Bioresource Technology Reports 5 (2019) 206–211

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Bioresource Technology Reports

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Dioxane-based extraction process for production of high quality lignin T

a,1 a,1 a a c
Mriganka Saha , Philip Bernstein Saynik , Arupjyoti Borah , Ritesh S. Malani , Prachi Arya ,
⁎
Shivangic, Vijayanand S. Moholkara,b,
a
Centre for Energy, Indian Institute of Technology Guwahati, Guwahati, India
b
Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati, India
c
Department of Biotechnology, Heritage Institute of Technology, Kolkata, India

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

Keywords: In the present study, lignin was extracted from debarked bamboo waste of paper industry by soxhlet extraction
Debarked bamboo waste method with 1,4–Dioxane as main solvent (along with small quantities of catalyst and water). 10 g of biomass
Lignin results in 1.5 g of lignin through soxhlet process. The purity of extracted lignin was determined, followed by
Soxhlet extraction structural and thermal properties using FTIR and TGA. The elemental composition and mass of lignin was de-
1,4–dioxane
termined by elemental analyser and gel permeation chromatography (GPC). The extracted lignin was found to be
Pyrolytic oil
highly pure, with very low (0.42% w/w) ash and negligible carbohydrate content. The solubility of extracted
lignin in various organic solvents like dioxane, THF, DMF, etc. makes it advantageous over lignin derived from
other processes. Pyrolytic oil and char were also obtained through pyrolysis of extracted lignin. The composition
of bio-oil and biochar was analysed. The results showed that pyrolytic oil was rich in aromatic content and
biochar was high in carbon content.

1. Introduction basically a carbohydrate polymer. It is a complex heteropolymer com-

Due to increasing concerns of global warming and climate change
risk, concurrent with fast depletion in fossil fuel reserves, researchers
have focussed their attention on lignocellulosic biomass as an alter-
native source of energy and commercially valuable chemicals.
Lignocellulosic biomass is one of the most abundant resources available
throughout the world. Conventionally, lignocellulosic biomass com-
prises of cellulose (40–60%), hemicellulose (10–40%) and lignin
(15–30%) (Chen, 2014; Kuhad et al., 2007). However, the biomass
composition varies with region and time.
Cellulose is the major component of lignocellulosic biomass.
Basically, it is a homopolymer comprised solely of glucose monomers
linked to each other by β–1,4–glycosidic bonds linearly with a degree of
polymerisation of 10,000–15,000 units (Hendriks and Zeeman, 2009).
Hydrogen bonds and van der Waals forces bind these polymeric chains
together that result in a rigid and crystalline structure. The degree of
crystallinity of cellulose may differ widely from amorphous to com-
pletely crystalline depending upon the origin of the biomass. Crystalline
cellulose is resistant to both enzymatic and microbial digestion (Chen,
2014; Kuhad et al., 2007).
Hemicellulose is the second major component of biomass, which is
prising of hexoses (mannose, galactose and glucose) and pentoses (xy-
lose and arabinose), in addition to sugars acids in side chains. In
hemicellulose, xylan is key element (Hendriks and Zeeman, 2009). The
amorphous nature of hemicelluloses makes it sensitive to high tem-
perature and chemical degradation. The degree of polymerisation of
hemicellulose is much lesser than that of cellulose and is about only a
few hundreds. Hemicellulose is soluble in water at elevated tempera-
ture, and it is the first to get dissolved during any pretreatment process
(Chen, 2014; Kuhad et al., 2007).
Lignin is an aromatic polymer available in biomass with varying
ratios. It is amorphous, irregular in nature and heteropolymer con-
sisting of oxygenated p–propylphenol units, viz. p–coumaryl, coniferyl
and sinapyl alcohol. It is formed in plant cells by free radical poly-
merisation of all the three units in a random order with the help of
laccase and peroxidase enzymes that polymerises the monomeric units.
It provides structural support and rigidity to plants as well as also
protects them from microbial attack or physical degradation by any
physical agents. It is non soluble in water, however, it dissolves in basic
or acidic conditions and its solubility increases with rise in temperature.
Lignin is soluble in various organic solvents such as 1,4–dioxane, THF,
and other solvents depending upon the chemical composition of lignin.

⁎
Corresponding author at: Centre for Energy, Indian Institute of Technology Guwahati, Guwahati, India.
E-mail address: vmoholkar@iitg.ac.in (V.S. Moholkar).
1
Authors have equal contribution.

https://doi.org/10.1016/j.biteb.2019.01.018
Received 28 November 2018; Received in revised form 23 January 2019; Accepted 25 January 2019
Available online 26 January 2019
2589-014X/ © 2019 Published by Elsevier Ltd.
M. Saha et al.
In plants cells, lignin is closely linked with cellulose and hemicellulose
results in lignin carbohydrate complexes (LCCs) which provides
strength (Chen, 2014; Kuhad et al., 2007; Schutyser et al., 2018).
Lignin after separation from cellulose and hemicellulose and pur-
ification has the potential to serve as a source of various petroleum-
derived products. Other than conventional use of lignin as fuel, it can be
used for the production of BTX, phenolic resins, emulsifiers, binding
agents, biodispersants, polyurethane foams, wood products, battery
additives, activated carbon, carbon fibre etc. (Fierro et al., 2003;
Gargulak and Lebo, 2000; Gosselink et al., 2004; Lora and Glasser,
2002). It also possesses antioxidant properties with anti-
microbial–antifungal properties, which enables its application in cos-
metic or food industry. It also acts as radical scavenger (Barclay et al.,
1997; Lu et al., 1998; Mai et al., 2000). After depolymerisation, lignin
can be used to produce vanillin. Vanillin is the precursor of vanilla
flavour, and has various applications in food industry as a flavouring
agent (Araújo et al., 2010; Fache et al., 2016).
The present study has utilized the debarking waste of bamboo from
Nagaon paper mill in Jagiroad, Assam, where the bamboo is the pri-
mary feedstock for paper production. In paper industry debarking is the
first process where the bark (outer hard surface) is removed from the
wooden logs or sticks to expose the soft surface of wood, before it is sent
for pulping. Debarking can be done either by mechanically powered
drum–type barker, in which wooden logs or sticks are passed through a
rotating barking drum and barks are knocked off by impact and abra-
sion, or by high–pressure water jets which removes the bark from the
logs. This debarking generates huge amount of waste in the paper in-
dustry which is generally burnt off in furnace to meet their energy re-
quirements. This debarked waste was selected for the study as it is al-
ready shredded, i.e. reduced particle size, which will save the energy
required for particle size reduction prior to any process. The lignin
extraction process reported in the present study has various advantages
like high purity without sulphur content in lignin and solubility in
various organic solvents. However, this process has relatively low yield
and longer extraction cycles. The extracted lignin was characterized by
various methods followed by pyrolysis.
2. Materials and methods
2.1. Materials
1,4-dioxane, hydrochloric acid, ammonium chloride, ethyl ether,
sulphuric acid (95% assay), tetrahydrofuran (GPC elutant) were pro-
cured from Himedia, India. All chemicals were AR grade. 0.22 μm nylon
filter was purchased from Axiva, India. All glasswares were made of
borosilicate glass and procured from Borosil Ltd., India.
2.2. Methodology
Soxhlet method was used for the extraction of lignin from biomass.
Lignin was further characterized for purity and structural properties
using FTIR. Other characterizations such as mass analysis, thermal
stability and elemental composition were also done. The lignin was
finally pyrolysed to obtain bio-oil and biochar, followed by their
characterization.
2.2.1. Extraction of lignin
Debarking bamboo waste was dried in hot air oven for 24 h at 80 °C
followed by grinding to fine powder. 10 g powdered biomass was taken
in a thimble and placed in Soxhlet apparatus. Solvent mixture was
prepared by adding 0.4% v/v HCl and 3% v/v water to 1,4-dioxane. A
small quantity of water was added to prevent peroxide formation while
the addition of HCl increases the yield. Soxhlet apparatus was set up
and solvent was added to the system. Extraction was done till there was
no release of colour in the extraction chamber indicating the comple-
tion of the extraction. Biomass was taken out and washed with distilled
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Bioresource Technology Reports 5 (2019) 206–211
water and dried in hot air oven. The solvent mixture (lignin dissolved)
was then concentrated by rotary evaporator (Buchi R–210). Lignin was
precipitated from the concentrate by adding lukewarm water (in the
ratio of 7:1) and a pinch of ammonium chloride (Pehrsson, 1949;
Pepper et al., 1959; Witcraft, 1949). The precipitate was filtered by
vacuum filtration setup using 0.22 μm nylon membrane. The filtrate
was analysed by HPLC for the sugar content. The precipitate was fur-
ther washed with ethyl ether to remove any further impurities and
dried in oven. The dry precipitate was weighed to calculate yield.
2.2.2. Characterization of lignin
The purity of lignin was determined on basis of its moisture, ash,
carbohydrate, lignin and mineral contents.
2.2.2.1. Determination of moisture and ash content. 2 g of lignin was
weighed and heated at 105 °C in hot air oven for 16 h and the weight
was recorded after drying. The sample was further placed in hot air
oven and weight was recorded after every 8 h till 3 successive readings
were constant. The ash content was determined by keeping dry lignin in
muffle furnace at 550 °C for 6 h and weight of ash was recorded
(Mansouri and Salvadó, 2006).
2.2.2.2. Determination of lignin and carbohydrate content. Lignin and
carbohydrate content was determined according to Biorefinery Test
Methods L2:2016 recommended by Innventia for the pulp, paper and
biorefinery industries. 100 mg of dry lignin was dissolved in 1 mL of
72% conc. Sulphuric acid. The mixture was incubated in water bath at
30 °C for 1 h. Next, 28 mL of distilled water was added to the mixture,
and the mixture was autoclaved at 121 °C and 15 psi pressure for 1 h.
The solution obtained was cooled and filtered through sintered glass
funnel. The filtrate obtained contains acid soluble lignin while the
precipitate retained in the funnel was acid insoluble lignin. The acid
insoluble lignin was washed with water followed by drying in hot air
oven and its weight was determined. The amount of acid-soluble lignin
was quantified using UV–visible spectrophotometer by recording the
absorbance of the filtrate at 205 nm. The filtrate was analysed by
UV–visible spectrophotometer and acid soluble lignin was quantified
with the following formula of Biorefinery test method L2:
A. D. V
Acid soluble lignin (ASL) = . 1000 mg/g
a. b. M
Different notations are: A = absorption at 205 nm, D = dilution
factor, V = volume of filtrate in litre (0.029 L), a = extinction coeffi-
cient of lignin in g/L (110 g/L as per TAPPI UM 250), b = cuvette path
length in cm (1 cm), M = weight of dry sample (in g). The sugar content
of filtrate obtained from lignin hydrolysis was analysed with HPLC.
2.2.2.3. Determination of minerals present. Presence of minerals in lignin
was affirmed by Energy dispersive X-ray spectroscopy (Zeiss, Sigma
Field Emission Scanning Electron Microscope).
2.2.2.4. Determination of thermal characteristics. Thermal
characterization of lignin was done by thermogravimetric analysis
(TGA, HITACHI STA 7200) (Watkins et al., 2015). The analysis was
done in inert environment under constant flow of nitrogen over a
temperature range of 30–800 °C with a heating rate of 10 °C/min with
initial lignin loading of 8.533 mg lignin.
2.2.2.5. Determination of structure. Structural characterization of lignin
was carried out by FT–IR (ShimadzuIRAffinity–1) (Jahan et al., 2012;
Watkins et al., 2015). Data was recorded in transmittance mode using
ATR method. 30 scans were recorded each from 400 to 5000 cm−1.
2.2.2.6. Determination of the elemental composition and molecular
weight. The elemental composition of lignin was analysed by CHNSO
(Thermo finnigan) analyser by which percentage composition of five
M. Saha et al.
Fig. 1. Line diagram of pyrolysis setup.
elements, viz. carbon, hydrogen, nitrogen, sulphur, and oxygen, in the
lignin was determined (Jahan et al., 2012; Mansouri and Salvadó,
2006). Molecular weight and degree of polymerisation of the extracted
lignin was determined by GPC (gel permeation chromatography)
(Waters corporation), equipped with UV–visible detector, refractive
index detector, HPLC pump, and Empower interface with THF as
mobile phase. The calibration curve was made by running
Polystyrene standards.
2.2.3. Pyrolysis of lignin and characterization of bio-oil and char
Lignin after depolymerisation can be used for production of deri-
vatives of benzene, toluene and xylene. Lignin was depolymerised at
high temperature in inert environment using reactor and muffle fur-
nace. The line diagram of the pyrolysis setup is shown in Fig.1. The
setup consisted of a stainless steel reactor which was placed in an
electrical furnace capable of attaining 900 °C, metallic condensers were
attached to achieve faster condensation and a funnel for removal and
collection of the bio-oil from time to time. The temperature in the
furnace was closely monitored using a sensitive PID controller. The
reactor was made up of SS 316 which is resistant to corrosion by acidic
compounds commonly found in bio-oil vapours. The reactor has a ca-
pacity of 600 mL. 19.78 g of the lignin was taken as the feed. The
pyrolysis experiment was carried out in the temperature range of
350–600 °C. The resulting bio-oil was analysed for chemical composi-
tion using gas chromatography and mass spectroscopy. The residual
char obtained after pyrolysis was analysed by CHNS analyser for ele-
mental composition. The thermal stability of char was analysed by TGA.
2.2.3.1. HPLC analysis. The filtrate obtained by precipitating lignin
from the concentrated solvent solution and the filtrate obtained from
acid hydrolysis of lignin both were analysed by HPLC (Agilent 1260
Infinity) to determine the sugars present in the filtrate by Agilent
Hi–plex H column maintained at 60 °C using column oven. 5 mM
sulphuric acid was used as mobile phase with RI detector.
2.2.3.2. GC–MS analysis. The pyrolytic oil obtained from lignin was
analysed for its chemical composition using a Varian 450–GC (Gas
Chromatography) and Varian 240–MS (Mass Spectroscopy) using a
VF–5MS column (inert 5% phenyl–methyl column). The instrument was
operated with a split ratio of 1:10. The GC oven temperature was kept
at 80 °C for 2 min followed by a heating rate of 8 °C/min up to 140 °C
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Bioresource Technology Reports 5 (2019) 206–211
and followed by a heating rate of 4 °C/min till 280 °C and held for
2 min. The pyrolysis oil was diluted with acetone (HPLC grade, Merck,
India) in 1:200 ratio and was filtered to screen out large particles
through a hydrophilic Millipore Polytetrafluoroethylene (PTFE) filter
(0.2 μm) before sample injection.
3. Results and discussion
3.1. Lignin extraction
1,4-dioxane was used as a solvent for extraction of lignin, as it has
the ability to dissolve lignin, and it does not have hydroxyl groups
which can result in chemical interaction with lignin. It generates per-
oxides during extraction process which can be dangerous. Previous
studies have reported that small amounts of catalysts, HCl or HAc, are
essential for better extraction. In present case, along with 1,4–dioxane
0.4% (v/v) HCl was used for better extraction, and 3% (v/v) water was
added to prevent peroxide formation. The soxhlet extractor minimizes
amount of solvent (per cycle) required for extraction. During soxhlet
extraction, solvent was heated up and distilled. The distilled solvent
passes through the biomass placed in thimble in each cycle, but in case
of reflux, the solvent comes in direct contact with the biomass. In
limiting situation, the solvent becomes saturated and with no more
dissolution of lignin. This necessitates repetition of the extraction pro-
cess multiple times with fresh solvent. Lignin in biomass is in close
association with carbohydrates, thus along with lignin, sugars also get
dissolved in the solvent and the extraction process cannot extract pure
lignin from biomass. The residual biomass has a portion of lignin with
majority of carbohydrates. On the basis of solubility, compounds dis-
solved in the solvent can be divided into three classes, viz. (1) soluble in
water which includes sugars, (2) soluble in alcohols which includes
tannis, pigments, and (3) soluble in ether like fats or fatty acids, waxes
etc. (Pehrsson, 1949; Pepper et al., 1959; Witcraft, 1949). The solvent
was thereafter concentrated to 10–15 mL using rotary evaporator. The
dioxane recovered during concentration can be used in next cycle. The
lignin was recovered using protocol stated in Section 2.2.1. The filtrate
contained 0.57 g xylose released from 10 g of biomass.
M. Saha et al.
3.2. Characterization of lignin
3.2.1. Lignin composition
3.2.1.1. Moisture and ash content. After 18 h of drying at 105 °C the
reduction in weight was about 10.5% of the total weight, i.e. 0.21 g
moisture was present in 2 g lignin. This moisture free lignin after ashing
(i.e. burning in presence of oxygen in muffle furnace) resulted in 7.5 mg
reddish brown coloured ash. This indicated that very low amount of
minerals were present in lignin, which concurrently resulted in very
low, 0.42 wt%, ash.
3.2.1.2. Lignin and carbohydrate content. Lignin was treated with
sulphuric acid to release sugars present in the solution. The solution
was then filtered and the filtrate was analysed with HPLC. The results
show that no sugar was released from lignin after acid treatment, which
means carbohydrate content of lignin was zero or in other words, there
was no carbohydrate in the dry lignin. The reason for zero carbohydrate
content can be attributed to washing of lignin by warm water which
dissolved sugar present in it. After acid treatment, the insoluble part
was washed with water and dried, which resulted in 82 mg of insoluble
precipitate. The results showed that the lignin consists of 82% (w/w)
acid insoluble lignin and 0.01% acid soluble lignin.
3.2.1.3. Mineral content. Results of EDX analysis are shown in
supplementary material. Lignin was free from minerals. It is mainly
comprised of carbon, oxygen and hydrogen; although hydrogen cannot
be detected in EDX. Traces of chlorine were also detected, possibly due
to the fact that ammonium chloride was used during precipitation of
lignin. Thus, the composition of lignin was 82% acid insoluble lignin,
0.01% acid-soluble lignin, 0.42% ash and 10.5% moisture. No metals or
other minerals or carbohydrates were detected. Rest few components
like volatiles or other components could not be detected –as they got
dissolved in the acid hydrolysate, and this would contribute to rest of
the mass of lignin.
3.2.2. Lignin analysis
3.2.2.1. Thermogravimetric analysis (TGA). Thermal stability and
decomposition of extracted lignin was evaluated using TGA under
inert environment. The TGA and DTG curves shown in supplementary
material and they highlight the nature and composition of the
compound. Lignin is a polymer composed of aromatic compounds
with various branching which lead to a wide range of temperatures
from 100 °C to 800 °C over which it gets thermally degraded or
decomposed. The degradation of lignin through TGA curve can be
divided into 3 parts. In the first part ranging from 30 °C to 120 °C, the
weight loss occurs mostly due to removal of moisture. In the second
part ranging from 150 °C to 350 °C, the weight loss is attributed to
degradation of volatile products of lignin to release CO, CO2, CH4 etc.
The third part of TGA curve ranges from 350 °C to 800 °C, where
aromatic compounds get degraded with the release of gaseous products
leaving behind at char amounting to 33%(w/w) of the total weight of
lignin, which cannot be degraded any further.
Jakab et al. (1997) have correlated the nature of DTG curve and the
peak degradation temperature with the composition of lignin. The lig-
nins of low methoxy group content (or guaiacyl lignins) give high char
yield, while lignins with high methoxy group content yield low amount
of char. The guaiacyl units of lignin are more prone to thermally in-
itiated condensation reaction than the syringyl units. The peak tem-
perature of DTG curve representing maximum thermal degradation rate
increases with increasing methoxyl group content. The peak of the DTG
curve shown in supplementary material occurs at 348 °C. This essen-
tially indicates greater content of syringyl units in the lignin.
3.2.2.2. FTIR analysis. The FTIR spectra of extracted lignin showed in
supplementary material depict different characteristic peaks which
represent presence of different functional groups. The peak at
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Bioresource Technology Reports 5 (2019) 206–211
2923 cm−1 is attributed to alkyl CeH group. The peak at 1729 cm−1
is due to C]O stretching, while peaks at 1600 cm−1 and 1508 cm−1 is
due to aromatic C]C bending, which can be attributed to aromatic
skeleton of lignin. The peaks at 1371 and 1424 cm−1 represent the
phenolic hydroxyl groups. The bands between 1300 and 1000 cm−1 are
attributed to stretching of CeO ether or ester linkage. The bands below
860 cm−1 represent aromatic CeH bending confirming the aromatic
skeleton of the compound.
3.2.2.3. Elemental analysis. Elemental analysis results showed that the
lignin comprises 64.39% carbon, 7.03% hydrogen, 28.08% oxygen and
0.5% nitrogen with no sulphur content. The lignin has comparable
carbon content as purified kraft and soda–anthraquinone lignin;
whereas organosolv lignin has carbon, oxygen and nitrogen content
comparable to lignin extracted in the present study. But
lignosulphonate has lower carbon and higher oxygen content, as
compared to lignin extracted in the present study. Lignosulphonate
has nearly 5% sulphur content and kraft lignin has small quantity of
sulphur, whereas the extracted lignin in present study has no sulphur
content (Mansouri and Salvadó, 2006).
3.2.2.4. GPC analysis. Molecular weight of the extracted lignin was
determined by GPC, the lignin was eluted from the column and detected
at 9.083 min. The number average weight (Mn) of the lignin was 2473
while weight average weight (Mw) was 3158, with a polydispersity
index of 1.277. The weight of the lignin was determined by comparing
with the weight of the polystyrene standards used for calibration. Kraft
and soda–anthraquinone lignins have much lower number average
weight and weight average weight as compared to extracted lignin in
present study. Notably, number average weight and weight average
weight of lignin resulting from organosolv and ethanol process have
weights comparable to the lignin extracted by dioxane in present case.
It is found that lignin extracted by organic solvents do not degrade and
have higher degrees of polymerisation (Mansouri and Salvadó, 2006).
3.3. Lignin pyrolysis and characterization of the products
Pyrolysis of the lignin resulted in 22.75% w/w yield of bio-oil and
23.5% w/w char. The bio-oil had a density of 1.32 g/mL. As per results
reported in previous literature on lignin pyrolysis (Kalogiannis et al.,
2015), yield of bio-oil varies in the range of 17%–37% w/w lignin
depending upon lignin source, operating conditions, pyrolysis tem-
perature, rate of temperature rise, etc. In the study of Kalogiannis et al.
(2015), the yield of bio-oil from pyrolysis of lignin from hardwood
reduced from 37% to 18% w/w with rise in pyrolysis temperature from
450 to 600 °C. The results of present study concur with the results of
Kalogiannis et al. (2015) as we have got bio-oil yield of 22.75% w/w
lignin at a temperature of 600 °C.
Similarly, low char yield in present study (23.5% w/w) can also be
attributed to high pyrolysis temperature (600 °C) of lignin. This result is
also in concurrence with previous literature. For example, as reported
by Sharma et al. (2004), char yield decreased rapidly in the tempera-
ture range from 400 to 600 °C, followed by relatively gradual decrease
at temperature > 600 °C. Char yields are known to increase with re-
duction in heating rate. Moreover, presence of oxygen in pyrolysis
medium causes reduction in char yield. When lignin samples are ex-
tracted and washed with acid solution prior to pyrolysis, the char yield
is higher, as compared to the char yield from un-extracted samples.
Washing and extraction of lignin samples results in removal of sodium
and potassium species. Jakab et al. (1993, 1997) have shown that
presence of sodium in lignin enhances dehydration, demethoxylation,
decarboxylation and char formation during pyrolysis, and concurrently
reduces yields of organic volatiles and CO. Sodium and potassium
carbonates also change the composition of aromatic products of lignin.
Thus, partial removal of sodium and potassium enhanced the de-vola-
tilization of lignin at the expense of char formation. Thus, relatively low
M. Saha et al. Bioresource Technology Reports 5 (2019) 206–211

Table 1 cost making it economically unfeasible. The lignin resulting from

GC–MS analysis of lignin pyrolytic oil. soxhlet extraction method in present study overcomes most of limita-
Name of the compound % Composition tions listed above such as high ash and sugar content. This lignin has
very low ash content (~0.4% w/w) as well as negligible carbohydrate
Benzene 2.44 content which makes it suitable for various commercial application
Toluene 5.3
without any pretreatment.
4-Hydroxy-4-methyl-2-pentanone 8.6
m-Xylene 1.32
Solubility of lignin in different organic solvents like di-
p-Xylene 2.74 methylformamide (DMF), tetrahydrofuran (TFH), dioxane, etc. is cru-
Phenol 4 cial for various applications such as the production of lignin based
Benzoin 3.2 polyol for PU foam. The lignin derived from previous processes re-
2-Methoxyphenol 6.65
ported in literature has very low solubility in organic solvents, which
Benzoylformic acid 2.82
Benzylcarbamate 17.05 requires oxypropylation of lignin for increasing the reactivity and li-
Cyclopropylidene methyl benzene 2.7 quefaction. On the other hand, the lignin extracted using dioxane is
2-Methoxy-4-methylphenol 4.35 readily soluble in different solvents, which adds to its compatibility for
Naphthalene 3.91
various applications. The lignin extracted by dioxane has higher mo-
4-Ethyl-2-methoxyphenol 5
2–6-Dimethoxyphenol 7.7
lecular weight as compared to Kraft and soda–anthraquinone lignin,
Biphenyl 2.43 which is representative of its resistance for degradation.
1–2-4-Trimethoxybenzene 3.81
Phenol-2-6-bis(1,1-dimethylethyl)-4methyl 10.2 4. Conclusion
1,2,3-Trimethoxy-5-methylbenzene 2.84
alpha-methyl stilbene 2.94
In the present study, lignin was extracted by soxhlet extraction
using dioxane. 15% (w/w) lignin is obtained from the debarked
Table 2 bamboo waste, which upon characterization was found to be highly
Relative distribution of compounds in bio oil resulting from pyrolysis of lignin. pure, free from carbohydrate and mineral content and with low ash
content. This lignin was readily soluble in various organic solvents
Compounds % Composition
making it suitable for various applications like production of poly-
Phenols 4 urethane foam, vanillin etc. The bio-oil obtained from pyrolysis of this
Metoxy-, dimethoxyphenol derivatives 23.7 lignin can be stabilised and used as precursor for various petrochem-
Aromatic compounds (oxygenates) 39.9 icals, while the char obtained can be used for applications in activated
Aromatic compounds (non‑oxygenates) 23.8
carbon-based processes.
Non-aromatic ketones 8.6

char yields in this study are consequence of high purity of lignin and
low inorganic content.
The chemical composition of the bio-oil obtained from GC–MS
analysis is given in Tables 1 and 2. This analysis shows that ~91% w/w
oil comprises of aromatics and only the rest 9% consisted of non–aro-
matics. This could be attributed to the fact that lignin which is a
crosslink of three basic components, viz. 3,5–dimethoxy–4–hydroxyl
phenylpropane, 4–hydroxyl phenylpropane and 4–hydro-
xy–3–methoxyphenylpropane, are mainly phenolic derivatives. Some of
the major components were benzylcarbamate, 2–6–bis(1,1–dimethy-
lethyl)–4methylphenol, 2–methoxyphenol and other phenolic deriva-
tives. The products ranged between C6 and C16 with 62.93% ac-
counting in the C6–C8 range, which are simple derivatives of phenol
and benzene.
CHNS analysis of char showed that it contains 92.04% w/w carbon,
1.61% w/w nitrogen, 1.21% w/w hydrogen and 5.14% w/w oxygen.
Thus, the char obtained from pyrolysis was a rich source of carbon. TGA
analysis of char, as depicted in supplementary material, showed that it
was highly stable in high temperature with very little loss in mass that
can be attributed to presence of moisture.
Several methods for lignin extraction are reported in literature, with
every method having certain merits and demerits. High ash content in
kraft lignin (~30% w/w) restricts its direct application in any com-
mercial product such as polyurethane foam, phenolic based resins, etc.
Thus, kraft lignin needs to be treated with conc. Sulfuric acid so as to
reduce the ash content. Soda–anthraquinone lignin also requires pre-
treatment before its use in any industrial application. It is generally
heated to 90–95 °C under rapid stirring followed by acidification by
sulphuric acid for precipitation. The precipitate has to be further wa-
shed with hot water to solubilise residual sugars to obtain purified
lignin. Ethanol process lignin is also subjected to acid treatment fol-
lowed by hot water washing, which reduces the sugar content. These
processing steps improve the quality of lignin but indulge additional
Acknowledgement
The authors acknowledge the Centre for Energy and Department of
Chemical engineering IIT Guwahati for providing necessary analytical
facilities required for carrying out the research. The authors also ac-
knowledge SAIF IIT Bombay for elemental analysis and SAIC, Tezpur
University for gel permeation chromatography analysis.
Declarations of interest
None
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.biteb.2019.01.018.
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