Energy Conversion and Management 201 (2019) 112181

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Energy Conversion and Management

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

Oligomers obtained from sequential fractionation of lignin pyrolysis oil T

⁎
Xiaohua Zhang, Hao Ma, Tengfei Li, Shubin Wu
State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, People’s Republic of China

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

Keywords: The existence of oligomers poses a huge challenge for the valorization and utilization of bio-oil, thus it is urgent
Lignin to develop cost-effective fractionation techniques to improve the quality of bio-oil and realize its valorization.
Pyrolysis oil Herein, developed a simple and novel process based on the combination of water and organic solvents (di-
Sequential fractionation chloromethane and diethyl ether) extraction of AL and CHRL POs to obtain oligomer-rich fractions for quali-
Oligomers
tative and quantitative analysis. Confirmation of both the DI and EEI fractions obtained from two POs were
lignin-derived oligomers by the combination of GC–MS and ESI+–HRMS analyses, where the AL- and CHRL-
derived oligomers accounted for 23.4% and 14.31% of the respective PO mass, respectively. The results showed
that the chemical compositions of each oligomer-rich fraction depended on the chemical nature of the extraction
solvent selected and chemical compositions exerted a greater influence on thermal degradation behavior of
oligomer-rich fraction than its molecular weight, and the “carbon residue” content was inversely proportional to
its methoxy content. In addition, 2D HSQC NMR indicated that the side chain structures of the EEI fraction were
more than the DI fraction derived from the same PO, which was attributed to the dichloromethane exhibits
better δH ability with hydroxyl group than diethyl ether, while the aromatic structures were similar.

1. Introduction added disadvantage, high MW oligomers are an important component

Lignocellulosic biomass represents a rich source of renewable en-
ergy for the production of fuels, chemicals and materials to replace
fossil fuels [1]. It has a complex structure composed of three major
types of biopolymers, viz., cellulose, hemicellulose, and lignin [2].
Lignin is the second most abundant organic substance after cellulose
and is widely considered as an excellent renewable raw material for the
production of chemicals due to its useful functional groups such as
hydroxyl, benzene, aldehyde, and so forth [3]. To date, a tremendous
amount of efforts have been made to develop effective methods for the
utilization of lignin, including pyrolysis, hydrothermal depolymeriza-
tion, hydrogenolysis and oxidation [4]. Among them, direct pyrolysis of
lignin is one of the most prevalent strategies for lignin utilization.
Pyrolysis is a thermal process of converting lignin into PO in the ab-
sence of oxygen [5]. However, it is a pity that PO suffers from sig-
nificant drawbacks, for example, high oxygen content, poor stability,
strong corrosiveness, high acidity and low calorific value [6,7]. As an
of PO, which are non-volatile, viscous and highly reactive, making them
difficult to process into valuable products [8,9]. Moreover, the presence
of a large amounts of oligomers is unfavorable for the direct use of PO
as a liquid fuel. On the other hand, if used for biorefining, the content
and structural features of oligomers will also be an important con-
sideration. Hence, there is an urgent need to develop fractionation
techniques to extract oligomers from bio-oil to facilitate the valoriza-
tion and high value utilization of bio-oil.
Fractionation technique is a mean to simplify the composition of PO
and enrich components with similar characteristics and structures, so as
to improve the purity of certain compounds and facilitate further
component analysis. In recent years, a large number of literatures have
reported on the fractionation techniques toward PO and realized its
high value utilization. Conventional fractionation methods including
solvent extraction [10–12], distillation [13,14], centrifugation [15],
membrane separation [16,17], and column chromatography [18,19].
Among these methods, one promising fractionation method is solvent

Abbreviations: AL, alkali lignin; CHRL, corn cob hydrolyzed residue lignin; PO, pyrolysis oil; WS, water-soluble; WI, water-insoluble; DS, dichloromethane-soluble;
DI, dichloromethane insoluble; EES, diethyl ether-soluble; EEI, diethyl ether insoluble; MW, molecular weight; PL, pyrolytic lignin; P, polarity index; δ, solubility
parameters; HSP, Hildebrand solubility parameters; BP, boiling point; V, molar volume; Ev, evaporation energy; δD, dispersion interaction; δP, polarity interaction; δH,
hydrogen bonding; EA, ethyl acetate; Mw, weight-average molecular weight; Mn, number-average molecular weight; PD, polydispersity; GC−MS, gas chromato-
graphy−mass spectrometry; ESI+–HRMS, high resolution mass spectrometry equipped with positive ion electrospray; FTIR, Fourier transform infrared spectroscopy;
HS-GC, headspace gas chromatography; 2D 1H–13C HSQC NMR, heteronuclear single quantum coherence; TG, thermogravimetry
⁎
Corresponding author.
E-mail address: shubinwu@scut.edu.cn (S. Wu).

https://doi.org/10.1016/j.enconman.2019.112181
Received 20 July 2019; Received in revised form 10 October 2019; Accepted 11 October 2019
Available online 15 October 2019
0196-8904/ © 2019 Elsevier Ltd. All rights reserved.
X. Zhang, et al.
extraction (or partitioning), which is repeated extraction based on the
different solubility or partition coefficient of different compounds in a
certain solvent or a series of solvents. Also, it is considered to be more
economical than other fractionation methods because the solvents can
be recovered and reused [10,20]. Moreover, it can be operated at room
temperature and atmospheric pressure [11]. As is known to us, bio-oil is
essentially a mixture of components with different polarities. The so-
lubility of these components in polar or non-polar solvents varies
widely, and the fractionation of bio-oil can be achieved by using this
difference. The components with similar characteristics and chemical
structures in bio-oil can be enriched by selecting suitable solvent, which
is convenient to select appropriate detection method for targeted ana-
lysis. However, to the best of our knowledge, the use of a single solvent
alone may not sufficiently extract and fractionate these chemicals from
the PO due to the heterogeneity of phenolic compounds. Accordingly,
many researchers have also carried out research on sequential solvent
extraction of PO. For instance, Ren and his co-authors adopted a series
of organic solvents to extract lignin-derived components and the results
showed that each solvent has a different extraction efficiency for dif-
ferent components based on the solvents polarity [21]. Dodge et al.
investigated sequential solvent extraction of two lignin POs and a
possible method for the fractionation of lignin-derived compounds was
proposed [10]. Furthermore, researchers have achieved a finer frac-
tionation of bio-oil via a combination of water and organic solvents,
which facilitates the enrichment of fractions with similar characteristics
and chemical structures for subsequent further targeted analysis. For
example, Nsimba et al. studied the sequential solvent fractionation of
Etek lignin fast PO and suggested that PL was a promising material for
the production of renewable aromatic compounds [22]. In order to
achieve the high value utilization of the WI phase of bio-oil, Wang et al.
used a combination of water and organic solvents to separate mono-
phenols and PL. The results showed that polymers with MW above
1000 Da dominated in the high MW PL, while the low MW PL contained
more phenolic hydroxyl groups [23]. Although these previous works
involved the exploration of the sequential extraction of lignin-derived
compounds, it is not clear whether the same protocol can be applied to
PO derived from different lignin raw materials. More critically, the
viewpoints of the fractionation, and detailed qualitative and quantita-
tive analysis of oligomers in PO has rarely been reported. Moreover, the
most of these studies were only discussed macroscopically. Accordingly,
the fractionation and detailed analysis of oligomers are necessary. This
is also one of the research directions to achieve high efficiency frac-
tionation of specific high value-added chemicals and solvent fractio-
nation of oligomers in the future.
Herein, the purpose of this work is to develop a simple fractionation
method, viz., sequential solvent fractionation of two lignin POs via ex-
traction with a combination of water and organic solvents to obtain
oligomer-rich fractions. Meanwhile, detailed qualitative and quantita-
tive analysis of the oligomer-rich fractions obtained after sequential
fractionation was carried out by GC–MS, ESI+-HRMS, GPC, 31P NMR,
HS-GC, FTIR, TG, elemental analysis, and 2D HSQC–NMR spectroscopy.
This study will help to better understanding of the content and struc-
tural properties of the oligomer-rich fraction in PO at the molecular
level, which will lay the foundation for an in-depth understanding of
the further research on the development of lignin pyrolysis oil valor-
ization strategies and its high value utilization.
2. Experimental
2.1. Lignin pyrolysis experiment
The lignin (AL and CHRL) pyrolysis experiments were shown in S1.2
(Supplementary Material).
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Energy Conversion and Management 201 (2019) 112181
2.2. Sequential fractionation experiments of liquid phase products
2.2.1. Solvent selection and fractionation process design
The solvent selection is based on three parameters, i.e., the P, the
HSP and BP.
The δ of a substance is defined as the square root of the gasification
energy per unit volume of matter [24].
Ev
δ=
V (1)
where δ (J/cm3)1/2 is the solubility parameter of a substance, V (cm3)
represents the molar volume of solvent, Ev (J) is the evaporation en-
ergy, respectively. Therefore, the Ev/V (J/cm3) represents the gasifi-
cation energy per unit volume of the substance, also known as cohesive
energy.
A substance with a high solubility parameter will require more
energy to disperse than a substance with a low δ. It is a useful numerical
value for characterizing the strength of simple liquid molecular inter-
actions and a physical constant for measuring the compatibility of li-
quid materials. In addition, the δ is a numerical estimate of the inter-
action between polymer and solvent and a good estimate of solubility. A
similar value of δ for the polymer and solvent indicates that the
polymer may be soluble in this solvent [25]. However, when hydrogen
bond is formed between polymers and solvent, the prediction result of
solubility parameter is not accurate due to the hydrogen bond exhibits a
great influence on the solubility.
This concept was subsequently extended by Hansen to polymer and
solvent systems. HSP, is an extension of the original δ, and further
extended the theory [26,27]. Hansen expressed substances as a vector
in three-dimensional space, and the components of that vector in each
dimension were respectively expressed as: δD (van der Waals forces), δP
and δH [25]. It is generally predicted that the HSP value of a new
polymer is based on the chemical structure of the repeating units in the
polymer, and finds a single solvent or solvent system that matches the δ
of the polymer [28]. The HSP can be used to predict the solubility of
polymers in different solvents [29]. Total δ is the geometric average of
the three HSP, as shown in the following formula (2):
δ= δD2+δP 2+δH2 (2)
This parameter is of great practical value and significance for
evaluating the merits of a certain solvent (mixed solvent) and effec-
tively selecting a suitable solvent and determining whether the dis-
solution process can be spontaneous or not in the case of a given solvent
and polymer. The values of P, δ and BP for several solvents selected are
shown in Table 1 [30].
In this study, a simple and novel sequential fractionation method
(three-step), which is cost-effective compatible, is employed to frac-
tionate the PO. Three solvents with different polarities were used: from
the most polar solvent to the least polar solvent, namely water, di-
chloromethane and diethyl ether. The flow chart for the fractionation of
PO via sequential solvent extraction is shown in Fig. 1. First, the PO is
separated into the WS and WI phases by water extraction. The upper
WS phase is enriched with low MW organic acids, ketones, and alde-
hydes, as well as a small amount of monophenolic compounds, all of
which have high to moderate polarity. However, some monophenolic
compounds and high MWs phenolic oligomers with less polarity and
multifunctional groups (possibly cross-linked) are concentrated in the
Table 1
HSP (δD, δP and δH) and BP (°C) of solvents used in this work.
Solvents δD δP δH HSP BP
Water 6.0 15.3 16.7 23.4 100
Dichloromethane 8.9 3.1 3.0 9.9 40
Diethyl ether 7.1 1.4 2.5 7.7 35
X. Zhang, et al.
Fig. 1. Flow chart for the fractionation of PO via sequential solvent extraction.
WI phase. Further fractionation of this phase can be achieved by dis-
rupting the intermolecular interactions of the WI components. The WI
fraction is further separated by dichloromethane extraction into two
fractions, i.e., DS and DI fractions with different MW distributions. The
DS fraction consists of low MW components, while the DI fraction is
enriched with high MW components. Due to the presence of monomers
and some high MW components in DS fraction, so the DS fraction is
necessary to further extracted with diethyl ether to achieve a finer the
fractionation of monomers and some high MW components. As a result,
yielding EES and EEI fractions. Another important reason for the se-
lection of these three solvents is that both of the dichloromethane and
diethyl ether are low BP organic solvents, which can be easily removed
by vacuum evaporation. Therefore, through the sequential extraction
by these two organic solvents, most monophenols and oligomers with
less polarity in the WI phase can be more finely separated, so as to
achieve the purpose of efficient fractionation between oligomers and
monomers.
2.2.2. Sequential fractionation of PO
The first step of water separation uses our previous method [31].
Briefly, under the condition of stirring speed of 1250 rpm min−1, an
appropriate amount of PO was added dropwise into distilled water
(20 °C). After the addition, the stirring was continued for 30 min.
Subsequently, the mixture was allowed to stand for 30 min to ensure
good phase separation. The upper WS fraction and the bottom WI
fraction were formed, the two phases were separated from one another
via decanting. The residual WI phase was mixed with water in same
condition and continued the extraction, repeated the above operation 3
times. The WS phase was collected together, and then the combined WS
fraction was extracted twice with EA and allowed to stand for 30 min.
The aqueous and EA phases were separated from one another by de-
canting. The EA phase was evaporated under a vacuum at 45 °C to re-
move the organic solvent, namely, WS fraction was obtained. The
second step was focused on the fractionation of the WI phase by di-
chloromethane extraction. At the same stirring speed, an appropriate
amount of WI fraction was added dropwise to dichloromethane under
stirring and continued for 30 min. Subsequently, it was allowed to stand
for 30 min and filtered. The filter cake was continued to be extracted
with dichloromethane until the filtrate was nearly colorless. The final
filter cake obtained was denoted as the DI fraction, and the collected
filtrate was concentrated by vacuum evaporation at 30 °C to remove the
organic solvent, thus the saved phase was denoted as the DS fraction.
Finally, the DS fraction was extracted with diethyl ether solvent under
3
Energy Conversion and Management 201 (2019) 112181
the same operating conditions. Also, the filter cake continued to be
extracted with diethyl ether until the filtrate was nearly colorless. The
precipitate was denoted as EEI, while the supernatant solution was
concentrated by vacuum rotary evaporation at 30 °C, and the residual
phase was denoted as EES. All the fractions obtained after fractionation
were dried overnight under a vacuum at 40 °C using P2O5 as a de-
siccant. The dried solids from fractionation were then weighed to de-
termine their masses. In each of the extraction steps, an extraction
solvent/oil ratio of 20:1 was used. Furthermore, the different pyrolysis
liquid products were recorded as AL-PO and CHRL-PO, respectively.
The oligomer-rich fractions obtained corresponding to the two lignin-
derived POs were recorded as AL-DI, AL-EEI, CHRL-DI and CHRL-EEI
fractions, respectively. The four samples are shown in Fig. S2.
2.3. Definitions
The partition ratio of a certain compound (Pi) was defined as the
ratio of the mass of the compound in the WI phase (Xorg) to the mass of
this compound in the WS (Xaq).
X org
Pi =
X aq (3)
The total recovery efficiency of a compound (Yi) was the ratio of the
total mass of the compound in the WS phase (Xaq) and WI phase (Xorg)
at equilibrium to the mass of this compound in the pyrolysis oil (Xpo).
X aq + X org
Yi = × 100%
Xpo (4)
The yield of the oligomers (Woli) was defined as the ratio of the mass
of a certain oligomer-rich fraction (Zi) to the total mass of the liquid
phase product (Mpo) used for the fractionation.
Zi
Woli = × 100%
Mpo (5)
3. Results and discussion
3.1. Determination of the oligomers
As is known to all, lignin-derived oligomers with high MW cannot
be identified by GC–MS due to its low volatility and the BP of most
oligomers are higher than the temperature of GC column. Accordingly,
the PO and its separated subfractions were detected by GC–MS (HP-
X. Zhang, et al.
5MS column and HP-INNOWax column) to preliminarily determine
whether there were oligomeric fractions in the separated subfractions.
Here, dimeric and higher MW compounds were defined as oligomeric
compounds [11].
The key volatile compounds identified in the two lignin-derived POs
and their separated fractions are summarized in Table S1 (AL) and S2
(CHRL), respectively. It was observed that the key functional groups in
PO and its subfractions were methoxy, hydroxyl, and carbonyl. Ac-
cording to their functional groups, the detected compounds can be di-
vided into phenols, aldehydes, ketones and aromatics. As shown in
Tables S1 and S2, a fantastic phenomenon was found in which no
compound was identified in the DI and EEI fractions obtained from the
sequential fractionation of the two POs. Moreover, as revealed in Fig.
S3 that only one compound of acetic acid was identified, and the acetic
acid may be derived from ethyl acetate. Based on these observations, it
was assumed that no monomer was present in the DI and EEI fractions,
all of which were lignin-derived oligomers. It should be pointed out that
although these oligomers cannot be analyzed by GC, they can be sub-
jected to MS analysis using the appropriate ionization techniques.
Therefore, to verify whether this hypothesis was correct or not, further
experiments were performed using HRMS/ESI+-MS (Fig. S4). One an-
ticipated finding was the absence of monomeric compounds, the MW of
the precursor ions peaks were greater than 230 Da in both of the DI and
EEI fractions (relative abundances less than 5% were not taken into
account). These findings suggested that both DI and EEI fractions
contained lignin-derived oligomers, which provided evidence to sup-
port the aforementioned hypothesis. Furthermore, it can be seen from
Fig. S2 that the different oligomer-rich fractions obtained after se-
quential fractionation were apparently (solid shape) similar to the
original lignin (not shown).
3.2. Evaluation of extraction capability
In order to explore the feasibility of sequential solvent extraction of
PO, thus eight main phenolic compounds in the PO, namely phenol, o-
cresol, p-cresol, guaiacol, 2,4-dimethylphenol, 4-methylguaiacol, 4-
ethylguaiacol and vanillin were selected to examine their respective
recovery efficiency and partition ratio.
The partition ratio of a certain compound depends on several fac-
tors, including the effective London forces in the solution, spatial ef-
fects, and electronic properties that affect the relative polarity of the
solute. The results were shown in Fig. 2a. Regardless of which lignin-
derived PO was selected as the extraction target, the order of the par-
tition ratio of these eight phenolic compounds was the same, i.e.,
phenol < o-cresol < p-cresol < guaiacol < 4-methylguaiacol <
2,4-dimethylphenol < 4-ethylguaiacol < vanillin. Although the par-
tition ratio of the homophenolic compound was slightly different, the
results were consistent with those reported in the literatures [32,33].
Fig. 2. Partition ratio (a) and recovery efficiency (b) of eight phenolic compounds of the WS and WI fractions.
4
Energy Conversion and Management 201 (2019) 112181
For example, the lowest partition ratio of phenol molecules because it
contains only one hydroxyl groups, which is easily accessible to interact
with water. The partition ratio of o-cresol and guaiacol is slightly larger
than that of phenol because these two compounds have one more me-
thyl or methoxy group in the ortho position of the hydroxyl group re-
lative to phenol, which increases their hydrophobicity, so the partition
ratio increases [31]. Compared with guaiacol or o-cresol, 2,4-di-
methylphenol, 4-methylguaiacol and 4-ethylguaiacol increased the
chain lengths of the p-substituent on guaiacol or o-cresol. Since alkyl
(methyl or ethyl) groups are hydrophobic groups and they can prevent
interactions between the hydroxyl groups on the monophenols with
water and reduce the water solubility of the compound. As a result,
partition ratio value of these three monophenols increased. For vanillin,
the presence of methoxy groups can form intramolecular hydrogen
bonds with hydroxyl groups on the phenolic compound [33], thus the
partition ratio was the highest.
Fig. 2b depicts the recovery efficiency of these eight phenolic
compounds in the WS and WI fractions during the water extraction
process, meanwhile the total recovery efficiency of these eight phenolic
compounds ranged from 85.99% to 95.01% (AL) and 82.13% to 95.71%
(CHRL), respectively. These results indicate that the total recovery ef-
ficiency of the proposed water extraction-based method is high and
show that water is a suitable solvent for the extraction of phenolic
compounds from two lignin-derived POs. On the other hand, the re-
covery efficiency of the eight phenolic compounds in the process of
sequential extraction of AL-PO and CHRL-PO via water, di-
chloromethane, and diethyl ether are shown in Fig. 3a and 3b, re-
spectively. It was found that the recovery efficiencies of eight phenolic
compounds by using water, dichloromethane and diethyl ether ex-
tractions ranged from 82.13% to 95.71%, 90.44% to 97.12%, and
84.83% to 96.11%, respectively. Moreover, the experimental results
showed good reproducibility. Based on these findings, it can be con-
cluded that either water, dichloromethane, or diethyl ether were sui-
table as extraction solvents for the recovery of phenolics compounds
from PO.
3.3. Molecular weight distribution of oligomer-rich fractions
In order to investigate the MW distribution of the oligomer-rich
fraction obtained by sequential fractionation, GPC analysis was per-
formed on the two POs and their fractions to obtain respective corre-
lation values of Mn, Mw, and PD. Just like other polymers, each oli-
gomer-rich fraction can be expressed as a combination of its average
molar masses (Mn and Mw) and it’s PD, the combination of which can
give information about the MW distribution and the degree of poly-
merization for a given oligomer-rich fraction.
The results relating to the MW distribution of the oligomer-rich
fractions and the two POs and their fractions are listed in Table 2 and
X. Zhang, et al. Energy Conversion and Management 201 (2019) 112181

Fig. 3. Recovery efficiency of eight phenolic compounds from AL-PO (a) and CHRL-PO (b) by three solvents.

Table 2 Table 3
The Mw, Mn and PD analysis. Hydroxyl and methoxy content (mmol/g) of oligomer-rich fractions corre-
sponding to the two POs determined by quantitative 31P NMR and HS-GC, re-
Sample AL-DI AL-EEI CHRL-DI CHRL-EEI
spectively.
Mn 1425 1167 852 661 Assignments AL-DI AL-EEI CHRL-DI CHRL-EEI
Mw 2051 1572 1235 1134
PD 1.44 1.35 1.45 1.72 Aliphatic 0.27 0.66 0.79 0.73
β-5 0.10 0.42 0.27 0.20
4-O-5 0.10 0.46 0.38 0.10
Table S3, respectively. By comparison, it was found that Mn and Mw of 5-5 0.18 0.90 0.47 0.24
Total 0.38 1.78 1.12 0.54
oligomer-rich fractions were higher than other corresponding fractions,
S 0.10 0.40 0.40 0.30
especially AL-DI and CHRL-DI. At the same time, it was observed that G 0.31 1.68 1.23 0.55
the PD of the DI fraction was smaller than the WI fraction, indicating Catechol type 0.08 0.43 0.89 0.28
that the DI fraction obtained after fractionation was relatively uniform. H 0.02 0.20 0.80 0.45
However, regardless of which PO was fractioned, the PD of the EEI Total phenolic 0.89 4.49 4.44 2.12
–COOH 0.09 0.25 0.79 0.32
fraction was slightly higher than the DS fraction. This is the result of the
Total OH 1.25 5.40 6.02 3.17
fractionation and purification of different solvents and the capability of Methoxy 1.82 2.93 2.69 4.87
the extraction solvent to establish δH with the hydroxyl groups in the
solute. The oligomer-rich fractions are usually oligomers and chain
fragments that are not produced by the fractionation process. Rather, the CHRL-EEI fraction showed a slightly decline trend, the content of
they are already present in the original fraction (i.e., the WI fraction) aliphatic hydroxyl in other three oligomer-rich fractions (AL-DI, AL-EEI
and increase their concentration in the respective insoluble fractions and CHRL-DI) increased with the MW (Table 2) decreased. Notably,
with solvent extraction. The difference in the size of MW and MW higher content of the phenolic hydroxyl and methoxy groups were
distribution between the oligomer-rich fractions is due to the ability of observed in the lower MW fractions (vide infra). These results indicate
dichloromethane with hydroxyl groups in the WI fraction to establish that the MW and oxygen-containing functional group content of the
stronger δH than the diethyl ether with hydroxyl groups in the DS oligomer-rich fractions obtained after sequential fractionation are de-
fraction. Thereby, more components with hydroxyl groups can be dis- termined by the nature and extraction properties of the organic solvent
solved during the extraction process. In contrast, the insoluble com- used itself. Comparison of the hydroxyl content in AL-DI and AL- EEI
ponents that cannot be extracted will be enriched in the form of oli- revealed that the content of aliphatic hydroxyl and phenolic hydroxyl in
gomers. In addition, the results indicated that the longer the chain of a AL-EEI fraction was generally higher than that of AL-DI, and the content
large MW component is, the more difficult it is for the extraction sol- of carboxyl group also showed the same trend as that of each hydroxyl
vent to penetrate its highly branched 3D structure [34]. This hindrance group. This phenomenon can be explained by the difference in δH
may be responsible for the limited chemical interaction between the ability between dichloromethane and diethyl ether solvent. Since di-
hydroxyl groups in the solute and the solvent, which are the main chloromethane solvent can establish a stronger δH with hydroxyl
causes of the dissolution of the WI and DS fractions. With the δH ability groups, resulting in a lower hydroxyl content in the dichloromethane
of the extraction solvent is enhanced, the component with larger MW insoluble fraction (i.e., AL-DI). Compared with dichloromethane, die-
gradually dissolves and is extracted. thyl ether exerts a lower δH binding energy, which makes the extracted
soluble material contains a lower content of hydroxyl groups, so the
3.4. Quantitative analysis of oxygen-containing functional groups in insoluble part of diethyl ether (AL-EEI) has a higher content of hydroxyl
oligomer-rich fractions groups. This result highlights the interaction between the δH ability of
the extraction solvent and the hydroxyl group in the solute. On the
In order to obtain further information about the content of oxygen- other hand, comparison of CHRL-DI and CHRL-EEI, the difference in
containing functional groups (hydroxyl, carboxyl and methoxy) in oli- hydroxyl content under different chemical environments was just the
gomer-rich fractions, thus the four oligomer-rich fractions were quan- opposite of the results of AL-DI and AL-EEI. This is ultimately due to the
titatively analyzed by 31P NMR and HS-GC. The results are shown in different components in PO derived from different lignin raw materials,
Table 3. Also, a simple principle of phosphating for different hydroxyl leading to the extraction capability of different solvents to solutes.
type compounds and the chemical shift of different hydroxyl groups are Therefore, the hydroxyl content and chemical components in the oli-
shown in Fig. S5 and Table S4, respectively. gomer-rich fractions were different. This is a further indication of the
As shown in Table 3, although the content of aliphatic hydroxyl in chemical compositions exhibits a significant effect on the binding

5
X. Zhang, et al.
Fig. 4. FTIR spectra of four oligomer-rich fractions.
energy of the selected solvent to the hydroxyl groups. On the other
hand, the higher free phenolic hydroxyl groups were present in the AL-
EEI and CHRL-DI fractions, indicating that they have good reactivity to
formaldehyde and can be used as phenolic substituents in phenol-for-
maldehyde production [35].
3.5. Absorbance intensity of various functional groups in oligomer-rich
fractions
To better clarify the interactions between solutes and extraction
solvents, and further understand the chemical structures of four oli-
gomer-rich fractions obtained after solvent sequential extraction, thus
FTIR spectral analysis was conducted on the four oligomer-rich frac-
tions. The strength of functional group in each oligomer-rich fraction is
shown in Fig. 4, and the band assignments of main functional groups
Fig. 5. Main oxygenated side chain structures identified in oligomer-rich fractions.
6
Energy Conversion and Management 201 (2019) 112181
are listed in Table S5.
All fractions exhibited a wide absorption peak of 3424–3444 cm−1
centered on the strongest absorbance, which can be attributed to the
stretching vibration of hydroxyl groups (O–H) from aliphatic and aro-
matic compounds [36]. At 1707 cm−1, the four oligomer-rich fractions
showed little difference in intensity, indicating that the carbonyl con-
centration in all fractions was comparable. In other words, di-
chloromethane and diethyl ether solvents with different extraction
capabilities exert little effect on the carbonyl groups during extraction
process. The two fractions of AL-DI and AL-EEI showed a distinct signal
at 1272 cm−1, while the CHRL-DI and CHRL-EEI fractions showed only
weak peaks in this region. This is mainly because oligomer-rich frac-
tions are derived from two lignin (AL and CHRL)-derived POs with
different proportions of G-type structure. It is noteworthy that the peaks
found at 1215 cm−1 in all fractions, presence of a slightly difference in
intensity between AL-DI and AL-EEI fractions, especially CHRL-DI and
CHRL-EEI fractions. This evidence suggests that a decrease in functional
group concentration (in the DI fractions) during solvent extraction,
which may be due to the poor δH ability of the diethyl ether to solutes
compared with dichloromethane. The C-O deformation vibration peak
in the secondary alcohol (1082 cm−1) was observed in both the AL-DI
and AL-EEI fractions, but was not observed in the CHRL-DI and CHRL-
EEI fractions. Significant signal peaks were observed at 836 cm−1 for
both CHRL-DI and CHRL-EEI fractions, but was not observed in the two
fractions of AL-DI and AL-EEI, mainly due to the two fractions derived
from two POs. Similarly, a higher concentration of S units was found at
1120 cm−1 (C–H stretching vibration peak) in both CHRL-DI and CHRL-
EEI fractions, while a very weak signal peak was found in the AL-DI and
AL-EEI fractions.
3.6. 2D HSQC NMR analysis
To further determine the chemical structures and linkages of the
oligomer-rich fraction obtained after sequential extraction of two POs,
2D NMR analysis was run on the four oligomer-rich fractions. The main
X. Zhang, et al.
cross peaks of the interunit linkages are listed in Table S6, which are
assigned by these literatures [37–39] and the main structures identified
are also shown in Fig. S6. The signals of the aliphatic oxygenated side
chain region and the aromatic region shown by the spectra are in the
range of δC/δH 50–90/2.8–5.8 ppm and δC/δH 100–150/6.0–8.0 ppm,
respectively.
(i) Aliphatic oxygenated side chain region. This region where carbons
attached to alcohol, ether and aromatic-methoxyl groups as well as
carbohydrate sugars resonate in 2D HSQC NMR. As demonstrated
in Fig. 5, all oligomer-rich fractions have a methoxyl signal, which
was the most abundant. Besides, the known aliphatic interunit
linkages β-O-4 and β-5 as well as carbohydrate sugars could be
found in the four oligomer-rich fractions. A notable that a small
amount of carbohydrates was observed, which are not easily re-
moved during the first step of water extraction because some car-
bohydrates are covalently bounds [23]. This is a further indication
of the carbohydrates removal is still difficult by extraction with
dichloromethane or diethyl ether solvent. As a result, it also re-
mained in oligomer-rich fractions after extraction. In respect to the
AL-derived oligomer-rich fractions, similar spectra was observed in
the comparison of AL-DI and AL-EEI, with resonance peaks of the
same structure types, only the abundance of each structure type
was a slightly difference. On the other hand, comparison of CHRL-
DI and CHRL-EEI found that the tetrahydrofuran and pinoresinol
were absent in the CHRL-DI fraction. Additionally, evidence of the
presence of more types of components in CHRL-EEI fraction than
the CHRL-DI fraction, and the similar result were also observed in
the comparison of AL-DI and AL-EEI fractions. This phenomenon
indicates dichloromethane extraction is more efficient than diethyl
ether extraction, so more components were extracted. This is re-
lated to the δP of the two organic solvents. The polar of organic
solvent is greater, the more polar compounds extracted, so the
components in the remaining fractions reduced. Notably, presence
of a clear difference between the side chain regions of these two
lignin-derived oligomer-rich fractions. It was a clear that α,β-diaryl
ethers (E, α-O-4, α-β, and β-O-4), Cα–Hα in the phenylcoumaran (C,
connected by α–O–4 and β–5), dibenzodioxocine (Di, 5–5, α-O-4,
and β-O-4), β-O-4 linked to guaiacyl units (G) and syringyl units (S)
structures were only observed in the two fractions of CHRL-DI and
CHRL-EEI, while these five structures were absent in the two frac-
tions of AL-DI and AL-EEI, as they were derived from two different
lignin raw materials, i.e., CHRL and AL (Fig. 6).
(ii) Aromatic region. As expected, significant differences between the
aromatic regions of these two lignin-derived oligomer-rich frac-
tions. The main difference was the S units, α-oxidized S units (S′),
α-oxidized H units (H′), tricin (T), p–coumarate (PCE), p-hydro-
xycinnamyl alcohol end-groups (I), stilbene units (SB) and ferulates
linkages (FA). For instance, the coupling peaks for C2,6-H2,6 of H'
units, Cα–Hα of I units, C7–H7 of PCE and FA were absent in the two
fractions of AL-DI and AL-EEI. Furthermore, evidence of the pre-
sence of more aromatic ring structures in CHRL-derived oligomer-
rich fractions than AL-derived oligomer-rich fractions. As men-
tioned above, this difference is primarily due to differences in the
chemical compositions of the two POs, resulting in different
structural units in these two lignin-derived oligomer-rich fractions.
On the other hand, comparison of corresponding oligomer-rich
fractions (derived from the same PO) found that the structures and
linkages of EEI fraction and DI fraction in this region were almost
similar. This may be due to the fact that most of the aromatic ring
structures in PO are non-polar compounds, while dichloromethane
and diethyl ether solvents are moderately or weakly polar organic
solvents. The extraction ability of these two solvents for most non-
polar oligomers is relatively weak, making it difficult to further
extract non-polar oligomers. Therefore, the difference between the
two insoluble fractions was small.
7
Energy Conversion and Management 201 (2019) 112181
Based on the aforementioned results, it can conclude that presence
of more side chain and aromatic ring structures in CHRL-derived oli-
gomer-rich fractions than AL-derived oligomer-rich fractions, and the
EEI fraction derived from the same PO exhibits more side chain struc-
tures than the DI fraction, while the aromatic structures were similar.
3.7. The thermal behavior analysis
To explore the relationship between the chemical characteristics of
the oligomer-rich fraction and its thermal properties, four oligomer-rich
fractions derived from two POs were tested using a thermogravimetric
analyzer. The TG and DTG curves of these four oligomer-rich fractions
are shown in Fig. 7. In general, the thermal properties of a given sample
are not only affected by its internal functional groups and degree of
branching and condensation, but also by the specific chemical struc-
tures.
As shown in Fig. 7, where TG thermograms (TG curves and corre-
sponding DTG curves) of all oligomer-rich fractions are shown. Below
150 °C is the first stage of thermal weight loss, which is mainly the
volatilization of free water, bound water and some small molecular
impurities in oligomer-rich fractions [40]. The main thermogravimetric
stage was between 200 °C and 600 °C, during which a large number of
volatiles were removed. Wherein the appearance of a mass loss at
200 °C was reported for the four oligomer-rich fractions, attributable to
the breaking of α- and β-alkyl-aryl-ether linkages [2], while the ali-
phatic side chains begin to break from the aromatic ring at about 300 °C
[41]. In particular, all samples exhibited a major mass loss in the
340–380 °C temperature range (Fig. 7b), likely attributed to the clea-
vage of carbon-carbon bonds between structural units and functional
groups [42,43]. Based on the maximum weight loss curves of the four
oligomer-rich fractions, it was observed the maximum weight loss
corresponds to the order of temperature: CHRL-DI (345.75 °C) <
CHRL-EEI (352.07 °C) < AL-EEI (365.47 °C) < AL-DI (380.31 °C). By
comparison, it seemed to be no correlation between the MW of oli-
gomer-rich fraction and its thermal stability. However, previous lit-
erature indicated that the thermal stability was not only affected by
MW, but also related to chemical compositions [44]. Accordingly, the
result can be inferred that the chemical compositions exerted a greater
influence on the thermal degradation behavior than the MW.
On the other hand, it was observed the difference between the
thermal weight loss characteristics of the three fractions of AL-DI, AL-
EEI and CHRL-DI was small, while the CHRL-EEI fraction showed sig-
nificantly different thermogravimetric characteristics compared to the
former three fractions. In addition, the “carbon residue” contents in AL-
DI, AL-EEI, CHRL-DI, and CHRL-EEI were observed to be 53.09%,
46.13%, 46.17%, and 2.53%, respectively. This result indicated that the
oligomer-rich fractions obtained by diethyl ether extraction contained
few condensation structures, and the condensed structures in the oli-
gomer-rich fractions obtained by dichloromethane extraction were
more, which was related to the extraction performance of these two
solvents. These results further conclude that by simply selection of
suitable fractionation solvents, the final residue after pyrolysis can be
fine-tuned by selectively controlling the MWs and chemical composi-
tions of fractions. Furthermore, the methoxy cleavage was believed to
occur at 400–600 °C [2], and it was found that the “carbon residue”
content was inversely proportional to the methoxy content (Table 3) of
the oligomer-rich fractions.
3.8. Physicochemical properties and yield
The yield and physicochemical properties (including elemental
content, high calorific value, and H/C and O/C atomic ratios) of the
four oligomer-rich fractions obtained after sequential extraction are
shown in Table 4. Furthermore, the physicochemical properties of two
POs are also given in Table S7. Comparison of these two POs showed
that the carbon and hydrogen content in CHRL-PO was higher than that
X. Zhang, et al. Energy Conversion and Management 201 (2019) 112181

Fig. 6. Main aromatic structures identified in oligomer-rich fractions.

Fig. 7. TG (a) and DTG (b) curves of the oligomer-rich fractions.

Table 4 sulfur content in AL-PO was higher.

Physicochemical properties and yield of the oligomer-rich fractions. Table 4 showed that the total yields of oligomer-rich fractions ob-
Sample AL-DI AL-EEI CHRL-DI CHRL-EEI tained by sequential fractionation process accounted for 23.04% (AL-DI
and AL-EEI) and 14.31% (CHRL-DI and CHRL-EEI) of the corresponding
Yield (%) 12.16 10.88 10.70 3.61 PO mass, respectively. From the result of the yields of AL-DI and AL-EEI
C (%) 60.47 65.93 67.09 68.87
was higher than that of CHRL-DI and CHRL-EEI, indicating that the
H (%) 5.46 5.72 6.23 6.31
O (%) 32.51 26.41 20.06 19.24
yield of oligomer-rich fractions obtained by sequential extraction of AL-
N (%) 0.17 0.25 5.88 4.77 PO by using the same extraction protocol was higher than extraction of
S (%) 1.39 1.69 0.74 0.81 CHRL-PO. There is no specific reason for this discrepancy to be ex-
H/C atomic ratio 1.08 1.04 1.11 1.10 plained, only due to the different sources of the two lignin raw mate-
O/C atomic ratio 0.40 0.30 0.22 0.21
rials and the complex nature of their respective PO, resulting in dif-
HHV (MJ/kg) 24.18 27.12 29.08 29.82
ferent amounts of oligomer-rich fractions obtained after fractionation.
It should be noted that the yield of oligomer-rich fractions only re-
of AL-PO, while the oxygen content was lower than that of AL-PO. presents the content of oligomers extracted by this solvent fractionation
Therefore, compared to AL-PO, CHRL-PO has a higher H/C atomic ratio method, and does not represent the total content of oligomers in PO.
and HHV, and a lower value of the O/C atomic ratio (Table S7). In This is due to the versatility of the components present in the fractions
addition, the sulfur content in AL-PO (1.64%) was higher than that in and the interaction between complex compounds, which makes it dif-
CHRL-PO (0.54%), which was mainly due to the introduction of sulfur ficult to extract all the oligomers from PO.
in the AL material during the sulfate pulping process. Therefore, the Comparison of the each element content in the four oligomer-rich

8
X. Zhang, et al.
fractions, it was observed that carbon and hydrogen content in the
corresponding oligomer-rich fraction was lower than that of PO, while
the oxygen content was higher than that of PO, so the corresponding
HHV was also lower than PO. Additionally, the sulfur content in the AL-
DI, AL-EEI, CHRL-DI and CHRL-EEI fractions was 1.39%, 1.69%, 0.74%
and 0.81%, respectively (Table 4). Previous study has shown that
fractions with lower MW contained higher content of sulfur element
[45]. In this study, the sulfur content of four oligomer-rich fractions
obtained by solvent fractionation of two POs was consistent with this
result (Table 2).
On the other hand, investigation of the elemental composition of the
different oligomer-rich fractions can be estimated by the H/C and O/C
atomic ratios. In respect to AL-derived oligomer-rich fractions, the
order of the H/C and O/C atomic ratios in the different oligomer-rich
fractions was found to be: AL-DI (1.08) > AL-EEI (1.04), AL-EEI
(0.30) < AL-DI (0.40), respectively. It has been reported that the lower
H/C atom ratio indicated higher aromaticity and polarity [46]. In terms
of CHRL-derived oligomer-rich fractions, CHRL-DI (1.11) > CHRL-EEI
(1.10), CHRL-EEI (0.21) < CHRL-DI (0.22). This result similar to the
result of AL-derived oligomer-rich fractions.
4. Conclusions
Oligomer-rich fractions obtained from sequential fractionation of
(AL and CHRL)-derived pyrolysis oils were successfully performed via a
novel method based on the combination of water and organic solvents
extraction. The three-step fractionation process reported provides a
valuable pathway towards the valorization of lignin pyrolysis oil, en-
abling the sequential extraction of pyrolysis oil to obtain oligomer-rich
fractions with clearly defined physicochemical properties (including
molecular weight distribution, oxygen-containing functional groups,
thermal behavior, elemental compositions, chemical structures and
linkages). All of these properties may enable realize scalable methods
with the potential of high efficiency and reduce process fractionation
costs. In addition, the availability of oligomer-rich fractions potentially
allows another lignin pyrolysis oil valorization strategies for the de-
velopment of bio-based polymers and for the preparation of key plat-
form chemicals, which facilitates pave the way for the effective devel-
opment of this remarkable resource.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors greatly acknowledge the support of the National
Natural Science Foundation of China (No. 31670582), National Key
Research and Development Program of China (No. 2018YFB1501404)
and the Science and Technology Project of Guangzhou City (No.
201607020025).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.enconman.2019.112181.
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