Bioenergy Conversion
Bioenergy Conversion
Bioenergy Conversion
Biomass and Waste Management Laboratory, School of Energy and Environmental Studies, Faculty of Engineering Sciences,
Devi Ahilya University, Khandwa Road Campus, Indore, MP PIN––452 017, India
Received 24 July 2003
Abstract
Batch digestion of municipal garbage was carried out for 100 days at room temperature (26 ± 4 C; average temperature 25 C)
and at ambient temperature (32 ± 10 C; average temperature 29 C) conditions for total solids concentrations varying between 45
and 135 g/l. A first order model based on the availability of substrate as the limiting factor was used to perform the kinetic studies of
batch anaerobic digestion system. Effect of organic solids concentration and digestion time on biogas yield was studied and mass
and energy balance analysis was conducted for batch digestion. The net bioenergy yield from municipal garbage and corresponding
bioprocess conversion efficiency over the length of the digestion time were observed to be 12,528 kJ/kg volatile solids and 84.51%
respectively. The methane content of the biogas generated from the reactors was in the range of 62–72% with the overall average
methane content of the biogas, computed over the total digestion period was 65 vol%.
2004 Published by Elsevier Ltd.
Keywords: Anaerobic digestion; Bioenergy; Municipal garbage; Kinetics; Mass and energy balance
and for different environmental and operating condi- 2.2. Reactor set-up
tions.
The objectives of the present study are Aspirator bottles of capacity 3.25 I made of glass with
bottom sampling outlets were used as bioreactors. The
• to investigate the way in which biogas yield, volume bottles were closed by rubber stoppers equipped with
of biogas produced per unit weight of organic mate- glass tubes for gas removal and for adjusting the pH.
rial fed, varies with digestion time and organic solids The glass tube was dipped inside the slurry to avoid gas
concentration; loss during the pH adjustments. A thermometer of range
• to evaluate the effect of organic loading on kinetics 0–60 C having an accuracy ±0.5 C was used to mea-
and bioprocess conversion efficiency of batch anaero- sure the slurry temperature in the reactors maintained
bic digestion system and to optimise the organic load- at room temperature where as a multi-channel digital
ing that can be fed to the reactor with digestion time; temperature indicator equipped with copper–constantan
and thermocouples (type ‘t’) having an accuracy ±0.1 C
• to assess the quality of the digested solids and liquid were used to measure the slurry temperature in the
effluent for their further use. reactors maintained at ambient temperature.
ambient and room temperatures respectively with equal 3. Data analysis and calculations
working volumes (2 l) but different total solids concen-
trations varying between 45 and 135 g/l. All the reactors 3.1. Kinetic study
were fed with municipal garbage, tap water and cattle
dung slurry (inoculum), used as the starter in the reac- Kinetic studies of anaerobic digestion process are
tors. Liquid samples were drawn from each reactor useful to predict the performance of digesters and design
periodically and analysed for pH, volatile fatty acids as appropriate digesters. Kinetic studies are also helpful in
acetic acid, chemical oxygen demand and alkalinity. The understanding inhibitory mechanisms of biodegrada-
pH was measured daily for the first 15 days of the tion. First-order kinetic models are the simplest models
experiment and measured for every 10 days thereafter. applied to the anaerobic digestion of complex substrates
Volatile fatty acids as acetic acid and alkalinity were as they provide a simple basis for comparing stable
measured daily for the first 10 days of the experiment process performance under practical conditions. There-
and measured every 10 days thereafter. Chemical oxy- fore, a first order model based on the availability of
gen demand was measured every 10 days throughout the substrate as the limiting factor was used (Llabres-
experiment. The characteristics of inoculum and di- Luengo and Mata-Alvarez, 1987; Hahimoto, 1989;
gested slurry are given in Table 2. The experiment was Turick et al., 1991; Mata-Alvarez et al., 1993; Chen and
carried out for 100 days at room temperature (26 ± 4 C; Hahimoto, 1996; Sanchez et al., 1996) to perform the
average temperature 25 C) for the first five reactors and present study. The basic equation is
at ambient temperature (32 ± 10 C; average tempera- dB=dt ¼ kB ð1Þ
ture 29 C) for the other five reactors, maintaining
similar total solids concentrations in reactors in both where k is the first-order substrate utilisation rate con-
conditions. One reactor each was fed with inoculum, stant (time1 ) and B (mg/l) represents the biodegradable
used as starter in the other 10 reactors and run parallel substrate concentration. On integration, Eq. (1) be-
at ambient and room temperature conditions. All the comes
gas productions were evaluated after deducting the gas B=B0 ¼ expðktÞ ð2Þ
production from the control, by first multiplying the
where B0 (mg/l) represents initial substrate concentra-
volume of gas produced by the control by 0.15 (the ratio
tion. Substrate concentration can be correlated with
of the volume of inoculum to bioreactor working vol-
biogas production (G), as mentioned below.
ume). All the gas volumes were measured at an average
temperature of 25 C and corrected to 0 C standard ðG1 GÞ=G1 ¼ B=B0 ð3Þ
temperature and 1 atm pressure. The substrate was where G1 (l) is the ultimate biogas production. From
mixed once each day, at the time of the gas measure- Eqs. (2) and (3), the integrated equation for the first-
ment, to maintain intimate contact between the micro- order model which gives an analytical relation between
organisms and the substrate. The C:N weight ratio of the volume of biogas produced and digestion time was
the organic matter was adjusted to 25:1 using urea, as obtained and used to quantify the extent of process
this is the optimum ratio for maximum microbial inhibition is as follows:
activity (Mata-Alvarez et al., 1992, 1993; Molnar and
Bartha, 1989). G ¼ G1 ½1 expðktÞ ð4Þ
Table 2
Inoculum and digested slurry (after 100 days) characteristics
Parameter pH Total VFA as acetic acid Total alkalinity as CaCO3 Total chemical oxygen demand
reactor (mg/l) (mg/l) (mg/l)
Inoculum 7.5 570 1600 20,400
Ambient conditions
R1 7.5 880 2240 6000
R2 7.4 1050 2450 11,890
R3 7.3 1840 2950 28,610
R4 7.3 3020 3600 34,810
R5 7.3 3580 4020 101,800
Room conditions
R1 7.5 780 2350 18,120
R2 7.4 870 2440 27,910
R3 7.3 940 2370 74,640
R4 7.3 2080 3020 107,110
176 M.S. Rao, S.P. Singh / Bioresource Technology 95 (2004) 173–185
where k (time1 ) is the first-order biogas production rate metric gas energy yield (m3 /kg volatile solids) was
constant. The values of G1 and k were obtained from an determined using the TOC:VS:COD ratio 1:2.21:2.84
exponential regression analysis using Curve Expert, obtained for municipal garbage by Rao et al. (2000). It is
version 1.3. evident from the fact that a certain amount of substrate
(energy) is consumed by the micro-organisms during
3.2. Mass balance analysis their reproduction and growth in the process. The en-
ergy consumed in the process was estimated indirectly
Mass balance analysis by the determination of vola- using the volumetric difference between the stoichio-
tile solid mass removal in the present study was done metric biogas energy potential of the substrate con-
based on the volume and composition of biogas pro- sumed (m3 /kg TOG) and the actual biogas produced.
duced. Biogas as produced contains methane, carbon Bioenergy yield was estimated using volumetric higher
dioxide, water vapour and trace amounts of other gases. heating value of biogas in energy per unit mass. The
From a volumetric point of view, the trace gases are biogas composition was assumed to contain CH4 and
neglected and considered only the dry biogas for deter- CO2 , neglecting the trace gases. The higher heating value
mining mass removals. Dry biogas is assumed to behave of the biogas was determined at pressure 1 atm and
as an ideal gas and consist entirely of carbon dioxide temperature 0 C based on the higher heating value of
and methane. The biogas volumes are measured at one CH4 at pressure 1 atm and temperature 20 C (Culp,
atmosphere so that no pressure correction is required. 1991) assuming that the mixture behaves as an ideal gas.
Conversion of as-measured biogas volumes to standard
conditions at 0 C and one atmosphere of pressure was
done in a way similar to that used by Richards et al. 4. Results and discussion
(1991) excluding volume occupied by water vapour and
thermal expansion effects. The biogas mass is calculated Degradation of substrate started almost immediately
using the molecular weights of methane and carbon and proceeded without problems in the reactors main-
dioxide (16 and 44 g/mol, respectively), the molar vol- tained at ambient temperature. However, for the reac-
ume of an ideal gas at STP (22.413 l/mol) and norma- tors maintained at room temperature, it took about 6–8
lised individual gas contents (vol%) as follows: days for initiation of biogas production. The cumulative
biogas production at different total solids concentration
Gm ¼ Vd ½ð16 CH4 =100Þ þ ð44 CO2 =100Þ=22:413
maintained at room and ambient temperature along
ð5Þ with the predicted values using the first-order kinetic
where Gm is the biogas mass (g); Vd , the dry biogas model described by Eq. (4) are shown in Figs. 1–5. It has
volume at STP (l); CH4 , the biogas normalised methane been observed that the cumulative biogas production
content (vol%); CO2 , the biogas normalised carbon was fit well with the first-order kinetic model as is evi-
dioxide content (vol%). dent from the standard error and correlation coefficient
(r) between the experimental and predicted values given
along with the parameter estimates in Table 3.
3.3. Energy balance analysis
A decrease in pH was observed during the first few
days of digestion due to the high volatile fatty acids
Net energy generation (NEG) from anaerobic diges-
formation, hence the pH was adjusted to 7.0 ± 0.2 using
tion process is determined by carrying out energy bal-
NaHCO3 solution, when the pH before adjustment and
ance analysis using stoichiometric energy potential of
immediately after mixing the substrate varied between
the substrate (SEP), bioprocess conversion factor
5.5 and 6.5. Thereafter, the pH was maintained between
(BCF); ratio of substrate utilised (mg/l) at time ‘t’ and
6.8 and 7.4, which is the optimum pH range for methane
total substrate available for bioconversion (mg/l) and
production. The profile of pH and volatile fatty acids as
energy consumed in the process (EC) at time ‘t’ as fol-
acetic acid (mg/l) over the length of the digestion period
lows:
at different organic loading concentrations under
NEG ðkJ=kg VSÞ ¼ ½fSEP ðkJ=kg VSÞ BCFg ambient and room temperatures are shown in Figs. 6
and 7 respectively. The maximum specific biogas pro-
fEC ðkJ=kg VSÞg ð6Þ
duction rates were observed to be 2 and 1.9 vol. gas/vol.
The stoichiometric gas energy yield (CO2 + CH4 ) that slurry/day, respectively, on the 4th and 6th days of the
can be obtained from anaerobic decomposition of or- digestion period observed for reactors fed at 59.74 g VS/l
ganic matter has been estimated from the total organic at ambient and room temperatures respectively. The
carbon (TOC), as 1 kg of carbon in the substrate will initial pH drop and high volatile fatty acid concentra-
yield 1/12 kmol of gas. Thus, per kg of carbon degraded, tion and high specific biogas production rates show that
the gas yield should be 1.866 m3 gas measured at 0 C the substrate contains some easily biodegradable con-
standard temperature and 1 atm pressure. The stoichio- stituents.
M.S. Rao, S.P. Singh / Bioresource Technology 95 (2004) 173–185 177
Table 3
Values of fitting functions and statistical measures for the kinetic model
TS concentration (g/l) Parameters Statistical measures
Ultimate biogas Biogas production Standard Correlation
production (l) rate constant (per day) error coefficient
Ambient temperature
35 42.195 0.0273 1.17 0.99
67.5 62.235 0.0269 1.90 0.99
90 99.485 0.0108 2.80 0.98
112.5 141.630 0.0087 3.04 0.99
135 54.471 0.0175 2.50 0.98
Room temperature
35 33.415 0.0217 1.40 0.98
67.5 48.440 0.0234 1.90 0.98
90 24.860 0.0244 1.04 0.98
112.5 21.675 0.0158 0.97 0.97
M.S. Rao, S.P. Singh / Bioresource Technology 95 (2004) 173–185 179
Fig. 6. Profile of pH and volatile fatty acids (VFA) concentration (ambient temperature).
The reactor fed with 135 g TS/l maintained at room VFA/l is grossly inadequate and digestion failure would
temperature was failed to continue with biogas pro- be anticipated. Stenstrom et al. (1983) have conducted
duction where high volatile fatty acids (VFA) formation experiments on anaerobic digestion of municipal solid
(18,500 mg acetic acid/l) lowered pH of slurry to 5.1 and waste and found that at high organic loading it was very
ultimately lead to formation of thick scum layer on the difficult to avoid forming a thick scum layer of undi-
top of the substrate. Though addition of NaHCO3 gested solids on the surface of the digesters. According
solution increased the pH of slurry to 7.3, it could not to Niekerk et al. (1987) foaming is a result of inadequate
revive gas production in this reactor. Failure of anaero- mixing, high alkalinity, ammonia and volatile fatty acid
bic reactors appears to have been due to inadequate levels. Therefore in the present study too, inadequate
levels of alkalinity to balance the levels of VFA in the mixing of substrate and presence of higher concentra-
digestion liquors. It was found that careful attention to tions of alkalinity and volatile fatty acids in the reactor
alkalinity levels during digestion of municipal garbage is might have caused formation of thick scum layer of
crucial to the success of the digestion. For stable undigested solids on the surface of the reactor. However,
digestions, it is imperative that a satisfactory ratio be this foaming problem was not encountered with the
maintained between VFA and alkalinity levels. This reactor fed with same volatile solids concentration but
ratio is given by the empirical relationship that for run at ambient temperature conditions.
balanced digestion, alkalinity (mg/l)––0.7 · VFA (mg/l) The biogas yield, biogas produced per kg organic
should not be less than 1500 (Lane, 1984). On the basis, solids (volatile solids) for different concentrations of
an alkalinity of 12,000 mg/l in the presence of 18,500 mg organic loading over a 100-day digestion time at room
180 M.S. Rao, S.P. Singh / Bioresource Technology 95 (2004) 173–185
and ambient temperatures are shown in Figs. 8 and 9 The relative methane yield as defined by Brummeler
respectively. The rates of biogas production differed and Koster (1990), is the sum of the methane produced
significantly according to the organic loading. It can be at any time divided by the potential methane yield of the
observed from Figs. 8 and 9 that bulk of substrate organic fraction, as determined in a batch assay at low
degradation takes place up to a period of 60 days sug- solids. The potential methane yield estimated in the
gesting that the digesters should preferably be run at a earlier study by Rao et al. (2000) was used for deter-
digestion time close to 60 days for optimum energy mining relative methane yields at different concentra-
yield. The methane content of the biogas generated from tions of organic loading. The relative methane yields
the reactors was in the range of 52–56% during the first obtained for different organic loadings over the length of
2–4 days of the digestion and remained in the range of the digestion period, 100 days are shown in Figs. 10 and
62–72% for the remaining period. The average methane 11. The effect of organic loading on methane production
content of the biogas generated from the reactors fed at rates at ambient and room temperatures are shown in
35 and 67.5 g TS/l maintained under room temperature Figs. 12 and 13. It was observed that methane produc-
was observed to be 70 vol%. The average methane tion rate was increased with the increase of organic
content of the biogas generated from the rest of the loading up to a concentration of 59.74 g VS/l and de-
reactors maintained at both room and ambient tem- creased thereafter. This means that the anaerobic
peratures was observed to be 65 vol%. digestion is inhibited significantly owing to the build-up
M.S. Rao, S.P. Singh / Bioresource Technology 95 (2004) 173–185 181
Fig. 10. Relative methane yield curves at different organic loading concentrations under ambient temperature.
Fig. 11. Relative methane yield curves at different organic loading concentrations under room temperature.
Fig. 12. Effect of organic loading on methane production rate (ambient temperature).
182 M.S. Rao, S.P. Singh / Bioresource Technology 95 (2004) 173–185
Fig. 13. Effect of organic loading on methane production rate (room temperature).
Fig. 14. Bioprocess conversion efficiency profile over time at different total solids (TS) concentration (ambient temperature).
Fig. 15. Bioprocess conversion efficiency profile over time at different total solids (TS) concentration (room temperature).
M.S. Rao, S.P. Singh / Bioresource Technology 95 (2004) 173–185 183
Degrada-
tion (%)
inoculum ratio) as well as due to the fact that increasing
19.61
22.14
24.21
15.84
33.66
9.95
the density of the solid waste tends to decrease the gas
production, possible because of a decrease in the effec-
tive surface area exposed to hydrolysis. It was also ob-
81.85
21.04
3.89
217.05
186.1
203.7
Final
served that methane production rates were more for the
first 20 days in all the reactors and decreased thereafter.
These results indicated that methane gas is produced
4.32
307.05
Initial
first at a high rate and then at a reduced rate which is a
239.0
270
108
25
R5
factor of 20–60 less than the initial rate over the length
of the digestion time of 100 days. The high initial rates,
Degrada-
tion (%)
which were sustained for up to 20 days, indicate that a
42.44
47.97
52.22
21.46
29.32
72.79
major amount of the gas-producing solid waste fraction
was readily and rapidly biodegradable.
The actual amount of energy recovery from the solid
17.67
69.62
2.83
waste will depend on the efficiency of the conversion
129.5
103.6
Final
43
process used. The bioprocess conversion efficiency, as
defined by Rao et al. (2000); ratio of biodegradable
substrate utilised and ultimate biodegradable substrate
255.88
Initial
3.6
199.1
available for bioprocess conversion multiplied by 100,
90
25
225
R4
over the length of the digestion period at different con-
Degrada-
centrations of organic loading are shown in Figs. 14 and
tion (%)
42.08
47.55
51.88
38.96
72.05
15. It is evident from Figs. 11–15 that biogas yields
21.2
obtained under ambient conditions were better than
those obtained under room temperature. It indicates
that temperature has shown to be the environmental
34.65
15.26
57.22
2.27
104.25
83.6
Final
variable having considerable effect on gas production
especially at higher organic loading. It was observed
that at organic solids concentration 59.74 g/l and at the
2.88
Initial
159.3
204.7
end of 60-day digestion time, the relative methane yield
180
72
25
R3
40.24
84.51
observed to be highest for the reactor fed at 99.56 g VS/l
22
14.94
23.79
1.68
Final
153.53
Initial
119.5
135
54
25
43.4
33.1
12.8
1.44
Initial
36
25
R1
Para-
C/N
Degrada-
stable and high quality compost (Molnar and Bartha,
tion (%)
10.11
11.11
16.28
8.93
4.56
6.72
1988). From Tables 4 and 5, it is evident that the com-
position of the digested substrate respectively at total
solids concentration between 35 and 90 g/l under
ambient temperature and total solids concentration be-
3.43
214.22
23.32
tween 35 and 67.5 g/l under room temperature can be
204.9
Final
179
80
used as compost or biofertilizer.
5. Conclusions
155.88
Initial
199.1
3.6
225
90
25
R4
27.072
16.57
17.71
11.24
9.11
7.28
22.19
2.67
149.28
204.70
Initial
159.3
72
25
R3
16.78
55.83
1.75
Final
87.6
72.1
Acknowledgements
2.16
153.53
Initial
119.5
financial assistance.
135
54
25
R2
References
Degrada-
tion (%)
35.78
40.43
46.17
19.00
33.20
64.58
36.25
1.16
Final
57.8
16.7
102.35
79.65
Initial
36
25
R1
COD (g)
TOC (g)
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