allowed glucose protonation for produ-
cing 2,3 unsaturated aldehyde intermediate, for further furfural pro-
duction.
Some advantages might be highlighted when comparing the pro-
posed UAAH process for biomass conversion with the conventional
protocols, such as the relatively short reaction time, low temperature
and atmospheric pressure condition. Additionally, even using real
feedstocks with different complexity (related to lignin, hemicellulose
and cellulose content), the proposed UAAH process was able to produce
furfural without any previous step of delignification. A comparison
between the proposed UAAH process with other ultrasound-assisted
processes described in literature is shown in Table 2.
4. Conclusion
Based on the results obtained in the present study, the proposed
UAAH was considered a promising alternative process for the furfural
production. It was observed that the cup horn system allowed to get
yields greater than those obtained when mechanical stirring (100
to 500 rpm) was used. The presented results demonstrate the influence
of physical and chemical effects provided by ultrasound, which con-
tributed for driving production of furfural. The optimized conditions
(0.1 g of substrate, 4 mol L−1 HNO3, at 30 °C, 50% amplitude and
60 min of sonication) bring several advantages of the proposed UAAH
process when it is compared with conventional processes, such as the
possibility of driving a reaction at low temperature, at atmospheric
pressure, and saving reagents. It is worth mention that no additional
step of lignin removal was performed, allowing furfural production a
single step. All these advantages result in economy of reagents and less
production of waste, in accordance with green chemistry re-
commendations.
Acknowledgements
The authors are grateful to Conselho Nacional de Desenvolvimento
Científico e Tecnológico (CNPq, Grant nr. 309549/2016-7, 309297/
2016-8), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
(CAPES, Finance Code 001) and Fundação de Amparo à Pesquisa do
Estado do Rio Grande do Sul (FAPERGS, Grant nr. 16/2551-0000226-6;
16/2551-0000226-6) for supporting this study.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.ultsonch.2018.09.011.
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