Industrial Crops & Products 145 (2020) 112091

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Industrial Crops & Products

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

Biphasic fractionation of rice straw under mild condition in acidified 2- T

phenoxyethanol/water system
Quan Zhanga,b,1, Yangzhen Denga,b,1, Xuesong Tana,*, Wen Wanga, Qiang Yua, Xiaoyan Chena,
Changlin Miaoa, Ying Guoa, Yu Zhanga, Xinshu Zhuanga,*, Zhenhong Yuanc
a
Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, CAS Key Laboratory of Renewable Energy, Guangdong Provincial Key Laboratory of New and
Renewable Energy Research and Development, Guangzhou, 501640, China
b
University of Chinese Academy of Sciences, Beijing, 10049, China
c
Collaborative Innovation Centre of Biomass Energy, Zhengzhou, 450002, China

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

Keywords: A novel biphasic organic solvent, 2-phenoxyethanol (EPH) was introduced to pretreat and fractionate rice straw
Biphasic organic solvent into glucose/glucan, xylose/xylan and lignin under mild conditions. In addition, the combined severity factor
2-phenoxyethanol (CSF) was used to evaluate the effect of pretreatment severity on the composition variation of rice straw. Under
Fractionation the biphasic system (0.05 M H2SO4, 70 % EPH:30 % H2O), 130 ℃ cooking rice straw 2 h, 86.48 % of cellulose
Rice straw
retention in solid residue, 92.10 % of hemicellulose removal and 63.16 % of lignin removal were obtained. Then,
Mild condition
the solid residue was enzymatically digested with a glucose yield of 80.94 % at 36 h, and the pure lignin (92.60
%) was recovered by simple precipitation. Based on the fractionation process, 96.69 % of glucose and glucan,
81.83 % of xylose and xylan, and 71.71 % of lignin in solid and liquid phase were recovered. Finally, the residue,
especially the retrieved lignin was characterized by SEM, XRD, FTIR, HSQC and thermogravimetric analysis.

1. Introduction Zhou et al., 2014). Most of the hemicellulose could be generally re-
moved, and > 80 % cellulose was usually kept in the solid residue by
Lignocellulosic biomass, an abundant natural feedstock for pro- acid or/and steam explosion pretreatment with the combined severity
duction of biofuels and valuable chemicals, has been a focus for the factors of 2.10–4.12 (Bonfiglio et al., 2019; Zhou et al., 2014). How-
development of green energy (Zhang et al., 2016). Amongst all bio- ever, the reaction conditions for acid or steam explosion pretreatment
masses, agricultural crop straw in China, with an annual production of are harsh, which in turn hindered its extensive application. In contrast,
787.4 million tons in 2015, is an important biomass material, of which the alkali pretreatment was mild in common. With aqueous alkali
rice straw holds about 30 % production share (Yu et al., 2019). Efficient pretreatment, > 60 % lignin would be removed, while > 50 % hemi-
utilization of rice straw is therefore a significant study for production of cellulose together with most of cellulose was kept in the solid residue at
environmentally-friendly fuels and green chemicals. The cell wall of conditions such as 50 ℃, 360 min and 2 % NaOH loading (Ma et al.,
rice straw with a complex and enzyme-resistant matrix structure, is 2015; Ravindran and Jaiswal, 2016). Taking these pretreatment
chemically composed of 35–45 % cellulose, 20–30 % hemicellulose and methods as references, > 80 % hemicellulose and > 50 % lignin could
20–25 % lignin (Hou et al., 2018). Fortunately, this complex structure be simultaneously decomposed with acid-catalyzed organosolv pre-
can be decomposed into carbohydrate and aromatic products after treatment with the combined severity factors of 2.10–4.00 (Wang et al.,
various pretreatments, resulting in various fractionation, which means 2016).
fractionation is the cornerstone of rice straw biorefinery, and pre- At present, one-phase systems and biphasic systems were most
treatment is an essential method to get effective fractionation. commonly used to pretreat lignocellulosic biomass. For one-phase
Several pretreatment methods, such as acid pretreatment, alkali system, > 90 % hemicellulose and > 80 % lignin could be removed by
pretreatment, organosolv pretreatment and steam explosion pretreat- ethanol or acetone or tetrahydrofuran-water- acid system at high tem-
ment, have been developed to degrade lignocellulosic biomass perature (> 160 ℃) (Kalogiannis et al., 2018; Mostofian et al., 2016).
(Bonfiglio et al., 2019; Ma et al., 2015; Ravindran and Jaiswal, 2016; In addition, formic/ acetic acid pulping methods also gave an efficient

⁎
Corresponding authors at: Guangzhou Institute of Energy Conversion, CAS, 2 Nengyuan Road, Wushan, Tianhe, Guangzhou, 510640, China.
E-mail addresses: [email protected] (X. Tan), [email protected] (X. Zhuang).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.indcrop.2020.112091
Received 18 September 2019; Received in revised form 31 December 2019; Accepted 2 January 2020
Available online 16 January 2020
0926-6690/ © 2020 Elsevier B.V. All rights reserved.
Q. Zhang, et al. Industrial Crops & Products 145 (2020) 112091

Table 1
The chemical composition variation of rice straw (RS) and residues.
Group EPH:water /V:V Tem./℃ Time/h SA loading/M Composition content/% Cellulose retention/% Removal/%

Cellulose Hemicellulose Lignin Hemicellulose Lignin

RS – – – – 41.93 ± 0.31 24.99 ± 0.22 23.85 ± 0.64 – – –

1 50 %:50 % 110 3 0.10 61.77 ± 0.33 9.91 ± 0.05 26.11 ± 0.41 85.63 ± 0.46 76.98 ± 0.11 36.54 ± 0.99
2 50 %:50 % 130 3 0.10 73.07 ± 0.14 4.91 ± 0.02 22.09 ± 0.62 68.38 ± 0.16 90.17 ± 0.05 53.71 ± 1.30
3 50 %:50 % 150 3 0.10 55.09 ± 1.00 0 47.33 ± 0.59 49.11 ± 0.90 100 26.04 ± 0.72
4 50 %:50 % 110 1 0.10 51.21 ± 0.11 14.97 ± 0.57 28.18 ± 1.36 86.58 ± 0.18 57.58 ± 1.61 16.47 ± 4.04
5 50 %:50 % 110 5 0.10 58.45 ± 1.22 9.29 ± 0.07 37.26 ± 2.15 75.15 ± 1.57 79.98 ± 0.14 16.03 ± 4.85
6 50 %:50 % 110 3 0.05 56.42 ± 1.10 11.86 ± 0.70 25.24 ± 0.80 92.70 ± 1.37 67.30 ± 0.70 27.10 ± 0.91
7 50 %:50 % 110 3 0.20 67.70 ± 0.87 7.61 ± 0.01 26.96 ± 2.06 86.36 ± 1.11 83.73 ± 0.01 39.71 ± 4.61
8 70 %:30 % 110 3 0.10 64.56 ± 0.62 9.33 ± 0.03 25.51 ± 0.66 88.22 ± 0.84 78.83 ± 0.08 41.05 ± 1.57
9 90 %:10 % 110 3 0.10 68.15 ± 0.73 6.55 ± 0.09 25.66 ± 0.30 85.02 ± 0.91 86.31 ± 0.18 43.23 ± 0.65

SA: Sulfuric acid; SA loading (mol/L) was based on the total solution volume.

delignification at 80–110 ℃ (Jahan et al., 2007; Lam et al., 2001). mixture, and the mixture was heated at target temperature. The mixture
Moreover, CIMV, based on this formic/ acetic acid method, had de- was cooled at the end of cooking and filtered with 40 ml glass filter
veloped an industrial process for vegetable refinery at pilot-scale (G3). The solid residue was swilled with hot water for at least three
(Delmas, 2008). However, cellulose formylation/ acetylation occurred times and oven dried at 105 ℃ to constant weight. The organic phase
due to 70–90 % of concentration of acid, which would hinder the en- was separated by filtering using a separatory funnel. The lignin was
zymatic hydrolysis of cellulose (Zhao and Liu, 2012). Encouragingly, precipitated from the organic phase with dimethyl carbonate (DMC)
several effective pretreatments with γ-valerolactone-water system and named LR. Enzymatic hydrolysis of rice straw was performed ac-
under relatively mild condition, in recent years, were reported cording to previous study (Zhang et al., 2019).
(Luterbacher et al., 2014; Shuai et al., 2016b). For biphasic system,
methyl isobutyl ketone (MIBK) or 2-Methyltetrahydrofuran (MeTHF)- 2.3. Analytical methods
water system could degrade > 90 % hemicellulose and > 50 % lignin
under similar conditions to one-phase system (Li et al., 2017; Zhang The chemical composition of rice straw and residues was analyzed
et al., 2017). Although one-phase system like γ-valerolactone could following the US National Renewable Energy Laboratory (NREL)
depolymerize more hemicellulose and lignin under similar condition, (Sluiter et al., 2012). Glucose and xylose were identified according to
biphasic system is still a good choice due to its convenience for se- our previous report (Zhang et al., 2019). To combine temperature,
paration (Katahira et al., 2014; vom Stein et al., 2011). cooking time and sulfuric acid (pH) into a single parameter, the com-
In this study, we chose a novel biphasic organic solvent, 2-phe- bined severity factor (CSF) was introduced to help to optimize the
noxyethanol (EPH) to fractionate rice straw. The effects of various pretreatment conditions (Overend et al., 1987; Studer et al., 2011).
temperature, cooking time, catalyst loading and EPH concentration Tr − Tb
were first investigated. Combining the results of pretreatment with the R 0 = t *exp( )
14.75
combined severity factor (CSF), an optimized condition was then ap-
plied to fractionate rice straw. Subsequently, the effects of fractionation CSF = logR 0-pH
on chemical compositions, enzymatic hydrolysis, structural features
Where t is the cooking time (min), Tr is the pretreatment temperature
and thermal stability of solid residue and retrieved lignin were also
(℃) and Tb is base temperature, i.e. 100 ℃.
comprehensively evaluated.
3. Results and discussion
2. Materials and methods
3.1. Organosolv pretreatment
2.1. Materials
The chemical composition of rice straw and residues were shown in
Rice straw composed of 41.93 % cellulose, 24.99 % hemicellulose, Table 1. These results showed that cellulose and hemicellulose removal
23.85 % lignin and 3.44 % ash, was provided by National Engineering increased with elevated temperature or extended cooking time. No-
Research Center of Plant Space Breeding, South China Agricultural tably, when temperature and cooking time were more than 130 ℃ and
University. Rice straw was first milled and then screened to 20 and 60 3 h, the lignin removal decreased. To explore this phenomenon, the
mesh. Subsequently, the selected rice straw was oven dried at 105 ℃ surface characteristic of raw rice straw and the residues from the group
overnight. 3 and 5 was analyzed by an X-ray photoelectron spectroscopy (XPS)
All reagents used in this study are analytical reagent (AR). Solid- technic. The results, as shown in Fig. S1 and Table S1, revealed that the
state cellulase with a filter paper activity of 191.7 FPU/g, was pur- surface lignin coverage (SL) of all residues increased compared with
chased from Jade Bio-technology Co., Ltd, China. The Milled-Wood that of rice straw, and then decreased to near that of the rinsed rice
Lignin (MWL) of rice straw was obtained and named LM referring to straw. Meanwhile, the corresponding SEM profile confirmed this var-
previous report (del Rio et al., 2012). iation of lignin condensation (Fig. S2). The results provided a caution
that high temperature or long time would inhibit the removal of lignin
2.2. Organosolv pretreatment and enzymatic hydrolysis in a given solvent system due to irreversible condensation of lignin
fragments (Shuai et al., 2016a). Accordingly, temperature and cooking
Pretreatment experiments were conducted in duplicate at tem- time should be selected within a proper range for efficient pretreat-
perature 110–150 ℃, cooking time 1−5 hours, sulfuric acid loading ment. Moreover, comparing the group 1, 8 and 9 in Table 1, it was
0.05-0.2 M and EPH concentration 50–90 % with the liquid: solid ratio found that increased proportion of EPH favored delignification. Based
of 20:1 (V/W). The oil bath was first heated to target temperature. 2 g on these results, it could be found that high delignification was gen-
rice straw (dry weight) was then added to acidified aqueous solvent erally accompanied by good removal effect of hemicellulose, and

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Q. Zhang, et al. Industrial Crops & Products 145 (2020) 112091

mainly consisted of xylose, glucose and xylan. Meanwhile, the pre-

cipitation from organic phase was composed of 92.60 % lignin and 4.66
% glucan. Compared with other organosolv pulp process, the residue in
this study showed a similar characteristic with that of ethanol pulp,
while the minimized degradation of hemicellulose was in line with that
of acetic/ formic acid pulp process, which indicated the biphasic EPH
system held a fractionation characteristic between acetic/formic acid
system and ethanol water system (Snelders et al., 2014, Institut
National de la Recherche Agronomique (INRA, 2014).
In addition, Fourier transform infrared (FTIR) spectroscopy and
Thermogravimetric (TG) were used to analyze the characteristic of rice
straw and the residue. Referring to the FTIR and TG analyses in sup-
plementary material, the residue showed the characteristic of highly-
enriched cellulose and low-level lignin/ hemicellulose, which was ac-
cordant with that of composition analysis. As shown in Fig. S5, XRD
analysis revealed that the characteristic of the residue was same as that
of cellulose I or Avicel. The enzymatic digestion of the residue at 36 h
Fig. 1. The composition retention or removal as a function of CSF.
reached to 80.94 %, 4.05 folds as much as that of rice straw, mainly due
to the removal of antidegradation barriers to cellulase which facilitated
raising delignification would thus be more significant for the applica- increased CrI of the residue.
tion of EPH-water system.
In order to optimize pretreatment, CSF was introduced to assess 3.3. Performance comparison of biphasic EPH
effect of pretreatment severity on delignification (Zhao et al., 2017).
The composition retention or removal as a function of CSF for the The pretreatment of rice straw with EPH, water, MeTHF or MIBK
groups with 50 % EPH was shown in Fig. 1. As CSF increased, cellulose under the optimized condition was shown in Table 2. Compared to the
and hemicellulose were more removed, but lignin removal showed a pretreatment with water/H2SO4, adding EPH into water/H2SO4 sig-
shape of upside-down arc, which may be due to the effect of organic nificantly improved delignification from 18.47%–63.16 %. Further-
solvent on lignin dissolution (Zhang et al., 2016). It was reported that more, replacing EPH with MeTHF or MIBK caused a dramatical de-
the typically selected CSF was in the range of 1.0–2.5 to obtain high crease of lignin removal from 63.16%–26.63 % or 27.74 %. Making
delignification for various materials (Zhao et al., 2017). In view of ef- comparison with other typically used biphasic solvents, EPH- water
ficient delignification, CSF with value of around 2, in this study, was system gave higher delignification and hemicellulose removal, and
supposed to be applicable. Considering the same trend generated only lower cellulose loss under moderate conditions, which was favorable
by various temperature, time or CSF, it hardly gave a correlation be- for biphasic fractionation of lignocellulosic materials. Referring to
tween lignin removal and CSF. For this reason, we selected four acetic acid/ formic acid based industrial biorefinery developed by
equivalent combinations of temperature, time and acid loading to CIMV, EPH fractionation gave an easily digested residue, and an easily
pretreat rice straw and assessed the feasibility of optimizing pretreat- recovered sugar mixture from aqueous phase (Snelders et al., 2014;
ment with CSF. These combinations were as follows: (1) 110 ℃, Institut National de la Recherche Agronomique (INRA, 2014). However,
120 min, 0.2 M H2SO4, CSF = 1.95; (2) 130 ℃, 60 min, 0.1 M H2SO4, the recovery of EPH and the fractionation on various materials, con-
CSF = 2.01; (3) 130 ℃, 120 min, 0.05 M H2SO4, CSF = 1.99; (4) 150 ℃, sidering its future application and potential pollution to environment,
30 min, 0.05 M H2SO4, CSF = 1.98, and EPH proportion for all com- will be a challenge, which deserves further study.
binations was 70 %.
After pretreatment under various conditions, CSF with values of 3.4. Characteristic of the precipitated lignin
1.95, 2.01, 1.99 and 1.98 gave a lignin removal of 61.76 %, 63.33 %,
63.16 % and 64.06 % respectively. This suggested that delignification FTIR spectra analysis, as shown in Fig. 3, revealed that the pre-
showed a correlation with CSF rather than alone temperature, acid cipitated fraction mainly showed the same characteristic with rice straw
loading or time. Based on these results, we selected 130 ℃, 120 min, lignin at the peaks of 1722 cm−1, 1245 cm−1, 1514 cm−1, 1461 cm−1
0.05 M H2SO4 (CSF = 1.99) as an optimized condition for further study. and 1168 cm−1 (Semerci and Guler, 2018; Singh and Dhepe, 2016;
Chen et al., 2016). This indicated that the precipitated fraction was
3.2. The fractionation of rice straw under the optimized condition mainly consisted of lignin. Composition of the precipitated fraction was
determined with the same method used in composition analysis of rice
The mass balance of the cellulose, hemicellulose and lignin in rice straw. The result showed that the precipitated fraction was mainly
straw during the process of fractionation was shown in Fig. 2. After composed of 92.60 % lignin and 4.66 % glucan.
pretreatment and fractionation, most of original cellulose (86.48 %) To obtain further information on the structure of LM and LR, side
was kept in the solid residue, and 10.21 % cellulose (as glucose and chain region (δC/δH 54.00–88.00/2.80-5.50) and aromatic region (δC/
glucan) was detected in the water phase, which contributed to a total δH 92.00–147.00/6.10-7.70) in 2D HSQC NMR spectra were analyzed
cellulose yield of 96.69 %. 81.83 % hemicellulose was retrieved mainly and shown in Fig. 4. Peak assignments in 2D HSQC spectra were listed
in form of xylose and xylan in water phase, and only 7.90 % xylan was in Table S4. HSQC spectra showed that the main interunit linkages of
kept in the solid residue. As to lignin, the residue held 36.84 % original rice straw lignin were β-O-4′ aryl ethers (A), β-5′ phenylcoumaran (B),
lignin, and 34.87 % lignin was retrieved from organic phase, which β-β′ resinol (C) and β-1′ spirodienone (D). Polysaccharide cross-peak
contributed to a total lignin retrieval of 71.71 %. This result revealed signals (Glc5, X2, X3 and X4) and G, H, and S units were present in the
that ∼28 % lignin could be hardly retrieved during the fractionation spectra of LM. The absence of those polysaccharide cross-peak signals in
process. In addition, 0.38 % and 5.22 % furfural was detected in water LR was in accordance with that in FTIR analysis. As shown in Fig. 4a
phase and EPH phase respectively, which indicated only small amount and b, β-β′ linkage in tetrahydrofuran structure (C’α) with the cross
of xylose degradation was presented during the pretreatment process. signal at δC/δH 83.21/4.90, was detected for LM and absent for LR,
In general terms, the pulp showed a purity of 73.87 % containing which suggested the β-β′ linkage was completely hydrolyzed in the
86.48 % original cellulose, and sugars mixture in aqueous phase was precipitated lignin. Signals at δC/δH 69.80/3.97 and δC/δH 80.19/4.02

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Q. Zhang, et al. Industrial Crops & Products 145 (2020) 112091

Fig. 2. Mass balance of the cellulose, hemicellulose and lignin in rice straw during the process of fractionation.

in the spectra of LR, were assigned to β-β′ resinol (Cγ) and β-1′ spir-
odienone (D) structure respectively. Hibbert ketone structures (Hk) at
δC/δH 67.12/4.11 was also observed in LR, which accorded with pub-
lished reports that lignin would be broken down into Hibbert ketone in
acidic aqueous (alcohol) reagent (Muley et al., 2019). In the aromatic
region (Fig. 4c and d), a large amount of tricin units was absent in the
spectra of LR, compared to that of LM, which indicated that tricin may
be easy to degrade in acidic aqueous organic solvents. The signal at δC/
δH 114.38/6.26 was assigned to C8-H8 in p-coumarate unites (pCA8),
and not present in the spectra of LR, which was mainly because of
complete hydrolyzation of the acylated γ-OH in PCA8 (de Menezes
et al., 2017).
The semiquantitative analysis of the interunit linkages and the units,
and the molecular weight distribution of LM and LR, as shown in Table
S3, showed the relative abundance of β-O-4′ aryl ether linkages in LR
decreased from 59.98 % to 12.71 %, compared to that in LM, which
contributed to high delignification. As to the dramatic increase of H
Fig. 3. FTIR spectra of rice straw lignin and the precipitated lignin.
units and decrease of S units as well as an unremarkable improvement
of G units in LR, it was primarily owing to the easy depletion of S units
and the facile enrichment of H units, along with a relatively stable 4. Conclusion
structure of G units at an increased pretreatment severity (de Menezes
et al., 2017), which provided a decreased S/G ratio of 1.06. In addition, In short, an effective biphasic fractionation system was proposed.
the average molecular weight (Mw) of the retrieved lignin, as shown in The rice straw was efficiently fractionated into glucose/glucan, xylose/
Table S3, increased from 3115 to 4975 compared to that of LM, which xylan and lignin with EPH-water-sulfuric acid system under mild con-
was not in line with that in some published reports (Singh and Dhepe, dition, most of glucose in the solid residue was easily released by en-
2016; Xue et al., 2018). While compared with CIMV’s industrial tech- zymatic hydrolysis, and simple precipitation gave an efficient lignin
nology, EPH fractionation still provided a moderate average molecular retrieval. Based on these processes, 96.69 % of glucose and glucan,
weight of the recovered lignin (Institut National de la Recherche 81.83 % of xylose and xylan, and 71.71 % of lignin were recovered.
Agronomique (INRA, 2014). During depolymerization of rice straw, the lignin removal was related

Table 2
Comparison of treatment with EPH to that with other typically used biphasic solvents.
Material Reaction condition Cellulose retention Hemicellulose removal Lignin removal Reference

Rice straw 70 %EPH, 0.05 M H2SO4 130 ℃, 120 min 86.48 % 92.10 % 63.16 % Current study
Rice straw 100 %Water, 0.05 M H2SO4 130 ℃, 120 min 88.17 % 80.99 % 18.47 % Current study
Rice straw 70 %MeTHF, 0.05 M H2SO4 130 ℃, 120 min 84.32 % 86.65 % 26.63 % Current study
Rice straw 70 %MIBK, 0.05 M H2SO4 130 ℃, 120 min 82.85 % 88.19 % 27.74 % Current study
Beechwood 60 %MIBK, 0.10 M H2SO4 175 ℃, 60 min 83.8 % 96.6 % 49.4 % Kalogiannis et al., 2018
Bamboo 50 %MeTHF, 1 M oxalic acid 140 ℃, 20 min – ∼85 % ∼35 % Li et al., 2017
Eucalyptus grandis 67 %MeTHF, 0.03 M formic acid 160 ℃, 90 min 31.48 % 99.74 % 74.33 % Zhang et al., 2017
Eucalyptus grandis 67 %MIBK, 0.03 M formic acid 180 ℃, 30 min 34.30 % 98.89 % 69.27 % Zhang et al., 2017

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Q. Zhang, et al. Industrial Crops & Products 145 (2020) 112091

Fig. 4. Side chain region (δC/δH 54.00–88.00/2.80-5.50) and aromatic region (δC/δH 92.00–147.00/6.10-7.70) in 2D HSQC NMR spectra of LM (a), (c), and LR (b),
(d).

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The authors declare that we have no competing financial interests or Katahira, R., Mittal, A., McKinney, K., Ciesielski, P.N., Donohoe, B.S., Black, S.K.,
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