Ecotoxicology and Environmental Safety 121 (2015) 100–104

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Ecotoxicology and Environmental Safety

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

Kinetic study on the effect of temperature on biogas production using

a lab scale batch reactor
B. Deepanraj a, V. Sivasubramanian b,n, S. Jayaraj a
a
Department of Mechanical Engineering, National Institute of Technology, Calicut, Kerala, India
b
Department of Chemical Engineering, National Institute of Technology, Calicut, Kerala, India

art ic l e i nf o a b s t r a c t

Article history: In the present study, biogas production from food waste through anaerobic digestion was carried out in a
Received 27 October 2014 2 l laboratory-scale batch reactor operating at different temperatures with a hydraulic retention time of
Received in revised form 30 days. The reactors were operated with a solid concentration of 7.5% of total solids and pH 7. The food
24 April 2015
wastes used in this experiment were subjected to characterization studies before and after digestion.
Accepted 28 April 2015
Modified Gompertz model and Logistic model were used for kinetic study of biogas production. The
Available online 8 May 2015
kinetic parameters, biogas yield potential of the substrate (B), the maximum biogas production rate (Rb)
Keywords: and the duration of lag phase (λ), coefficient of determination (R2) and root mean square error (RMSE)
Anaerobic digestion were estimated in each case. The effect of temperature on biogas production was evaluated experi-
Biogas
mentally and compared with the results of kinetic study. The results demonstrated that the reactor with
Food waste
operating temperature of 50 °C achieved maximum cumulative biogas production of 7556 ml with better
Temperature
Modified Gompertz model biodegradation efficiency.
Logistic model & 2015 Elsevier Inc. All rights reserved.

1. Introduction bacteria breaks down polymers to monomers; acidogen-

esis – acidogenic bacteria converts monomers to short chained
Biomass has been considered as a major source of renewable carboxylic acids, carbon dioxide, hydrogen and alcohol; acet-
energy to replace the fast declining fossil fuel resources (Demirbas, ogenesis – the products of the previous steps are converted to
2007; Ozcimen and Karaosmanoglu, 2004; Jefferson, 2006). Bio- acetic acid; methanogenesis – methane is produced from the
mass appears to be an attractive feedstock for three main reasons. acetic acid (Weiland, 2010; Kumar et al., 2010; Decker and Menrad,
First, it is a renewable resource that could be sustainably devel- 2007; Barik et al., 2013).
oped in the future. Second, reportedly it has positive environ- The major advantage of the anaerobic digestion process is the
mental properties resulting in no net release of carbon dioxide production of biogas, a renewable energy source, which can be
(CO2) and very low sulfur content. Third, it also has significant used as fuel for automobiles, for direct heating and for power
economic potential provided that, fossil fuel prices continuously generation (Appels et al., 2011). The production of biogas, de-
increase in the future (Cadenas and Cabezudo, 1998). Production of pending on the biomass feedstock used, helps in the reduction of
biofuels from biomass can slow down the climate change by fossil fuel usage and enables the lowering of carbon dioxide levels.
substantially reducing the greenhouse gas emissions (Meena et al., Apart from biogas yield, anaerobic digestion liberates solid and
liquid by-products which can be used as fertilizer or soil
2011). Among various renewable technologies, anaerobic digestion
amendment.
is a commercially proven and widely employed technology for
The biogas produced during anaerobic digestion process is a
treating biomass, especially like agricultural and forest residues,
blend of methane (CH4: 55–65% by volume), carbon dioxide (CO2:
municipal solid waste, etc. (Meena et al., 2011).
30–40% by volume), and traces of hydrogen sulphide (H2S), hy-
Anaerobic digestion is a natural process by which complex or-
drogen (H2) (Deepanraj et al., 2014). Due to the intricacy of the
ganic materials are broken down into simpler compounds in the
bioconversion processes, various factors like solid concentration,
absence of air by several micro-organism communities (Samir
pH, temperature, mixing/agitation, C/N ratio, etc. are affecting the
et al., 2010; Cioabla et al., 2012). Anaerobic digestion comprises of
performance of an anaerobic digestion process. Among those fac-
a series of four biochemical reaction steps: hydrolysis – hydrolytic tors, temperature is one of the important factor and lot of re-
searchers investigated the effects of temperature on biogas pro-
n
Corresponding author. Fax: þ91 4952287250 . duction using various feedstock and reported their findings (El-
E-mail address: babudeepan@gmail.com (B. Deepanraj). Mashad et al., 2004; Ji-Shi et al., 2006; Vanegas and Bartlett, 2013;

http://dx.doi.org/10.1016/j.ecoenv.2015.04.051
0147-6513/& 2015 Elsevier Inc. All rights reserved.
 B. Deepanraj et al. / Ecotoxicology and Environmental Safety 121 (2015) 100–104 101

Ghatak and Mahanta, 2014). The present study aims to investigate Table 1
the effect of temperature on biogas production from food waste Characteristics of substrate and digestate.
experimentally in an anaerobic batch digester. The experimental
Characteristics Substrate Digestate
kinetics was also analyzed for the goodness of fit with modified
Gompertz model. 30 °C 40 °C 50 °C 60 °C

TS (g/l) 75 37.92 36.28 34.23 35.17

VS (g/l) 71.34 35.02 34.00 31.02 32.74
2. Materials and methods FS (g/l) 3.66 2.90 2.28 1.4 0.53
TDS (g/l) 0.732 1.78 1.90 2.12 2.08
2.1. Feedstock COD (g/l) 69.92 42.70 40.17 37.95 38.88

Food waste used in this experimental study was collected from

a hostel mess of National Institute of Technology Calicut, Kerala.
Food waste is a highly desirable substrate for anaerobic digestion
with regards to its higher biodegradability and biogas/methane
yield. This contains a substantially large amount of organic matter,
which can be digested anaerobically to produce biogas. Also, the
nutrient content analysis showed that the food waste contained
well balanced nutrients for anaerobic microorganisms ([Zhang
et al., 2007,Zhang et al., 2012]). The elemental composition of the
food waste was determined using elemental analyzer. The carbon,
hydrogen, oxygen, nitrogen and sulfur compositions present in the
feedstock are 49.96%, 10.35%, 1.13%, 38.28% and 0.28% respectively.
The food wastes obtained were shredded, mixed and stored at 5 °C
until it is introduced into the anaerobic digester. The solid con-
centration and pH values were already optimized in the previous
experiments (Deepanraj et al., 2014; Jayaraj et al., 2014). Water
was added to obtain the desired total solid concentration (7.5% of Fig. 1. Cumulative biogas production.

total solids) and 1 N sodium bicarbonate solution was used to

maintain the pH value as 7. The characteristics of the substrate modified Gompertz model and Logistic model. Using these mod-
used were determined before and after digestion. For all the ex- els, the biogas production potential of the substrate, maximum
periments, cow dung was used as inoculum (10% inoculum to feed biogas production rate and the lag phase of the reaction can be
ratio). determined with available experimental results. The kinetic data
obtained from all digesters were checked for the fitness of mod-
2.2. Experimental setup ified Gompertz model and Logistic model. The modified Gompertz
model and Logistic model describes cumulative biogas production
Laboratory-scale anaerobic batch digesters made of glass with a from batch digesters, assuming that biogas production is a func-
total volume of 2 l and working volume 1.6 l were used in all the tion of bacterial growth (Nopharatana et al., 2006; Pommier et al.,
experiments. Biogas production from the digesters was measured 2007). The equations are given by
daily by the water displacement method. The reaction mixtures ⎧ ⎡ Rb e ⎤⎫
were stirred twice a day. Each reactors were maintained with C = B exp ⎨ − exp ⎢ (λ − t ) + 1⎥ ⎬
⎩ ⎣ B ⎦⎭ (1)
different temperatures (30, 40, 50 and 60 °C) using water bath.

2.3. Analytical methods B

C=
1 + exp ⎡⎣4R b + 2⎤⎦
λ−t
B (2)
Characterization of feedstock is one of the most significant
steps in the biogas production process. Determining the general where ‘C' is cumulative biogas production at digestion time
composition of the substrate (input feed) is essential for calculat- ‘t’ days; ‘B’ is biogas yield potential of the substrate; ‘Rb’ is max-
ing the quantity and composition of the biogas generated. The imum biogas production rate; ‘e’ is exp (1) ¼2.718; ‘λ’ is the
total solids, volatile solids, fixed solids and chemical oxygen de- duration of lag phase.
mand of the substrate and digestate were determined as per the The kinetic parameters of each of the reactor were estimated
standard method (APHA Standard methods for examination of using nonlinear least-square regression analysis with the help of
water and waste water, 1989). Total dissolved solids were de-
termined using TDS meter (Model-161, Deep Vision Instruments, Table 2
Results of experimental study.
India) and pH of the substrate and digestate was determined using
pH meter (pH-201, Lutron Electronic Enterprise, Taiwan). The Parameter 30 °C 40 °C 50 °C 60 °C
elemental composition was determined using elemental analyzer
(Elementar Vario EL III, ELEMENTAR Analysensysteme, Germany). TS removal efficiency (%) 49.44 51.62 54.36 53.10
TS removed (g/l) 37.08 38.72 40.77 39.83
The methane and carbon dioxide composition in the biogas were
VS removal efficiency (%) 50.91 52.34 56.51 54.16
measured using infrared gas analyzers (PIR-89, Technovation VS removed (g/l) 36.32 37.34 40.32 38.70
Analytical Instruments, India). COD removal efficiency (%) 38.93 42.54 45.72 44.39
COD removed (g/l) 27.22 27.22 29.75 31.27
2.4. Kinetic study Cumulative biogas produced – experimental 5673 6449 7556 7081
(ml)
CH4 (%) 60.8 60.5 61.2 59.1
Many dynamic models are available to give a detailed de- CO2 (%) 36.3 38.0 37.1 38.5
scription of bioconversion mechanism. In this study, we used
102 B. Deepanraj et al. / Ecotoxicology and Environmental Safety 121 (2015) 100–104

Fig. 2. (a) Cumulative biogas production – experimental and modified Gompertz model. (b) Comparison of experimental and predicted (modified Gompertz model) cu-
mulative biogas production.

Table 3
Results of kinetic study – modified Gompertz model and Logistic model.

Parameter Modified Gompertz Model Logistic Model

30 °C 40 °C 50 °C 60 °C 30 °C 40 °C 50 °C 60 °C

Cumulative biogas produced – experimental (ml) 5673 6449 7556 7081 5673 6449 7556 7081
Cumulative biogas produced – predicted (ml) 5588.5 6417.2 7517.4 7003 5476.9 6289 7360.6 6859.9
Max biogas potential from Gompertz model (ml) 5628.6 6463.3 7583.2 7062.3 5482.7 6295.2 7369.9 6868.7
Rb (ml/day) 432.4 504.6 581.8 537 430.6 508.0 587.4 538
Lag phase (λ) 1.5 1.9 2.4 2.0 1.8 2.4 2.8 2.4
R2 0.9988 0.9996 0.9998 0.9994 0.9922 0.9962 0.9961 0.9941
RMSE 2.80 1.91 1.71 3.17 11.55 9.74 13.24 13.92

Fig. 3. (a) Cumulative biogas production – experimental & Logistic model. (b) Comparison of experimental and predicted (Logistic model) cumulative biogas production.

s
MATLAB (R2012a). The statistical indicators R2 (coefficient of determina- The cumulative biogas production with respect to retention time
tion) and RMSE were calculated for this analysis (Kafle et al., 2013). for all the reactors is shown in Fig. 1. The cumulative biogas yield
obtained by the reactor with 30, 40, 50 and 60 °C are 5673, 6449,
⎛ m ⎛dj ⎞2⎞
1/2
7556 and 7081 ml respectively. According to the results, the cu-
⎜1
RMSE = ⎜
⎜m
∑ ⎜⎜ ⎟⎟ ⎟⎟⎟ mulative gas production was high at 50 °C, followed by 60, 40 and
Y
j=1 ⎝ j ⎠ ⎠
⎝ (3) 30 °C. The total cumulative gas production increases with increase
in temperature upto 50 °C and then decreases. The cumulative
where ‘RMSE’ is Root Mean Square Error; ‘m’ is number of data
biogas produced by reactor with temperature 50 °C is 24.92%,
pairs; ‘d’ is the difference between experimental and predicted
14.65% and 6.28% higher than the yield of reactors with 30, 40 and
methane yield; and ‘Y’ is the measured biogas yield.
60 °C. Similar trend was observed by Kim et al., 2006 who studied
the effect of temperature on biogas production from anaerobic
digestion of food waste. The amount of biogas produced from the
3. Results and discussions reactors at 50 °C and 60 °C is more than that of 30 °C and 40 °C.
This result suggests that the activity of the methanogenic bacteria
3.1. Experimental study used in this study depends on to operation temperature. There-
fore, a thermophilic temperature 50–60 °C is more effective for
The characteristics of substrate and digestate before and after biogas production than a mesophilic temperature. The specific
digestion process are given in Table 1. The temperature of the biogas yield of 138.94, 144.51, 161.09 and 152.08 ml/g of COD re-
reactors was maintained at 30, 40, 50 and 60 °C using water bath. moval were obtained at 30, 40, 50 °C and 60 °C respectively.
 B. Deepanraj et al. / Ecotoxicology and Environmental Safety 121 (2015) 100–104 103

Table 2 shows the results of experimental study carried out at biogas production values were plotted against the measured va-
different operating temperatures. The variation of total solids (TS), lues, as shown in Fig. 3 a. With operating temperature 30, 40, 50
volatile solids (VS) and chemical oxygen demand (COD) degrada- and 60 °C, the biogas yield potential of the substrate (B) are found
tion efficiencies are shown in Fig. 3. The TS degradation efficiency to be 5482.7, 6295.2, 7369.9 and 6868.7 ml respectively. Calculated
of the reactors with operating temperature 30, 40, 50 and 60 °C lag time was found to be in between 1.8 and 2.8 days, because of
are 49.44%, 51.62%, 54.36% and 53.1% respectively. The reactor with the inoculum added and the ready biodegradation component
operating temperature of 50 °C produced better TS degradation available in the substrate. The coefficient of determination (R2)
efficiency (40.77 g/l), which is 9.05, 5.04 and 2.31% higher than the values for the reactors with operating temperature 30, 40, 50 and
reactors of 30, 40 and 60 °C respectively. The VS degradation ef- 60 °C are 0.9922, 0.9962, 0.9961 and 0.9941 respectively. The
ficiency of the reactors with operating temperature 30, 40, 50 and coefficient of determination (R2) values shows that the predicted
60 °C are 50.91%, 52.34%, 56.51% and 54.16% respectively. The COD values were best fitted with experimental values. The root mean
degradation efficiency of the reactors with operating temperature square errors values are in between 9.74 and 13.92.
30, 40, 50 and 60 °C are 38.93%, 42.54%, 45.72% and 44.39% re- Fig. 3b shows the comparison of experimental and predicted
spectively. Similar to that of TS degradation efficiency, VS and COD cumulative biogas production for all the reactors. Using Logistic
degradation efficiency of the reactor with operating temperature model, the overall root mean square error (RMSE) and R2 were
of 50 °C is higher compared to other three reactors. obtained as 5.31% and 0.9960% respectively. The overall percentage
deviation for all the reactors with different temperatures is 725%.
3.2. Kinetic study This shows that Logistic model was well fitted for kinetic study of
biogas production and to determine the lag phase of the reaction
3.2.1. Using modified Gompertz model and maximum biogas potential. But compared to the modified
The modified Gompertz equation was used to fit cumulative Gompertz model, the mean square error (RMSE), coefficient of
biogas production data obtained from anaerobic digestion process. determination value (R2) and the overall percentage deviation of
The estimated kinetic parameters based on modified Gompertz the Logistic model are higher. This shows that modified Gompertz
equation are given in Table 3. This indicates that the modified model suits well for the kinetic study of biogas production com-
Gompertz equation can be used to estimate biogas yield potential, pared to Logistic model.
maximum biogas production rate and duration of lag phase. To
evaluate the soundness of the model results from the modified
Gompertz model, the predicted cumulative biogas values were 4. Conclusion
plotted against the measured values, as shown in Fig. 2 a.
Biogas yield potential of the substrate (B) with operating The effect of temperature on biogas yield from food waste was
temperature 30, 40, 50 and 60 °C are found to be 5628.6, 6463.3, investigated experimentally in 2 l batch anaerobic reactors. Kinetic
7583.2 and 7062.3 ml respectively. This shows that the reactor model of biogas production was obtained using modified Gom-
with operating temperature 50 °C have a maximum biogas yield pertz model and Logistic model. The experimental results were
potential followed by 60, 40 and 30 °C. Calculated lag time was compared with the predicted values. The best performance was
found to be in between 1.5 and 2.4 days, because of the inoculum observed in digester operating at a temperature of 50 °C. However,
added and the ready biodegradation component available in the this result does not mean the higher temperature is more optimal,
substrate. The coefficient of determination (R2) values for the re- due to the larger energy requirement at higher digesting tem-
actors with operating temperature 30, 40, 50 and 60 °C are 0.9988, peratures. Therefore, careful consideration of the net energy bal-
0.9996, 0.9998 and 0.9994. This shows that the predicted values ance between the increased heating energy demands and im-
were best fitted with experimental values. The root mean square proved additional methane production at higher operating tem-
errors values are in between 1.71 and 3.17. Similar type of results peratures must be simultaneously taken into account when de-
was reported by researchers who used modified Gompertz equa- ciding the economical digesting temperature. The modified Gom-
tion for their experiments to evaluate the kinetic study of cumu- pertz model and Logistic model were used to evaluate the per-
lative gas production. Budiyono and Syaichurrozi (2014) studied formance parameters of anaerobic digestion. By this study, the
the kinetics of anaerobic digestion process from vinasse with re- biogas yield potential of the substrate, lag phase of the reaction
spect to total solids and obtained R2 value in between 0.993 and and the maximum biogas production rate were determined. The
0.999 and lag phase in between 0.432 and 2.547 days. Cheong and statistical analysis showed that the modified Gompertz model was
Hansen (2006) experimented the cattle manure sludge for anae- better consisted with the experimental data than the Logistic
robic hydrogen production and reported that modified Gompertz model. This was proved by comparing the R2 values and root mean
equation was best fitted for the kinetic study. They obtained the R2 square errors of the two models.
value in between 0.997 and 1.0 and RMSE in between 0.16 and
7.06.
Fig. 2b shows the comparison of experimental and predicted References
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