Polymer Degradation and Stability 135 (2017) 54e60

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Polymer Degradation and Stability

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

Lignin depolymerization to aromatic monomers and oligomers in

isopropanol assisted by microwave heating
Qian Liu, Pengfei Li 1, Nana Liu, Dekui Shen*
Key Laboratory of Energy Thermal Conversion and Control of Ministry of Education, School of Energy and Environment, Southeast University, Nanjing
210096, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Degradation of lignin to aromatic compounds in isopropanol was investigated under the mild
Received 19 July 2016 microwave-assisted heating. The highest yield of liquid product was 45.35% achieved at 120
C with the
Received in revised form reaction time of 30 min, together with the yield of char as 38.65% and 14.73% residual lignin. The aro-
16 November 2016
matic compounds in liquid product (both monomers and oligomers) were identified by Gas
Accepted 20 November 2016
Available online 23 November 2016
Chromatography-Mass Spectrometry and Matrix-assisted Laser Desorption/Ionization Time-of-Flight
Mass Spectrometry. Ethanone, 1-(4-hydroxy-3-methoxyphenyl) (G2) and ethanone, 1-(4-hydroxy-3, 5-
dimethoxy phenyl) (S2) were evidenced as the prominent aromatic monomers in the liquid product.
Keywords:
Lignin
Fragments from the aromatic oligomers detected by MALDI-TOF MS were mainly located from 248 m/z to
Microwave heating 496 m/z. The chemical structure of the specific oligomers with the molecular weight of 274 m/z, 290 m/z,
Depolymerization 316 m/z, 332 m/z, 362 m/z, 406 m/z, 454 m/z was proposed to understand the possible relationship with
Aromatic compounds the formation of prominent monomers.
MALDI-TOF MS © 2016 Elsevier Ltd. All rights reserved.

1. Introduction investigated an effective approach to selectively produce 4-

ethylphenolics in an optimizing system with ethanol/water as
Lignin, one of the three main constituents in biomass, is a three- solvent, achieving the production of 3.1% 4-Ethylphenol and 1.3%
dimensional biopolymer consisting of three main phenylpropane 4-ethylguaiacol [19]. Barta et al. examined organosolv lignin using
units (guaiacyl alcohol, syringyl alcohol and p-coumaryl alcohol) supercritical methanol, finding lignin conversion over 90% and over
[1]. Utilization of lignin as the potential feedstock for chemical 70% of methanol-soluble products were achieved at 180
C [20].
production attracts more and more attention during recent years During recent decades, microwave irradiation is attracting more
thanks to its outstanding characteristics as renewable, low-cost and and more attentions owing to its high heating efficiency [21]. Ana
ready availability [2e5]. Solvolysis of lignin is vigorously discussed et al. studied lignin depolymerization with hydrogen-donating
as one of the promising approaches for transforming lignin to solvents by using a microwave-assisted approach, presenting that
value-added chemicals, with regard to the moderate conversion the best conversion could be obtained at 150
C within 30 min [22].
condition, efficient precipitation of target products and low cost for Xiao et al. compared liquefaction of corn stover under conventional
the process [6e11]. and microwave-assisted heating, finding that microwave induced
A number of different solvents applied in the solvolysis of lignin more intense oxidation cleavage of the lignocellulosic material and
have been reported in recent reviews [12e14]. Formic acid, widely more extensive solvolysis reaction than conventional liquefaction
considered as hydrogen-donor solvent, was used under mild re- [23]. The mechanism for lignin degradation under microwave
action conditions, resulting in almost no production of coke heating needs to be further investigated, in order to promote the
[15e17]. Connor et al. described the effect of organic solvent- formation of the value-added aromatic compounds.
tetralin in the hydrocracking of kraft lignin [18]. Ye et al. In this work, lignin depolymerized in isopropanol under mi-
crowave heating is carried out regarding the effect of reaction
temperature and reaction time on the yield of liquid product, re-
* Corresponding author. sidual lignin and char. The liquid product including aromatic
E-mail address: [email protected] (D. Shen). monomers and oligomers was identified by Gas Chromatography
1
This author contributed equally to this work and should be considered co-first coupled with Mass Spectrometry (GC-MS) and Matrix-assisted
author.

http://dx.doi.org/10.1016/j.polymdegradstab.2016.11.016
0141-3910/© 2016 Elsevier Ltd. All rights reserved.
 Q. Liu et al. / Polymer Degradation and Stability 135 (2017) 54e60 55

laser desorption/ionization time-of-flight mass spectrometry the chromatographic separation; the oven temperature was pro-
(MALDI-TOF MS). Chemical structures of the aromatic oligomers grammed from 40
C (kept for 3 min) to 180
C (kept for 2 min)


are proposed according to the molecular weight determined by with a 5 C/min heating rate and then up to 280
C (kept for
MALDI-TOF MS, in order to address the possible mechanism for 2 min) with a 10
C/min heating rate; and the mass spectra were
lignin depolymerization and secondary repolymerization under operated in electron ionization mode at 70 eV and obtained from
microwave heating. m/z 50 to 850.

2. Materials and methods 2.3.2. MALDI-TOF MS analysis

AB SCIEX MALDI TOF/TOFTM5800 Analyzer (MALDI-TOF MS)
2.1. Materials was employed to examine the molecular weight distribution of the
aromatic oligomers in liquid product. The irradiation source was
Lignin was precipitated from black liquor obtained as the ND: YAG laser with a wavelength of 335 nm and the length of one
condensed byproduct from a pulping company in Yueyang (China). laser pulse was 3 ns. The measurements were carried out as fol-
The extraction, purification of lignin and chemical structural char- lows: polarity-negative, flight path-linear, mass-high (20 kV ac-
acteristics were analysed and described in authors' previous pub- celeration voltage), and 50e150 pulses per spectrum. CHCA (a-
lished work [24]. Cyano-4-hydroxycinnamic acid) was used as matrix in the analysis.
It was useful to speculate the possible chemical structures of the
2.2. Lignin depolymerization process aromatic oligomers from the MALDI-TOF MS analysis.

Lignin depolymerization in isopropanol were carried out in a 3. Results and discussion

microwave digestion instrument (MDS-6) purchased from Xinyi
Microwave Chemical Technology Co., Ltd., Shanghai, China. The 3.1. Yield of liquid product, char and residual lignin
procedure for lignin degradation in isopropanol and the product
separation is illustrated in Fig. 1. The digestion tank was filled with a Effect of reaction temperature on the yield of products was
fixed lignin: solvent ratio of 1 g: 16 ml. The experimental conditions shown in Fig. 2a. Yield of the liquid product was notably increased
were set to be: power: 600 W, reaction temperature: 100e180
C when the temperature was increased from 100
C to 120
C,
and reaction time: 5e60 min. After each experiment, the reaction achieving the maximum yield of 43.35% at 120
C. When the
mixture was washed by isopropanol and then filtrated to liquid and temperature exceeded 120
C, the yield of liquid product gradually
solid fraction. The solid fraction was dissolved in THF and filtrated, declined to 37.41% at 180
C. The yield of char changed opposite to
achieving residual lignin (as the unreacted lignin) and char. The that of liquid product when the temperature was larger than
yield of liquid product was calculated as the ratio of the weight of 120
C, suggesting that part of char formation can be designated to
liquid product to the weight of original lignin sample, while the the repolymerization of liquid product under the high reaction
residual lignin and char yields were calculated as the ratio of the temperatures. The yield of liquid product was increased from
weight of residual lignin and char to the weight of original lignin 39.08% to 45.35% with the increase of reaction time from 5 min to
sample. 30 min, and then decreased after 30 min (Fig. 2b). It confirms that
the recondensation of fragments from lignin depolymerization can
be promoted by the longer residence time [25].
2.3. Characterization of liquid products

3.2. Distribution of aromatic monomers identified by GC-MS

2.3.1. GC-MS analysis
The liquid product was identified by GC-MS (Agilent7890A-
Distribution of aromatic monomers in liquid product obtained
5975C) with the operating conditions as follows: the injector
from lignin depolymerization under different temperatures and
temperature was 300
C; TR-35MS capillary column was used as
reaction times was determined by GC-MS and shown in Fig. 3a and
Fig. 3b. It can be found that most of the identified aromatic
monomers are guaiacol-type and syringol-type compounds,
agreeing with the original monomeric structure in black-liquor
lignin sample [24]. The aldehyde-type and ketone-type aromatic
compounds were abundantly produced, resulting from the cleavage
inter-unit aryl ether linkages on Ca or Cb atoms of the aliphatic side
chain [26].
Yields of vanillin (G1) and ethanone, 1-(4-hydroxy-3-
methoxyphenyl) (G2) were increased with the increased reaction
temperature from 100
C to 120
C,while yields of both two com-
pounds were slightly changed with the temperature. Benzalde-
hyde, 4-hydroxy-3,5-dimethoxy (S1) and ethanone, 1-(4-hydroxy-
3,5-dimethoxy phenyl) (S2) achieved their highest yields at 120
C.
Yields of S1 and S2 were substantially declined when the temper-
ature exceeded 120
C, due to the vigorous demethoxylation re-
action of syringyl compounds for promoting the guaiacyl
compounds formation [27]. Formation of G1 can be originated from
guaiacyl fragments, while S1 should be designated to the released
syringyl intermediate [28]. G1 and S1 can not be detected by GC-MS
when the reaction time was 5 min, and longer reaction time was
required for the carbonyl formation on Ca. Yields of G2 and S2 were
Fig. 1. The procedure for lignin degradation in isopropanol and the product separation. achieved the maximum value at the reaction time of 30 min, and
56 Q. Liu et al. / Polymer Degradation and Stability 135 (2017) 54e60

Fig. 2. Yield of liquid product, char and residual lignin from lignin depolymerization in isopropanol.

Fig. 3. Distribution of aromatic monomers generated from lignin depolymerization.

then declined sharply at the longer reaction time. It can be evi- an opposite trend as the temperature, achieving the highest value
denced that G2 and S2 are the two prominent aromatic monomers at 30 min (Table 2). The aromatic monomer vanillin (G1) achieved
from lignin depolymerization in isopropanol regardless of the re- its highest production at 120
C (Table 1), suggesting that G1 can be
action temperature and reaction time (Fig. 3a and b). preferably produced at 120
C at the consumption of oligomer I.
The production of the oligomer II (290 m/z) with the variation of
3.3. Analysis of aromatic oligomers by MALDI-TOF MS temperature was opposite as that of oligomer I, achieving its
highest value as 7.24% at 140
C. The formation of oligomer II with
The fragments of the aromatic oligomers with the molecular the reaction time was in a reverse trend as that of G1. These phe-
weight from 248 m/z to 496 m/z from lignin depolymerization in nomena suggest that formation of oligomer II and G1 might be
isopropanol under different reaction temperatures and times was competitive in the primary degradation of lignin, and the long re-
detected and recorded by MALDI-TOF MS (Fig. 4a and Fig. 4b). The action time can enhance the formation of G1 from the cracking of
aromatic oligomers with the molecular weight of 274 m/z, 290 m/z, oligomer II.
316 m/z, 332 m/z, 362 m/z, 406 m/z and 454 m/z were considered to Production of oligomer III (316 m/z) was found to be decreased
be the major compounds in the liquid product. Distribution of the firstly, achieved the minimum value of 5.52% at 120
C and 30 min,
designated aromatic oligomers under different reaction tempera- and then increased with the reaction temperature and reaction
tures and reaction times was shown in Tables 1 and 2. The total time. It can be found that the variation of oligomer III production
amount of relative peak area for the oligomers achieved the with temperature is much more sensitive than that of reaction time
maximum value of 72.82% at 120
C and 30 min. (Tables 1 and 2). The oligomer III from lignin depolymerization
The formation of oligomer I (molecular weight: 274 m/z) was might be the important precursor for the formation of ethanone, 1-
firstly decreased, achieved its minimum value of 3.98% at 120
C (4-hydroxy-3-methoxyphenyl) (G2) due to their opposite forma-
and then increased with the elevated temperature (Table 1). The tion trends with reaction temperature and time. The production of
production of oligomer I with the variation of reaction time was in oligomer VI (406 m/z) containing the G2 structure was vigorously
 Q. Liu et al. / Polymer Degradation and Stability 135 (2017) 54e60 57

enhanced with the increased temperature (from 0.99% at 100
C to VII (454 m/z), as the potential precursor for the formation of aro-
15.42% at 120
C). This suggests that the formation of oligomer VI matic monomer S2, was substantially declined with the elevated
from lignin depolymerization was more competitive than that of G2 reaction temperature, even no oligomer VII can be detected at
under the temperatures around 120
C. 180
C (Table 1). The production of S2 was remarkably decreased
Production of oligomer V (362 m/z) with the variation of reac- with the reaction temperature and time, indicating that oligomer
tion temperature and time was in an opposite situation with aro- VII was preferably repolymerized to char or cleavaged to other
matic monomer ethanone, 1-(4-hydroxy-3,5-dimethoxy phenyl) oligomers (such as oligomer IV) under high temperatures and long
(S2). This implies that oligomer V (362 m/z) might be the prominent residence time.
precursor for the formation of S2 under lower temperatures.
Considering the possible chemical structure, the formation of 3.4. Possible mechanism for lignin depolymerization in isopropanol
oligomer IV (332 m/z) is possibly related to oligomer VII (454 m/z)
(Fig .5). The production of oligomer IV was slightly changed when According to the above discussion on distribution of specific
the temperature exceeded 120
C while oligomer VII was sub- aromatic compounds from lignin degradation under different re-
stantially declined, indicating that the formation of oligomer IV action temperatures and times, a mechanism is proposed for
from the secondary cracking of the oligomer VII was balanced with describing the lignin depolymerization in the in-situ hydrogen
the condensation of oligomer IV (332 m/z) to fragments. Oligomer donation solvent (isopropanol) (Fig .6) [29]. Lignin can be

Fig. 4a. MALDI-TOF MS analysis for liquid product from lignin depolymerization under different reaction temperatures.
58 Q. Liu et al. / Polymer Degradation and Stability 135 (2017) 54e60

Fig. 4b. MALDI-TOF MS analysis for liquid product from lignin depolymerization at different reaction times.

Table 1
Distribution of the specific oligomers from lignin depolymerization under different reaction temperatures with the reaction time of 30 min.

No Molecular weight Fragment Relative peak area(%)

Range(m/z)
100
C 110
C 120
C 140
C 160
C 180
C

I 274 267e274 4.95 4.21 3.98 4.1 4.22 4.65

II 290 280e288 5.74 6.85 6.96 7.24 4.14 0.08
III 316 310e316 7.99 6.98 5.52 12.28 14.45 23.35
IV 332 325e332 23.19 14.38 12.68 12.04 12.41 11.9
V 362 350e362 16.16 14.19 13.62 14.64 17.03 18.62
VI 406 398e406 0.99 12.09 15.42 9.78 8.94 8.61
VII 454 451e454 11.59 12.52 14.64 12.19 6.65 0
total 70.61 71.22 72.82 72.27 67.84 67.21

Table 2
Distribution of the specific oligomers from lignin depolymerization under different reaction times under 120
C.

No Molecular weight Fragment Relative peak area(%)

Range(m/z)
5 min 15 min 30 min 45 min 60 min

I 274 267e274 2.54 3.88 3.98 3.62 3.06

II 290 280e288 7.76 7.45 6.96 5.66 5.92
III 316 310e316 8.72 6.57 5.52 5.56 6.05
IV 332 325e332 14.52 13.22 12.68 11.16 13.06
V 362 350e362 20.23 19.05 13.62 22.08 23.98
VI 406 398e406 11.96 14.09 15.42 15.93 12.28
VII 454 451e454 5.02 7.65 14.64 8.01 7.12
total 70.75 71.91 72.82 72.02 71.47

effectively depolymerized to aromatic products (monomers and through condensation reaction [30].The monomeric compounds of
oligomers) through the cleavage of inter-unit linkages (such as ethanone, 1-(4-hydroxy-3-methoxyphenyl) (G2) can be produced
bO4 and b5 bonds). Oligomers can be converted to mono- from secondary cracking from the oligomer III (316 m/z), while
mers through secondary cracking reaction and solid residue ethanone, 1-(4-hydroxy-3,5-dimethocy phenyl) (S2) is produced
 Q. Liu et al. / Polymer Degradation and Stability 135 (2017) 54e60 59

Fig. 5. The possible chemical structure of the specific oligomers in the liquid product.

Fig. 6. Mechanism for lignin depolymerization to the aromatic products.

through the cleavage of from the CbO bond from the oligomer V. the monomer G2 [31]. The presence of oligomer IV can be
When the reaction temperature exceeded 120
C, productions of designated to the secondary cracking of oligomer VII relying on
oligomer III and V were substantially strengthened while yields of their possible chemical structures. The production of oligomer VII
monomer G2 and S2 were decreased. This means that condensa- which was formed from primary cracking of lignin was signifi-
tion of the monomers to oligomers was enhanced with the high cantly inhibited with the increased temperature, presenting that
reaction temperature. Similar mechanism can be proposed for the repolymerization of the produced fragments (such as oligomer IV)
production of monomer G2 and S2 at different reaction times, could not be easily commenced. In conclusion, suitable reaction
indicating that the condensation of monomers can be promoted at temperature and time can be chosen to balance depolymerization
long reaction time. The high reaction temperature can facilitate of lignin and condensation of monomers, achieving higher yields
the removal of the methoxyl group, enhancing the formation of of target products.
60 Q. Liu et al. / Polymer Degradation and Stability 135 (2017) 54e60

4. Conclusion 1 (7) (2008) 626e629.

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