Fuel 263 (2020) 116651

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Anaerobic digestion of cattle manure, corn silage and sugar beet pulp T
mixtures after thermal pretreatment and kinetic modeling study
⁎
Halil Şenola, , Ünsal Açıkelb, Serkan Demirc, Volkan Odad
a
Giresun University, Genetic and Bioengineering Department, Giresun, Turkey
b
Cumhuriyet University, Department of Chemical Engineering, Sivas, Turkey
c
Giresun University, Industrial Engineering Department, Giresun, Turkey
d
Giresun University, Finance Program Department, Giresun, Turkey

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

Keywords: In this study, biogas production was investigated from cattle manure (CM), corn silage (CS) and sugar beet pulp
Biogas (SBP) mixtures under mesophilic conditions. In anaerobic digestion (AD), CM, CS and SBP were mixed in dif-
Cattle manure ferent ratios and the optimum mixture ratio was determined as 2:1:1, w/w/w respectively. In this mixture,
Corn silage biogas production was 180.5 mL/g TS. After the optimum mixing ratios of CM, CS and SBP were determined,
Sugar beet pulp
thermal pretreatments were applied to this mixture ratio. Thermal pretreatments were performed at 100, 120,
Thermal pretreatments
Modified Gompertz model
150 and 180 °C with 10, 20, 30, 60 and 120 min for each temperature. Considering biogas production after
Modified Bertalanffy model thermal pretreatment, the best thermal pretreatment time was determined as 60 min for all pretreatment
temperatures. The highest biogas yield was 362.1 mL/g TS in the reactor which is pretreated at 180 °C for
60 min. After thermal pretreatment at 180 °C for 60 min, the SCOD value in the reactor increased by 124.6%
compared to the control. This reactor produced 100.6% higher biogas production compared to the control. In
addition, the solubilization of cellulose, hemicellulose and lignin in this reactor was 38.2%, 32.9% and 23.2%,
respectively. Cumulative biogas production (CBP) fitted to modified Gompertz and modified Bertalanffy models.

1. Introduction
With the rapid growth of countries during industrialization and
population growth, energy demands increase day by day. The increase
in energy demand leads to a reduction of fossil fuels, i.e. natural energy
sources such as coal, petroleum coke, lignite and natural gas [1]. Ex-
cessive attention has been paid to the search for alternative energy
owing to the emergence of environmental problems associated with
fossil fuels and the depletion of fossil fuels [2,3]. One of the alternative
energy sources is biogas energy. Biogas produced by anaerobic diges-
tion (AD) of by-products of livestock and crop attracts worldwide at-
tention in terms of being clean and renewable energy [2,4] Biogas is
currently used for vehicle fuel, heat and electricity production [5].
CS is an energy plant which is formed by the corn plant after being
matured and stored in an airless medium [6]. AD of CS and animal
manures have been emphasized with good results [7]. SBP is a by-
product of sugar production. 170 kg of wet sugar beet pulp is produced
after 1 ton of sugar production [8]. According to Boe and Angelidaki
[9], low biogas production yields could be a result of the low biode-
gradability of fibrous matters, which can account for 40–50% of the
total solids (TS) in CM. CM is one of the most widely used substrates in
AD [6]. Approximately 20 m3 of methane was obtained from 1 ton of
CM [10].
Hydrolysis, one of the AD steps, is known as the rate limiting step
[11]. Organic matter disintegration methods have been investigated as
pretreatment processes to increase the efficiency of AD and eliminate
this step (hydrolysis) [12]. These pretreatments are physical, chemical
and chemical pretreatments. Pretreatments increase biogas yield. The
pretreatments are remarkable in terms of low cost and considerably
increase biogas/methane yield [13]. However, chemical pretreatments
produces secondary pollution and biological pretreatments are also
difficult to control. Therefore, physical pretreatment and thermal pre-
treatment are frequently used due to operational convenience and low
investment [14]. Pretreatments are applied to ensure high content
cellulose, lignin and hemicellulose in wastes such as SBP and CS at-
tractive [15]. Rajpur et al. [14] performed thermal pretreatment of
wheat straw at different temperatures (120–180 °C) for constant time,
and reported that methane yield was increased by 53%. Ferreira et al
[16] performed thermal pretreatment of wheat straw at 150–220 °C for
1–15 min and then methane yield was increased by 20%. Ennouri et al

⁎
Corresponding author.
E-mail addresses: halilsenol@yahoo.com (H. Şenol), serkan.demir@giresun.edu.tr (S. Demir), volkanoda@hotmail.com (V. Oda).

https://doi.org/10.1016/j.fuel.2019.116651
Received 14 May 2019; Received in revised form 9 November 2019; Accepted 12 November 2019
Available online 24 November 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
H. Şenol, et al. Fuel 263 (2020) 116651

[17] reported that biogas yield increased by 27–37% after thermal Table 1
pretreatment of urban solid wastes at 60–120 °C for 30 min. In the Characteristics of organic raw materials.
literature, thermal pretreatment was applied to different organic wastes Parameters Cattle manure Corn silage Sugar beet pulp
at different temperatures and durations. However, the pretreatment
results on organic matter were not stable and varied according to the TS (% w/w) 18.80 32.10 84.62
VS (TS %) 82.80 92.54 86.62
type of organic matter. In addition, each pretreatment temperature was
Ash (% w/w) 3.23 2.39 11.32
not optimized over a wide period of time. In order to better understand Moisture (% w/w) 81.20 77.90 15.38
the specific results of thermal pretreatments, a wider range of tem- C (% w/w) 32.12 44.92 43.25
peratures and application times should be studied. Further, pretreat- N (% w/w) 1.65 1.39 1.09
ment temperatures and pretreatment times must be optimized for costs. SCOD (mg O2/Lslurry) 22,680 12,320 5800
C/N 19.46 32.31 39.68
The aim of this study was to investigate the effect of thermal pre-
pH 6.88 3.78 4.08
treatments at different temperatures for different times on organic Cellulose (% w/w) 22.30 25.90 30.55
matter and biogas yield. Biogas yields from CM, CS and SBP were in- Hemicellulose (% w/w) 18.92 19.49 25.92
vestigated with and without thermal pretreatment under mesophilic Lignin (% w/w) 12.85 4.01 3.91
conditions. The optimum mass mixing ratio of CM, CS and SBP was
found for AD. Then, thermal pretreatments were applied to the op-
timum mixing ratio. Thermal pretreatments were performed at 100, pretreatments were applied at temperatures of 100 °C, 120 °C, 150 °C
120, 150 and 180 °C. Each pretreatment temperature was applied for and 180 °C each with 10, 20, 30, 60 and 120 min. Thermal pretreat-
10, 20, 30, 60 and 120 min, respectively. In addition, changes in lig- ments were applied in the incubator (DOL-EKO brand ILW-115-STD
nocellulosic structure resulting from thermal pretreatment were also model, Germany). As a result of the pretreatment, the solubility was
investigated. Moreover, biogas production rate was evaluated for all determined by filtering the slurry with glass cotton. Increase in SCOD %
thermal pretreatment temperatures based on experimental data with value after thermal pretreatments was calculated from the difference of
the help of two different kinetic models. final SCOD thermal pretreated and initial SCODuntreated, ralative to the in-
itial SCOD (SCOD untreated) (Eq. (1)) [20].
2. Experimental (SCODthermalpretreated − SCODuntreated)
incrementalSCOD% = × 100
SCODuntreated (1)
2.1. Preparation of raw materials and products

The CM was collected from Giresun, Turkey. The raw CM was

transformed into pure form by distinguishing it from impurities such as
gravel, straw and plant seed. CS and SBP were collected from Samsun,
Turkey. Each of the organic materials was milled to a particle size of
0.5–1 mm. They were stored at −18 °C for later use in AD experiments.
2.2. Anaerobic digestion
AD experiments were performed in 500 mL batch reactors. The
heating temperature was set to 39 ± 2 °C. Heating was provided by a
magnetic stirrer heater with continuous stirring of each reactor at
100 rpm during digestion. The optimum pH for AD is neutral [6]. The
pH of reactors was adjusted to 7.0 using 1 M solution of H2SO4 or NaOH
at the beginning of the experiments. At the beginning of each AD ex-
periment, the batch reactors were flushed with N2 gas for 5 min to
ensure anaerobic conditions and eliminate oxygen from the reaction
medium. Biogas yield was determined according to the water dis-
placement method [18,19].The dry matter ratio was 10% w/w in all
reactors. Initially, optimum mixing ratio determination studies were
performed. Mixture ratios of CM:CS:SBP with the ratios of 1:0:0, 0:1:0,
0:0:1, 1:1:1, 2:1:1, 2:2:1, 2:1:2, 1:1:2, 1:2:1 w/w/w were adjusted in
each batch reactors. For each set of experiment, one control reactor was
used. The experiments were carried out with 3 replications. Biogas
yields were measured every 5 days. The AD time was approximately
30 days for the batch reactors. AD was terminated when the last mea-
sured value was less than 2% of the previously measured value. The
biogas production was provided in terms of volume per gram of total
solid (TS) (mL/g TS).
2.3. Thermal pretreatments
Thermal pretreatments are widely used in biogas production [14].
The optimum ratio was chosen for the reactor with the highest biogas
production and then thermal pretreatments were applied to this re-
actor. Thermal pretreatments were performed in autoclave bottles. 50 g
of the optimum mixture from each reactor was added to the autoclave
bottle. 10 g of distilled water was added to prevent burning of the dry
biomass during thermal pretreatment. In this study, thermal
2.4. Analytical method
In Table 1, total solids (TS), volatile solids (VS), ash, moisture,
carbon (C), nitrogen (N), SCOD, pH, cellulose, hemicellulose and lignin
analysis were performed before applying AD to organic waste. TS and
VS were analyzed according to APHA standards [21]. The carbon to
nitrogen ratio (C:N) of the lignocellulosic substrates was determined by
the COSTEC elemental analyzer (Elemental Analyzer NA 2500). The
cellulose, hemicellulose and lignin contents were measured using fiber
analyzer (ANKOM A2000i, US) [22]. A Hitachi SU-1510 (Hitachi, Ltd.
Tokyo, Japan) scanning electron microscope (SEM) was used to scan
the surfaces of the organic waste. Liquid samples were centrifuged at
10,000 rpm for 10 min at room temperature and filtered with a 0.25 μm
membrane filter. SCOD analyzes were performed according to closed
reflux titrimetric method [21]. Physicochemical properties and analysis
results of CM, CS and SBP are given in Table 1.
2.5. Kinetic study
The estimated values of cumulative biogas production (CBP) rate
measured every 5 days were obtained using modified Gompertz model
[23,24] and Modified Bertalanffy model [25]. For the transformation to
the mechanical model, biologically significant parameters can be ob-
tained with the help of the first and second derivatives [25]. In addi-
tion, for the transformation to the mechanical model, biologically sig-
nificant parameters were obtained with the help of the first and second
derivatives. The Bertalanffy function defined for growth functions was
first developed by Von Bertalanffy in 1934 and later changed by Bev-
erton and Holt (1957) [26].
Table 2 shows the modified Gompertz and modified Bertalanffy
models.
Where; y is the estimated methane yield (mL/g TS), with respect to
time t (day); λ is lag phase (day); A is ultimate methane yield at t = ∞
(mL/g TS) and e is a Euler's function equal to 2.71828. In this study,
Statistical Package for the Social Sciences (SPSS 23.0) program was
used to calculate kinetic constants (λ, µm, A) from growth curves.

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H. Şenol, et al. Fuel 263 (2020) 116651

Table 2 biogas production and incremental SCOD % value are given in Table 4.
Modified Gompertz and modified Bertalanffy models. The reactors at different thermal temperatures and times were labeled
Models Equations from R10 to R29.
In one study, it was reported that thermal pretreatments were
Modified Gompertz ⎡ μm e (λ − t ) + 1⎤ generally carried out between 50 and 240 °C and pretreatments below
⎢ A ⎥
y = Ae (e⎣ ⎦
100 °C should be applied for longer periods [14]. In another study, it
Modified Bertalanffy 2 9μm 3
was emphasized that pretreatments are expensive when the tempera-
1 ⎡ .(λ − t ) ⎤
y=− A −3 + e3 + 4A
27 ⎢ ⎥
⎣ ⎦ ture exceeds 180–200 °C [13]. Therefore, in this study, thermal pre-
treatments were performed between 100 and 180 °C.
Table 1 shows the lignocellulosic component in the highest SBP and
2.6. Statistical analysis in the lowest CM. Pretreatment technologies are needed to benefit from
these lignocellulosic components. But these technologies are fertile as
All statistical analyses were carried out using SPSS 23.0. Normal well as they are cost effective [13]. Therefore, the optimization of
distribution was assumed based on the agreement of parametric and pretreatment technologies was investigated in this study.
non-parametric testing and thus all inference was carried out using two- The thermal pretreatment temperatures and times took place great
way ANOVA. Significance level (p) was determined as 0.05. Therefore, differences on biogas production. Except for 120 °C, the highest biogas
Pearson correlation coefficients between reactors were calculated. The production at other pretreatment temperatures occurred after pre-
statistical analysis was applied separately to the reactors at each pre- treatment time of 60 min. Among the reactors that were pretreated at
treatment temperature (100, 120, 150 and 180 °C). 120 °C, the highest biogas yield was achieved in the reactor with a
pretreatment time of 120 min. Among 120 °C pretreated reactors, the
3. Results and discussion difference between the reactor pretreated for 120 min and the reactor
pretreated for 60 min is 2.6 mL/g TS. In terms of pretreatment costs, the
3.1. Optimum mixing ratio determination studies most ideal reactor at all thermal pretreatment temperature is the re-
actor pretreated for 60 min. The highest biogas production among these
Table 1 presents the physicochemical properties of CM, CS and SBP reactors was 362.1 mL/g TS.
and the amount of lignocellulosic components. SBP has the highest Biogas yields of organic matter was affected significantly
lignocellulosic component ratio. In order to find the appropriate mixing (p < 0.05) from thermal pretreatment as shown by two-way ANOVA
ratio of CM, CS and SBP in AD, 9 reactor types in Table 3 are given. results. It was concluded that the data in all pretreatment temperatures
These reactors were labeled R1 to R9 according to different mixing ra- exhibited normal distribution (p > 0.05). Therefore, correlation
tios. Biogas yields varied depending on the amount of lignocellulosic coefficients among reactors were calculated. In pretreated reactors of
components. Reactors with C/N ratios between and close to 20–30 100 °C, the strongest correlation was found between R10–R13 and the
achieved high yield, while reactors outside this range showed low yield. weakest correlation was between R12 and R13. Biogas yields of reactors
When this ratio rises above 20, low biogas yield was reported by Dioha pretreated at 100 °C ranged from 195.5 to 242.1 mL/g TS due to dif-
et al. [27]. At reactor R1 containing only CM, biogas yield was ferent pretreatment times. Biogas production increased as the pre-
162.0 mL/g TS. In one study, methane yield of CM was reported to be treatment time increased from 10 min to 60 min, but it decreased after
210 mL/g VS under thermophilic conditions [28]. The possible reason 120 min pretreatment. This result can be attributed to the excess or-
for this difference originates from different production temperatures. ganic solubility in the medium after 120 min of pretreatment. The re-
The highest biogas production from these reactors was 180.5 mL/g TS actors pretreated at 100 °C produced 8.3–41.5% higher biogas pro-
(R4). Thus, all thermal pretreatments were applied to the mixing ratio duction compared to the control. After 100 °C pretreatments, the
(2:1:1, w/w/w) in R4. AD of CM, CS and SBP has not been studied in the optimum pretreatment time was determined as 60 min. Biogas yields of
literature. Therefore, the reactor R4 was selected as the control. reactors pretreated at 120 °C ranged from 201.4 to 288.1 mL/g TS.
Turkey, especially in Central Anatolia cattle, corn and sugar beet are Biogas yield increased as pretreatment time increased. The reactors
grown together [29]. Therefore, the appropriate mixture of the wastes pretreated at 120 °C has 11.5–59.6% higher biogas yield than the
of these three organic substances according to C/N ratios can be eval- control. According to the two-way ANOVA results, in pretreated re-
uated in the production of biogas in the regions where the source is. actors at 120 °C, the strongest correlation was found between R17–R18
and the lowest correlation between R15 and R18. Biogas yields of pre-
3.2. Thermal pretreatment results treated reactors at 150 °C ranged from 222.5 to 280.0 mL/g TS. In
pretreated reactors at 150 °C, the strongest correlation was found be-
After the thermal pretreatment applied at different temperature and tween R20 and R24 and the lowest correlation between R21 and R22.
different time intervals, biogas yields were provided under anaerobic Pretreated reactors at 150 °C produced 23.2–55.1% higher biogas yield
conditions. As a result of this process, biogas yield, % incremental than the control. After pretreatment at 150 °C, the optimum pretreat-
ment time was 60 min. Significant increases in biogas production were
Table 3 observed when the pretreatment temperature increased from 150 °C to
Optimum mixing ratio determination studies for AD. 180 °C. In pretreated reactors at 180 °C, the strongest correlation was
found between R26 and R29 and the lowest correlation between R25 and
Reactor CM:CS:SBP C/N ratio Total amount of Biogas
Mixing ratio lignocellulosic production R26. Biogas yields of pretreated reactors at 180 °C ranged from 232.2 −
(w/w) component (% w/w) (mL/g TS) 325.5 mL/g TS due to different pretreatment times.
Incremental SCOD values were also controlled to better observe the
R1 1:0:0 19.46 54.07 162.0
stability and effects of thermal pretreatments. Incremental SCOD %
R2 0:1:0 32.31 49.40 105.5
R3 0:0:1 39.68 60.38 95.2 values after thermal pretreatments are shown in Table 4. After thermal
R4 2:1:1 27.73 54.48 180.5 pretreatment in different conditions, the SCOD values varied among
R5 1:1:2 32.76 56.06 145.8 10.1–155.4. SCOD % values increased as pretreatment temperature and
R6 1:2:1 30.94 53.31 140.5 time increased. However, there was no significant change in biogas
R7 1:1:1 30.48 54.62 170.8
yields when the pretreatment time for all pretreatment temperatures
R8 2:2:1 28.64 53.46 175.8
R9 2:1:2 30.12 55.66 149.9 changed from 60 min to 120 min. This phenomenon can be attributed
to the presence of volatile fatty acids due to high SCOD values.

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H. Şenol, et al. Fuel 263 (2020) 116651

Table.4
Thermal pretreatment results.
Pretreatment temperature (°C) Pretreatment time (min) Reactor Biogas yield (mL/g TS) Incremental biogas yield (%) Incremental SCOD value (%)

100 10 R10 195.5 ± 9.2 8.3 10.1 ± 2.4

20 R11 215.5 ± 11.4 19.3 22.4 ± 3.5
30 R12 235.5 ± 10.8 30.4 34.3 ± 4.7
60 R13 255.5 ± 9.7 41.5 70.0 ± 5.5
120 R14 242.1 ± 11.5 34.1 78.9 ± 4.8

120 10 R15 201.4 ± 8.7 11.5 15.1 ± 2.9

20 R16 212.0 ± 9.5 17.4 21.1 ± 3.7
30 R17 242.9 ± 7.8 34.5 43.0 ± 4.6
60 R18 285.5 ± 9.1 58.1 79.6 ± 5.5
120 R19 288.1 ± 8.8 59.6 85.5 ± 5.1

150 10 R20 222.5 ± 10.2 23.2 22.0 ± 3.8

20 R21 235.8 ± 11.5 30.6 34.1 ± 4.5
30 R22 245.0 ± 12.1 35.7 45.2 ± 4.8
60 R23 280.0 ± 11.8 55.1 73.0 ± 5.8
120 R24 275.6 ± 12.5 52.6 77.3 ± 4.9

180 10 R25 232.2 ± 11.1 28.6 30.1 ± 5.1

20 R26 245.0 ± 9.8 35.7 44.2 ± 4.9
30 R27 355.0 ± 14.1 96.6 105.0 ± 3.4
60 R28 362.1 ± 12.2 100.6 124.6 ± 2.7
120 R29 325.5 ± 10.7 80.3 155.4 ± 3.5

Table 5
Comparison of the increments in biogas production with current literature values as a result of thermal pretreatment.
Thermal pretreatment conditions Results of AD after pretreatment Type of organic matter Reference

at 100 °C for 1 h 41.5% incremental biogas 2:1:1 mixtures of CM:CS:SBP This study
at 180 °C for 1 h 100.6% incremental biogas 2:1:1 mixtures of CM:CS:SBP This study
at 200 °C for 15 min 27% incremental biogas wheat straw [16]
at 120 °C for 1 h 37% incremental biogas urban solid waste [17]
at 121 °C for 1 h 29% incremental biogas wheat straw [31]
at 121 °C for 1 h 11% incremental biogas sugar cane [14]
at 180 °C for 1 h 53% incremental biogas wheat straw [30]
at 120 °C for 1 h 64% incremental biogas wheat straw [30]
at 120 °C for1 h 32% incremental methane rice straw [30]
at 120 °C for 1 h 41% incremental methane barley straw [30]
125 °C for 37.5 min 34% incremental biogas cattle manure [32]

Table 5 shows the comparison for the incremental biogas produc-
tion and methane production in literature after thermal pretreatment.
In this study, after pretreatment at 100 °C for 1 h and at 180 °C for 1 h
incremental biogas yields were 41.5% and 100.6% respectively. Ac-
cording to Ferreira et al.[16], 27% higher methane production was
achieved after pretreatment at 200 °C for 15 min. Although the thermal
pretreatment was applied at a higher temperature, the lower applica-
tion time did not increase the biogas yield [30].
In the current literature, the biogas production increased as the
pretreatment times increased at constant pretreatment temperature
[14,16,30]. However, different biogas yields of different organic wastes
have been reported in the literature, despite pretreatment under the
same conditions [30]. Thermal pretreatment results in this study sup-
port this situation.
3.3. Effects of thermal pretreatments on lignocellulosic solubilization
When the recent studies in the literature and the results of this study
are taken into consideration, the presence of different biogas yields
under the same thermal pretreatment conditions can be attributed to
the difference in lignocellulosic content of organic matter. Cellulose,
lignin and hemicellulose are disintegrated by thermal pretreatment.
Thus, higher yields are obtained in AD [33,34]. For this reason, solu-
bilization of cellulose, hemicellulose and lignin after thermal pretreat-
ment was also investigated. Table 6 gives the solubilization percentages
of the cellulose, hemicellulose and lignin after thermal pretreatments at
different temperatures and times. The highest cellulose, hemicellulose
and lignin solubilization at 100 °C was 14.8%, 22.2% and 13.4% re-
spectively. There was no significant difference between the amount of
lignocellulosic solubilization after 60 min and 120 min at 100 °C. A
similar situation occurred at temperatures of 120, 150 and 180 °C.
Therefore, the optimum pretreatment time for thermal pretreatments
was 60 min.
In 120 °C pretreatment, the cellulose solubilization was determined
as 15.9% in the ideal reactor. However, in the reactor applied for
60 min, the cellulose value was reduced to 15.7%. Similarly, the
hemicellulose was removed by 22.9% in 60 min, while it was removed
by 22.9% in 60 min. After pretreatment at 120 °C, the amount of lignin
solubilization in the R28 and R29 reactors was close to each other. Thus,
when thermal pretreatment at 120 °C was evaluated in terms of lignin,
the ideal rector was R18. Cellulose solubilization after thermal pre-
treatments at 150 °C and 120 min was 22.9%. However, in the reactor
at which thermal pretreatment of 60 min was applied at the same
temperature, the cellulose removal was 20.8%. Hemicellulose was re-
moved at 32.4% in 60 min, while it decreased by 33.5% in the pre-
treatment period of 120 min. In R23 and R24, the amounts of cellulose,
hemicellulose and lignin were close to each other. At 180 °C of thermal
pretreatment, cellulose, hemicellulose and lignin solubilization started
to increase significantly after 30 min.
Table 7 shows the comparison of cellulose, hemicellulose and lignin
solubilizations according to different thermal pretreatment conditions.
According to Jiang et al. [35], the highest lignin removal in the lit-
erature was obtained as 57.5% at 230 °C. In this study, 13.4% lignin
solubilization occurred after 100 °C and 1 h. According to Kim et al.

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H. Şenol, et al. Fuel 263 (2020) 116651

Table 6
Lignocellulosic solubilization component in raw material after thermal pretreatments.
Pretreatment temperature (°C) Time (min) Reactor Cellulose solubilization (% w/w) Hemicellulose solubilization (% w/w) Lignin Solubilization (% w/w)

100 10 R10 5.1 ± 1.1 2.3 ± 0.8 2.4 ± 2.1

20 R11 9.8 ± 2.1 15.7 ± 1.7 10.1 ± 2.2
30 R12 14.1 ± 2.0 21.8 ± 1.8 13.5 ± 2.9
60 R13 14.5 ± 1.9 21.9 ± 1.9 13.5 ± 3.5
120 R14 14.8 ± 1.5 22.2 ± 2.5 13.4 ± 3.2

120 10 R15 4.2 ± 1.0 2.5 ± 1.5 2.9 ± 2.0

20 R16 12.6 ± 1.5 18.0 ± 1.9 10.5 ± 1.9
30 R17 14.6 ± 1.9 20.2 ± 2.5 12.1 ± 2.5
60 R18 15.7 ± 2.7 22.9 ± 2.9 13.6 ± 3.1
120 R19 15.9 ± 3.0 23.2 ± 2.7 13.9 ± 2.4

150 10 R20 8.3 ± 1.5 3.2 ± 1.8 6.5 ± 2.2

20 R21 10.2 ± 2.1 5.8 ± 1.5 9.2 ± 2.8
30 R22 17.6 ± 2.3 30.1 ± 3.8 17.1 ± 1.9
60 R23 20.8 ± 2.0 32.4 ± 2.5 19.9 ± 2.8
120 R24 22.9 ± 1.9 33.5 ± 3.1 20.2 ± 3.1

180 10 R25 17.0 ± 2.4 18.4 ± 1.1 6.5 ± 1.8

20 R26 25.2 ± 2.2 22.4 ± 1.8 11.2 ± 2.7
30 R27 35.1 ± 1.8 30.0 ± 2.4 20.1 ± 2.9
60 R28 38.2 ± 1.9 32.9 ± 2.7 23.2 ± 3.1
120 R29 39.1 ± 1.8 33.1 ± 3.0 23.4 ± 3.5

Table 7 After the thermal pretreatment, each pretreatment periods and rates
Comparative analysis of lignocellulosic solubilization values with current lit- were examined during the anaerobic process. Biogas volume was
erature values after thermal pretreatment. measured every 5 days during the anaerobic process. Fig. 1 shows the
Thermal Pretreatment results Type of organic Reference CBPs of organic matter applied at different thermal pretreatment tem-
pretreatment matter peratures. Total digestion time varied between 40 and 45 days de-
conditions pending on lignocellulosic content. Rajput and Visvanathan [14] re-
ported digestion time of 45 days of lignocellulosic material.
100 °C and 1 h Cellulose = 14.8% 2:1:1 mixtures of This study
Hemicellulose = 22.2% CM:CS:SBP The reactors with the highest biogas yield after pretreatment at 100,
Lignin = 13.4% 120, 150 and 180 °C and with different time intervals were R13, R19, R23
180 °C and 1 h Cellulose = 38.2% 2:1:1 mixtures of This study and R28, respectively. The change between TS, VS and SCOD values of
Hemicellulose = 32.9% CM:CS:SBP
these reactors after pretreatments is given in Fig. 2. Initially, the SCOD
Lignin = 23.2%
100 °C and 1 h Cellulose = 14.7% Rice straw [36]
value of control reactor was 15,870 mg/L. This value was 26,990 mg/L
Hemicellulose = 20.1% after thermal pretreatment at 100 °C for 60 min. The SCOD values for
Lignin = 13.6% reactors R19, R23 and R28 were 28,500 mg/L, 27,450 mg/L and
55 °C and 8 day Cellulose = 22.7% Rice straw [37] 35,650 mg/L, respectively. After the pretreatments, SCOD values of the
Hemicellulose = 14.6%
reactors and biogas yields were consistent. TS and VS values decreased
Lignin = 39.9%
170 °C and 10 min Cellulose = 15.0% Giant reed [35] depending on the degree of thermal pretreatment. This mass loss can be
Hemicellulose = – attributed to lignocellulosic dissolution during pretreatments. The
Lignin = 24.8% change in VS and TS amounts after the thermal pretreatment in this
190 °C and 10 min Cellulose = 10.9% Giant reed [35] study was consistent with the results of the Rajput and Visvanathan
Hemicellulose = –
Lignin = 32.9%
[14].
210 °C and 15 min Cellulose = 14.3% Giant reed [35] SEM images give information about the surface morphology of or-
Hemicellulose = % – ganic lignocellulosic material. Fig. 3 shows SEM images of different
Lignin = 49.1% post-treatment and untreated organic materials. In Fig. 3, according to
230 °C and 5 min Cellulose = 15.4% Giant reed [35]
1 and 2, it is observed that there is no porous structure with the surface
Hemicellulose = % –
Lignin = 57.5% crystal of the organic sample and the surface consists of a hard layer.
According to 3 and 4, the surface sample of the organic sample has little
fractures and has a porous structure. The pore size appears to be around
[36], similar lignin removal values were obtained. In the literature, the 10–20 µm. It appears that these pores did not open upon pretreatment
maximum cellulose removal was 22.7% in organic samples kept at at 100 °C for 60 min. According to 5 and 6, the surface sample of the
55 °C for 8 days [37]. In this study, 38.2% cellulose solubilization oc- organic sample was broken and approximately 1–10 µm cracks were
curred at 180 °C for 1 h of pretreatment. This showed that the cellulose observed. These cracks were not observed at the pretreatment tem-
solubility at high temperatures was time dependent. In the literature, perature of 100 °C, 120 °C and 120 min pretreatment conditions. It was
maximum hemicellulose solubilization was 20.1% at 100 °C and 1 h observed that surface crystal began to decrease and cracks started to
[36]. In the same conditions, hemicellulose solubilization in this study form. According to 7 and 8, the surface crystal of the organic sample
was 22.2%. When the current literature is considered, lignocellulosic was broken and appeared to have cracks of around 1–5 µm. As the
solubilization values have changed depending on the temperature va- pretreatment temperature increased, the number of cracks also in-
lues and application times of thermal pretreatments. However, pre- creased according to 9 and 10. It is seen that the fractures and reduc-
treatment under the same conditions resulted different lignocellulosic tions of the surface sample of the organic sample have reached the
solubilization values of different organic substances. This phenomenon maximum level compared to the other lower pretreatments. Patowary
can be attributed to the content of cellulose, hemicellulose and lignin and Baruah [38] observed that the rice straw, which was kept at 90 °C
present in different amounts in the organic material. thermal pretreatment temperature for 10 h, did not pass into a porous

5
H. Şenol, et al. Fuel 263 (2020) 116651

Fig. 1. Cumulative biogas productions after thermal pretreatments.

130 VS
(R4, R13, R19, R23 and R28). In previous studies, CBP was evaluated by
TS
35000 Gompertz model [41]. However, in the literature, there are limited
sCOD
110 applications of the modified Bertalanffy model, which is an alternative
30000
sigmoidal model.
Table 8 shows the maximum biogas potential, specific biogas pro-
90
duction rate, lag phase and determination coefficients (R2) of the op-
SCOD (mg/L)
TS and VS (g/L)

25000 timum reactors in which the untreated and thermal pretreatments were
70
60 min 60 min applied according to the Gompertz and Bertalanffy model. In R4 and
(R13) (R23 ) R13, the biogas yields were 180.5 and 255.5 mL/g TS respectively.
20000
50 60 min However, the estimated values for the maximum biogas production of
120 min (R28 )
(R19) the modified Gompertz model were 194.998 and 290.760 mL/g TS,
15000 respectively. Similarly, the maximum biogas production rates estimated
30
by the modified Bertalanffy model were 220.154 and 351.580 mL/g TS.
10000
The maximum biogas production rates estimated by modified Gompertz
10
and modified Bertalanffy models were determined as 427.440 and
538.728 mL/g TS, respectively. The most fitted reactors for the mod-
control 100 120 150 180
-10 5000 ified Gompertz and modified Bertalanffy models were R4 and R13 re-
Thermal pretreatment temperature (ºC) spectively.
Fig. 4 shows the time-dependent value of the CBP for the R4, R13,
Fig. 2. The changes in the amounts of TS, VS and SCOD of organic matter after
thermal pretreatment.
R19, R23 and R28 reactors. In all reactors, the R2 value of the modified
Bertalanffy model is higher than the R2 value of the modified Gompertz
model. Based on these values, it can be said that modified Bertalanffy
structure and only breakages began to occur. Similarly Momayez et al. model was more fitted than modified Gompertz model. In modified
[39] determined has a rigid structure after thermal pretreatment at Gompertz model, the lag phase for the untreated reactor was lower than
130 °C for 30 min and the surface crystallinity decreases after pre- that in modified Bertalanffy model. Although the modified Bertalanffy
treatment at 190 °C for 60 min. SEM images of cassava anaerobic re- model was more fitted for all reactors than the modified Gompertz
sidue were examined after thermal pretreatment. According to these model, it found the maximum biogas production estimates higher. In
images, it was observed that the surface morphology of organic matter previous studies, CBP was examined for its applicability for modified
was disrupted and passed from a crystal structure to a soft structure as a Gompertz model [42-45]. In some studies, the modified Gomperz model
result of thermal pretreatment applied at 160 °C [40]. was compared with the modified Logistic model [14,46-48]. However,
there is no comparison of modified Gompertz and modified Bertalanffy
3.4. Applications of modified Gompertz and modified Bertalanffy models models in the literature. In this study, modified Bertalanffy model va-
lues for biogas production for the first time were found to be quite
Modified Gompertz and modified Bertalanffy models were applied compatible in CBP.
to the optimum reactors which have the maximum biogas production

6
H. Şenol, et al.
Fig. 3. SEM images of orgaic samples as a result of thermal pretreatment.
4. Conclusion
In the anaerobic process, optimum mixing ratio of CM, CS and SBP
was found in order to evaluate waste together. Thus, it was experi-
mentally proposed that CM, CS and SBP form a good mixture in AD.
Thermal pretreatments were applied from 100 °C to 180 °C for optimum
mixing ratio and biogas production in these temperature ranges varied
7
Fuel 263 (2020) 116651
among 41.5% and 100.6%. Thermal pretreatments played a role in the
lignocellulosic solubilization. After thermal pretreatments, cellulose,
hemicellulose and lignin solubilizations were 14.8–39.1%, 22.2–33.5%
and 13.5–23.4%, respectively. As the pretreatment times for all pre-
treatment temperatures increased, the SCOD values increased accord-
ingly. At all thermal pretreatment temperatures, the thermal pretreat-
ment time increased biogas yield up to 60 min, but after 60 min there
H. Şenol, et al. Fuel 263 (2020) 116651

Table 8
Kinetic constants of Modified Gompertz and modified Bertalanffy models with experimental data.
Reactors Modified Gompertz model Modified Bertalanffy model

Λ(day) µm (mL/g TS.d) A (mL/g TS) R 2

Λ(day) µm (mL/g TS.d) A (mL/g TS) R2

R4 2.786 4.017 194.998 0.996 4.112 3.620 220.154 0.998

R13 4.537 8.771 290.760 0.997 3.654 8.281 351.580 0.999
R19 4.738 9.817 333.583 0.996 3.901 9.099 417.783 0.997
R23 3.976 9.607 318.484 0.995 3.054 8.928 386.302 0.997
R28 2.778 11.322 427.440 0.990 2.098 10.535 538.728 0.993

350
250 R4-Gompertz
Cumulative biogas production (mL/gTS)

Cumulative biogas production (mL/gTS)

R4-Bertalanffy
300
200 R4
250
150
200

100 150

50 100

50
0
0 5 10 15 20 25 30 35 40 45 50 0
Days 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71
Day
450
Cumulative biogas production (mL/gTS)

400
Cumulative biogas production (mL/gTS)

400
350
350
300
300
250 250

200 200
150 150
100 100
50
50
0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 0
1 6 11 16 21 26 31 36 41 46 51 56 61 66 71
Day Day

600
Cumulative biogas production(mL/g TS)

500

400

300

200

100

0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70
Day

Fig. 4. Cumulative biogas productions fitted curves of modified Gompertz and modified Bertalanffy model curves according to different pretreatment temperature
conditions.

8
H. Şenol, et al.
was no significant increase in biogas yield. After the thermal pretreat-
ment, experimental data successfully fitted to modified Gompertz and
Bertalanffy models.
CRediT authorship contribution statement
Halil Şenol: Conceptualization, Data curation, Formal analysis,
Funding acquisition, Investigation, Methodology, Project administra-
tion. Ünsal Açıkel: Writing - original draft. Serkan Demir: Writing -
review & editing. Volkan Oda: Supervision, Validation, Visualization.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgement
This research was supported by the Sivas Cumhuriyet University
Scientific Research Projects Unit (CUBAP) under grant no M-665. The
authors wish to thank this institution for their support.
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