Journal of Environmental Management 221 (2018) 45–52

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Journal of Environmental Management

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Research article

Effect of thermal pretreatment on chemical composition, physical structure T

and biogas production kinetics of wheat straw
Asad Ayub Rajputa, Zeshana,∗, Chettiyappan Visvanathanb
a
Institute of Environmental Sciences and Engineering (IESE), School of Civil and Environmental Engineering (SCEE), National University of Sciences and Technology
(NUST), Islamabad 44000, Pakistan
b
Environmental Engineering and Management, School of Environment, Resources and Development, Asian Institute of Technology, Bangkok, Thailand

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

Keywords: Hard lignocellulosic structure of wheat straw is the main hindrance in its anaerobic digestion. Thus, a laboratory
Thermal pretreatment scale batch experiment was conducted to study the effect of thermal pretreatment on anaerobic digestion of
Wheat straw wheat straw. For this purpose, different thermal pretreatment temperatures of 120, 140, 160 and 180 °C were
Lignocellulosic material studied and the results were compared with raw wheat straw. Significant differences in biogas production were
Biogas production
observed at temperature higher than 160 °C. Highest biogas yield of 615 Nml/gVS and volatile solids reduction
Kinetic model
of 69% was observed from wheat straw pretreated at 180 °C. Wheat straw pretreated at 180 °C showed 53%
higher biogas yield as compared to untreated. Further, FTIR analysis revealed change in chemical bonds of
lignocellulosic structure of wheat straw. Modified Gompertz model was best fitted on biogas production data and
predicted shorter lag phase time and higher biogas production as the pretreatment temperature increased.
Overall, change in lignocellulosic structure and increase in cellulose content were the main reason in enhancing
biogas production.

1. Introduction
Energy is a vital element for continued economic growth and de-
velopment. Unfortunately, Pakistan is facing numerous problems due to
energy deficiency. To overcome severe power crisis the country is
looking for different renewable and sustainable energy options. In this
scenario bioenergy can play a crucial role since bioenergy is considered
as fourth largest energy resource in the world. Enormous source of
agricultural biomass is available for bioenergy production in Pakistan.
It is estimated that the country generates around 69 million tons of field
based agricultural crop residues annually (Raheem et al., 2016). Wheat
straw is one of crop residue types produced in huge quantities from
agricultural fields. Pakistan produces approximately 25 million tons of
wheat straw every year (Arshadullah et al., 2012).
Anaerobic digestion of wheat straw could be a promising way of
bioenergy production as it reduces various problems originated from its
inadequate disposal. However, the process consists of many stages in-
cluding hydrolysis, acidogenesis and methanogenesis, out of which
hydrolysis is considered as the rate-limiting step in anaerobic digestion
of wheat straw due to its lignocellulosic nature. In a lignocellulosic
biomass like wheat straw, the connected structure of lignin and hemi-
cellulose provides physical barrier to degradation of cellulose and
hence limits its biodegradation rate. Thus, suitable pretreatment is re-
quired to enhance digestibility of lignocellulosic wheat straw.
Various pretreatment methods are used for increasing the anaerobic
digestibility of lignocellulosic waste. These include dilute acid pre-
treatment (Schell et al., 2003), mechanical pretreatment for size re-
duction (Mshandete et al., 2006), microbial pretreatment (Mustafa
et al., 2016) and microwave pretreatment (Sapci, 2013). These pre-
treatments alter the lignocellulosic structures by breaking the chemical
bonds, which may increase the potential of cellulose hydrolysis and
biogas production (Fang et al., 2015; Jaffar et al., 2016; Wang et al.,
2016). However, there are certain limitations in the use of these pre-
treatments. For instance, chemical pre-treatment produces secondary
pollution and biological pre-treatment conditions are difficult to con-
trol, and combined pre-treatment usually has the disadvantages of both
chemical and biological methods. In comparison, physical pre-treat-
ment methods are most commonly used due to operational convenience
and low investment (Haghighi Mood et al., 2013).
Thermal pretreatment is a type of physical pretreatment in which
the lignocellulosic biomass is subjected to heating at a certain tem-
perature and pressure. The temperature range for this purpose could be
50–240 °C. Depending on the type of heating method, it could be called
as thermal pretreatment, hydrothermal pretreatment, steam explosion

∗
Corresponding author.
E-mail addresses: zeshansheikh@iese.nust.edu.pk, zeshan90@gmail.com (Zeshan).

https://doi.org/10.1016/j.jenvman.2018.05.011
Received 12 December 2017; Received in revised form 29 April 2018; Accepted 5 May 2018
Available online 26 May 2018
0301-4797/ © 2018 Elsevier Ltd. All rights reserved.
A.A. Rajput et al.
Table 1
Overview of effect of thermal pretreatment on AD of lignocellulosic biomass.
Biomass Pretreatment Pretreatment conditions
Wheat straw Thermal pretreatment 150–220 °C for 1–15 min
Wheat straw Steam explosion 180 °C for 15 min
Washed vinegar residue Hydrothermal 80, 120 and 160 °C for
pretreatment 30 min
Rice straw Hydrothermal 90, 150, 180 and 210 °C for
pretreatment 15 min
Urban and industrial waste Thermal 60, 80, 100, 120 °C for
activated sludge Pretreatment 30 min
Dewatered sludge Thermal 160 °C and 0.55 Mpa for
Pretreatment 30 min
Wheat straw and sugarcane Thermal pretreatment 121 °C for 60 min
bagasse
or microwave heating (Table 1). Menardo et al. (2012) studied the ef-
fect of thermal pretreatment on anaerobic digestion of wheat, barley
and rice straw and maize stalk at pretreatment temperature of 90 and
120 °C for 30 min and found 64.2, 40.8, 32.4 and 7.1% increase in
methane yield respectively at 120 °C compared to untreated control.
Similarly, hydrothermal pretreatment of wheat straw at 200 °C for
10 min showed 20% increase in methane yield (Chandra et al., 2012).
Another study reported 27% increase in methane yield from thermally
pretreated wheat straw at 200 °C for 5 min as compared to control
(Ferreira et al., 2014). Most of the studies mentioned here and in
Table 1 used high temperature with a short pretreatment time. On the
other hand, a relatively long pretreatment time of 60 min at lower
pretreatment temperatures of 60, 70, 80, 90 and 100 °C has been used
in a recent study (Chen et al., 2017) for thermal pretreatment of textile
dying sludge, in which the highest methane yield was produced from
the sludge pretreated at 100 °C. Thus, effect of thermal pretreatment of
wheat straw at medium temperatures and long residence time on biogas
production has not been studied before and it may produce new in-
formation in the area.
Mathematical kinetic models play vital role in design and optimi-
zation of any process (Batstone, 2006). To assess the performance of
anaerobic digestion (AD) process, several kinetic models have been
used by researchers, which include Chen and Hashimoto model (Chen
and Hashimoto, 1980), Monod model (Zamanzadeh et al., 2013), first
order model (López et al., 2015), substrate mass balance model (Zhang
et al., 2015), and modified Gompertz model (Syaichurrozi and
Sumardiono, 2013). Modified Gompertz model is considered very effi-
cient in explaining lag phase time and sigmoidal growth curves (Pham
et al., 2014) of methane production. As pretreatment of biomass affects
lag phase time of the anaerobic process, it could be well explained by
Gompertz model. The proposed kinetic models would be helpful to
address the theoretical contextual for AD experimental data and hence
the effectiveness of the applied pretreatment.
The overall objective of the study is to assess the effect of thermal
pretreatment on the biogas production of wheat straw. In addition,
chemical and structural changes due to thermal pretreatment were also
studied. Further, biogas production rate was assessed in relation to
various thermal pretreatment temperatures by using experimental data
with the help of three different kinetic models.
2. Materials and methods
2.1. Inoculum and substrate
Digested manure was used as an inoculum in the study. Fresh di-
gested manure, collected from local biogas plant, was sieved to obtain a
uniform particle size of less than 2 mm and pre-incubated under
anaerobic conditions at 35 °C for 14 days to remove residual organic
matter. Wheat straw was used as a substrate and collected from local
farmer near the study area.
46
Journal of Environmental Management 221 (2018) 45–52
Findings References
20% increase in methane production Ferreira et al. (2013)
Increased 20% methane yield Bauer et al. (2009)
160 °C pretreated biomass showed 55.99% higher Ran et al. (2018)
methane yield
3% increase in biogas yield at 90 and 180 °C and 30% Wang et al. (2018)
decrease at 210 °C compared to control
Increased in biogas yield of 27 and 37% at 120 °C Ennouri et al. (2016)
45.7% increase in biogas production Chen et al. (2018)
29% increase in methane production from wheat Bolado-Rodríguez et al.
straw and 11% from sugarcane bagasse (2016)
2.2. Thermal pretreatment
The thermal pretreatment of wheat straw was performed in a
250 mL stainless steel reactor with an inserted Teflon box. In Teflon
inserted reactor, 80 g sample of wheat straw was taken, and 20 g of
distilled water was added into it to avoid burning of dry biomass during
pretreatment. The stainless-steel reactor was fully tightened and placed
in a high temperature box resistance furnace – x series (SX-5-12, China).
Thermal pretreatment temperatures were set at 120, 140, 160 and
180 °C, and after 60 min of thermal pretreatment the reactor was cooled
down using cold water. Finally, the pretreated wheat straw samples at
different temperatures were dried and stored in a vacuum plastic bag
until use. Thermal pretreatment of wheat straw was performed in tri-
plicate.
2.3. Batch anaerobic digestion experiments
In this study, wheat straw pretreated at four different thermal pre-
treatment temperatures was compared for biogas production. Serum
bottles of 300 mL with working volume of 225 mL were used as batch
reactors. Calculated quantities of substrate and pre-incubated inoculum
(20% of working volume) were taken in reactors to achieve the organic
loading of 10 gVS L−1 at substrate to inoculum (S/I) ratio of 1 (on gVS
basis). After taking the substrate and inoculum, the reactors were flu-
shed with nitrogen gas for ensuring anaerobic condition. The reactors
were tightly closed with rubber stopper and alumina crimp cap and
placed in an incubator at 35 °C for 45 days. Mixing was provided to
every reactor twice a day for 2–3 min. A glass gas syringe was used to
measure daily biogas production from reactors. No external nutrients
were added, all the required nutrients were provided by fresh inoculum
(digested manure). The experiment was carried out in triplicate. To get
the biogas production from untreated substrate, control reactor of un-
treated wheat straw was also prepared and run. Therefore, five sets of
reactors were prepared viz., untreated wheat straw, pretreated wheat
straw at 120, 140, 160 and 180 °C.
2.4. Analytical parameters
Analyses for total solids (TS), volatile solids (VS) and total kjeldahl
nitrogen (TKN) of wheat straw before and after pretreatment were
carried out according to standard methods (APHA, 2005). Total organic
carbon (%TOC) was calculated by dividing the value of volatile solid
content (%VS) with a factor of 1.8 (Adams et al., 1951). Biogas was
collected in gas collection bags and methane content in biogas was
analyzed using gas analyzer (Biogas 5000, Geotech, UK).
Lignin, hemicellulose and cellulose contents in different wheat
straw samples were measured with the help of chemical method as
described in Li et al. (2004). The detail of the analysis is as follows.
First, the amount of extractives in the biomass was determined by using
solvent extraction, for which, 60 mL acetone was used for 1 g of dried
A.A. Rajput et al. Journal of Environmental Management 221 (2018) 45–52

Table 2 Rm . e
Initial characteristics of substrate and inoculum. M = Pb × exp ⎧ −exp ⎡ (λ − t ) + 1⎤ ⎫
⎨
⎩ ⎢
⎣ Pb ⎥
⎦⎬⎭ (2)
Parameter Digested Manure Wheat Straw Wheat Straw (Elsayed et al.,
2016) Transference function model that follow first order curve for re-
lating microbial community with biogas production (Redzwan and
pH 6.9 ± 0.11 5.9 ± 0.1 – Banks, 2004) was also used in the study as shown in Eq. (3)
TS % 6.8 ± 0.1 90 ± 0.25 90.82 ± 0.20
VS 70.7 ± 0.26 94.4 ± 0.23 95.64 ± 0.05 R . (t − λ ) ⎞ ⎫
TOC 41 ± 0.11 54.7 ± 0.11 47.62 ± 0.58 M = Pb ⎧1 − exp ⎛− m ⎜ ⎟

⎨
⎩ ⎝ Pb ⎠⎭⎬ (3)
TKN 4.2 ± 0.1 1.11 ± 0.11 0.30 ± 0.04

wheat straw sample at a constant temperature of 90 °C for 2 h. After
that biomass sample was oven dried at 105 °C until constant weight was
achieved. The weight difference before and after extraction gave the
amount of extractives. For determining hemicellulose content in dif-
ferent wheat straw samples, 150 mL of sodium hydroxide (NaOH) so-
lution was added to 1 g of extractive-free dried biomass, which was kept
at constant temperature of 80 °C for 3.5 h. After that the biomass sample
was washed with deionized water until the value of pH approached 7.
The sample was then dried to constant weight. The weight difference
before and after the treatment gave the content of hemicellulose. Lignin
was determined by using 30 mL of 98% sulfuric acid for each gram of
extractive-free dried biomass sample. After that sample was kept at
ambient temperature for 24 h and then boiled at 100 °C for 1 h. The
mixture was then filtered, and residues were washed until the ions of
sulfate was detectable by titration of 10% solution of barium chloride.
The sample was then dried until constant weight is achieved. The
weight difference before and after the treatment gave lignin content.
Cellulose content was calculated by difference method as it was as-
sumed that extractives, lignin, hemicellulose and cellulose are the only
components in biomass.
Fourier transform infrared (FTIR) spectrophotometer (Alpha pla-
tinum ATR, Bruker, Germany) was used to analyze the change in
functional groups before and after thermal pretreatment. The spectra
were formed from 4000 to 500/cm with 32 times scanning. Essential
FTIR and Origin Pro 6 software were used for the analysis. X-ray dif-
fraction (XRD) analyses of pretreated and untreated wheat straw were
performed at an angle of 2θ, for the determination of crystallinity index
(C.I). For this purpose, Bruker D8 Advance diffractometer (Bruker,
Germany) was used. The C.I was used to describe the crystallinity of
pretreated and untreated samples based on reflected intensity, com-
puted with the help of Eq. (1) described by Segal et al. (1959).
C . I (%) = (I002 − Iam)/ I002 × 100
where, I002 = Peak intensity at crystalline region; Iam = Peak intensity
at amorphous region.
2.5. Kinetic study
Logistic function model as shown in Eq. (4) was also used to predict
the kinetics of biogas production.
Pb
M=
1 + exp { 4 . Rm . (λ − t )
Pb
+2 } (4)
where M is the biogas yield (NmL/gVS) with respect to time t (days), Pb
is the maximum biogas potential (NmL/gVS), Rm is the maximum
biogas production rate (NmL/gVS/d), λ is lag phase (days) and e is a
Euler's function equal to 2.7183.
2.6. Statistical analysis
All the experiments and analyses were performed in triplicate and
results were reported as average values. Analysis of variance (ANOVA)
was performed on results of biogas production and solids removal by
using SPSS 16 software at 5% level of significance to know the differ-
ences between the treatments. The kinetics fitting was performed in
SPSS 16.
3. Results and discussion
3.1. Feedstock characteristics
Feedstock characteristics are very important parameters in design
and operation of an anaerobic digester. The initial characteristics of
feedstock strongly affect startup, process stability and biogas produc-
tion during anaerobic digestion. Initial pH of wheat straw was 5.9,
while it was 6.9 for digested manure. Table 2 presents the character-
istics of pre-incubated digested manure and raw wheat straw and its
comparison to the results of another study (Elsayed et al., 2016). Wheat
straw had very high volatile solid (VS) content, i.e., 94.4% as compared
to digested manure. The VS in the manure was low as it had already
undergone through the process of digestion. C/N ratios of individual
(1)
substrates used in this study were either lesser or greater than that of
optimum range of C/N ratio for anaerobic digestion i.e., 20–30. C/N
ratio of wheat straw was 49, which was comparatively higher than that
of digested manure (9.76). Low C/N ratio of digested manure might
have adjusted the C/N ratio of wheat straw to optimum range without
addition of any external nutrients.

3.2. Effect of thermal pretreatment on characteristics of wheat straw

Averaged data of biogas production obtained from anaerobic di-
gestion experiment was used in kinetic model fitting. Non-linear kinetic
In this study characteristics of raw wheat straw and thermally pre-
model fitting was performed by using modified Gompertz model as
treated wheat straw were analyzed. The pH, total solids, volatile solids,
shown in Eq. (2). It was used to simulate cumulative biogas production
TOC and TKN of wheat straw before and after its thermal pretreatment
(Zwietering et al., 1990)
are presented in Table 3, while lignocellulosic components such as

Table 3
Comparison of chemical characteristics for untreated and pretreated wheat straw.
Conditions pH TS (%) VS (%) TOC (%) TKN (%)

Untreated 5.9 ± 0.1 90 ± 0.25 94.4 ± 0.23 54.7 ± 0.11 1.11 ± 0.11
120 °C 5.6 ± 0.23 91.4 ± 0.23 94.9 ± 0.1 55 ± 0.10 1.11 ± 0.01
140 °C 5.6 ± 0.1 92.1 ± 0.05 95.2 ± 0.17 55.2 ± 0.09 1.08 ± 0.01
160 °C 5.2 ± 0.11 94.1 ± 0.1 95.6 ± 0.34 55.4 ± 0.2 1.02 ± 0.01
180 °C 4.8 ± 0.26 96.8 ± 0.1 97.9 ± 0.2 56.7 ± 0.15 0.98 ± 0.02

47
A.A. Rajput et al.
Fig. 1. Effect of thermal pretreatment on lignocellulose content of wheat straw.
lignin, hemicellulose and cellulose are presented in Fig. 1. As the pre-
treatment temperature increased, pH values decreased as shown in
Table 3. The reason may be the release of organic acids from solid phase
of wheat straw to liquid phase that caused a drop in pH due to thermal
pretreatment. About 23% decrease in original pH was observed when
the thermal pretreatment of the straw was performed at 180 °C for
60 min. Jin et al. (2016) reported 27% decrease in pH due to thermal
pretreatment of kitchen waste when the pretreatment was performed at
temperature of 120 °C for 55 min. In the present study, however, the pH
of untreated and pretreated wheat straw was adjusted to neutral con-
dition by adding alkali solution and anaerobic inoculum. With increase
in thermal pretreatment temperature from 120 to 180 °C, the TS, VS and
TOC content of wheat straw increased as shown in Table 3. Thermal
pretreatment of wheat straw sufficiently removed moisture content.
The increase in TS, VS and TOC values of pretreated wheat straw may
be attributed to removal of moisture content during thermal pretreat-
ment. TOC values of pretreated wheat straw increased whereas TKN
values decreased as shown in Table 3. Similar chemical changes have
been observed upon fast pyrolysis pretreatment of corn stover due to
removal of moisture content (Wang et al., 2016).
Influence of thermal pretreatment on lignocellulosic composition of
wheat straw was also investigated. Total lignocellulosic fraction of raw
wheat straw used in the study was 83.2% as shown in Fig. 1, which is
comparable to that of Prasad et al. (2007). Cellulose content of raw
wheat straw was 34.5% originally, which increased to 47% after
thermal pretreatment at 180 °C. In contrast, hemicellulose content of
wheat straw decreased as the pretreatment temperature increased. The
reason for these changes in lignocellulosic composition could be the
presence of water during thermal treatment, which might have gener-
ated hydronium ions due to autoionization and led to hydrolysis of the
material (Garrote et al., 1999) converting the lignocellulosic material
into simpler compounds. No noticeable difference in lignin content was
observed at temperature below 180 °C, however, at pretreatment tem-
perature of 180 °C, the difference in lignin content was relatively
higher. Hemicellulose and cellulose contents show that the total fer-
mentable sugar was very high in wheat straw. After thermal pretreat-
ment of wheat straw, increase in cellulose content was accompanied by
the decrease in hemicellulose, which is in line with the findings of Zhou
et al. (2017).
Cellulose content increased by about 35% due to thermal pretreat-
ment at 180 °C as compared to untreated wheat straw. Ran et al. (2018)
reported about 43% increase in cellulose contents due to hydrothermal
pretreatment of lignocellulosic biomass at 160 °C. According to results
of the present study, hemicellulose removal depends upon the thermal
pretreatment temperature. Hemicellulose removal was not quite sub-
stantial up to pretreatment temperature of 160 °C, however, the re-
moval increased at pretreatment temperature of 180 °C, which was 23%
as compared to raw wheat straw. Increase in hemicellulose removal due
to heating pretreatment of biomass at higher temperature has also been
48
Journal of Environmental Management 221 (2018) 45–52
Fig. 2. Daily biogas production (a) and cumulative biogas production (b) from
untreated and pretreated wheat straw.
reported in other research studies (Santucci et al., 2015). In conclusion,
the characteristics of thermally pretreated wheat straw indicate that
thermal pretreatment of wheat straw at 180 °C increases its digestibility
due to degradation of hemicellulose. The reason is that hemicellulose is
digested slowly, and it also hampers the access of cellulose to micro-
organisms.
3.3. Effect of pretreatment on biogas production and solids removal
3.3.1. Biogas production
Biogas production from untreated and thermally pretreated wheat
straw is presented in Fig. 2. Wheat straw pretreated at four different
thermal pretreatment temperatures (120, 140, 160 and 180 °C) was
compared for biogas production with raw wheat straw sample. Highest
daily biogas yield of 46 Nml/gVS was observed from wheat straw
pretreated at 180 °C as shown in Fig. 2a. Lowest biogas yield was ob-
served from untreated wheat straw. Rapid biogas production was ob-
served from wheat straw pretreated at 160 and 180 °C during the
starting days of digestion. There were minor differences in terms of
biogas production from raw and 120 °C pretreated wheat straw. Ther-
mally pretreated wheat straw showed shorter lag phase as compared to
raw wheat straw and exhibited rapid biogas generation at the start of
digestion. Wang et al. (2016) reported a similar shortened lag phase
time due to pyrolysis pretreatment of corn stover and rapid biogas
production in the starting days of digestion which is in line with results
of the present study. Another study also observed decrease in lag phase
due to microwave heating pretreatment (Bastiaens et al., 2017).
Cumulative biogas yield from untreated, 120, 140, 160 and 180 °C
pretreated wheat straw was 404, 496, 522, 557 and 615 Nml/gVS re-
spectively as shown in Fig. 2b. Highest cumulative biogas production of
615 Nml/gVS was observed from wheat straw pretreated at 180 °C and
lowest cumulative biogas yield of 404 Nml/gVS was observed from raw
wheat straw. Cumulative biogas yield of 404 Nml/gVS was observed
from raw wheat straw which is in line with another study (Elsayed
et al., 2016). Similarly, Bolado-Rodríguez et al. (2016) showed 29%
increase in biogas production from wheat straw at thermal pretreat-
ment temperature of 121 °C which is comparable to biogas production
A.A. Rajput et al. Journal of Environmental Management 221 (2018) 45–52

at 120 and 140 °C in the present study. Biogas production of wheat

straw was affected significantly (p < 0.05) with its thermal pretreat-
ment as shown by ANOVA results. Wheat straw thermally pretreated at
temperature of 160 and 180 °C produced more cumulative biogas as
compared to that at temperature of 120 and 140 °C as shown in Fig. 2b.
Zhou et al. (2017) reported similar findings due to hydrothermal pre-
treatment of Miscanthus at temperature above 150 °C for 30 min which
saved 50% digestion time. Therefore, higher pretreatment temperature
during pretreatment of lignocellulosic biomass such as wheat straw is
more favorable. In this study 95% of biogas was produced during the
first 30 days of digestion as compared to raw wheat straw which sug-
gests that for anaerobic digestion of pretreated wheat straw 30-day time
was enough. Higher biogas production in the starting days of anaerobic
digestion indicates the effectiveness of thermal pretreatment. Biogas Fig. 3. Volatile solids removal of untreated and pretreated wheat straw.
production from 120, 140, 160 and 180 °C thermally pretreated wheat
straw was 22, 29.2, 37.8 and 53% higher than the raw wheat straw. A (p < 0.05) than that of raw wheat straw. The lowest volatile solids
study reported 52% increase in biogas yield from thermally pretreated reduction of 42% was measured from raw wheat straw as shown in
food waste as compared to untreated control (Ariunbaatar et al., 2014). Fig. 3. The study established strong relationship between biogas yield
Increase in biogas production from pretreated wheat straw might be and volatile solids removal, and thermal pretreatment temperature.
attributed to following reasons. Degradation of hemicellulose and its Among different pretreatment temperatures studied in this research,
conversion into smaller molecules like monosaccharides and volatile pretreatment at 180 °C yielded the highest biogas which lead to the
fatty acids VFAs (Merali et al., 2013) could have been the main reason highest solids removal. Abudi et al. (2016a) found 76.9% volatile solids
in enhancing biogas production from pretreated wheat straw. Due to removal and observed increase in solids reduction due to pretreatment
heating pretreatment, surface area of biomass increases (Remli et al., of rice straw and municipal solid waste as present study also observe
2013), which might have ultimately enhanced the efficiency during increase in solids removal due to pretreatment. Elsayed et al. (2016)
enzymatic hydrolysis. The complex lignocellulosic structure of wheat also observed relationship between solids reduction and biogas yield
straw might be another reason for production of lower biogas yield and found VS removal of 71.77% which is also comparable to present
from raw wheat straw. Thermal pretreatment alters the lignocellulosic study as shown in Fig. 3. These studies correlate volatile solids removal
structure of wheat straw and more cellulose fiber becomes accessible efficiency with maximum utilization of feedstock during biochemical
for microbial population (Paul and Dutta, 2018), which might have process and influence of lignin content. In the present study higher,
enhanced biogas production. Another reason behind increase in biogas volatile solids removal was observed from wheat straw pretreated at
production might be the enhancement of microbial community due to 180 °C in which lignin content was decreased due to thermal pretreat-
thermal pretreatment. Ennouri et al. (2016) concluded an increase in ment (Fig. 1) which might have increased the volatile solids removal
archaea from 34 to 86% and 46–83% in industrial and urban sludge due to better availability of cellulose for anaerobic bacteria.
respectively upon thermal pretreatment at 120 °C and suggested the
increase was due to increased growth of hydrogen consuming metha-
3.4. Effect of thermal pretreatment on insight of wheat straw
nogens. Another study reported increase in functional microbial po-
pulation due to microwave - H2O2 pretreatment of concentrated sewage
3.4.1. Change of chemical bonds
sludge and suggested the increase in microbial population a major
Change in chemical bonds of wheat straw due to thermal pretreat-
reason for enhancing methane yield (Liu et al., 2018).
ment was analyzed with the help of Fourier Transform Infrared
Cumulative methane yield from untreated, 120, 140, 160 and
Spectroscopy (FTIR). FTIR spectra of pretreated and untreated wheat
180 °C thermally pretreated wheat straw were 218, 270, 284, 307 and
straw samples in the region of 4000–500 cm−1 were analyzed for
344 NmlCH4/gVS. Wheat straw pretreated at 180 °C showed 57.7%
changes in chemical bond as shown in Fig. 4.
higher cumulative methane yield as compared to untreated wheat
Cellulose is considered as the main lignocellulosic component for
straw. These results of pretreatment are also comparable to other heat
biogas production. It is basically a polysaccharide consisting of a
treatment process. Bauer et al. (2009) conducted a study on steam ex-
plosion pretreatment of wheat straw at 180 °C for 15 min and observed
20% increase in methane yield. Another study on steam explosion
pretreated wheat straw at 200 °C for 5 min showed 27% increase in
methane yield as compared to untreated control (Ferreira et al., 2014).
The increase in methane yield due to pretreatment in both the studies
was lower than that in the present study. The reason may be the use of
long pretreatment time of 60 min in the present study. In conclusion,
the biogas production experiments indicate that: (1) thermal pretreat-
ment of wheat straw significantly enhanced biogas production; (2) due
to thermal pretreatment, lag phase time reduced and most of the biogas
produced in first 29 days, which means digestion is time reduced. This
would lead to cost saving.

3.3.2. Solids removal

Volatile solids reduction is another parameter after biogas produc-
tion in assessing the effectiveness of thermal pretreatment. In this study
volatile solids removal from untreated, 120, 140, 160 and 180 °C
thermally pretreated wheat straw were 42, 46, 56, 61 and 69% re-
spectively. The highest volatile solids removal of 69% was observed
from wheat straw pretreated at 180 °C, which was significantly higher Fig. 4. FTIR analysis of untreated and pretreated wheat straw.

49
A.A. Rajput et al.
linearly formed chain of hundred to ten thousand D-glucose β (1 → 4)
linked units (Sticklen, 2008). In lignocellulosic biomass, cellulose is
found in the form of microfibrils. These microfibrils have cable-like
insoluble structures which are composed of glucan hydrogen-bonded
chain. Cellulose microfibrils have both crystalline and amorphous re-
gions. The amorphous or soluble region is the region in which cellulose
molecules are relatively less compact and cellulases can easily hydro-
lyze it. Cellulose quantity plays a vital role in any biochemical process.
As described in Fig. 4, the absorption band at 3350 cm−1, which be-
longs to the OeH stretching in the hydrogen bond of cellulose, reduced
as the thermal pretreatment temperature of wheat straw increased. This
implies that crystalline cellulose of wheat straw was disrupted by
thermal pretreatment as the pretreatment temperature increased.
However, it should be noted that cellulose is difficult to degrade below
temperature 200 °C, and only a few degradation products including
glucose and 5-hydroxymethylfurfural are detected. Fan et al. (2016)
quoted that the maximum degradation of glucan was only 2.8% at
160 °C which increased to 14.7% after the pretreatment at 200 °C for
120 min.
Hemicellulose is a type of heterogeneous polysaccharides and con-
tains hexoses, pentoses, uronic acids and small amounts of other sugars
such as α-L-fucose and α-L-rhamnose. Hydroxyl group of sugars is par-
tially replaced with acetyl group in hemicellulose structure. The ab-
sorption band at 1726 cm−1 is associated to ester-linked acetyl, feruloyl
and p-coumaroyl groups present between lignin and hemicellulose (Sun
et al., 2015). Due to increase in thermal pretreatment temperature,
relative absorption intensity decreased as shown in Fig. 4, which in-
dicates the fracture of lignin-hemicellulose in ester-linked acetyl bonds.
Lignin is composed of basic monomeric units such as guaicyls, p-hy-
droxyphenyls and syringyls. Presence of lignin is a vital factor which
limits the extent and rate of hydrolysis by enzymes during the bio-
chemical reaction of lignocellulosic biomass. Research has showed that
removal of lignin from lignocellulosic biomass increases cellulose di-
gestibility. The absorption peaks in the region of 1125–1525 cm−1 re-
duced with increase in pretreatment temperature, and these peaks are
attributed to the aromatic C]C stretching from lignin and aliphatic
CeH stretching in methyl and phenol OH, and syringyl units of lignin
(Wang et al., 2015).
In conclusion, FTIR spectra in the present study shows (Fig. 4) that
the absorption peaks in all the above-mentioned regions reduced which
implies that the lignocellulosic structure of wheat straw got disrupted
with increase in temperature of thermal pretreatment. Thus, protective
layer (hemicellulose-lignin) of cellulose was broken by thermal pre-
treatment which changed the chemical structure of wheat straw (Fig. 4)
as compared to raw material. These findings are comparable to those
observed in a hydrothermal pretreatment study of sunflower stalk
(Hesami et al., 2015). Higher biogas production observed for wheat
straw pretreated at temperature of 180 °C as shown in Fig. 2 may be
corresponded to these changes in chemical bonds as these changes
might have made cellulose fibers become more available for enzymes
attack to convert it into fermentable sugars as suggested by Mosier et al.
(2005).
3.4.2. Change in crystallinity
Cellulose fibers of lignocellulosic biomass consist of both amor-
phous and crystalline regions. Similarly, hemicellulose is mainly
amorphous in nature. As crystalline material is relatively more resistant
to chemical and biological biodegradation compared to amorphous
material, the property of crystallinity can be used to assess the effec-
tiveness of pretreatment of lignocellulosic biomass. The XRD analysis
(Fig. 5) is one of the methods to analyze crystallinity of cellulose. Un-
treated and 120, 140, 160 and 180 °C thermally pretreated wheat straw
samples showed increase in crystallinity with temperature. Crystallinity
index (C.I) of raw and pretreated wheat straw at 120, 140, 160 and
180 °C were 39.7, 43.9, 44.2, 47.2 and 48.5%. This increase of crys-
tallinity might be due to removal of lignin, hemicellulose and
50
Journal of Environmental Management 221 (2018) 45–52
Fig. 5. XRD analysis of pretreated and untreated wheat straw.
amorphous cellulose, which might have caused an increase in the
crystallinity of pretreated wheat straw.
With increase in thermal pretreatment temperature, damage in
lignin and hemicellulose structure might also be supported with the
results of change in lignocellulosic composition as shown in Fig. 1,
which resulted increase in the crystallinity of the pretreated wheat
straw. Therefore, crystalline region of cellulose was exposed to XRD,
which ultimately increased the crystallinity. Presence of lignin inter-
links hemicellulose and cellulose, which formed the recalcitrant struc-
ture of lignocellulosic biomass and ultimately affected the subsequent
biochemical conversion efficiency of biomass in case of no pretreat-
ment. However, in case of pretreatment, the hemicellulose and amor-
phous region of cellulose might have been degraded (Zhou et al., 2017)
making the crystalline region of cellulose available for subsequent
biochemical process. Thus, crystallinity of lignocellulosic biomass in-
creased upon thermal pretreatment. Increase in crystallinity index due
to urea pretreatment of wheat straw was also observed in another study
(Yao et al., 2018).
3.5. Kinetic study of biogas production
The cumulative biogas production data achieved for raw and ther-
mally pretreated wheat straw were subsequently simulated using three
kinetic models to examine the effectiveness of thermal pretreatment of
wheat straw on biogas production. Kinetics parameters of biogas pro-
duction such as biogas production potential, lag phase time and biogas
production rate were predicted based on cumulative biogas production
data obtained from batch experiment as shown in Table 4. Modified
Gompertz model followed by logistic function model produced the sa-
tisfactory biogas production from the raw and thermally pretreated
wheat straw. Under the batch AD condition, the logistic function model
and modified Gompertz model assume that the specific growth rate
(SGR) of methanogens is proportional to the gas produced with sig-
moidal production trend (Altaş, 2009). At all the wheat straw pre-
treatments, the value of parameter M in transference function model
was enormously higher than predicted values and the model could not
replicate well the biogas production data. Transference function model
is used where there is a nearly or zero lag phase and it only considers
the stationary and exponential phase in the biogas production (Donoso-
Bravo et al., 2010; Li et al., 2012). All the three models predicted an
increase in biogas production rate and decrease in lag phase time with
increase in thermal pretreatment temperature as shown in Table 4.
Overall, modified Gompertz model best fitted on the biogas pro-
duction data as compared to transference and logistic function models.
A.A. Rajput et al. Journal of Environmental Management 221 (2018) 45–52

Table 4
Kinetic parameters of different models for untreated and pretreated wheat straw.
Pretreatment condition Rm (mL/gVS-d) Pb (mL/gVS) λ (d) R2 Kinetic Model

Untreated 19.63 388.90 12.69 0.992 Modified Gompertz

18.77 338.92 5.70 0.856 Transference Function
18.87 396.50 23.73 0.997 Logistic Function
120 °C 23.56 483.33 8.96 0.998 Modified Gompertz
27.51 442.58 4.82 0.908 Transference Function
22.88 490.86 20.27 0.998 Logistic Function
140 °C 24.06 511.24 6.13 0.998 Modified Gompertz
32.55 481.34 4.06 0.946 Transference Function
23.01 518.53 17.77 0.989 Logistic Function
160 °C 31.08 552.73 6.02 0.999 Modified Gompertz
39.77 527.72 3.75 0.936 Transference Function
30.17 556.51 15.91 0.996 Logistic Function
180 °C 33.83 611.70 3.37 0.999 Modified Gompertz
51.57 597.17 2.78 0.969 Transference Function
32.05 614.23 13.09 0.992 Logistic Function

λ = Lag phase time.

Rm = Maximum biogas production rate.
Pb = Maximum biogas production.

Biogas production rate of pretreated wheat straw predicted by modified
Gompertz model was higher as compared to untreated wheat straw as
shown in Table 4. Modified Gompertz model predicted shorter lag
phase time of 3.37 days for wheat straw pretreated at 180 °C as com-
pared to that of untreated wheat straw, which was 12.69 days. The
coefficient of determination R2 values of modified Gompertz model for
biogas production data of the untreated and thermally pretreated wheat
straw were in the range of 0.992–0.999. Veluchamy and Kalamdhad
(2017) used three different models on data of methane production from
thermally pretreated lignocellulose waste material to examine the effect
of F/M ratio. They found that modified Gompertz model was the one
with the best fit followed by logistic function and transference function
models, which is in line with the results of present study. Abudi et al.
(2016b) also best predicted biogas production kinetics with modified
Gompertz model.
3.6. Practical application and future research direction
Huge quantity of agricultural biomass is produced annually in an
energy deficient country such as Pakistan, which can be used for pos-
sible production of biogas to overcome the crisis. But its lignocellulosic
composition is the main hindrance in anaerobic digestion which ne-
cessitates a pretreatment step. This study provides a detailed informa-
tion about the effect of thermal pretreatment on biogas production of
lignocellulosic biomass which will be helpful in designing the pre-
treatment and biogas production system efficiently. More specifically,
use of the present study for practicing engineers is as follows; (i) Due to
thermal pretreatment, lag phase time reduces and most of the biogas is
produced in first 30 days, which means digestion time is reduced. This
would lead to cost saving, (ii) thermal pretreatment of wheat straw at
180 °C significantly enhances biogas production (by 53%) as compared
to raw wheat straw. This information opens new avenues of bioenergy
production from lignocellulosic agricultural biomass, (iii) the results of
the present study provide the practicing engineers an opportunity to
develop full scale thermal pretreatment systems to pretreat lig-
nocellulosic biomass for subsequent biogas production.
In future, the microbial community balance and structure should be
assessed for understanding the possible effect of thermal pretreatment
on microbial community. Effect of thermal pretreatment on the che-
mical parameters like availability of carbohydrates, proteins and sugars
should be assessed. Thermal pretreatment of lignocellulosic waste and
subsequent biogas production should be performed under continuous
mode of operation to get the information closer to the real field con-
ditions which will be helpful in implementation of pretreatment at in-
dustrial level. Comparison of various pretreatment methods like
chemical, physical, biological and combination of all these should also
be assessed to get the best available pretreatment for treating lig-
nocellulosic biomass to enhance biogas production and cost effective-
ness. Energy balance and material balance in overall pretreatment and
anaerobic digestion of lignocellulosic materials should be studied.
Moreover, the environmental issues caused using different pretreatment
methods should also be thoroughly studied.
4. Conclusion
This study used thermal pretreatment to enhance the biogas pro-
duction of wheat straw. Significantly high biogas production and vo-
latile solids reduction was observed at thermal pretreatment tempera-
ture of 180 °C as compared to untreated control. Considerable reduction
in hemicellulose and lignin was observed due to thermal pretreatment
which also contributed to higher biogas production. Chemical bonds of
wheat straw changed with thermal pretreatment. The modified
Gompertz model showed the best fit followed by logistic function
model.
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