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Preliminary Studies on Furfural Production from Lignocellulosics

Article  in  Journal of Wood Chemistry and Technology · July 2014

DOI: 10.1080/02773813.2013.844167

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Journal of Wood Chemistry and Technology, 34:178–190, 2014
Copyright © Taylor & Francis Group, LLC
ISSN: 0277-3813 print / 1532-2319 online
DOI: 10.1080/02773813.2013.844167

Preliminary Studies on Furfural Production

from Lignocellulosics

BIANCA MOREIRA BARBOSA,1 JORGE LUIZ COLODETTE,2

DALTON LONGUE JÚNIOR,2 FERNANDO JOSÉ BORGES
GOMES,2 AND DANIELA CORREIA MARTINO2
1
Department of Chemistry, Federal University of Viçosa, Viçosa, Minas Gerais,
Brazil
2
Department of Forestry Engineering, Federal University of Viçosa, Viçosa,
Minas Gerais, Brazil

Abstract: This study focused on the production of furfural from agricultural and in-
dustrial biomass residues by a hydrodistillation process. Corncobs, sugarcane bagasse,
and eucalypt wood were treated with sulfuric, hydrochloric, and phosphoric acids as
catalysts, with different acid concentrations (1.5 to 5.2 mol.L−1). In addition, the euca-
lypt liquor from the auto-hydrolysis, kraft-dissolving pulp production process was also
investigated as a source of furfural, using sulfuric and hydrochloric acids as a cata-
lyst (0.9 and 3.9 mol.L−1). Furfural yields of 30.2, 25.8, and 13.9% were achieved for
corncob, sugarcane bagasse, and eucalypt wood, respectively, on the basis of biomass
dry weight. The efficiency of conversion from pentose to furfural using eucalypt liquor
from the auto-hydrolysis kraft process was 71.5% using HCl 3.9 mol.L−1. Due to the
presence of a high amount of pentose, corncob produced the highest amount of furfural,
followed by sugarcane bagasse and then eucalypt wood.

Keywords Furfural, mineral acids, auto-hydrolysis, hemicelluloses, dissolving pulp

production

Introduction
Interest in chemical production based on renewable sources has increased in the last decade
due to the declining reserves and increasing prices of fossil materials. Among the different
types of available biomass, agricultural crops, non-woody materials, annual plants or grasses
present a special interest due to their abundance, renewability, and as an inexpensive source
for polymeric materials, energy, or chemicals.[1–3]
Agricultural and agro-industrial residues are mainly constituted of three structural
components (lignin, cellulose, and hemicellulose) and each compound has specific prop-
erties destined for different uses for chemical production. Biomass residues available from

Funding provided by the Minas Gerais State Research Foundation (FAPEMIG) and by the
Brazilian National Council for Science and Technology Development (CNPq) is greatly appreciated.
Address correspondence to Bianca Moreira Barbosa, Department of Chemistry, Federal
University of Viçosa, Campus Viçosa, CEP 36570-900, Viçosa, Minas Gerais, Brazil. E-mail:
bianca.barbosa@ufv.br

178
 Furfural Production from Lignocellulosics 179

agricultural and forest processing constitute a potential source for chemical production
such as ethanol, reducing sugars and furfural, using enzyme or acid-catalyzed hydrolysis.
All pentosans containing fibrous material could, in theory, be used as a raw material for
furfural production; however, furfural industrial production requires a minimum pentosans
content of around 15 to 20%.[4] Only about one third of the pentosans in raw materials can
be converted into furfural through the existing production processes.
Furfural is an important chemical because it is a selective solvent for separating
saturated and unsaturated compounds in petroleum refining, gas, oil and diesel fuel, and
for the high demand of its derivatives, especially furfuryl alcohol, used mainly in the
production of furan resins for foundry sand binders, which is considered the major market for
furfural.[5] So far, there is no synthetic route available for furfural production in the chemical
industry; consequently, it is exclusively produced by acid hydrolysis and dehydration of
pentoses (mainly xylose) contained in lignocellulosic biomass (like corncobs, cotton stalks,
sunflower stalks, sugarcane bagasse, etc.).[5–7]
There are two main types of technologies to produce furfural. The first is a one-stage
technology where the pentosans’ depolymerization in xylose and dehydration to furfural
occur simultaneously.[1,8] The second is a two-stage technology where the dissolution
and depolymerization of pentosans occur under mild conditions, followed by dehydration
of xylose to furfural.[9] The advantage of the two-stage technology is that the residual
lignocellulose is less degraded and can be used for conversion to other chemicals (glucose,
ethanol, phenols, etc.) in a subsequent step.
Several researchers have investigated the production of furfural by hydrolysis of ligno-
cellulosic residue materials in the presence of a mineral acid as catalyst, such as hydrochloric
acid (HCl),[10–12] nitric acid (HNO3 ),[13] sulfuric acid (H2 SO4 ),[6,14,15] and phosphoric acid
(H3 PO4 ).[5,16,17] Among these acids, HCl, H2 SO4 , and H3 PO4 produce high furfural yield
whereas HNO3 is not so effective. Raw materials used for furfural production reported
in the literature included sugarcane bagasse,[13,17] wood,[15,18] date-palm trees,[14] sorghum
straw,[5,11] corncobs,[9,19] rice hull,[20] and rice straw.[21]
Currently, many studies have been developed by using lignocellulosic materials as
feedstock for chemicals production, such as furfural, for example,[9,22] In this context,
the biorefinery concepts are being applied which use pretreatments for an organized de-
construction of the biomass aiming at bioproducts and chemicals production. Among the
pre-treatments for lignocellulosic biomass, the auto-hydrolysis treatment recovers high
quantities of hemicelluloses, converting them into soluble saccharides, while both cellulose
and lignin are largely retained in the solid phase.[23] The solid fraction obtained from auto-
hydrolysis treatments can be used for bioethanol production or some biobased added-value
products.[24,25] Liquid rich in hemicellulose can be used as a raw material for furfural,
hydroxymethylfurfural, and alcohol production and to extract phenols from the dissolved
lignin fractions.[26–28]
In the production of dissolving pulp by the auto-hydrolysis kraft process, the auto-
hydrolysates extracted from the first phase of the process are rich in xylose oligomers and
monomers and are usually burnt along with the black liquor extracted in the second phase.
Burning such material is not cost-effective because its heating value is very low and its
load decreases overall mill production; it occupies space in the recovery boiler, which is the
bottleneck in most mills. Ideally, such material should be discarded, but this would cause
significant environmental issues. Therefore, its use as a raw material for furfural production
could be an interesting alternative given its high content of C5 sugars (pentoses). The acid
hydrolysis of this material for furfural production, as it relates to eucalypt wood, was an
important novelty of this work.
180 B. M. Barbosa et al.

The aim of this study was to investigate furfural production from corncob, sugarcane
bagasse, and eucalypt wood using different concentrations of mineral acids (HCl, H2 SO4 ,
and H3 PO4 ), since these mineral acids are commonly used in furfural production due to
their high furfural yield and low cost. In addition, an auto-hydrolyzate derived from the
auto-hydrolysis kraft process from eucalypt wood was investigated for furfural production,
using hydrochloric and sulfuric acid as catalysts. To the best of our knowledge, this latter
source of raw material (eucalypt auto-hydrolysate) has never been investigated for furfural
production.

Experimental

Materials
Corncob (CC) and sugarcane bagasse (SCB), harvested at Federal University of Viçosa,
a Brazilian experimental station, and also Eucalyptus urophylla x Eucalyptus grandis
chips (EUCA), supplied by a Brazilian forest company, were used in this study. The raw
materials were dried at room temperature and ground in a laboratory mill, then sieved and
classified according to T257 cm-12 standard procedure. All samples were extracted with
ethanol/toluene 1:2, ethanol 95%, and hot water and subjected to moisture determination
in accordance with T264 cm-07.

Quantitative Chemical Characterization

The carbohydrate composition of raw materials was determined by High Performance
Anion Exchange Chromatography with Pulse Amperometric Detection (HPAEC-PAD)
after pre-treatment (30◦ C, 1 h) of the materials with aqueous 72% H2 SO4 followed by
hydrolysis with 3% H2 SO4 in an autoclave (100◦ C, 3 h). HPAEC-PAD was carried out in a
Dionex ICS-3000 system equipped with a CarboPac PA1 (250 × 4 mm) analytical column.
The monosaccharides were separated isocratically with 0.001 M NaOH (45 min, flowrate
1 mL/min), according to Wallis et al.[29] The solid residue after hydrolysis was considered to
be a Klason lignin, according to T222 cm-11 standard procedure. Ashes were determined by
calcination, according to TAPPI standard T211 om-12. Acid-soluble lignin was determined
by measuring the UV-absorbance of the filtrate at 205 nm, according to Goldschimid.[30]
Total uronic acids in raw materials hydrolysates were measured by the colorimetric method
involving 3,5-dimethylphenol addition, according to Scott.[31] The acetyl group content in
samples wood was determined according to Solár et al. [32] All results were calculated from
two replicate determinations.

Auto-Hydrolysis (AH)
The auto-hydrolysis treatment for EUCA chips was carried out in a 7 liter M/K digester
equipped with a heat exchanger, circulating pump, and computer-controlled time and tem-
perature, under the following fixed conditions: 1000 g oven-dry (OD) of chips, 4/1 (m3/t)
liquid/material ratio, 170◦ C maximum temperature, 90 minutes to maximum temperature,
15 minutes at maximum temperature, and 2.5 to 3.0 final pH, according to a previous
study.[25]
 Furfural Production from Lignocellulosics 181

Furfural Production
The raw materials (CC, SBC, and EUCA) were used for furfural production by hydrodis-
tillation, while the hydrochloric acid (HCl), sulfuric acid (H2 SO4 ), and phosphoric acid
(H3 PO4 ) were used as catalysts to improve the reaction. The experimental parameters of the
acid catalysts concentrations used for each raw material were the following concentrations:
1.5; 2.3; 2.6; 3.0; 3.9; 5.2 mol.L−1.

Furfural Production from EUCA Liquor Auto-Hydrolysate

From the hemicelluloses present in the EUCA auto-hydrolysate, furfural was obtained.
To determine the maximum production of furfural by transformations of pentoses into
furfural, two different experimental designs were carried out, varying the catalyst type
(HCl and H2 SO4 ), the catalyst concentration, and the reaction temperature and time. From
the hemicelluloses present in the EUCA auto-hydrolysate, furfural was obtained by two
different experimental designs. In the experimental design with H2 SO4 , the following
conditions were used: temperature 170◦ C, 0.9 mol.L−1, three hours reaction time, and 3/1
liquid/solid ratio, according to optimized conditions in a similar paper.[33] The experimental
design with HCl (3.9 mol.L−1) used to determine the maximum production of furfural was
by hydrodistillation transformations of pentoses into furfural.

Hydrodistillation
Furfural production in the two-stage process was carried out initially with a pre-hydrolysis
of 1 g OD sample in a boiling flask with 100 mL of mineral acids at different concentration
and reflux times (time was recorded immediately after initiation of boiling). The flask was
connected to the simple distillation apparatus, and 300 mL of mineral acids was added
into a separatory funnel, previously assembled as in T223 cm-10. During the boiling time,
furfural was recovered by steam distillation. In the next step, the hydrolysate was heated
and the distillate was collected in a 500 mL erlenmeyer flask immersed in an ice bath.
For each 30 mL of hydrolysate obtained in the distillation, 30 mL acid was added until it
reached 300 mL of hydrolysate. Results were calculated from two replicate determinations.

Furfural Quantification
Furfural was determined by using a spectrophotometric method developed by Nascimento
et al.[34] The analysis is based on the reaction of furfural with aniline in acetic acid and
ethanol 95% to stabilize the color. The test was conducted in the dark and under stirring
for 15 minutes. Spectral analyses were done at 510 nm (Varian Cary 50 Probe UV-visible,
USA) and compared with a calibration curve for pure furfural, and the furfural yield was
calculated according to Equation (1):
w0
% Furfuralyield = ×100% (1)
w1
where w0 = furfural mass concentration of total distillate; w1 = the total mass of raw
material.
The furfural conversion efficiency was calculated according to Equation (2):
w0
% Furfuralefficiency = ×100% (2)
w2
182 B. M. Barbosa et al.

where w0 = furfural mass concentration of total distillate; w2 = the mass of pentose (xylose
and arabinose) in the raw material.
The furfural productivity was calculated by Equation (3):
Furfuralyield (1) × Furfuralefficieny (2)
% Furfuralproductivity = (3)
100

Results and Discussion

Chemical Composition of Raw Materials

The chemical compositions of CC, SCB, and EUCA (percentage on oven-dry weight
basis) are shown in Table 1, as well as the standard deviation of data based on two replicate
determinations. The raw materials are defined by their content of glucose, xylose, arabinose,
galactose, mannose, acetyl groups, lignin, ash, and uronic acid. Due to the presence of ash,
acid-insoluble lignin analysis gave an overestimation of lignin content; therefore, the lignin
values were corrected by their ash content.[35]
Also, the data showed that the pentose content (xylose + arabinose) was 33.4%
for CC, 30.8% for SCB, and 12.6% for EUCA, which constitutes an adequate content
comparable to that found in wheat hulls, cotton seeds, and nut shells commonly used
for furfural production.[20] Because of the current importance of lignin as a raw material
for the production of bioproducts and biofuels,[36] samples were also analyzed for their
acid-insoluble lignin and acid-soluble lignin.
The chemical composition of CC showed that total lignin was 17.8%, while the uronic
acid and ash contents were 2.2% and 1.2%, respectively. In relation to glucose content
(47.1%), the experimental result was higher than reported by other authors,[19,37,38] a fact
which can be explained by the method used by each author for quantification of carbohy-
drates. Values of xylose (28.0%), arabinose (5.4%), mannose (0.2%), and acetyl groups
(2.9%) for samples determined in this study are closely comparable to those reported by
them[19,37] for similar samples.
The structural carbohydrates (glucose and xylose), which are the major substrates for
furan production, accounted for approximately 74.6% of the SCB (Table 1). These values
are in the range found by other researchers for this kind of material.[39–41] It is known that
pentoses and hexoses, respectively, are the precursors for furfural and HMF formed during
the conversion of lignocellulosic biomass.[7] Determination of the initial quantity of the
main constituents available in biomass allowed the calculation of the yields and theoretical
conversion rates of furfural from raw material by the calculation of furfural-production
efficiency.
The chemical composition of the Eucalyptus urophylla x Eucalyptus grandis hybrid
was similar to the one reported for other eucalypti reported by other authors,[25,39] except in
relation to glucose content (53.1%), as shown in Table 1. However, glucose values similar
to the ones observed in this work have been previously reported.[42]

Auto-Hydrolysis
Auto-hydrolysis (AH) has the advantage of removing significant amounts of xylans. In
comparison to acid hydrolysis, autohydrolysis generates lower quantities of by-product,
minimizes equipment corrosion, and decreases operational costs. The eucalypt xylan con-
tent decreased 48.9%, from 12.3% in the original material to 7.1% in the AH chips. The
 Furfural Production from Lignocellulosics 183

Table 1
Chemical composition results of CC, SCB, EUCA and reported by other authors

Corncob (CC)

Van Dongen Lili Garrote

Component, % Results et al., 2011 et al., 2011 et al., 2007
Glucose 47.1 34 34.6 34.3a
Xylose 28.0 28 27.0 31.1a
Arabinose 5.4 2.4 3.6 3.01a
Galactose 2.2 0.8 — —
Mannose 0.2 0.1 — —
Acetyl groups 2.9 — 0.3 3.07
Uronic acids 2.2 1.8 — 3.45
Ligninc 17.8 18.3 9.4b 18.8
Ash 1.2 — 2.5 1.3
Component, % Sugarcane bagasse (SCB)

Hamzeh Alves Canilha

Results et al., 2013 et al., 2010 et al., 2007
Glucose 46.4 40.5d 43.1 48.2
Xylose 28.2 14.5 23.8 24.8
Arabinose 2.6 2.2 1.5 1.66
Galactose 1.0 2.6 0.4 —
Mannose 1.0 — 0.3 —
Acetyl groups 3.0 — 3.0e 2.83
Uronic acids 1.5 — 1.2 —
Ligninc 21.4 28.2 23.2 24.1
Ash 2.3 4.8 2.5 —
Component, % Eucalypt (EUCA)

Garcı́a-Domı́nguez Batalha Alves

Results et al., 2013 et al., 2012 et al., 2010
Glucose 53.1 42.8 47.9a 46.5
Xylose 12.3 17.1 11.2a 12.1
Arabinose 0.3 0.4 0.1a 0.5
Galactose 2.1 — 0.9a 1.2
Mannose 1.4 — 0.9a 1.0
Acetyl groups 2.8 3.5 2.0 2.8e
Uronic acids 3.1 — 5.9 2.2
Ligninc 30.1 21.2 26.6 29.2
Ash 0.2 0.2 0.3 0.3
a
All sugars expressed as anhydro-units in polymers;
b
Lignin values were measured as acid insoluble lignin contents;
c
Lignin values were measured as acid insoluble lignin contents and acid soluble;
d
Glucose values measured were α-cellulose contents;
e
Acetyl groups values were measured by NMR.
184 B. M. Barbosa et al.

Table 2
Eucalypt chip auto-hydrolysis (AH) result

AH Yield, Xylans, Xylans Spent Hydrolyzate

Result % % on wt. Removal, % liquor pH solids, %
EUCA 88.6 7.1 48.9 2.5 2.2

yield loss in the auto-hydrolysis treatment was 11.4% (Table 2). According to the literature,
the liquor derived from the AH treatment contains a mixture of sugar oligomers, mostly
xylo-oligosaccharides (XOS), monosaccharides (xylose and arabinose), acetic acid (from
acetyl groups), and sugar decomposition products. Moreover, it was found that the forma-
tion rate of these compounds depends on the autohydrolysis conditions (e.g., temperature
and reaction time), in agreement with previous reports.[43,44]

Furfural Production
Sulfuric, hydrochloric, and phosphoric acids are widely used as catalysts in industrial
furfural production. The results presented in Figure 1 indicate the yield of the furfural
production with different acids for CC, SCB, and CC. The furfural yield increases with
increasing acid concentration regardless of raw material and acid type. The highest furfural
yields were achieved with HCl as a catalyst. Based on the biomass dry weight, yields of
30.2, 25.8, and 13.9% were obtained for CC, SCB, and EUCA, respectively. These yields
were achieved with 5.2 mol.L−1 HCl for CC and SCB and 3.9 mol.L−1 HCl for EUCA.
When H2 SO4 was used as the catalyst, the maximum yields attained were 27.3, 21.0, and
11.4% for CC, SCB, and EUCA, respectively, under the same acid molar concentrations
previously reported for HCl. In the case of H3 PO4 , the highest furfural yields were 26.0,
18.2, 7.6 for CC, SCB, and EUCA, respectively, under the same acid molar concentrations
previously reported for HCl.
Yemis and Mazza[7] reported an increase in furfural yield from xylose from 9.3 to
36.1 g/100 g when the HCl concentration increased from 0.01 to 0.1 mol.L−1. Recently,
Rong et al.[45] reported that the furfural yield was higher in high concentration of H2 SO4
systems compared to that in low concentrations and the highest furfural conversion effi-
ciency (75%) was achieved with 10% (w/w) H2 SO4 , but the conversion efficiency decreased
to 51% when the concentration of H2 SO4 was raised to 12.5% (w/w).

Figure 1. Furfural yield on the basis of CC, SCB, and EUCA dry weight for various mineral acid
catalysts concentrations.
 Furfural Production from Lignocellulosics 185

Figure 2. Furfural conversion efficiency on the basis of CC, SCB, and EUCA pentose contents for
various mineral acid catalysts concentrations.

The fact that the highest furfural yield obtained in this study was with HCl can be
explained by the greater availability of H+ ions in HCl solutions compared to phosphoric
and sulfuric acid solutions at a given molar concentration. Similar results have been reported
by Yemis and Mazza[7] comparing the effect of four strong mineral acids (hydrochloric,
sulfuric, nitric, and phosphoric acids) and two organic acids—acetic (CH3 COOH) and
formic acids (HCOOH)—on furfural yield. The furfural yields obtained from xylose in
the presence of HCl, H2 SO4 , HNO3 (nitric acid), H3 PO4 , CH3 COOH, and HCOOH were
37.5%, 31.9%, 3.5%, 27.6%, 15.8%, and 23.8% at pH 1.12, respectively.
The gradual decrease in furfural concentration beyond the maximum value achieved
indicates that, in addition to certain achieved furfural concentrations, the rate of furfural loss
to decomposition products becomes higher than the rate of furfural production. Moreover,
the nature of the solvent chosen and the biomass type were the major factors influencing
conversion of pentose to furfural. Thus, the furfural conversion efficiency is an important
parameter for each raw material used in this study in order to know the rate of pentose
conversion into furfural. The results for furfural conversion efficiency are shown in Figure 2.
According to Figure 2, the furfural conversion efficiency was higher for EUCA in
relation to CC and SCB when HCl and H2 SO4 were used as catalysts. The highest furfural
conversion efficiency was found when HCl was used as a catalyst, reaching 90.5% for
CC (5.2 mol.L−1) 83.6% for SCB (5.2 mol.L−1), and 110.6% for EUCA (3.9 mol.L−1).
The highest furfural conversion efficiencies for H2 SO4 were 81.6 (5.2 mol.L−1), 68.1
(5.2 mol.L−1), and 90.6 (3.0 mol.L−1) for CC, SCB, and EUCA, respectively. Finally, the
highest conversion efficiencies for H3 PO4 were 77.8 (5.2 mol.L−1), 59.2 (5.2 mol.L−1),
and 60.6% (3.9 mol.L−1) for CC, SCB, and EUCA, respectively. These results indicate
that the initial pentose concentration is a very important parameter for furfural conversion
efficiency. Yang et al.[46] reported that furfural conversion efficiency decreased from 70 to
60% when the xylose concentration increased from 40 to 120 g/L. It could be concluded
that furfural conversion efficiency decreases with increasing pentose concentration.
This fact may be explained considering that furfural formation is followed by side re-
actions, such as resinification of the furfural formed, condensation of furfural with pentose-
to-furfural intermediates, and fragmentation of pentose, all of which decrease the furfural
conversion efficiency. According to Burket,[47] the initial pentose concentration greatly af-
fects the maximum obtainable furfural conversion efficiency in an aqueous solution. The
dilute pentose concentrations help in reducing the undesirable side reactions between fur-
fural and its precursors, such as the resinification of the furfural produced and condensation
of the furfural with pentose-to-furfural intermediates.
186 B. M. Barbosa et al.

Figure 3. Furfural productivity calculate on the basis of CC, SCB, and EUCA furfural yields and
furfural conversion efficiencies for various mineral acid catalysts concentrations.

However, in commercial processes, low initial pentose concentrations are undesirable,

since they require larger reactors and more heat to produce the furfural. So, for economical
reasons, initial pentose concentration should not be too low. The optimal initial pentose
concentration is also decided by furfural yield, operating costs, and the pentose concentra-
tion in the hydrolysate. Moreover, it is important to calculate the furfural productivity in
order to determine the adequate raw material with high yield and high furfural conversion
efficiency from pentoses. The results of furfural productivity are shown in Figure 3.
In spite of EUCA having the highest furfural conversion efficiency using HCl and
H2 SO4 due to the low initial concentration of pentoses, it showed lower furfural produc-
tivities than CC and SCB; this occurred because EUCA showed very low furfural yield.
The highest furfural productivity was found when HCl was used as a catalyst, resulting
in productivities of 27.4% for CC using 5.2 mol.L−1, 21.5% for SCB using 5.2 mol.L−1,
and 15.4% for EUCA using 3.9 mol.L−1. The highest furfural productivity for H2 SO4 was
22.3 (5.2 mol.L−1), 14.3 (5.2 mol.L−1), and 10.4% (3.0 mol.L−1) for CC, SCB, and EUCA,
respectively. For H3 PO4 , the highest furfural productivities were 20.2 (5.2 mol.L−1), 10.8
(5.2 mol.L−1), and 4.6% (3.9 mol.L−1) for CC, SCB and EUCA, respectively.
A low initial concentration of pentoses showed high furfural conversion efficiency;
however, the overall cost per gallon of furfural produced is a much better criterion for a
process design than the achievement of high furfural yields.
The mass balance of total furfural production is shown in Figure 4. Among the raw
materials, CC was one with high furfural yield in relation to SCB and EUCA, but EUCA
had higher furfural conversion efficiency than the other raw materials used in this study.

Figure 4. Mass balance of the furfural production from CC, SCB, and EUCA.
 Furfural Production from Lignocellulosics 187

Table 3
Correlation between yield, efficiency, and productivity when using HCl and H2SO4 for
EUCA liquor AH

Acids / Concentration % Furfural % Furfural % Furfural

(mol.L−1) yield efficiency productivity
HCl 3.9 8.8 71.5 6.3
H2 SO4 0.9 8.8 70.8 6.2

Overall, the best raw material for furfural production was corncobs, and HCl was the best
catalyst.

Furfural Production from EUCA Auto-Hydrolysis Liquor

Results of yield, conversion efficiency and furfural productivity from EUCA liquor AH are
shown in Table 3. The highest furfural concentration obtained from EUCA auto-hydrolysis
liquor by hydrodistillation using 3.9 mol.L−1 of HCl as a catalyst was 9.3 g/L. This furfural
concentration corresponds to a furfural yield of 8.8%, conversion efficiency of 71.5% with
respect to total pentoses present in the EUCA liquor AH, and 6.3% furfural productivity. A
9.2 g/L of furfural concentration was obtained using 0.9 mol.L−1 H2 SO4 as a catalyst for
three hours at 170◦ C; this concentration corresponds to a furfural yield of 8.8%, conversion
efficiency of 70.8% with respect to pentoses in the EUCA liquor AH, and 6.2% furfural
productivity.
From the xylans obtained from EUCA autohydrolysis, a high concentration of furfural
can be produced. It is a way of consuming renewable agro-industrial residues of dissolving
pulp production. From 1 ton of dissolving pulp, it is possible to produce 100 kg of furfural,
consuming 1537 kg of HCl. The process must be improved due to its poor economics.
Furfural production from CC, SCB, EUCA, and EUCA liquor AH (liquors rich in
xylans) can be achieved using a high-concentration mineral acid catalyst. Thus, it is relevant
to considerer the amount of acid spent in the processes (g produced furfural/g spent acid).
A summary of optimum conditions for furfural production on the basis of the results of this
study are shown in Table 4.

Table 4
Optimum conditions of furfural production

Material Acid Concentration Yield Efficiency Productivity g furfural/

(mol.L−1) (%) (%) (%) g acid
CC HCl 5.2 30.2 90.5 27,4 0.40
SCB HCl 5.2 25.8 83.6 21,5 0.34
EUCA HCl 3.9 13.9 110.6 15,4 0.24
EUCA HCl 3.9 8.8 71.5 6.3 0.07
liquor
AH
188 B. M. Barbosa et al.

Conclusions
The maximum yield, efficiency, and furfural productivity were found when HCl was used
as a catalyst in the hydrodistillation process, in relation to H2 SO4 and H3 PO4 .
The most attractive raw material was corncobs, which resulted in the highest furfural
production (e.g., 302 kg furfural/ dry ton of biomass), with sugarcane bagasse coming in
second.
Furfural yields increased with increasing raw material pentosan content, but furfural
conversion efficiency from pentose increased with decreasing pentose concentration.
Furfural productivity increased with increasing furfural yield and furfural conversion
efficiency.
The eucalyptus liquor from auto-hydrolysis, kraft-dissolving pulp production proved
to be technically feasible for the furfural production; the process must be improved to
provide better results.

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