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Experimental and kinetic study on anaerobic


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DOI: 10.1063/1.4935559

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Experimental and kinetic study on anaerobic digestion of food waste: The effect of total
solids and pH
B. Deepanraj, V. Sivasubramanian, and S. Jayaraj

Citation: Journal of Renewable and Sustainable Energy 7, 063104 (2015); doi: 10.1063/1.4935559
View online: http://dx.doi.org/10.1063/1.4935559
View Table of Contents: http://scitation.aip.org/content/aip/journal/jrse/7/6?ver=pdfcov
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JOURNAL OF RENEWABLE AND SUSTAINABLE ENERGY 7, 063104 (2015)

Experimental and kinetic study on anaerobic digestion


of food waste: The effect of total solids and pH
B. Deepanraj,1,a) V. Sivasubramanian,2 and S. Jayaraj1
1
Department of Mechanical Engineering, National Institute of Technology Calicut,
Kozhikode 673601, Kerala, India
2
Department of Chemical Engineering, National Institute of Technology Calicut,
Kozhikode 673601, Kerala, India
(Received 1 April 2015; accepted 29 October 2015; published online 9 November 2015)

This paper presents the results of laboratory experiments carried out on an


anaerobic digestion of food waste with respect to the effect of solid concentration
and pH. Total solid (TS) content ranging from 5.0% to 15.0% and pH value
ranging from 5 to 9 were analyzed. Laboratory scale experiments using 2 l
bioreactors were performed in batch mode operated at mesophilic temperature
condition with a hydraulic retention time of 30 days. The cumulative volume of
biogas produced was used to measure the reactor performance. The methane and
carbon dioxide composition of the gas produced was measured using infra-red
gas analyzers. The kinetics of biogas produced has been predicted using three dif-
ferent models (Gompertz model, modified Gompertz model, and Logistic model).
The experimental results showed that the solid concentration 7.5% of TS and 7
pH produced a maximum biogas yield. The kinetic study showed that modified
Gompertz model produced perfect goodness of fit and root mean square error
when compared to other two models. V C 2015 AIP Publishing LLC.

[http://dx.doi.org/10.1063/1.4935559]

I. INTRODUCTION
Fast industrialization and hiking population growth are among the leading factors for the
rising trend in the global energy demand. With the current laws and policies governing energy
consumption, the global energy demand for the year 2030 is forecasted to increase from the
current total of 472 quadrillion Btu to 678 quadrillion Btu which is 43.64% of monumental
raise.1 The fossil fuel (oil, natural gas, and coal) will still remain as the dominant source of
energy by 2030. An immense dependence on the fossil fuel is contributed towards the fossil
fuel depletion and climate change.2 These concerns have stimulated a crave for development
and utilization of alternative/renewable energy technologies. Alternate energy sources such as
biomass, solar, wind, hydro, etc., are the few renewable sources for such a huge demand.
Among the alternate energy sources, biomass is the third largest primary energy used in the
world, after coal and oil,3 and provides about 1250  106 tons oil equivalent (Mtoe) of primary
energy which is about 14% of the world’s annual energy consumption.4,5 Biomass is a renew-
able and sustainable fuel source that can deliver a significant reduction in net carbon emissions
with proper management. Techniques such as briquetting, gasification, anaerobic digestion,
ethanol fermentation, etc., are used to convert raw biomass into fuel products of usable forms.
Among the above conversion techniques, anaerobic digestion technology is highly interest-
ing; the process involves the decomposition of organic matter by microorganisms in an oxygen
free environment.6 It is a natural process occurring in an anaerobic environment such as the
ocean/lake sediments and digestive tracts of human beings. This process comprises a series of
complex reactions that convert a wide array of polymeric organic substances such as

a)
Author to whom correspondence should be addressed. Electronic mail: babudeepan@gmail.com. Tel: þ91 495 2286477.

1941-7012/2015/7(6)/063104/12/$30.00 7, 063104-1 C 2015 AIP Publishing LLC


V

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carbohydrates, proteins, and lipids into one-carbon molecule. The products of anaerobic diges-
tion are biogas and the digestate. The biogas produced through anaerobic digestion typically
contains 60%–75% methane, 20%–40% of carbon dioxide and trace amounts of other gases.7,8
Anaerobic digestion process follows four-stage scheme, namely, hydrolysis, acidogenesis,
acetogenesis, and methanogenesis.9 In the hydrolysis stage, the complex organic structure of
the substrate is broken down into a simpler structure. During acidogenesis, the simpler organic
compounds of the first stage are converted into volatile organic acids (acetate, propionate, bu-
tyrate, and valeric acid), carbon dioxide, and hydrogen. Subsequently, in the acetogenesis stage
acetate, hydrogen, and carbon dioxide are synthesized from the organic acids. Finally, in metha-
nogenesis, the products of the third stage are converted into biogas which mainly consists of
methane and carbon dioxide as its major constituents.10–12
The gas yield in an anaerobic digestion process depends on the number of operating param-
eters such as solid concentration, temperature, pH, and retention time. Many researchers investi-
gated the effects of operating parameters on biogas production and reported their findings.
Budiyono et al.13 studied the effect of substrate concentration (2.6, 4.6, 6.2, 7.4, 9.2, 12.3, and
18.4% of total solids (TSs)) on biogas production from cattle manure with rumen fluid as inoc-
ulum and reported that the substrate concentration of 9.2% of total solids yielded more biogas
(186.28 ml/g of volatile solid (VS)) followed by 7.4% (184.09 ml/g of VS). Sivakumar et al.14
studied the effect of pH on biogas production from spoiled milk. Experiments were conducted
with substrate of different pH values (5–8) and reported that the substrate with 7 pH resulted
better biogas yield. Daniel and Lucie15 investigated the effect of temperature (20, 25, and
30  C) on slaughterhouse wastewater treatment in the anaerobic sequencing batch reactors.
They found that high methanogenic activity was found for the temperature of 30  C followed
by 25 and 20  C. Siddiqui et al.16 studied the effect of C/N ratio using processed industrial
food waste co-digested with sewage sludge. Various C/N ratios (15%–30%) were analyzed in
an anaerobic batch reactor and reported that the C/N ratio of 20 achieved highest volatile solid
destruction followed by 30 and 10, respectively.
The objective of the present investigation is to evaluate the effect of total solids and pH on
an anaerobic batch digestion of food waste through experimental and kinetic studies. Three
mathematical models (Gompertz model, modified Gompertz model, and Logistic model) were
used to predict the biogas production rate from the experimental data.

II. MATERIALS AND METHODS


A. Experimental setup
Anaerobic batch digesters made of glass vessel with total volume of 2 l and working vol-
ume of 1.6 l were used for laboratory experiments. The digesters were operated at ambient tem-
perature in the mesophilic range with a hydraulic retention time of 30 days. All the reactors
were stirred using magnetic stirrers twice in a day. Biogas production from the digesters were
measured daily by a water displacement method. The volume of water displaced from the flask
was equivalent to the volume of gas generated.

B. Feedstock
Food waste is a highly desirable substrate for anaerobic digestion with regard to its higher
biodegradability and biogas/methane yield. This contains a substantially large amount of or-
ganic matter, which can be processed anaerobically to produce biogas. Also, the nutrient con-
tent analysis showed that the food waste contained well balanced nutrients for anaerobic micro-
organisms.17 Food waste used in this experimental study was collected from a hostel mess of
National Institute of Technology Calicut, Kerala. These wastes were shredded, mixed, and
stored at 5  C until it was put into the anaerobic digester. Water was added to obtain the five
desired total solid concentration (5, 7.5, 10, 12.5, and 15% of total solids). In order to perform
experiments with respect to pH, substrate with different pH (5, 6, 7, 8, and 9) were prepared
using 1N sodium bicarbonate solution. The characteristics of the substrate used were

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determined before and after digestion. For the entire experiments, cow dung was used as inocu-
lum (10% inoculum to feed ratio).

C. Analytical methods
Feedstock characterization is one of the important steps in the biogas production process.
Determining the general composition of the substrate (input feed) is essential for calculating the
quantity and composition of the biogas generated. The TSs, VSs, fixed solids (FSs), and chemi-
cal oxygen demand (COD) of the substrate and digestate were determined as per the standard
method.18 Total dissolved solids (TDSs) were determined using TDS meter (Model-161, Deep
Vision Instruments, India) and pH of the substrate and digestate was determined using pH me-
ter (pH-201, Lutron Electronic Enterprise, Taiwan). The methane and carbon dioxide composi-
tion in the biogas was measured using infrared gas analyzers (PIR-89, Technovation Analytical
Instruments, India).

D. Kinetic study
The experimental data obtained from the digesters were checked for the fitness using three
different models. The cumulative biogas production can be described by means Gompertz
model19,20 as follows:

C ¼ B½1  expðktÞ; (1)

where C is the cumulative biogas production at digestion time “t” days; B is the biogas poten-
tial of the substrate; k is the first order disintegration rate constant (biogas production rate con-
stant); t is the time in days.
Apart from the specific and cumulative biogas production, the duration of the lag phase is
also an important factor in determining the efficiency of anaerobic digestion. The lag phase (k)
can be calculated with the help of modified Gompertz model20–22 and Logistic model.22 The
equations for modified Gompertz model and Logistic model are given in the following equa-
tions, respectively:
  
Rb e
C ¼ Bexp exp ðk  t Þ þ 1 ; (2)
B

B
C¼  ; (3)
kt
1 þ exp 4Rb þ2
B

where C is the cumulative biogas production at digestion time “t” days; B is the biogas poten-
tial of the substrate; Rb is maximum biogas production rate; k is the lag phase; t is the time in
days; and e is the exp(1) ¼ 2.7183. The kinetic parameters for each reactor were evaluated by
best fitting the experimental data on cumulative biogas production and biomass concentration in
Eqs. (1)–(3) using the non-linear curve fitting toolbox available in MATLAB (R2012a). The
statistical indicators, coefficient of determination (R2) and root mean square error (RMSE),
were calculated from this analysis23
 2 !1=2
1X m
dj
RMSE ¼ ; (4)
m j¼1 Yj

where m is the number of data pairs; d is the difference between experimental and predicted
methane yield; and Y is the measured biogas yield.

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TABLE I. Characterization of substrate before anaerobic digestion. (Initial SC: Initial Solid Concentration.)

Reactor TS (g/l) VS (g/l) FS (g/l) TDS (g/l) pH COD (g/l)

R1 (Initial SC: 5% of TS) 50 47.7 2.3 0.54 4.65 64.95


R2 (Initial SC: 7.5% of TS) 75 71.55 3.45 0.71 4.69 69.85
R3 (Initial SC: 10% of TS) 100 95.4 4.6 1.10 4.72 74.30
R4 (Initial SC: 12.5% of TS) 125 119.5 5.5 1.82 4.68 83.40
R5 (Initial SC: 15% of TS) 150 143.4 6.6 1.94 4.74 84.26

III. RESULTS AND DISCUSSION


A. Effect of total solids
Tables I and II show the characteristics of substrate and digestate before and after diges-
tion, respectively, for all the solid concentrations. The cumulative biogas production for the
reactors with different solid concentrations (5, 7.5, 10, 12.5, and 15%) is shown in Fig. 1. From
the figure, it can be understood that the reactor with 7.5% of total solids produced maximum
biogas yield compared to other solid concentrations. The maximum biogas yield for all the five
solid concentrations is shown in Fig. 2. From Fig. 2, it is observed that the amount of biogas
produced increased with an increase in the solid concentration up to 7.5% of total solids. This
was due to the abundant availability of readily biodegradable materials present in the substrate.
After 7.5% of total solids, the biogas yield decreased with respect to solid concentration,
because of poor microbial/enzymatic substrate contact with increased amount of substrate pres-
ent in the reactor. The maximum biogas produced by 7.5% of TS was 4394 ml followed by
10% of TS, which was 3913 ml. Reactors with 5, 12.5, and 15% of total solid concentration
produced 3040, 3739, and 3582 ml of biogas, respectively. The methane content in the biogas
produced was 54.31, 57.95, 56.86, 54.93, and 52.18% (v/v) for 5, 7.5, 10, 12.5, and 15% of
solid concentration, respectively. Similarly, the carbon dioxide content in the biogas produced
was 40.60, 39.81, 40.07, 40.97, and 42.57% in 5, 7.5, 10, 12.5, and 15% of solid concentration,
respectively.
The degradation efficiency is also considered to be important in evaluating the performance
of an anaerobic digestion process. From the results of characterisation study before and after
digestion process (Tables I and II), the TS, VS, and COD removal eficiencies were calculated
which are shown in Fig. 3. The TS removal efficiencies of 5, 7.5, 10, 12.5, and 15% of TS are
found to be 38.32, 39.20, 33.58, 24.64, and 27.92, respectively. TS removal efficiency of 7.5%
of TS was more followed by 5, 10, 12.5, and 15% concentrations. VS removal efficiencies of 5,
7.5, 10, 12.5, and 15% of TS were 45.78, 43.01, 37.48, 29.89, and 34.73%, respectively.
Similarly, COD removal efficiencies of 5, 7.5, 10, 12.5, and 15% of TS were 19.47, 29.89,
26.66, 21.82, and 26.61, respectively. In case of volatile solid degradation, 5% of TS achived
better efficiency than others; 7.5% of TS achieved better efficiency in the COD degradation.
Similar trend was observed by Balsam24 and Zennaki et al.25 who studied the effect of solid
concentration on biogas production from animal waste and cattle manure. This was due to the
function of water in digester, since the total solid content will directly correspond to water

TABLE II. Characterization of digestate after anaerobic digestion.

Reactor TS (g/l) VS (g/l) FS (g/l) TDS (g/l) pH COD (g/l)

R1 (Initial SC: 5% of TS) 30.84 25.86 4.98 1.12 4.27 52.3


R2 (Initial SC: 7.5% of TS) 45.6 40.77 4.82 1.74 3.61 48.97
R3 (Initial SC: 10% of TS) 68.13 59.64 8.49 1.79 4.76 54.49
R4 (Initial SC: 12.5% of TS) 94.2 83.78 10.42 1.9 3.89 65.20
R5 (Initial SC: 15% of TS) 108.12 93.59 14.52 2.67 3.74 63.78

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FIG. 1. Cummulative biogas production (effect of total solids).

content. According to Sadaka and Engler,26 water content is one of the very important parame-
ters affecting anaerobic digestion of solid wastes by two main reasons. Water makes the possi-
ble movement and growth of bacteria facilitating the dissolution and transport of nutrient; water
reduces the limitation of mass transfer of non-homogenous or particulate substrate. Budiyono
et al.27 and Baserja28 reported that below 7% of total solid level, the process degradation of
materials into biogas was unstable while total solid level of above 10% caused an overloading
of the fermenter.29
The Gompertz model, modified Gompertz model, and Logistic model were used to fit cu-
mulative biogas production data obtained from the anaerobic digestion process. The estimated
kinetic parameters based on all the three models were summarized in Tables III–V. This indi-
cates that these models can be used to estimate biogas yield potential, maximum biogas produc-
tion rate, and duration of lag phase. To evaluate the soundness of the model results, the pre-
dicted cumulative biogas values from all the three models were plotted against the measured
values, as shown in Figs. 4–6.
Comparing the performance models, the best fit was obtained from modified Gompertz
model with highest coefficient of determination in all cases (above 0.9966). The coefficient of
determination of Gompertz model ranged over from 0.9916 to 0.9986. The coefficient of deter-
mination of Logistic model ranged over from 0.9929 to 0.9960. The biogas yield potential (B)
of substrate with 7.5% of total solid was found to be higher for all the three models. The biogas
yield potential values of Gompertz model, modified Gompertz model, and Logistic model are

FIG. 2. Maximum biogas yield (effect of total solids).

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FIG. 3. VS, TS, and COD removal efficiencies (effect of total solids).

TABLE III. Comparison of results with Gompertz model.

Parameter R1 R2 R3 R4 R5

C-Experimental (ml) 3040 4364 3913 3739 3582


C-Predicted (ml) 3121.27 4542.62 4089.10 3910.28 3749.91
B (ml) 3751 5249 4992 4464 4560
k 0.0594 0.0668 0.0569 0.0695 0.0575
R2 0.9986 0.9916 0.9963 0.9941 0.9946
RMSE 3.90 11.6 6.6 10.28 9.6

TABLE IV. Comparison of results with modified Gompertz model.

Parameter R1 R2 R3 R4 R5

C-Experimental (ml) 3040 4364 3913 3739 3582


C-Predicted (ml) 3006.4 4298.3 3930.5 3726.7 3576
B (ml) 3117.1 4358 4075.6 3786.6 3674.1
Rb (ml/day) 164.9 292 217.4 244.1 212.8
k (days) 0.1 1.0 0.1 0.6 0.6
R2 0.9973 0.9983 0.9966 0.9984 0.9987
RMSE 2.76 2.1 5.36 4.56 3.88

TABLE V. Comparison of results with the Logistic model.

Parameter R1 R2 R3 R4 R5

C-Experimental (ml) 3040 4364 3913 3739 3582


C-Predicted (ml) 2939.1 4213.2 3864.1 3657.8 3507.2
B (ml) 2971 4225.6 3908.9 3671.4 3532.6
Rb (ml/day) 162.2 287.5 213.4 239.1 210.9
k (days) 0.1 1.2 0.4 0.9 1.0
R2 0.9929 0.9935 0.9947 0.9955 0.9960
RMSE 5.17 4.7 4.75 3.72 5.69

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FIG. 4. Cumulative biogas production from the first order kinetic model (effect of total solids).

5249, 4358, and 4225.6 ml, respectively, for substrate with 7.5% of total solids. In most of the
cases, the estimated lag phase time is less than or equal to 1, due to the addition of inoculum
added and the ready biodegradation component available in the substrate.

B. Effect of pH
The characteristics of substrate and digestate before and after digestion are summarized in
Tables VI and VII, respectively. The pH of the substrate used in the reactors was adjusted to
the required value (5–9) by adding 1N sodium bicarbonate solution. Figure 7 shows the cumu-
lative biogas production for the reactors with different pH, starting 5–9. From the figure, it can
be understood that the reactor with a substrate of pH 7 produced maximum biogas yield com-
pared to other pH values. The maximum biogas yield for all the reactors with different pH is
shown in Fig. 8. The results show that pH of the substrate has significant effect on biogas pro-
duction, because it affects the activity of micro-organisms involved in the digestion process

FIG. 5. Cumulative biogas production from the modified Gompertz model (effect of total solids).

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FIG. 6. Cumulative biogas production from the Logistic model (effect of total solids).

TABLE VI. Characterization of substrate before anaerobic digestion. Except pH, the characteristics remains same in all the
reactors (R1–R5).

TS (g/l) VS (g/l) FS (g/l) TDS (g/l) COD (g/l)

75 71.34 3.66 0.73 69.39

particularly methanogenic bacteria. The maximum cumulative biogas yield obtained by the re-
actor with pH 5, 6, 7, 8, and 9 are 4594, 5021, 5673, 5347, and 4889 ml, respectively. This
shows that pH 7 resulted in higher biogas production followed by 8, 7, 9, and 6. The methane
composition in the biogas produced with pH 5, 6, 7, 8, and 9 was determined to be 56.7, 58.6,
60.8, 60.1, and 59.4% (v/v), respectively. Espinoza-Escalante et al.30 reported that biogas pro-
duction from vinasse at pH 6.5 was greater than that of pH 4.5 and 5.5.
From the characterization study of samples before and after digestion process (Tables VI
and VII), the TS, VS, and COD removal eficiencies were calculated which is shown in Fig. 9.
The TS removal efficiency of the reactor with pH 5, 6, 7, 8, and 9 were 40.18, 43.25, 49.44,
45.62, and 41.96, respectively. The VS removal efficiency of the reactor with pH 5, 6, 7, 8, and
9 were 44.63, 47.37, 50.91, 48.45, and 46.22, respectively. Similarly, COD removal efficiency
of the reactor with pH 5, 6, 7, 8, and 9 were 30.14, 33.42, 38.93, 35.35, and 32.16, respectively.
In all the cases, better degradation efficiency was achieved with pH 7 compared to others.
Compared to TS and VS removal efficiencies, the COD removal efficiency was low in all the
cases because of the solid content available in the substrate.

TABLE VII. Characterization of digestate after anaerobic digestion.

Reactor TS (g/l) VS (g/l) FS (g/l) TDS (g/l) COD (g/l)

R1 (pH 5) 44.86 39.50 5.36 1.74 48.84


R2 (pH 6) 42.56 37.54 5.02 1.92 46.55
R3 (pH 7) 37.92 35.02 2.90 1.78 42.70
R4 (pH 8) 40.78 36.77 4.01 2.06 45.20
R5 (pH 9) 43.53 38.36 5.17 1.95 47.43

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FIG. 7. Cummulative biogas production (effect of pH).

FIG. 8. Maximum biogas yield (effect of pH).

FIG. 9. VS, TS, and COD removal efficiencies (effect of pH).

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FIG. 10. Cumulative biogas production from the first order kinetic model (effect of pH).

The kinetic parameters estimated for all the reactors using Gompertz model, modified
Gompertz model, and Logistic model are summarized in Tables VIII–X, respectively. Figs.
10–12 shows the results of experimental and predicted (modelled) cumulative biogas production
with respect to the retention time. The best fit was obtained using the modified Gompertz model
(highest coefficient of determination in all cases-above 0.9970). The coefficient of determina-
tion of the Gompertz model ranged over from 0.9754 to 09861. The coefficient of determina-
tion of the Logistic model ranged over from 0.9902 to 0.9942. Using Gompertz model, the bio-
gas production rate constant (k) was determined as 0.0633, 0.0675, 0.0726, 0.0687, and 0.0615
for 5, 6, 7, 8, and 9 pH, respectively. The lag phase time of the modified Gompertz model
ranged over 1.2–1.8 days. The lag phase time of the Logistic model ranged over 1.5–2.1 days.
The biogas yield potential (B) of substrate with pH 7 was found to be higher for all the three
models followed by 8, 6, 9, and 5 pH. The biogas yield potential values of Gompertz model,
Modified Gompertz model, and Logistic model are 6707, 5628.6, and 5482.7 ml, respectively,
for substrate with pH 7.

FIG. 11. Cumulative biogas production from the modified Gompertz model (effect of pH).

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FIG. 12. Cumulative biogas production from the Logistic model (effect of pH).

TABLE VIII. Comparison of results with Gompertz model (effect of pH).

Parameter R1 R2 R3 R4 R5

C-Experimental (ml) 4594 5021 5673 5347 4889


C-Predicted (ml) 4765.17 5249.62 5947.52 5603.23 5151.64
B (ml) 5604 6046 6707 6420 6116
k 0.0633 0.0675 0.0726 0.0687 0.0615
R2 0.9861 0.9852 0.9754 0.9790 0.9781
RMSE (%) 14.2 14.9 17.3 19.3 20.1

TABLE IX. Comparison of results with the modified Gompertz model (effect of pH).

Parameter R1 R2 R3 R4 R5

C-Experimental (ml) 4594 5021 5673 5347 4889


C-Predicted (ml) 4483.7 4952.1 5588.5 5253.3 4815.6
B (ml) 4545.9 5009.5 5628.6 5295.9 4866.1
Rb (ml/day) 307.5 350.5 432.4 399.9 353.7
k (days) 1.2 1.2 1.5 1.6 1.8
R2 0.9972 0.9987 0.9988 0.9985 0.9970
RMSE 4.03 2.92 2.5 3.64 4.38

TABLE X. Comparison of results with Logistic model (effect of pH).

Parameter R1 R2 R3 R4 R5

C-Experimental (ml) 4594 5021 5673 5347 4889


C-Predicted (ml) 4358.2 4852.8 5476.9 5144.3 4714.7
B (ml) 4397 4863.4 5482.7 5150.6 4723.1
Rb (ml/day) 305.5 346.8 430.6 399.7 353.4
k (days) 1.5 1.5 1.8 1.9 2.1
R2 0.9902 0.9940 0.9942 0.9934 0.9938
RMSE 6.46 6.49 6.3 9.61 9.45

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063104-12 Deepanraj, Sivasubramanian, and Jayaraj J. Renewable Sustainable Energy 7, 063104 (2015)

IV. CONCLUSION
It was observed that the amount of biogas production was affected by the total solid con-
centration and the pH of the substrate. From the laboratory experiments, it was found that solid
concentration of 7.5% of TS and pH 7 yielded more biogas production and higher degradation
efficiency compared to others. Based on the results of the statistical curve fitting, the modified
Gompertz model was observed to adequately describe cumulative biogas production with very
high goodness of fit (R2) and RMSE values compared to the Gompertz and logistic models.
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