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Keywords: This study investigates the biorefinery approach to utilize Finger millet straw (FMS) for bioethanol, bio-oil and
Finger millet straw char production through fermentation and pyrolysis for the first time. The FMS was pretreated with sulphuric
Xylose fermentation acid along with autoclaving and then detoxified. The detoxified hydrolysate (DH) was fermented in the absence
Ethanol
and presence of additional supplements except xylose using Pichia stipitis NCIM-3497 at 30 ◦ C, pH 5.0 and 150
Pyrolysis
Char
rpm for 96 h. The presence of additional supplements in DH enhanced the ethanol production by 35% as
Bio-oil compared the only DH. The pyrolysis of pretreated solid residue resulted in 42% (w/w) bio-oil and 27.2% (w/w)
char. The pH of bio-oil was 3.5 with a density of 1.1 g/mL. The bio-oil contained 50% (v/v) aromatics, 13.7% (v/
v) heterocyclics and 12% (v/v) non–aromatic compounds. The upgradation of obtained bio-oil is required to
refine the valuable compounds such as furfural, 1-(2-hydroxy-5-methylphenyl)-ethanone and 4-allyl syringol.
* Corresponding author at: Department of Biosciences and Bioengineering, Indian Institute of Technology Guwahati, Guwahati 781039, India.
E-mail address: arungoyl@iitg.ac.in (A. Goyal).
https://doi.org/10.1016/j.biteb.2021.100630
Received 13 October 2020; Received in revised form 31 December 2020; Accepted 1 January 2021
Available online 11 January 2021
2589-014X/© 2021 Elsevier Ltd. All rights reserved.
S.B. Jamaldheen et al. Bioresource Technology Reports 13 (2021) 100630
Physical detoxification involves employment of evaporation technique achieve neutral pH and dried at 70 ◦ C in a hot-air oven for 24 h. The
to remove the volatile inhibitors such as acetic acid and furfural from the filtrate and the residual solid were used for fermentation and pyrolysis,
hydrolysate (Palmqvist et al., 1996). The chemical detoxification in respectively as described the upcoming sections.
volves the use of calcium hydroxide, Ca(OH)2 and sodium sulphite,
Na2SO3 to reduce the concentrations of hydroxymethyl furfural (HMF), 2.2. Overliming of the acid hydrolysate
furfural and other phenolic compounds (Zyl et al., 1988; Palmqvist and
Hahn-Hagerdal, 2000). Among above mentioned detoxification The filtrate containing acid hydrolysate (1 L) from the above pre
methods, the chemical detoxification serves as the most efficient treatment was heated up to 100 ◦ C for 15 min to remove the volatile
method, as it consumes lesser time and energy (Palmqvist and Hahn- compounds. The solution was overlimed by adding Ca(OH)2 while
Hagerdal, 2000). Chemical detoxification can be carried out through stirring until pH 10.0 was achieved. The overlimed hydrolysate was
the neutralization or overliming of the acid hydrolysate by NH4OH or Ca centrifuged at 5000 rpm for 15 min and the pellet was discarded. The
(OH)2, respectively (Agbogbo and Wenger, 2007; Ranatunga et al., supernatant was reacidified to pH 6.0 by adding 1 N H2SO4 and filtered
2000). Pichia stipitis, Pachysolen tannophilus and Candida shehatae are through Whatman No. 1 filter and then stored at 4 ◦ C until further use
naturally-occurring microorganisms which can ferment pentose sugars for fermentation (Kumar et al., 2009b).
(Agbogbo and Coward-Kelly, 2008). Pichia stipitis is an active and
industrially promising C5 fermenting yeast that grows under anaerobic 2.3. Microorganism and maintenance
conditions and gives high ethanol yield (Diaz et al., 2009; Shrivastava
et al., 2014). 1% (v/v) H2SO4 with autoclaving was one of the evaluated The pentose fermenting yeast, Pichia stipitis NCIM-3497 was pro
pretreatments on the agrowaste, Finger millet straw (FMS) in our earlier cured from National Collection of Industrial Microorganisms (NCIM),
study (Jamaldheen et al., 2019). The treatment was not suitable for the Pune, India. The yeast was grown in the malt extract medium containing
biochemical route towards hemicellulose saccharification, as xylanase 30 g/L malt extract, pH 5.5 at 30 ◦ C and 150 rpm for 24 h and then
was not able to access the acid treated FMS. Interestingly, the above aliquoted as glycerol stocks and maintained at − 20 ◦ C. The inoculum to
treatment hydrolysed all the hemicellulose content and brought them be used for fermentation was grown in the YPMX medium containing the
into the liquid fraction (acid hydrolysate) as xylose (~8 g/L) and following media components in g/L: 20.0 D-xylose, 1.5 yeast extract, 5.0
arabinose (~3 g/L). This was correlated with the composition analysis peptone and 3.0 malt extract, pH 5.0 (Magdum et al., 2012).
data of the pretreated FMS (residual solid), which contained no hemi
cellulose content but only high cellulose and lignin contents as reported 2.4. Pentose fermentation by Pichia stipitis NCIM-3497 for ethanol
in our previous study (Jamaldheen et al., 2019). This gives a scope to production
utilize the acid hydrolysate as a potential nutrient source for ethanol
production through pentose fermentation. Therefore, this study focuses Two fermentation media for pentose fermentation by using Pichia
on the detoxification of acid hydrolysate resulting from the acid pre stipitis NCIM-3497 to produce ethanol were compared.
treatment (1% (v/v) H2SO4 with autoclaving) of FMS by overliming with
Ca(OH)2. Pichia stipitis NCIM-3497 was used for the ethanol production i) DH at pH 5 was used as the fermentation medium.
from the DH. Biorefinery approach was applied to utilize the residual ii) DH supplemented with the following additional medium compo
solid obtained from the pretreatment of FMS from the above study, nents at pH 5 (Kumar et al., 2009b) (g/L): KH2PO4 - 2; (NH4)2SO4 - 1;
while utilizing the acid hydrolysate for fermentation. Yeast extract - 1; MgSO4.7H2O - 0.5; Trace element mixture - 1 mL/L.
Biorefinery concept involves production of two or more valuable Trace element mixture was prepared with the following chemicals
products from a desired bioresource through one or multiple processes (g/L): CuSO4.5H2O - 2.5; CuSO4.5H2O - 2.7; MnSO4.H2O - 1.7;
(Cherubini, 2010). Pyrolysis is an attractive thermochemical method for Na2MoO4.2H2O - 2.42; CaCl2.6H2O - 2.4; ZnSO4.7H2O - 2.87.
converting of any kind of waste material to biofuel or valuable chemicals
(Wang et al., 2017; Xue and Bai, 2018). A variety of solid wastes from 5% (v/v) inoculum by Pichia stipitis NCIM-3497 having 0.6 OD was
agrowaste to sewage sludge have been pyrolysed to produce char and added to 50 mL of either fermentation medium in a 100 mL screw cap
bio-oil in earlier reports (Sanna et al., 2011; Callegari and Capodaglio, bottle in order to maintain anaerobic condition. The fermentation was
2018). For the complete utilization of the residual solid from the acid performed in an incubation shaker for 4 days at a temperature, pH and
treatment of FMS, pyrolysis can be carried out aiming to produce various rpm of 30 ◦ C, pH 5 and 150, respectively. Each experiment was carried
valuable products. The pyrolysis of residual solid obtained from the out in duplicate and sampling was done at a regular interval of 12 h to
pretreatment of FMS for production of bio-char and bio-oil was carried determine the cell mass, xylose, arabinose and ethanol concentration.
out. This study gives a preliminary overview of the biorefinery approach
to produce ethanol, bio-oil and biochar from an agrowaste, Finger millet 2.5. Cell mass estimation
straw (FMS). Characterization of the bio-oil from pyrolysis of acid
treated FMS is being reported for the first time. One millilitre of Pichia stipitis NCIM-3497 culture was taken at every
12 h interval in a pre-weighed micro-centrifuge tube and then centri
2. Materials and methods fuged at 5000 rpm for 10 min. Supernatant from the tube was trans
ferred to another 1.5 mL micro-centrifuge tube and the cell pellet was
2.1. Acid pretreatment of Finger millet straw dried at 60 ◦ C and weighed until a constant weight was observed to
determine the dry cell weight.
The collection, processing and acid pretreatment of Finger millet
straw (FMS) was carried out as described in the earlier report 2.6. Analysis of xylose, arabinose and ethanol concentration from
(Jamaldheen et al., 2019). The pretreatment chosen for this study was fermentation by HPLC
1% (v/v) H2SO4 with autoclaving for 20 min at 121 ◦ C and 15 psi, as it
was able to comprehensively hydrolyse the entire hemicellulose fraction The supernatant samples (1 mL) from both fermentations (0 h to 96
of FMS (Jamaldheen et al., 2019). The acid pretreatment of FMS was h) were filtered by using polyvinylidene fluoride (PVDF) filter mem
performed by soaking 5% (w/v) of powdered raw biomass in 2 L of 1% brane with a pore size of 0.45 μm. The xylose, arabinose and ethanol
(v/v) H2SO4 and autoclaving at the above mentioned conditions. The contents in the filtrate were determined by HPLC linked with an auto
hydrolysed biomass was then filtered by using muslin cloth and the sampler and RI detector from Shimadzu corporation, Japan. The HPLC
remaining residual solid was thoroughly washed with distilled water to column setup consisted of Rezex ROA (H+) organic acid and
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S.B. Jamaldheen et al. Bioresource Technology Reports 13 (2021) 100630
monosaccharide column and a guard column from Phenomenex. The 2.10. Characterization of the bio-oil
mobile phase, 5.0 mN H2SO4 was passed through the column at 0.6 mL/
min (Jamaldheen et al., 2019). The concentration of xylose, arabinose The chemical composition analysis of the bio-oil from pyrolysis was
and ethanol in the sample were calculated from their respective peak performed by Gas Chromatography (Clarus 680-GC) linked with Mass
area. Spectroscopy (Clarus 600-MS) using a 60 m × 250 μm VF–5MS, inert 5%
phenyl–methyl column. 99.99% Helium was used as the carrier gas. The
bio-oil sample was diluted with HPLC grade acetone (Merck, India) at a
2.7. Statistical analysis of fermentation data ratio of 1:200 and then filtered through hydrophilic Polytetrafluoro
ethylene (PTFE) filter membrane having 0.2 μm pore size (Millipore,
The fermentation experiments were carried out in duplicates. Sta USA). The injection volume was 1.5 μL. Injection point temperature was
tistical significance of the data observed from the two experimental set at 280 ◦ C to instantaneously vaporize the acetone-solubilized bio-oil.
categories i.e., DH fermentation in the presence and absence of addi The GC–MS was operated with a 1:10 split ratio. The temperature of the
tional medium components was analysed by performing two sample t- GC oven was initially maintained at 60 ◦ C for 2 min. It was then ramped
test. up to 140 ◦ C at 5 ◦ C/min and then held at 140 ◦ C for 5 min. It was further
heated at a rate of 5 ◦ C/min up to 300 ◦ C and then held at 300 ◦ C for 5
2.8. Proximate and ultimate analysis of acid pretreated FMS min.
Proximate analysis of the dried residual solid obtained after the acid 3. Results and discussion
pretreatment of FMS was performed by following the standard ASTM
(D7582–15) procedure. The analysis was carried out by using Thermo 3.1. Fermentation of the detoxified hydrolysate
gravimetric analyser (TGA, STA7200, Hitachi, Japan). The sample was
loaded in the pan and weighed initially at 30 ◦ C in nitrogen environment The detoxification of the hydrolysate from acid treatment of FMS by
(100 mL/min). Temperature of the sample was increased until 107 ◦ C at overliming with Ca(OH)2 precipitated most of the suspended solids
a rate of 10 ◦ C/min and then held at 107 ◦ C for 10 min to determine the thereby reducing the turbidity of acid hydrolysate. Furfural and HMF
moisture content. It was further heated up to 900 ◦ C at the same heating concentrations in the detoxified hydrolysate (DH) were not analysed,
rate and held for 10 min in the nitrogen environment to determine the because HMF was not present in the acid hydrolysate before detoxifi
volatile matter present in the acid treated FMS. The gas was switched cation and furfural concentration of the acid hydrolysate was very low
from nitrogen to oxygen (100 mL/min) and the sample was ignited at 0.04 g/L, as reported in our previous study (Jamaldheen et al., 2019).
900 ◦ C for 15 min to determine the fixed carbon present in the sample. Bellido et al. (2011) reported that furfural concentration less than 2 g/L
The residue remained after the above last step was the ash content of the does not affect ethanol fermentation by using Pichia stipitis. Fermenta
acid treated FMS. Ultimate analysis to determine C, H, N and S tion of the DH by Pichia stipitis NCIM-3497 was carried out at 30 ◦ C, pH 5
composition in the acid treated FMS was carried out using the Elemental and 150 rpm in shaking incubator for 96 h (Fig. 1). Initial analysis of DH
Analyser (EuroEA3000) from Euro Vector, Italy. showed 6.0 g/L and 2.3 g/L of xylose and arabinose, respectively at 0th
h. The fermentation medium contained 2.8 ± 0.7 g/L xylose at the end of
96 h and hence the xylose consumption during the fermentation was
2.9. Pyrolysis of acid pretreated FMS calculated to be 3.2 g/L in 96 h. The analysis of the fermentation me
dium also showed negligible change in concentration of arabinose,
The residual solid obtained from the acid pretreatment of FMS was showing that it was not utilised by the yeast, Pichia stipitis NCIM-3497
pyrolysed. The pyrolysis setup consisted an inert gas system, heating (Fig. 1). The concentration of ethanol produced in the DH at the end
unit, batch pyrolysis reactor vessel, bio-oil vapour condensation system of 96 h fermentation was 1.3 ± 0.2 g/L. Therefore, the ethanol yield
and collection system. 99.9% pure nitrogen gas was used as the inert gas. from the fermentation of xylose from the DH was 0.39 g/g xylose
The pyrolysis reactor vessel of capacity 600 mL made up of stainless steel consumed. The unutilized xylose by the microorganism remained 2.8 g/
316 grade was highly corrosion resistant to protect the inner surface L. The cell biomass concentration after 96 h of fermentation was 3.1 ±
from the acidic nature of the bio-oil. The pyrolysis reactor vessel was 0.1 g/L. The results from the two sample t-test are shown in Table 1. The
placed inside an electrical furnace that was capable of heating up to statistical analysis showed that the inclusion of additional medium
900 ◦ C. The approximate heating rate of the furnace was 25 ◦ C/min and
could reach the maximum temperature of 900 ◦ C within 45 min. The
temperature within the reactor was monitored by a sensitive thermo
couple. The electrical furnace temperature was controlled by using a PID
controller. Condenser made up of stainless steel was used to achieve
faster heat transfer rates, that assisted in rapid condensation of the
produced bio-oil vapors. The cold water at around 10 ◦ C was circulated
outside the bio-oil outlet vapour flow line for condensation. The bio-oil
collection system consisted of separating funnels, where the condensed
vapors were collected. Funnels were used, so that the bio-oil samples
could be collected periodically for analysis. 30 g of acid treated FMS was
taken in the reactor and the furnace was set at 600 ◦ C for 1 h. Chemical
composition of the collected bio-oil was analysed by gas chromatog
raphy and mass spectroscopy (GC–MS). Char obtained from the pyrol
ysis was weighed and stored at room temperature. The gaseous product
from pyrolysis was calculated by subtracting the wt% of bio-oil and char
from the initial pretreated biomass used for pyrolysis as given in Eq. (1),
below (Durak et al., 2019; Yücedağ and Durak, 2019):
Gasous product (wt%) = 100% − (bio − oil (wt%) + char (wt%) ) (1)
Fig. 1. Fermentation profile of DH from acid treated FMS by Pichia stipitis
NCIM-3497.
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Table 1 production from acid hydrolysate of corn stover using Pichia stipitis. The
Statistical analysis of experimental data from fermentation. higher xylose consumption, cell growth and ethanol production in the
Ethanol Xylose Biomass hydrolysate containing additional supplements, in the present study,
concentration concentration concentration might be due to the availability of the lacking nutrients for cell func
Plain DH Plain DH Plain DH tioning. The low ethanol concentration (2 g/L) from the fermentation of
DH AMC DH AMC DH AMC DH supplemented with additional medium components was due to the
Mean 1.3 2.0 2.8 0.8 3.1 4.2
low concentration of xylose (6 g/L) available in the hydrolysate. Xylose
Variance 0.06 0.14 0.6 0.0005 0.02 0.08 concentration in the DH can be further increased by vacuum evapora
Observations 2 2 2 2 2 2 tion as reported (Kumar et al., 2009b; Magdum et al., 2012) to increase
Df 2 2 2 the ethanol titre.
p-Value 0.08 0.03 0.02
For the level of xylose present in the above medium, the yeast, Pichia
DH = detoxified hydrolysate. stipitis NCIM-3497 performed well by utilizing 85% of xylose to attain an
DH AMC = detoxified hydrolysate containing additional medium components. ethanol yield of 0.39 g/g xylose utilised. The ethanol yield obtained in
Df = degrees of freedom. the present study is similar to those earlier reported ethanol yields from
the fermentation of DHs of wheat straw and rice straw (Nigam, 2001a;
components during fermentation gave more significant effect on xylose Huang et al., 2009) using other strains of Pichia stipitis as shown in the
consumption (p-value ˂ 0.05, CL ˃ 95%) and cell growth (p-value ˂ 0.05, Table 2. This could be attributed to the similar phytomorphology of the
CL ˃ 95%) than on the ethanol production (p-value ˂ 0.1, CL ˃ 90%). wheat, rice and finger millet straws. However, instead of using DH from
Amartey and Jeffries, 1994 reported that without the additional acid treated FMS alone for ethanol production, it can be mixed with
supplements, acid hydrolysate from corn steep liquor served as a good hydrolysate from acid treated wheat or rice straw as a co-substrate to
fermentation medium for Pichia stipits for ethanol production (Amartey achieve a high ethanol titre.
and Jeffries, 1994). The use of additional medium components has been
reported for the acid hydrolysate of water hyacinth for ethanol pro 3.2. Characterization of acid pretreated FMS
duction (Kumar et al., 2009b; Magdum et al., 2012). Since, the acid
hydrolysate from FMS is a new medium, therefore, in this regard, the The results of proximate analysis of the residual solid resulted from
fermentation was carried out in the presence and absence of additional the acid treatment of FMS are shown in Table 3. The acid treated FMS
supplements to compare their effects on the ethanol production by Pichia contained 83% (w/w) of volatile matter and 8% (w/w) of fixed carbon
stipits. In the DH supplemented with synthetic fermentation medium content. These values fall in the commonly observed volatile matter
components without the xylose, the ethanol concentration increased (71–88% (w/w)) and fixed carbon content (8–21% (w/w)) ranges of
from 1.3 ± 0.2 g/L to 2 ± 0.4 g/L at 96 h (Fig. 2). The xylose con various feedstocks as reported earlier (Klinger et al., 2018). The fixed
sumption also increased from 3.2 g/L to 5.2 g/L, thus only 0.8 g/L of carbon content of the biomass accounts for the coke formation in the
xylose remained unutilized. Irrespective of the presence of synthetic char and volatile matter corresponds to the production of gas, oil and tar
medium components, arabinose remained unutilized by Pichia stipitis during pyrolysis (Mierzwa-Hersztek et al., 2019; Chouhan and Sarma,
NCIM-3497. This showed that xylose was more favourable substrate 2013). The CHNS content of the acid treated FMS are shown in the
than arabinose for the yeast, Pichia stipitis NCIM-3497. The ethanol yield Table 3. Our previous study showed that the raw powdered FMS con
was found to be 0.39 g/g xylose consumed, which is similar to the tained 43.9% (w/w), 5.7% (w/w) and 1.7% (w/w) of carbon, hydrogen
ethanol yield from the plain DH without any addition of synthetic me and nitrogen, respectively (Jamaldheen et al., 2019). The acid treated
dium components. The cell biomass concentration was found to be 4.2 FMS in the present study, contained similar carbon content (41.6%, w/
± 0.3 g/L at 96 h in the presence of synthetic medium components. This w) and 36% lesser hydrogen than the raw FMS. This led to a reduction in
clearly showed that the presence of other synthetic medium components H/C ratio of the acid treated FMS to 1.0 from 1.6 of the raw FMS. The O/
favoured both cell growth of Pichia stipitis NCIM-3497 and ethanol C ratio of the acid treated FMS increased to 0.99 from 0.83 of raw FMS. It
production. Yeast needs a main carbon source along with Nitrogen,
Sodium, Potassium, Ammonium, Magnesium and other trace elements Table 2
like Copper, Manganese, Calcium and Zinc for its growth and desired Ethanol yield from fermentation of the detoxified acid hydrolysates from various
product formation (Nigam, 2001b). Agbogbo and Wenger (2007) also lignocellulosic feedstocks.
reported the positive effect of additional nitrogen on the ethanol
Feedstock Pretreatment Fermenting Ethanol Reference
yeast strain Yield
(P. stipitis) (Yp/s)
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Table 3 Table 4
Proximate and ultimate analysis of the acid treated FMS. GC–MS analysis of bio-oil.
Proximate analysis % (w/w)a Retention time Name of the compound % Composition
(min) (v/v)
Moisture content 3.2 ± 0.3
Volatile matter 83.1 ± 0.4 10.60 Furfural 10.3
Fixed carbon 7.9 ± 0.02 14.16 n-Butyl ether 1.4
Ash content 5.8 ± 0.1 14.26 1-(Acetyloxy)-2-butanone 1.1
Ultimate analysis % (w/w) 14.61 5-Methyl-2-furaldehyde 3.4
C 41.6 16.90 2-Hydroxy-3-methyl-2-cyclopenten-1-one 2.0
H 3.6 18.46 1-(2-Methyl-1-cyclopenten-1-yl)-ethanone 4.4
N 0.03 21.45 2-Ethylphenol 2.0
S Nil 21.82 Creosol 3.8
O 54.8b 24.61 2,3-Dihydrobenzofuran 7.1
a 25.31 4-Ethylguaiacol 2.7
Mean ± SD (n = 2). 27.45 1-(2-Hydroxy-5-methylphenyl)-Ethanone 12.4
b
By difference. 29.93 Syringol 3.4
31.21 1-Ethyl-1-methoxy-1-silacyclohexane 2.5
32.06 Eugenol 3.0
was reported that the lower H/C ratio and higher O/C ratio of the acid
32.66 1,2,4-Trimethoxybenzene 3.4
pretreated biomass (Arundo donax) as compared with the untreated 34.77 1,2,3-Trimethoxy-5-methyl-benzene 1.5
biomass yields higher bio-oil during pyrolysis (Saynik and Moholkar, 36.31 1-(3,4-Dimethoxyphenyl)-ethanone 1.5
2020). Therefore, the acid treated FMS may also serve as a good 37.15 D-allose 2.0
candidate for bio-oil production. The pretreatment (1% (v/v) H2SO4 39.64 4-Allylsyringol 8.4
42.29 1,1′ -Butylidenebis-benzene 0.8
with autoclaving) has removed 98% of nitrogen from the raw FMS. It
was reported that the lower nitrogen content in the lignocellulosic
feedstock decreases the production of toxic gases including ammonia, degraded to give furfural (Bai et al., 2019). The acid treated FMS used in
hydrogen cyanide, isocyanic acid and nitrogen oxides during pyrolysis the present study did not contain hemicellulose (Jamaldheen et al.,
(Chen et al., 2012). The elemental analysis of the acid treated FMS 2019), which implies clearly that the furfural was produced from the
(Table 3) showed favourable properties for pyrolysis. cracking of cellulose. It was reported that the selective furfural pro
duction can be up to 60% (w/w) through pyrolysis of commercial cel
3.3. Pyrolysis of acid pretreated FMS lulose fibres in the presence of Na/Fe solid acid catalyst (Bai et al.,
2019). Similar investigation with catalyst on the acid treated FMS,
The pyrolysis of acid pretreated FMS resulted in 41.98% (w/w) of considering high cellulose content, may lead to higher furfural yield in
bio-oil, 27.20% (w/w) char and 30.82% (w/w) of gaseous product. A bio-oil.
review report by Chouhan and Sarma, 2013 showed the positive cor The classification of compounds was done based on the work of Staš
relation between the volatile matters of various lignocellulosic bio et al. (2014), who categorized a large number of compounds obtained by
masses and their corresponding bio-oil yields from pyrolysis (Chouhan conventional GC–MS analysis of bio-oils produced from pyrolysis of
and Sarma, 2013). Therefore, the higher bio-oil yield than char from the different feedstocks. They classified the chemicals into various groups
pyrolysis of pretreated FMS, in the present study, was due to the higher such as non-aromatic, heterocyclic, carbohydrate and aromatic com
volatile matter present in the biomass. The density of the obtained bio- pounds. The chemical compounds found in the bio-oil (Table 4) in this
oil was 1.09 g/mL and the pH was 3.5. Fig. 3 shows the GC–MS chro study were grouped (Table 5) with reference to the classification given
matogram of bio-oil from the pyrolysis of residual solid resulted after the by Staš et al. (2014). Table 5 shows that around 50% (v/v) of the bio-oil
acid treatment of FMS. The prominent peaks were analysed with respect comprised aromatics, 13.7% (v/v) heterocyclics and 12% (v/v) of
to the GC–MS library and earlier literature (Branca et al., 2003). The non–aromatics. A major part of the aromatic compounds is classified
chemical composition of the bio-oil analysis is listed in Table 4. One of under methoxyphenol derivatives which are attributed to the thermal
the major products in the bio-oil was furfural (10%, v/v), which is a cracking of lignin (Branca et al., 2003). The compounds which come
derivative produced from biomass carbohydrate. The thermal break under the methoxyphenol derivatives category are syringol, creosol,
down of cellulose and hemicellulose during pyrolysis leads to the for eugenol and a few derivatives of syringol. 12% (v/v) of bio-oil compo
mation of the anhydrosugar (levoglucosan) and furfural, respectively nents being heterocyclic in nature are purely attributed to the presence
(Fan et al., 2019). On further heating, levoglucosan gets further of furans which are obtained as a result of the ring fission and cyclization
Fig. 3. GC–MS chromatogram of the bio-oil obtained after pyrolysis of acid pretreated (1% (v/v) H2SO4 with autoclaving) FMS.
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