Sie sind auf Seite 1von 6

Energy Conversion and Management 173 (2018) 539–544

Contents lists available at ScienceDirect

Energy Conversion and Management


journal homepage: www.elsevier.com/locate/enconman

Preparation of furfural from Eucalyptus by the MIBK/H2O pretreatment with T


biphasic system and enzymatic hydrolysis of the resulting solid fraction

Shaolong Suna, Xuefei Caob, Huiling Lic, Xue Chenb, Jianing Tangb, Shaoni Sunb,
a
College of Natural Resources and Environment, South China Agricultural University, Guangzhou, Guangdong 510642, China
b
Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University, Beijing 100083, China
c
College of Forestry and Landscape Architecture, South China Agricultural University, Guangzhou, Guangdong 510642, China

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

Keywords: Forest wood biomass can be a sustainable and cost-effective feedstock for the biorefinery industries, but the rigid
Biphasic system and compact structure of plant cell is a major barrier for production of clean energy and biochemical. In this
Furfural case, the MIBK/H2O pretreatment with biphasic system was applied to treat Eucalyptus and then systematically
MIBK/H2O evaluated pretreatment conditions (e.g., MIBK/H2O ratio, reaction temperature and time, NaCl concentration,
Enzymatic hydrolysis
and HCl dosage) on the effect of furfural yield. The resulting solid fraction obtained from the optimum pre-
Eucalyptus
treatment condition for furfural yield was to produce fermentable glucose by enzymatic hydrolysis. Study on
enzymatic hydrolysis of the raw material and resulting solid fraction obtained by single aqueous system was also
contrastively investigated. The furfural yield was 65.9% and the recovery of residue was 46.9% under an optimal
reaction condition (VMIBK:VH2O = 5:5, 150 °C, 60 min, 0.3 M HCl). Meanwhile, the yield of glucose of cellulose
was improved after the pretreatments with different systems and a maximum value was up to 60.2% by the
MIBK/H2O pretreatment. The effective fermentable glucose production was mainly affected by the significant
removal of hemicelluloses, change of CrI, and destruction of surface morphology of Eucalyptus. The MIBK/H2O
pretreatment can be considered as a potential approach for efficient conversion of Eucalyptus to clean energy and
biochemicals.

1. Introduction white rot fungus, biphasic system, and some integrated techniques
[5–10]. Generally, preparation of furfural from hemicelluloses of lig-
Furfural is a green and renewable bio-based chemical derived from nocelluloses must pass a two-step reactions under acidic conditions:
hemicelluloses of lignocelluloses that can be further converted into first, depolymerization of hemicelluloses (mainly D-xylan) to mono-
biofuels and biochemicals, which has been identified as one of the 30 saccharides; secondly, D-xylose further convert to furfural by dehy-
high value platform compounds by US Department of Energy [1,2]. As dration [11]. For enzymatic hydrolysis of cellulose in lignocelluloses,
one of the most important paper sources, Eucalyptus has a great po- many factors affect its hydrolysis efficiency, such as surface mor-
tential as a raw material for production of clean energy and biochem- phology, crystallinity and polymerization degree of cellulose as well as
ical, such as bioethanol, furfural, and other industrial products, owing content of lignin and hemicelluloses [3].
to its high content of carbohydrates (cellulose and hemicelluloses). For the past few years, the furfural yield in a single aqueous system
Unfortunately, Eucalyptus is recalcitrance to deconstruction of carbo- is usually constricted due to the limitation of solubility of furfural [12].
hydrates due to the compact and rigid cell walls structure [3]. Thus, In addition, among all the pretreatment techniques, the pretreatment
pretreatment is generally required for improving the preparation of with organic/aqueous biphasic system is a potential approach for en-
furfural and fermentable glucose by enzymatic hydrolysis from Eu- hancing the furfural yield and/or enzymatic hydrolysis of lig-
calyptus [4]. nocelluloses, since its high efficiency and mild reaction conditions [13].
Hitherto, various physical, chemical, biological, and combined More importantly, furfural component produced during the biphasic
techniques have been proposed to reduce recalcitrance and enhance system is quick transferred from the aqueous phase to the organic
biochemicals yield and/or enzymatic hydrolysis in different lig- phase, which ceases interfering side reactions [14]. Therefore, organic/
nocelluloses, including the steam explosion, dilute acid, ionic liquid, aqueous biphasic system pretreatment has been developed and applied


Corresponding author.
E-mail address: sunshaoni@126.com (S. Sun).

https://doi.org/10.1016/j.enconman.2018.08.006
Received 2 July 2018; Received in revised form 2 August 2018; Accepted 2 August 2018
Available online 07 August 2018
0196-8904/ © 2018 Elsevier Ltd. All rights reserved.
S. Sun et al. Energy Conversion and Management 173 (2018) 539–544

broadly in improving the furfural yield and subsequent fermentable 2.3. Enzymatic hydrolysis
glucose yield by enzymatic hydrolysis. Generally, γ-valerolactone, 2-
methyltetrahydrofuran (MTHF), alkylphenols, and methyl isobutyl ke- The resulting solid fraction obtained from the optimum pretreat-
tone (MIBK) as an organic phase in organic/aqueous biphasic system ment conditions for furfural yield was performed to produce fermen-
were selected [15–18]. Among these solvents, MIBK deserves particular table glucose by enzymatic hydrolysis. Meanwhile, enzymatic hydro-
attention due to its high immiscibility with water, easy recycle and lysis experiments of RM and the resulting solid fraction by single
stability under acidic conditions [18]. Hence, a systematic evaluation aqueous system with HCl were also contrastively studied. The hydro-
on preparation of furfural from lignocelluloses by the MIBK/H2O pre- lysis experiments were implemented at 50 °C for 72 h. In addition, 2%
treatment with biphasic system and enzymatic hydrolysis of the re- of substrate (w/v) using 50 mM sodium acetate buffer (pH 4.8, 10 mL)
sulting cellulose fraction was very necessary. was applied in this study by a shaking incubator. The rotational speed
Our preliminary experiment showed that the pretreatment with was controlled at 150 rpm and the cellulases (15 FPU/g substrate) were
single aqueous system by adding HCl as catalyst was a relatively effi- used. The hydrolyzates were detected using a high-performance liquid
cient way for preparation of furfural from Eucalyptus as compared to the chromatography (HPLC) system (Agilent 1200 series, Agilent
pretreatment by adding some metal chlorides (e.g., SnCl2, AlCl3, FeCl3, Technologies, USA). More details of the test conditions for the hydro-
ZnCl2, MgCl2, and SnCl4). Therefore, in the present study, the MIBK/ lyzates were described in a recent publication [20]. All the hydrolysis
H2O pretreatment with HCl was applied to treat Eucalyptus and then experiments were performed in triplicate, and average values were
systematically evaluate pretreatment conditions (e.g., MIBK/H2O ratio, given.
reaction temperature and time, NaCl concentration, and HCl dosage) on
the effect of furfural yield. In addition, the resulting solid fraction ob- 2.4. Analysis methods
tained from the optimum pretreatment conditions for furfural yield was
performed to produce fermentable glucose by enzymatic hydrolysis. The yields of furfural and 5-hydroxymethylfurfural (HMF) in the
Meanwhile, enzymatic hydrolysis experiments of the raw material and organic phase were detected by HPLC as described previously [10]. The
solid fraction obtained by single aqueous system with HCl were also measurements were conducted in triplicate, and the average values
contrastively studied. Chemical constituents, Fourier transform infrared were given. The chemical constituents (%, w/w) of the resulting solid
(FT-IR), X-ray diffraction (XRD), and scanning electron microscopy fraction obtained by different systems were also analyzed by NREL
(SEM) of the three substrates obtained were measured. In short, all the procedure [19]. FT-IR was measured by a FT-IR microscope (Thermo
data will provide some useful guide information in the utilization of Nicolet Corporation, Madison, WI, USA) equipped. XRD in reflection
Eucalyptus for improving the preparation of furfural and enzymatic mode was recorded using a D/MAX 2500PC diffractometer (Rigaku
hydrolysis of the resulting solid fraction in the prospective biorefinery Corporation, Japan) with Ni-filtered Cu Kα radiation operated at 40 kV
industries. and 20 mA. SEM images were carried out using a JSM 6700F NT
(Tokyo, Japan) instrument at 5 kV acceleration voltages.

2. Materials and methods 3. Results and discussion

2.1. Materials 3.1. Furfural yields by the MIBK/H2O pretreatment with biphasic system

Eucalyptus was obtained from Shaanxi province, China. They were To obtain a higher furfural yield, the MIBK/H2O pretreatment with
first dried and then ground in a micro plant grinding machine to obtain biphasic system was developed to reduce recalcitrance of Eucalyptus
powder (20–40 mesh). The powder was extracted with 2:1 vol ratio of and cease interfering side reactions. Fig. 1 shows the effects of the
toluene-ethanol to remove extractives and then dried to serve as raw pretreatment at 160 °C for 60 min with 0.4 M HCl under different vo-
material (RM). The RM was mainly composed of cellulose (43.3%), lume ratios of MIBK/H2O (3:7, 4:6, 5:5, 6:4, 7:3, and 8:2) on the fur-
hemicelluloses (15.6%), and lignin (29.0%) based on the standard fural yields from Eucalyptus. As can be seen, when the volume ratios of
National Renewable Energy Laboratory’s (NREL) method [19]. All MIBK to H2O were 5:5 and 6:4, the furfural yields were reached to
chemicals used were purchased from Sigma–Aldrich and Megazyme. 64.2% and 65.6%, respectively, which were higher than that of the
Liquid-state cellulases (Cellic@ CTec2, 100 FPU/ml) were purchased
from Novozymes (Beijing, China).

2.2. Preparation of furfural by the MIBK/H2O pretreatment with biphasic


system

The biphasic system pretreatments at 160 °C for 60 min with 0.4 M


HCl under different volume ratios of MIBK/H2O (3:7, 4:6, 5:5, 6:4, 7:3,
and 8:2) were applied to produce furfural from Eucalyptus. To obtain
the optimum pretreatment conditions for the production of furfural,
different pretreatment reaction temperatures (130, 140, 150, 160, 170,
180, 190, and 200 °C), times (20, 40, 60, 80, 100, 120, and 140 min),
NaCl concentrations (0, 5, 10, 15, 20, 25, 30, and 36%), and HCl do-
sages (0.0, 0.1, 0.2, 0.3, 0.4, 0.5, and 0.6 M) were further used to treat
Eucalyptus. Typically, the MIBK/H2O pretreatment with biphasic system
was performed in a batch reactor (20 mL capacity, 1:20 g/mL). At the
end of the reaction, the mixtures were cooled down to 25 °C and then
filtrated using a Buchner funnel. The organic phase was filtered with
syringe filter (0.22 μm) for further analysis. The resulting solid fraction Fig. 1. Furfural and HMF yields from Eucalyptus during the MIBK/H2O pre-
was dried at 60 °C for 16 h. treatment at 160 °C for 60 min with 0.4 M HCl under different volume ratio of
MIBK/H2O.

540
S. Sun et al. Energy Conversion and Management 173 (2018) 539–544

Fig. 2. Furfural and HMF yields by the MIBK/H2O pretreatment with biphasic system under different conditions: (a) reaction temperatures; (b) reaction times; (c)
NaCl concentrations; (d) HCl dosages.

MIBK/H2O volume ratios being 3:7, 4:6, 7:3, and 8:2. In addition, to Eucalyptus. Fig. 2b exhibits the furfural yields at 150 °C for
evaluate the degree of cellulose degradation during the MIBK/H2O VMIBK:VH2O = 5:5 with 0.4 M HCl under different pretreatment times
pretreatment with biphasic system, the HMF yields were also measured (10–150 min). It was found that the pretreatment time affected the
by HPLC (Fig. 1). The results indicated that the biphasic pretreatment furfural yield, releasing furfural with the highest yield (63.6%) ob-
under different volume ratios of MIBK/H2O contained relatively low tained at 150 °C for 60 min.
HMF yields (2.2–4.7%), suggesting that the MIBK/H2O pretreatment Adding salts (e.g., NaCl) could significantly influence production of
had a better degradation effect on hemicelluloses and little effect on furfural from xylose in both single aqueous system and organic solvent/
cellulose. Taking into consideration the price of MIBK, the volume ratio aqueous biphasic system under the acid conditions [17,21,22]. It was
of VMIBK:VH2O = 5:5 was selected for preparation of furfural from Eu- reported that Cl− anion favors the formation of 1,2-enediol and reacts
calyptus during the MIBK/H2O pretreatment. to form furfural in presence of an acid [21]. In addition, the Cl− anion
Fig. 2 shows the furfural and HMF yields by the MIBK/H2O pre- may promote the isomerization of glucose via a 1,2-hydride shift path
treatment with biphasic system under different conditions, such as re- and accelerate the dehydration of fructose, thus driving the selective
action temperature and time, NaCl concentration, and HCl dosage. As formation of HMF [23]. Thus, under the conditions above
expected, the furfural yields were significantly affected by the pre- (VMIBK:VH2O = 5:5, 150 °C, 60 min, 0.4 M HCl), different NaCl con-
treatment conditions, while the HMF yields were almost unaffected. As centrations (0, 5, 10, 15, 20, 25, 30, and 36%) were added to the bi-
shown in Fig. 2a, after the end of the reactions at VMIBK:VH2O = 5:5 for phasic system for assessing its effect on the furfural and HMF yields
60 min with 0.4 M HCl, the furfural yields presented notable increase (Fig. 2c). In this study, as compared to the furfural yield without adding
from 36.6 to 64.2% with the pretreatment temperatures increased from NaCl (63.6%), the furfural yield was slightly increased to 64.4% with
130 to 160 °C. The increasing phenomenon was attributed to the en- 5% NaCl concentration. However, the furfural yields began to decrease
hancement of depolymerization of hemicelluloses and dehydration of when the NaCl concentration (10–36%) was relatively high, which was
D-xylose with the pretreatment temperatures increased. However, as probably related to the complex structure of lignocelluloses. Therefore,
the pretreatment temperatures further increased to 200 °C, the yields of it is not necessary to add NaCl for preparation of furfural during the
furfural gradually decreased from 64.2 to 18.8%, which was mainly as a biphasic system. Moreover, the effect of the HCl dosage (0.0, 0.1, 0.2,
result of the degradation of furfural during the pretreatment, especially 0.3, 0.4, 0.5, and 0.6 M) on furfural production was analyzed and the
at higher temperatures. This was also in accordance with the previous results are shown in Fig. 2d. The fact indicated that the highest furfural
results based on microwave-assisted dehydration of xylose into furfural yield (65.9%) was obtained with HCl dosage of 0.3 M. In short, the
in water-cyclopentyl methyl ether as a biphasic system [11]. In other optimal reaction conditions for preparation of furfural from Eucalyptus
words, the furfural was unstable and degraded rapidly at high tem- by MIBK/H2O pretreatment with biphasic system was obtained at
peratures. In combination with the data of Fig. 1, it was found that the 150 °C for 60 min with 0.3 M HCl when the volume ratio of MIBK/H2O
furfural yields were only increased by 0.6% when the temperatures was 5:5.
were raised from 150 to 160 °C under the other same conditions. Based
on the economic feasibility of industrial production, the higher the 3.2. Solid yield and compositional analysis of the resulting solid fraction
temperature for preparation of furfural, the higher the production cost.
Thus, in this work, the pretreatment temperature of 150 °C was selected During the MIBK/H2O pretreatment with biphasic system, hemi-
as an optimal reaction temperature for preparation of furfural from celluloses were mainly converted into furfural through

541
S. Sun et al. Energy Conversion and Management 173 (2018) 539–544

Table 1
Solid yields and chemical compositions (%, w/w) of Eucalyptus before and after
the pretreatments with different systems.
Solid yield (%) Chemical composition (w/w, %)

Cellulose Hemicellulose Lignin

RM 100.0 43.3 15.6 29.0


R(H2O-HCl) 54.6 52.4 Tra 32.7
R(MIBK/H2O- 46.9 59.0 NDb 30.0
HCl)

a
Tr, trace, i.e. < 0.2%.
b
ND, not determined.

depolymerization and dehydration reactions. As a biorefinery process,


the resulting solid fraction (cellulose-rich) obtained from the biphasic
system can be converted into fermentable glucose by enzymatic hy-
drolysis, which contributes to the high-valued utilization for Eucalyptus.
Our preliminary experiment showed that the pretreatment with single
MIBK system had little effect on the physicochemical properties of Fig. 3. FT-IR spectra of Eucalyptus before and after the pretreatments with
Eucalyptus. Therefore, in the present study, the expansion experiment different systems.
was performed by the MIBK/H2O pretreatment with biphasic system
under the optimum reaction conditions (VMIBK:VH2O = 5:5, 150 °C, 1427 cm−1 could be clearly observed in all the spectra, indicating the
60 min, 0.3 M HCl) for the furfural production. By comparison, the pretreatments with both single aqueous system and organic/aqueous
pretreatment with single aqueous system under the same reaction biphasic system did not significantly remove the lignin from RM [26].
conditions (150 °C, 60 min, 0.3 M HCl) was also applied to treat Crystallinity of cellulose (CrI) is regarded as a main factor influ-
Eucalyptus. At the end of the two reactions, the resulting solid fraction enced on the yield of glucose of cellulose in lignocelluloses [27]. The
obtained from the corresponding pretreatment systems were named as CrIs of Eucalyptus before and after the pretreatments with different
R(MIBK/H2O-HCl) and R(H2O-HCl), respectively. systems were determined by XRD patterns (Fig. 4). The crystal structure
Table 1 shows the solid yields and chemical compositions of Eu- of cellulose in Eucalyptus before and after the pretreatments did not
calyptus before and after the pretreatments with different systems. As change, but there was a significant variation in the CrIs for RM, R(H2O-
compared to the solid yield of 54.6% after the pretreatment with single HCl) and R(MIBK/H2O-HCl). As compared to the CrI of RM (55.1%), the
aqueous system, the solid yield after the pretreatment with biphasic CrIs of R(H2O-HCl) and R(MIBK/H2O-HCl) increased to 65.5% and
system was reduced to 46.9%. This was mainly due to the thorough 67.9%, respectively. The increasing trend was attributed to the removal
degradation of hemicelluloses in Eucalyptus during the pretreatment of amorphous hemicelluloses during the pretreatments, as also revealed
with biphasic system as compared to the pretreatment with aqueous by the decreasing intensities of the FT-IR bands at 1716 and
system. As shown in Table 1, trace of hemicellulosic polysaccharide was 1234 cm−1.
detected in R(H2O-HCl), suggesting that the hemicelluloses was sig-
nificantly destroyed and degraded during the pretreatment with aqu- 3.4. Surface morphology of the resulting solid fraction
eous system under the conditions given, resulting in relatively higher
contents of cellulose and lignin in R(H2O-HCl). Similarly, hemi- To observe the surface morphology changes caused by the pre-
celluloses were also completely destroyed and degraded during the treatments with different systems, SEM images of RM, R(H2O-HCl), and
pretreatment with biphasic system. Specially, as compared to R(H2O- R(MIBK/H2O-HCl) were observed at magnifications of 5000 (Fig. 5).
HCl), R(MIBK/H2O-HCl) contained a relatively higher content of cel- The surface of RM exhibited a smooth and dense morphology, resulting
lulose (59.0%), but a lower lignin content (30.0%), indicating that the in that cellulase was difficult to access cellulose [28]. By contrast, the
pretreatment with biphasic system was more effective to obtain the surfaces of R(H2O-HCl) and R(MIBK/H2O-HCl) were broken and ap-
digestible cellulose-rich residue for the production of fermentable glu- peared small particle-sized debris and some cracks. The surface mor-
cose. phology of R(MIBK/H2O-HCl) became looser than R(H2O-HCl). It was
interesting to note that the single aqueous system and organic/aqueous
3.3. FT-IR and XRD of the resulting solid fraction biphasic system under the same pretreatment conditions showed dif-
ferent effects on the surface morphology of Eucalyptus. In short, the
To compare the structural changes of Eucalyptus before and after the pretreatments led to large amounts of adsorption sites of enzymes on
pretreatments with different systems, the FT-IR spectra of RM, R(H2O- the fiber surface, thereby enhancing the enzymatic hydrolysis efficiency
HCl), and R(MIBK/H2O-HCl) are presented in Fig. 3. For the RM, two of the resulting solid fraction, which was further confirmed by the re-
obvious bands at 1716 and 1234 cm−1 were observed, which are ori- sults of the subsequent enzymatic hydrolysis experiment [29].
ginated from the C]O and CeO stretching vibrations of the acetyl ester
of hemicelluloses, respectively [24]. However, the two bands dis- 3.5. Enzymatic hydrolysis of the resulting solid fraction
appeared almost completely in the FT-IR spectra of the R(H2O-HCl) and
R(MIBK/H2O-HCl), which was due to the significantly removal of During the pretreatments with different systems, hemicelluloses
hemicelluloses during the pretreatments, especially during the MIBK/ were converted into furfural through depolymerization and dehydra-
H2O pretreatment with biphasic system. In addition, the intensity of a tion reactions, along with obtaining cellulose-rich residues. Combining
sharp band at 899 cm−1, which is attributed to the β-glucosidic linkages the results of characterization of the physicochemical properties of the
in carbohydrate (hemicelluloses and cellulose), was also weakening cellulose-rich residues above, it is inferred that the cellulose-rich re-
after the pretreatments [25]. This further indicated that the carbohy- sidue can be used as an ideal sugar feedstock for enzymatic hydrolysis.
drates (mainly in hemicelluloses) were degraded during the pretreat- To verify this hypothesis, the glucose production of R(H2O-HCl) and R
ment process. Moreover, four intense bands at 1605, 1508, 1454, and (MIBK/H2O-HCl) by enzymatic hydrolysis was investigated and

542
S. Sun et al. Energy Conversion and Management 173 (2018) 539–544

Fig. 4. XRD spectra of Eucalyptus before and after the pretreatments with different systems.

compared with RM. As shown in Fig. 6, the yield of glucose was just
19.3% for RM after 72 h enzymatic hydrolysis. After the pretreatment
with single aqueous system, this value reached to 45.9%. By contrast,
the yield of glucose of R(MIBK/H2O-HCl) reached a maximum of
60.2%, which was related to the removal of hemicelluloses and de-
struction of surface morphology of Eucalyptus during the MIBK/H2O
pretreatment with biphasic system. In short, the yield of glucose of
cellulose was improved after the pretreatments with different systems
and a maximum value was obtained by pretreating with MIBK/H2O. In
addition, recovery of the residual lignins after enzymatic hydrolysis
should deserve some attention in future research due to its potential
application value as biomaterials or biochemicals for industries, which
can be used for the production of lignin–phenol–formaldehyde resins,
lignin–polyurethane films, antioxidants, and phenols or liquid fuels
[30–34]. The structural properties and potential application of the re-
sidual lignins will be investigated thoroughly in another article.

3.6. The correlation between physiochemical properties and enzymatic


Fig. 6. The yield of glucose of cellulose in Eucalyptus before and after the
hydrolysis pretreatments with different systems.

To explicate the effect of the physiochemical changes of Eucalyptus


lignin in Eucalyptus was very limited during the pretreatments, the yield
after the pretreatments with different systems on the enzymatic hy-
of glucose of R(H2O-HCl) and R(MIBK/H2O-HCl) did not increase sig-
drolysis of cellulose, the correlation between physiochemical properties
nificantly than reported in some integrated pretreatments, especially
and enzymatic hydrolysis should be discussed. As can be seen from
the integrated treatments with alkali [40–42].
Table 1 and Fig. 3, the optimal yield of glucose was observed in R
Based on the CrI and the data of enzymatic hydrolysis of the sub-
(MIBK/H2O-HCl). The effective conversion was mostly affected by the
strates, it was found that a positive correlation between the CrI and
removal of hemicelluloses and the similar result was obtained in a
enzymatic hydrolysis. However, the CrI was lowered during some
previous publication [35]. In addition, lignin in lignocelluloses also
specific conditions, such as phosphoric acid and ionic liquid pretreat-
impedes enzymes accessibility to cellulose during conversion process,
ments, which resulted in the substrates obtained were more readily
leading to a relatively low yield of glucose of cellulose in unpretreated
hydrolysis by cellulase [43,44]. Moreover, the destruction of morpho-
material [36,37]. Therefore, an effective process is often required to
logic structure by the pretreatments with different systems exhibited
remove or delocalize lignin, which can improve the conversion of
large amounts of adsorption sites of enzymes, leading to enhancing the
biomass to glucose [38,39]. However, in this study, since the removal of

Fig. 5. SEM images of Eucalyptus before and after the pretreatments with different systems.

543
S. Sun et al. Energy Conversion and Management 173 (2018) 539–544

enzymatic hydrolysis efficiency. In short, yield of glucose of the sub- Bioresour Technol 2015;183:188–94.
strate was influenced by many factors, such as removal of hemi- [17] Gürbüz EI, Wettstein SG, Dumesic JA. Conversion of hemicellulose to furfural and
levulinic acid using biphasic reactors with alkylphenol solvents. ChemSusChem
celluloses, change of CrI, and destruction of surface morphology. 2012;5:383–7.
[18] Weingarten R, Cho J, Conner JWC, Huber GW. Kinetics of furfural production by
4. Conclusions dehydration of xylose in a biphasic reactor with microwave heating. Green Chem
2010;12:1423–9.
[19] Sluiter A, Hames B, Ruiz R, Scarlata C, Sluiter J, Templeton D, et al. Determination
The MIBK/H2O pretreatment with biphasic system was a promising of structural carbohydrates and lignin in biomass. Lab Anal Proc 2008;1617:1–16.
manner to convert lignocellulose into furfural and fermentable glucose [20] Sun SL, Zhang LD, Liu F, Fan XL, Sun RC. One-step process of hydrothermal and
alkaline treatment of wheat straw for improving the enzymatic saccharification.
by enzymatic hydrolysis. The results demonstrated that the MIBK/H2O Biotechnol Biofuel 2018;11:137.
pretreatment with biphasic system had a significant effect on the yields [21] Marcotullio G, De Jong W. Chloride ions enhance furfural formation from Dxylose
of furfural and fermentable glucose. The furfural yield was 65.9% and in dilute aqueous acidic solutions. Green Chem 2010;12:1739–46.
[22] Enslow KR, Bell AT. The role of metal halides in enhancing the dehydration of
the recovery rate of solid residue was 46.9% under the optimal reaction
xylose to furfural. ChemCatChem 2015;7:479–89.
conditions (VMIBK:VH2O = 5:5, 150 °C, 60 min, 0.3 M HCl). The yield of [23] Li XC, Zhang YY, Xia QN, Liu XH, Peng KH, Yang SH, et al. Acid-Free Conversion of
glucose of cellulose was improved after the pretreatments with different cellulose to 5-(hydroxymethyl) furfural catalyzed by hot seawater. Ind Eng Chemi
systems and a maximum value was up to 60.2% by the MIBK/H2O Res 2018;57:3545–53.
[24] Kumar R, Wyman CE. Access of cellulase to cellulose and lignin for poplar solids
pretreatment. Overall, the MIBK/H2O pretreatment can effectively produced by leading pretreatment technologies. Biotechnol Prog 2009;25:807–19.
convert Eucalyptus into furfural and fermentable glucose by enzymatic [25] Kacurakova M, Capek P, Sasinkova V, Wellner N, Ebringerova A. FT-IR study of
hydrolysis of the resulting solid fraction (cellulose-rich), which is mild plant cell wall model compounds: pectic polysaccharides and hemicelluloses.
Carbohydr Polym 2000;43:195–203.
to environment and requires low energy, thus is an ideal approach to [26] Li MF, Yu P, Li SX, Wu XF, Xiao X, Bian J. Sequential two-step fractionation of
the for production of clean energy and biochemical. lignocellulose with formic acid organosolv followed by alkaline hydrogen peroxide
under mild conditions to prepare easily saccharified cellulose and value-added
lignin. Energy Convers Manage 2017;148:1426–37.
Acknowledgements [27] Fan LT, Lee YH, Beardmore DH. Mechanism of the enzymatic hydrolysis of cellu-
lose: effects of major structural features of cellulose on enzymatic hydrolysis.
The authors are extremely grateful to financial support from the Biotechnol Bioeng 1980;22:177–99.
[28] Kumari S, Das D. Biologically pretreated sugarcane top as a potential raw material
National Natural Science Foundation of China (21706015, 31700518), for the enhancement of gaseous energy recovery by two stage biohythane process.
National Natural Science Foundation of China (No. 31700506), and Bioresour Technol 2016;218:1090–7.
Natural Science Foundation of Guangdong Province, China (No. [29] Hidayat BJ, Felby C, Johansen KS, Thygesen LG. Cellulose is not just cellulose: a
review of dislocations as reactive sites in the enzymatic hydrolysis of cellulose
2017A030310550).
microfibrils. Cellulose 2012;19:1481–93.
[30] Tejado A, Pena C, Labidi J, Echeverria JM, Mondragon I. Physico-chemical char-
References acterization of lignins from different sources for use in phenol–formaldehyde resin
synthesis. Bioresour Technol 2007;98:1655–63.
[31] Ciobanu C, Ungureanu M, Ignat L, Ungureanu D, Popa VI. Properties of lig-
[1] Li XD, Jia P, Wang TF. Furfural: a promising platform compound for sustainable nin–polyurethane films prepared by casting method. Ind Crops Prod
production of C4 and C5 chemicals. ACS Catal 2016;6:7621–40. 2004;20:231–41.
[2] Werpy T, Petersen G, Aden A, Bozell J, Holladay J, White J, Manheim A, et al. Top [32] Sun SL, Wen JL, Ma MG, Sun RC, Jones GL. Structural features and antioxidant
value added chemicals from biomass. Volume 1-Results of screening for potential activities of degraded lignins from steam exploded bamboo stem. Ind Crops Prod
candidates from sugars and synthesis gas (No. DOE/GO-102004-1992). Department 2014;56:128–36.
of Energy Washington DC; 2004. [33] Li HY, Wang B, Wen JL, Cao XF, Sun SN, Sun RC. Availability of four energy crops
[3] Himmel ME, Ding SY, Johnson DK, Adney WS, Nimlos MR, Brady JW, et al. Biomass assessing by the enzymatic hydrolysis and structural features of lignin before and
recalcitrance: engineering plants and enzymes for biofuels production. Science after hydrothermal treatment. Energy Convers Manage 2018;155:58–67.
2007;315:804–7. [34] Li XC, Guo TY, Xia QN, Liu XH, Wang YQ. One-pot catalytic transformation of
[4] Demirbaş A. Biomass resource facilities and biomass conversion processing for fuels lignocellulosic biomass into alkylcyclohexanes and polyols. ACS Sustain Chem Eng
and chemicals. Energy Convers Manage 2001;42:1357–78. 2018;6:4390–9.
[5] Cherubini F. The biorefinery concept: using biomass instead of oil for producing [35] Yang HY, Chen Q, Wang K, Sun RC. Correlation between hemicelluloses-removal-
energy and chemicals. Energy Convers Manage 2010;51:1412–21. induced hydrophilicity variation and the bioconversion efficiency of lig-
[6] Emmel A, Mathias AL, Wypych F, Ramos LP. Fractionation of Eucalyptus grandis nocelluloses. Bioresour Technol 2013;147:539–44.
chips by dilute acid-catalysed steam explosion. Bioresour Technol 2003;86:105–15. [36] Zeng YN, Zhao SA, Yang SH, Ding SY. Lignin plays a negative role in the bio-
[7] Lam MK, Lee KT, Mohamed AR. Homogeneous, heterogeneous and enzymatic cat- chemical process for producing lignocellulosic biofuels. Curr Opin Biotech
alysis for transesterification of high free fatty acid oil (waste cooking oil) to bio- 2014;27:38–45.
diesel: a review. Biotechnol Adv 2010;28:500–18. [37] Akhtar N, Goyal D, Goyal A. Characterization of microwave-alkali-acid pre-treated
[8] Wang G, Zhang S, Xu W, Qi W, Yan Y, Xu Q. Efficient saccharification by pre- rice straw for optimization of ethanol production via simultaneous saccharification
treatment of bagasse pith with ionic liquid and acid solutions simultaneously. and fermentation (SSF). Energy Convers Manage 2017;141:133–44.
Energy Convers Manage 2015;89:120–6. [38] Öhgren K, Bura R, Saddler J, Zacchi G. Effect of hemicellulose and lignin removal
[9] Ma F, Yang N, Xu C, Yu H, Wu J, Zhang X. Combination of biological pretreatment on enzymatic hydrolysis of steam pretreated corn stover. Bioresour Technol
with mild acid pretreatment for enzymatic hydrolysis and ethanol production from 2007;98:2503–10.
water hyacinth. Bioresour Technol 2010;101:9600–4. [39] Yoo CG, Li M, Meng XZ, Pu YQ, Ragauskas AJ. Effects of organosolv and ammonia
[10] Zhang XD, Bai YY, Cao XF, Sun RC. Pretreatment of Eucalyptus in biphasic system pretreatments on lignin properties and its inhibition for enzymatic hydrolysis.
for furfural production and accelerated enzymatic hydrolysis. Bioresour Technol Green Chem 2017;19:2006–16.
2017;238:1–6. [40] Sun SN, Cao XF, Sun SL, Xu F, Song XL, Sun RC, et al. Improving the enzymatic
[11] Le Guenic S, Delbecq F, Ceballos C, Len C. Microwave-assisted dehydration of D- hydrolysis of thermo-mechanical fiber from Eucalyptus urophylla by a combination
xylose into furfural by diluted inexpensive inorganic salts solution in a biphasic of hydrothermal pretreatment and alkali fractionation. Biotechnol Biofuels
system. J Mol Catal A-Chem 2015;410:1–7. 2014;7:116.
[12] Mellmer MA, Sener C, Gallo JMR, Luterbacher JS, Alonso DM, Dumesic JA. Solvent [41] Moodley P, Kana EG. Development of a steam or microwave-assisted sequential salt-
effects in acid-catalyzed biomass conversion reactions. Angew Chem Int Edit alkali pretreatment for lignocellulosic waste: Effect on delignification and enzy-
2014;53:11872–5. matic hydrolysis. Energy Convers Manage 2017;148:801–8.
[13] Saha B, Abu-Omar MM. Advances in 5-hydroxymethylfurfural production from [42] Bjerre AB, Olesen AB, Fernqvist T, Plöger A, Schmidt AS. Pretreatment of wheat
biomass in biphasic solvents. Green Chem 2014;16:24–38. straw using combined wet oxidation and alkaline hydrolysis resulting in convertible
[14] Ordomsky VV, Van der Schaaf J, Schouten JC, Nijhuis TA. Glucose dehydration to cellulose and hemicellulose. Biotechnol Bioeng 1996;49:568–77.
5-Hydroxymethylfurfural in a biphasic aystem over solid acid foams. [43] Wang K, Yang HY, Xu F, Sun RC. Structural comparison and enhanced enzymatic
ChemSusChem 2013;6:1697–707. hydrolysis of the cellulosic preparation from Populus tomentosa Carr., by different
[15] Gürbüz EI, Gallo JMR, Alonso DM, Wettstein SG, Lim WY, Dumesic JA. Conversion cellulose-soluble solvent systems. Bioresour Technol 2011;102:4524–9.
of hemicellulose into furfural using solid acid catalysts in γ-valerolactone. Angew [44] Yuan TQ, Wang W, Xu F, Sun RC. Synergistic benefits of ionic liquid and alkaline
Chem Int Edit 2013;52:1270–4. pretreatments of poplar wood. Part 1: Effect of integrated pretreatment on enzy-
[16] Wang WJ, Ren JL, Li HL, Deng AJ, Sun R. Direct transformation of xylan-type matic hydrolysis. Bioresour Technol 2013;144:429–34.
hemicelluloses to furfural via SnCl4 catalysts in aqueous and biphasic systems.

544