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Anaerobic treatment of apple waste with swine manure for biogas production:

Batch and continuous operation


Gopi Krishna Kae
1
, Sang Hun Kim

Department of Biosystems Engineering, Kangwon National University, Chuncheon, Kangwon-do, Republic of Korea
h i g h l i g h t s
" Apple waste (AW) was co-digested with swine manure (SM).
" Mixture of AW and SM produced a higher biogas yield than SM only.
" Mixture of AW and SM produced a higher biogas yield at 55 C than at 36.5 C.
" Modied Gompertz model best tted to the substrates used.
" Positive synergetic effect up to 33% AW during continuous digestion.
a r t i c l e i n f o
Article history:
Received 13 July 2012
Accepted 4 October 2012
Available online 12 December 2012
Keywords:
Anaerobic treatment
Apple waste
Batch and continuous test
Biogas
Kinetic study
Swine manure
a b s t r a c t
This study evaluated the performance of anaerobic digesters using a mixture of apple waste (AW) and
swine manure (SM). Tests were performed using both batch and continuous digesters. The batch test
evaluated the gas potential, gas production rate of the AW and SM (Experiment I), and the effect of
AW co-digestion with SM (33:67,% volatile solids (VSs) basis) (Experiment II) at mesophilic and thermo-
philic temperatures. The rst-order kinetic model and modied Gompertz model were also evaluated for
methane yield. The continuous test evaluated the performance of a single stage completely stirred tank
reactor (CSTR) with different mixture ratios of AW and SM at mesophilic temperature. The ultimate bio-
gas and methane productivity of AW in terms of total chemical oxygen demand (TCOD) was determined
to be 510 and 252 mL/g TCOD added, respectively. The mixture of AW and SM improved the biogas yield
by approximately 16% and 48% at mesophilic and thermophilic temperatures, respectively, compared to
the use of SM only, but no signicant difference was found in the methane yield. The difference between
the predicted and measured methane yield was higher with a rst order kinetic model (4.618.1%) than
with a modied Gompertz model (1.23.4%). When testing continuous digestion, the methane yield
increased from 146 to 190 mL/g TCOD added when the AW content in the feed was increased from
25% to 33% (VS basis) at a constant organic loading rate (OLR) of 1.6 g VS/L/d and a hydraulic retention
time (HRT) of 30 days. However, the total volatile fatty acids (TVFA) accumulation increased rapidly
and the pH, methane content, and biogas production decreased continuously when the AW content in
the feed was increased to 50%.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Approximately 150,000 tons/day (wet basis or w.b.) of waste is
produced on swine farms in Korea, and approximately 5.7% of that
waste is disposed of by ocean dumping [1,2]. Swine waste is a
major source of odour production, vermin attraction, toxic gas
emissions and groundwater contamination. Meanwhile, approxi-
mately 14,452 tons/day (w.b.) of food waste is produced in Korea
[3], including approximately 55% fruit and vegetable waste
(FVW). The moisture content in FVW is very high (7595%), and
it decomposes readily, leading to many unpleasant environmental
consequences when it is abandoned in elds or near factories.
Anaerobic digestion can be used to convert organic matter into
biogas for energy recovery and achieve waste stabilisation and
odour reduction. Although there are many successful anaerobic
digesters currently treating swine manure, the high ammonia con-
tent in this type of manure is a major limitation that has plagued
digesters for many years [46]. Similarly, FVW has major limita-
tions to its usefulness in anaerobic digestion because of how
0306-2619/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apenergy.2012.10.018

Corresponding author. Address: Department of Biosystems Engineering, Kang-


won National University, 192-1 Hyoja 2-dong, Chuncheon, Kangwon-do 200-701,
Republic of Korea. Tel.: +82 33 250 6492; fax: +82 33 255 6406.
E-mail addresses: gopikae@yahoo.com (G.K. Kae), shkim@kangwon.ac.kr
(S.H. Kim).
1
Tel.: +82 33 250 6490; fax: +82 33 255 6406.
Applied Energy 103 (2013) 6172
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rapidly it acidies, stressing and inhibiting the activity of methano-
gens [7,8]. Apples are one of the most popular fruits in Korea, and a
large amount of AW is generated everyday from markets, agro-
industries and kitchens, making them a possible candidate for
use in anaerobic digestion. However, the experimental data on
the biomethanisation of AW are limited. Lane [9] and Contreras Lo-
pez and Lopez Bobo [10] conducted anaerobic digestion of AW in
continuous digesters. Similarly, Llaneza Coalla et al. [11] investi-
gated the anaerobic digestion of apple pulp, in which AW was
co-digested with slaughterhouse waste in a laboratory scale 10 L
CSTR.
Although biodegradable organic matter can be used as the sole
feedstock in anaerobic digestion, the digestion process tends to fail
without the addition of external nutrients and buffering agents
[12]. Co-digestion with substrates that have high buffering capac-
ity (alkalinity) such as manure can be good alternatives for the
effective treatment of highly biodegradable materials. During the
co-digestion of plant materials and animal manure, the manure
provides buffering capacity and various nutrients, while the plant
material provides high carbon content. The result is a more bal-
anced C/N ratio, and the co-digestion of manure and plant materi-
als decreases the risk of ammonia inhibition [13,14] and
acidication. Additionally, the input of readily biodegradable or-
ganic matter into animal manure digesters could signicantly in-
crease biogas production [15,16]. Utilising apple waste with
swine manure in biogas production could be an appropriate solu-
tion for the manures effective treatment and energy recovery.
In co-digestion, the digester performance is inuenced by the
mixing ratio or inuent composition. Kaparaju and Rintala [5] sug-
gested that 1520% (on a VS basis) potato waste can be included
when treating swine manure for successful digester operation. Cal-
laghan et al. [17] improved the methane yield from 0.23 to
0.45 m
3
/kg VS added by increasing the proportion of FVW from
20% to 50% during co-digestion with cattle manure, but it was also
observed that a high concentration of VFA was produced when the
proportion of FVW reached 30% or more. Similarly, Li et al. [16]
recommended 75% (VS basis) kitchen waste as optimal for co-
digestion with cow manure. The above studies showed that,
depending on the characteristics of the substrates used, the opti-
mal mixing ratio will be different for different waste products
being co-digested. To the best of our knowledge, no previous study
has examined the anaerobic co-digestion of AW with SM; there-
fore, this study co-digested apple waste with swine manure, rst
in batch digesters and then in continuous co-digestion tests based
on the batch test results.
The objective of this study was to evaluate the performance of
anaerobic digesters for the treatment of AW with SM. The specic
objectives were (1) to determine the biochemical methane poten-
tial (BMP) and gas production rate of AW and SM, (2) to investigate
the performance of batch digesters with the mixture of AW and SM
(AW:SM = 33:67) under mesophilic and thermophilic tempera-
tures, (3) to predict methane production using a rst-order kinetic
model and modied Gompertz model, and (4) to investigate the
performance of a continuous digester with different AW:SM ratios
at mesophilic temperature.
2. Materials and methods
2.1. Collection and characterisation of test materials
Swine manure was obtained from the Anseong swine farm lo-
cated in Gyeonggi Province, Korea, and stored at 4 C. Fresh apples
were obtained from a market in Korea. The apples were crushed in
a blender and stored at 4 C. The mesophilic anaerobic digested
sludge (inoculum) was obtained from a 13 L CSTR installed at the
Department of Biosystems Engineering, Kangwon National Univer-
sity, Korea. Thermophilic inoculum was obtained from a biogas
plant at the Anseong swine farm. Swine manure was used as a sub-
strate in both the mesophilic and thermophilic reactors from
which the inoculum was obtained. The characteristics of the feed-
stock and inoculum used for the batch and continuous tests are
shown in Table 1.
2.2. Batch digester start-up and experimental design
The batch test was divided into two experiments labelled I and
II. The experimental design for each portion is shown in Table 2.
Experiment I used 1.2 L glass bottles (liquid volume of 0.8 L) and
Experiment II used 2.3 L glass bottles (liquid volume of 1.8 L) to
carry out the anaerobic digestion tests. The biogas potential and
production rate of apple waste and swine manure were studied
in Experiment I. Tests were then performed in Experiment II with
a feed mixture ratio of AW:SM = 0:100 (SM-100%) and
AW:SM = 33:67 (AW-33%) on a VS basis at an OLR of 5.0 g VS/L
and feed-to-microbe (F/M) ratio of 1.0 under mesophilic and ther-
mophilic conditions (Table 2). The F/M ratio was calculated based
on the initial VS of the substrate and inoculum.
F=M
Substrate added g VS
Inoculum added g VS
1
Table 1
Characteristics of materials used in batch and continuous tests.
Particular Units Batch test Continuous test
AW SM Inoculum SM
Experiment I Experiment II Days 174 Days 7598 Days 99146
Mesophilic Mesophilic Thermophilic
TS % 13.714.2 5.9 1.39 2.02.5 2.6 3.41 5.57 4.334.8
VS % 1313.1 3.85 0.56 0.911.2 1.4 2.42 3.9 2.913.50
VS/TS ratio 0.920.95 0.65 0.40 0.460.48 0.54 0.70 0.71 0.670.73
pH 4.054.15 7.95 8.1 8.608.75 8.2 6.33 6.74 7.807.85
TCOD mg/L 139,200156,800 85,000 4373 63,947 73,067 68,20072,100
SCOD mg/L 112,000119,200 37,760 3413
TVFA mg/L 1900 14,168 1014 11831910 2060 13,371 16,329 14,00015,031
TA mg/L 0 17,096 11,160 14,19217,300 20,320 3600 5887 11,71312,100
TVFA/TA ratio 0.829 0.091 0.0680.135 0.101 3.71 2.77 1.151.28
NH
3
N mg/L 370450 5160 2540 34803860 3220 3360 55005830
TKN mg/L 25212661 8054 2647
TOC mg/L 72,22272,778 21,390 2139
C/N ratio 27.328.9 2.7 0.80
C/N ratio: TOC to TKN ratio.
62 G.K. Kae, S.H. Kim/ Applied Energy 103 (2013) 6172
After adding the required amounts of inoculum and substrate,
each digester was lled with tap water to maintain a designated
volume. The digester was ushed with 100% N
2
for 23 min before
sealing. The mesophilic and thermophilic digesters were kept at
36.5 C and 55 C, respectively, in a temperature-controlled incu-
bator. Experiment I was performed in triplicate, and Experiment
II was performed in duplicate; the results were expressed as a
mean. Each digester was mixed manually for 2030 s once a day.
Assays with the inoculum alone were used as controls. The biogas
and methane produced from the inoculum was subtracted from
the sample assays [18,19].
2.3. Continuous test setup and design
A single-stage continuous process was performed in a 5.5 L
CSTR with 4.5 L of working volume. The reactor was installed in-
side a temperature-controlled chamber (3638 C) and fed once a
day using a peristaltic pump. An equivalent volume of digester
content was discharged prior to feeding. The reactor was stirred
(7 min for each hour) by circulating the produced biogas using
the peristaltic pump. A continuous anaerobic digestion test was
performed with different mixture ratios of SM and AW. The exper-
imental design for the continuous test is shown in Table 2. In this
case, the reactor was inoculated on day 0 with 4.25 L of digested
sludge (inoculum), and anaerobic conditions were created by
ushing the head space with nitrogen gas. Then, different mixture
ratios of SM and AW were fed at a constant HRT of 30 days. The ap-
ple waste content in the feed was increased from 25% to 50% based
on the VS content (Table 2). Different OLRs were used with differ-
ent mixtures of SM and AW to maintain a constant HRT.
2.4. Biogas measurement and analytical methods
The daily biogas production of each digester in the batch test
was determined by the volume of biogas produced, which was cal-
culated from the volume and pressure in the headspace of the di-
gester. The pressure was measured using a WAL-BMP-test
system pressure gauge (type 3150, Wal, Germany) [20]. In the con-
tinuous test, the biogas was collected in a gas collector by the
water displacement method. The methane concentration and H
2
S
concentration in the biogas were analysed using a gas analyser
(BioGas Check-Geotechnical Instruments (UK) Ltd.). The gas ana-
lyser was calibrated using a certied gas containing methane
(50.13, 15.01, 5.01, %) and carbon dioxide (49.87, 15.01, 5.00, %).
The measured wet biogas and methane volumes were then ad-
justed to the volumes at standard temperature (0 C) and pressure
(1 atm) [2022].
V
STP

V
T
273 760 p
w

273 T 760
2
where V
STP
is the volume of gas measured at standard temperature
and pressure (L), V
T
is volume of gas measured at temperature T (L),
T is temperature of the fermentation gas or of the ambient space
(C), p
w
is the Vapor pressure of the water as a function of temper-
ature (mm Hg), The corrected methane content (CH
4 Corr
) in the bio-
gas was calculated using Eq. (3) as proposed in German standard
procedure [22].
CH
4 Corr

C
CH
4
100
C
CH
4
C
CO
2
3
where CH
4 Corr
is the Corrected methane content in the dry gas (% by
volume), C
CH4
is Measured methane content in the gas (% by vol-
ume), C
CO2
is the Measured carbon-dioxide content in the gas (%
by volume).
The total solids (TSs) and VS in the well-mixed samples were
determined in triplicate according to standard methods [23]. The
closed reux titration method was used for TCOD and soluble
chemical oxygen demand (SCOD) analysis, and the pH value was
determined using a pH metre (YK-2001 PH, Taiwan) at digester
temperature (3638 C). The total Kjeldahl nitrogen (TKN) was
analysed using a Kjeldahl apparatus (Kjeltec 2100, Foss, Sweden),
and the ammonia nitrogen (NH
3
N) was measured using the Ness-
ler method and determined using a spectrophotometre (DR 2500,
Hach, USA). The TVFA, total alkalinity (TA) and TVFA/TA ratio were
determined using the Nordmann-titration method [24]. The bicar-
bonate alkalinity (BA) was calculated using the relationship
BA = 0.71 TVFA [25], and the total organic carbon (TOC) was cal-
culated using the relationship TOC = VS/1.8 [26].
The mass removal of biogas at the conclusion of the experiment
was calculated using a formula (Eq. (4)). The density of CH
4
was ta-
ken as 0.000668 g/mL and the density of CO
2
as 0.00184 g/mL [27].
The TCOD removal was calculated using Eq. (5) [22].
BR
V
0
q
mix
m
4
TCOD removal of feed %
V
0
CH
4 Corr
320 m
5
where BR is the mass of biogas removed per gram TCOD added (g/g
TCOD added), V
0
is volume of biogas produced (mL, at STP), q
mix
is
mass concentration of CH
4
+ CO
2
in the biogas (g/mL), m is the
Amount of TCOD added (g).
Table 2
Experimental design for batch and continuous tests.
Particular Experimental design
a
F/M ratio Substrate loading (g VS/L
b
or g VS/L/d
c
) Feed composition (% VS basis) Temperature (C) Number of replications
Batch test Experiment I 0.5 2.5
b
AW: SM = 100:0(AW-100%) 36.5 3
0.5 2.5
b
AW: SM = 0:100(SM-100%) 36.5 3
Experiment II 1.0 5.0
b
AW: SM = 0:100(SM-100%) 36.5 2
1.0 5.0
b
AW: SM = 33:67(AW-33%) 36.5 2
1.0 5.0
b
AW: SM = 33:67(AW-33%) 55.0 2
Continuous test Days 190 1.0, 1.4,1.6
c
AW: SM = 25:75(AW-25%) 3638 1
Days 91123 1.6
c
AW: SM = 33:67(AW-33%) 3638 1
Days 124146 1.7
c
AW: SM = 50:50(AW-50%) 3638 1
: Not determined.
SM: Swine manure; AW: Apple waste.
a
Based on oven dried VS.
b
Gram volatile solids per litre.
c
Gram volatile solids per litre per day.
G.K. Kae, S.H. Kim/ Applied Energy 103 (2013) 6172 63
2.5. Kinetic study
Assuming rst-order kinetics for the hydrolysis of particulate
organic matter, the cumulative methane production can be de-
scribed by means of the following equation:
Gt G
o
1 e
Kt
6
where G(t) is the cumulative methane yield at digestion time t days
(mL/g TCOD added), G
o
is methane potential of the substrate (mL/g
TCOD added), K is methane production rate constant (rst order dis-
integration rate constant) (1/day), t is the time (days).
Apart from specic methane yield and the cumulative methane
yield, the duration of the lag phase is also an important factor in
determining the efciency of anaerobic digestion. The lag phase
(k) can be calculated with the modied Gompertz model as de-
scribed by Lay et al. [28] as follows:
M P exp exp
R
max
e
P
k t 1
_ _ _ _
7
where M is the cumulative methane production (mL/g TCOD), P is
methane production potential (mL/g TCOD), R
max
is maximum
methane production rate (mL/g TCOD-d), k is lag phase (day), t is
time (day), e is the exp(1) = 2.7183.
A nonlinear least-square regression analysis was performed
using SPSS program (IBM SPSS statistics 19 (2010)) to determine
the K, R
max,
k, and the predicted methane yield. The predicted
methane yield obtained from the SPSS program was plotted with
the measured methane yield using Matlab software R2011b
(7.13.0.564). The statistical indicators, Correlation coefcient (R
2
)
and root mean square error (RMSE) were calculated [29,30].
RMSE
1
m

m
j1
d
j
Y
j
_ _
2
_ _1
2
8
where m is the number of data pairs, j is jth values, Y is measured
methane yield (mL/g TCOD), d is the Deviations between measured
and predicted methane yield.
2.6. Statistical analysis and data processing
2.6.1. Data processing
It is known that during batch digestion, the biogas production
rates and methane content considerably change over the digestion
time [20]. The methane content of biogas of intermediate days dur-
ing batch tests were calculated using linear interpolation by IN-
TERP1 function in Matlab software R2011b (7.13.0.564). The
weighted average corrected methane content (CH
4 Corr, WA
) over
the digestion period was calculated as follows:
CH
4 Corr; WA
%

n
i1
BP
i
CH
4 Corr; i

n
i1
BP
i
9
Based on the weighted average corrected methane content and
the interpolated data, the standard deviation (r) was calculated in
Excel software 2007 as follows:
r

CH
4 Corr; i
CH
4 Corr; WA

2
n 1

10
where BP
i
is the biogas production on day i, CH
4 Corr, i
is corrected
methane content on day i, n is the number of observations.
2.6.2. Statistical analysis
The signicance of differences in the average biogas yield,
methane yields, methane content, and pH was determined by
using single factor Analysis of Variance (ANOVA) in Excel software
2007. If the calculated F value was higher than the tabulated F
value, Least Signicant Difference (LSD) was calculated to judge
whether two or more averages are signicantly different or not.
LSD was calculated at a = 0.05 (LSD
0
.
05
) and at a = 0.01 (LSD
0
.
01
)
as follows [31,32].
LSD
a
t
a

2s
2
r
_
11
where t
a
is the t value chosen for the degree of freedom for error
and level of signicance(a) desired, s
2
is mean square for error
(MSE), r is the number of replications on which the means to be sep-
arated are based.
3. Results and discussion
3.1. Substrate characterisation
The results of the feedstock characterisation are summarised in
Table 1. The AWs TS percentage was approximately 2.44.0 times
higher than that of the SM, and its VS percentage was 3.45.4 times
higher. Similarly, the AW contained much higher TCOD and SCOD
(approximately two and three times higher, respectively) than the
SM. The VS/TS ratio of the AW was 0.920.95, while that of the SM
was 0.650.71, indicating that AW contained more digestible or-
ganic matter than SM. The AW was very acidic (pH = 4.054.15)
compared to the SM (pH = 6.337.95). The TVFA concentration in
the SM was 13,37116,329 mg/L, and its TA concentration was
360017,096 mg/L. There was no alkalinity (TA) in the apple waste
due to its low pH, which could cause acidication in the reactor if
used alone. The VS/TS ratio and COD values of the SM in this study
were similar to that reported by [33].
The carbon-to-nitrogen ratio (C/N) ratios of the AW (27.328.9)
were within the optimal range (2530) for anaerobic digestion
[34], but the SMs C/N ratio (2.7) was very low. The TKN concentra-
tions in the SM were more than three times higher than in the AW.
Most of the nitrogen in the AW existed as organic nitrogen, while
the majority of the SMs nitrogen was ammonia. Ammonical nitro-
gen is responsible for maintaining alkalinity in the digester, but the
concentration of ammonical nitrogen inhibits methanogen activity
when it exceeds 3000 mg/L [35]. The mixture of AW and SM was
expected to improve the efciency of the anaerobic digester com-
pared to using SM alone. Molinuevo-Salces et al. [36] observed bet-
ter digester performance when the high buffer capacity of swine
manure was coupled with the high C/N ratio supplied by vegetable
wastes.
3.2. BMP and biogas production rate of AW and SM (Experiment I)
The cumulative biogas yield (mL/g TCOD added), daily biogas
production (mL/g TCOD-d), methane content, and H
2
S concentra-
tion in the biogas produced during the digestion of AW and SM
at an OLR of 2.5 g VS/L and a F/M ratio of 0.5 under mesophilic con-
ditions are shown in Fig. 1. Biogas production started immediately
on the rst day of digestion in all of the digesters. The biogas pro-
duction was very low in the SM-100% digesters until day 5 (0.1
3.1 mL/g TCOD-d), when the gas production began to continuously
increase until day 13. Thereafter, gas production remained almost
constant, with some uctuations, until day 27 (Fig. 1b). After day
27, the biogas production from the SM-100% digesters slowly de-
creased and almost ceased after day 34. The peak value of biogas
production rate for SM-100% was 21 mL/g TCOD-d on day 22.
The AW-100% digesters showed different biogas production pat-
tern compared to the SM-100% examples. In the AW-100% digest-
ers, the biogas production rate abruptly increased until the third
day of digestion and then rapidly dropped until day 10. The peak
value of the biogas production rate was 61.5 mL/g TCOD-d on
64 G.K. Kae, S.H. Kim/ Applied Energy 103 (2013) 6172
Fig. 1. (a) Cumulative biogas yield; (b) biogas production rate; (c) methane content; and (d) H
2
S concentration in biogas produced from apple waste (AW-100%) and swine
manure (SM-100%) at OLR of 2.5 g VS/L and F/M ratio of 0.5 under mesophilic conditions (Experiment I).
G.K. Kae, S.H. Kim/ Applied Energy 103 (2013) 6172 65
day 3. After day 10, the biogas production rate slowly increased
again until day 31, with some uctuations, and thereafter, the
gas production rate declined and almost ceased after day 35. The
specic biogas yield increased until approximately day 33 and
day 31 in the AW-100% and SM-100% digesters, respectively, grad-
ually levelling off thereafter. Approximately 90% of the biogas yield
was obtained within 31 days and 30 days of digestion for the AW-
100% and SM-100% digesters, respectively. The average biogas
yields from the digesters with feed compositions of SM-100% and
AW-100% were 510 and 329 mL/g TCOD added, respectively (Ta-
ble 4). Thus, the biogas yield from 100% AW was signicantly high-
er (p < 0.01) than that of 100% SM (LSD
0.05
= 41 mL/g TCOD added
and LSD
0.01
= 51 mL/g TCOD added). The higher biogas yield from
AW-100% illustrates the possibility of improving the biogas yield
from an SM digester with the addition of AW.
The methane content in the biogas produced from the SM-100%
digesters was 13% on day 1 and increased rapidly until day 12
(approximately 79%), after which it remained almost constant
throughout the rest of the test period (Fig. 1c). The AW-100%
digesters showed a different pattern of methane content than the
SM-100% digesters. The methane content in biogas produced from
the AW-100% digesters was 4.5% on day 2 and increased continu-
ously until end of the test, reaching a value of 72% on day 32.
The methane content increased slowly until day 10 and then in-
creased rapidly, similar to gas production. The methane concentra-
tion and gas production pattern in the AW-100% digesters showed
that methanogenesis was inhibited during days 410 due to acid-
ication in the digester, even at a low F/M ratio of 0.50 (OLR = 2.5 g
VS/L). The anaerobic digestion of AW alone at higher F/M ratios
(>0.50) and a higher OLR (>2.5 g VS/L) can cause acidication in
the digester and digester failure. Thus, the results suggested that
when running digesters with AW at higher OLRs (and F/M ratios),
additional alkalinity must be added or co-digested with alkaline-
rich substrates such as SM to achieve better digester performance.
The average methane content of the biogas produced was 49.3%
and 81.3% for AW-100% and SM-100% digesters, respectively (Ta-
ble 4). Thus, the methane content of biogas produced from SM
was signicantly higher (p < 0.01) than that produced from AW
(LSD
0.05
= 7% and LSD
0.01
= 10%).
Fig. 1d shows the pattern of H
2
S concentrations in the biogases
produced from SM and AW. The H
2
S concentration in biogas pro-
duced from SM was almost constant (18962280 ppm (ppm)) dur-
ing days 117 and then decreased slowly. The H
2
S concentration in
biogas produced from AW-100% digesters was higher than that
from SM-100% digesters (Fig. 1d) and increased rapidly during
the digester start-up period (days 16), after which it decreased
(Fig. 1d). The H
2
S concentration in the biogas produced from AW
digesters fell within the range of 11203300 ppm and reached its
peak value on day 6 (3300 ppm). In an anaerobic digestion process,
there is competition between sulphate-reducing bacteria (SRB) and
methanogens. Some SRB may oxidise VFAs (e.g., propionic and bu-
tyric acid) completely to CO
2
in the presence of sulphates and gen-
erate sulphide during the process. Others may break down VFAs
incompletely to acetate, also producing sulphide. SRB are espe-
cially effective in competing with methanogens for acetate and
hydrogen in the presence of sulphate [37,38]. The rapid drop in
biogas production, slow increase in methane content, and rapid in-
crease in H
2
S concentration during the digester start-up period
(days 410) of the AW-100% digesters showed that SRB activity
was higher than methanogen activity during this start-up period.
The rapid acidication of AW may explain the low methanogen
activity during the digester start-up period.
Table 3
Initial and nal characteristics of the digester contents for batch tests.
Experiment Experiment I Experiment II
Feed composition (VS basis) AW-100% SM-100% SM-100% AW-33% AW-33%
Temperature (C) 36.5 36.5 36.5 36.5 55
OLR (g VS/L) 2.5 2.5 5.0 5.0 5.0
F/M ratio 0.50 0.50 1.0 1.0 1.0
Number of replications (n) 3 3 2 2 2
TVFA (mg/L) Initial 881 1300 2130 2593 2423
Final 682 970 1046 848 1489
TA (mg/L) Initial 9765 9956 9077 10,276 8870
Final 10,093 11,815 11,122 11,357 9352
TVFA/TA ratio Initial 0.090 0.131 0.235 0.252 0.273
Final 0.068 0.080 0.090 0.075 0.159
pH Initial 8.22 8.25 8.20 8.25 8.10
Final 7.77 7.90 7.77 7.8 7.89
NH
3
N (mg/L) Initial 2280 2360 2600 2760 2310
Final 2333 2560 2760 2370 2090
Values are expressed as mean for Experiment I (n = 3) and Experiment II (n = 2).
Table 4
Gas potential, BR and TCOD removal for batch tests.
Experiment Experiment I Experiment II
Feed composition (VS basis) AW-100 % SM-100% SM-100% AW-33% AW-33%
Temperature (C) 36.5 36.5 36.5 36.5 55.0
OLR (g VS/L) 2.5 2.5 5.0 5.0 5.0
Biogas yield (mL/g TCOD added) 510 329 342 398 505
Methane yield (mL/g TCOD added) 252 268 259 267 276
Methane (%)
a
49.3(20.0) 81.3(14.2) 75.8(5.5) 67.0(13.0) 54.6(20.0)
COD removal (%) 79 84 81 83 86
BR (g/g COD added) 0.644 0.292 0.325 0.420 0.606
Values are expressed as mean for Experiment I (n = 3) and Experiment II (n = 2).
a
Values in parenthesis are standard deviations.
66 G.K. Kae, S.H. Kim/ Applied Energy 103 (2013) 6172
The initial and nal characteristics of the digester contents
during Experiment I are shown in Table 3. The TVFA, TVFA/
TA ratio, and pH decreased, while the TA and NH
3
N increased
after anaerobic digestion. The nal pH value was signicantly
higher (p < 0.01) (LSD
0.05
= 0.04 and LSD
0.01
= 0.06) in the SM-
100% digester than in the AW-100% digester. The nal pH va-
lue of 7.77 and TVFA/TA ratio of 0.068 in the AW-100% diges-
ter showed that the available alkalinity was sufcient to
maintain stability in the reactor, although VFA inhibition was
observed during the start-up period. Raposo et al. [39] ob-
served stable digestion operation under batch conditions, with
a TVFA/TA ratio in the range of 0.300.40 or less, but destabil-
isation of the digester was observed at a TVFA/TA ratio of
approximately 0.70.
Fig. 2. (a) Cumulative biogas yield; (b) biogas production rate; (c) methane content; and (d) H
2
S concentration in biogas produced from SM-100% and AW-33% under
mesophilic and thermophilic conditions at OLR of 5 g VS/L and F/M ratio of 1.0 (Experiment II).
G.K. Kae, S.H. Kim/ Applied Energy 103 (2013) 6172 67
3.3. Co-digestion of AW and SM under mesophilic and thermophilic
conditions (Experiment II)
The results of Experiment I showed that SM could be used at an
OLR higher than 2.5 g VS/L, but the use of 100% AW at a higher OLR
(>2.5 g VS/L) can cause acidication and possible failure of the di-
gester process. Therefore, tests were conducted only with SM (SM-
100%) and a mixture of AW and SM (AW-33%) at an OLR of 5 g VS/L
and a F/M ratio of 1.0 under both mesophilic and thermophilic con-
ditions during Experiment II.
The cumulative biogas yield (mL/g TCOD added), biogas produc-
tion rate (mL/g TCOD-d), methane content and H
2
S concentration
in biogas for SM-100% under mesophilic conditions and AW-33%
under both mesophilic and thermophilic conditions are shown in
Fig. 2. Experiment II lasted for 85 days, and the gas production rate
was measured daily for the rst 60 days, after which gas produc-
tion was measured in 3- to 5-day time intervals due to low gas pro-
duction (that had almost ceased), as shown in Fig. 2a. As in
Experiment I, biogas production commenced immediately on the
rst day of digestion. The biogas production rate (mL/g TCOD-d) in-
creased continuously for the SM-100% until day 10 with some uc-
tuations, after which the biogas production rate started declining
slowly with some uctuations. Under mesophilic conditions, the
biogas production rate for AW-33% digesters increased until day
2 and then decreased rapidly until day 8. After day 9, the biogas
production rate increased until day 24 and then declined slowly,
similar to the SM-100% from days 1033. Under thermophilic con-
ditions, the biogas production rate from the AW-33% digesters in-
creased until day 2, similar to its behaviour under mesophilic
conditions, and then dropped rapidly on day 3. A constant low bio-
gas production rate was achieved from days 36, and thereafter, it
increased rapidly until day 10. The biogas production rate again
dropped rapidly until day 17. From day 18 on, the biogas produc-
tion rate increased and reached its peak on day 22. Finally, the rate
decreased slowly from day 23 until day 43 with some uctuations.
These results showed that the gas production trend was very dif-
ferent in thermophilic conditions and mesophilic conditions. Three
major peaks in daily biogas production were obtained under ther-
mophilic conditions, compared to two peaks during mesophilic
conditions. The peak value in the biogas production rate was 21,
18 and 45 mL/g TCOD-d on days 10, 24 and 10 for SM-100%, AW-
33% under mesophilic conditions and AW-33% under thermophilic
conditions, respectively.
The specic biogas yield (mL/g TCOD added) increased until
approximately day 30 for SM-100% digesters and approximately
days 45 and 38 for AW-33% digesters under mesophilic and ther-
mophilic conditions, respectively, after which it gradually levelled
off in all the digesters. Approximately 90% of the biogas yield was
obtained within 26 days of digestion in the SM-100% digesters and
within 42 and 38 days in the AW-33% digesters under mesophilic
and thermophilic conditions, respectively. The average biogas yield
from the digester with SM-100% was 342 ml/g TCOD added and
398 and 505 ml/g TCOD added in the AW-33% digesters under
mesophilic and thermophilic conditions, respectively (Table 4).
Thus, the biogas yield from the mixed feed (AW-33%) increased
signicantly (p < 0.01) under both mesophilic (by 16%) and ther-
mophilic conditions (by 48%) compared to the SM-100% material.
The increase in biogas yield with the mixed feed was due to the
higher biogas potential of AW than SM along with the synergetic
effect, which was found to be higher under thermophilic condi-
tions than under mesophilic conditions.
The methane concentration in biogas produced from SM-100%
was signicantly (p < 0.01) higher than that produced from AW-
33% (Fig. 2b). The rapid drop in biogas production rate during the
digester start-up period and the very low methane content in
AW-33% compared with that in SM-100% showed some inhibition
during the digester start-up period in AW-33% digesters under
both mesophilic and thermophilic conditions. This inhibition may
be due to the rapid acidication of apple waste. Thus, the results
suggested that for high rate anaerobic digesters (F/M ratio > 1.0
and OLR > 5.0 g VS/L) the AW should not exceed 33%, or else addi-
tional alkalinity should be added. The average methane contents
were calculated to be 75.8% for SM-100% and 67.0 and 54.6% for
AW-33% under mesophilic and thermophilic conditions, respec-
tively (Table 4). The average methane yields were calculated to
be 259 mL/g TCOD added for SM-100% and 267 and 276 mL/g
Table 5
Results of kinetic study using rst-order kinetic model.
Experiment Feed composition
VS basis (%)
OLR g VS/L F/M ratio Temperature
(C)
K
a
(1/day)
R
2
Methane yield (45 days digestion time)
Measured (mL/g TCOD) Predicted (mL/g TCOD) Difference (%)
Experiment I AW-100 2.5 0.5 36.5 0.042 0.844 242 213 12
SM-100 2.5 0.5 36.5 0.044 0.823 264 238 9.8
Experiment II SM-100 5.0 1.0 36.5 0.072 0.899 263 249 5.3
AW-33 5.0 1.0 36.5 0.032 0.828 249 204 18.1
AW-33 5.0 1.0 55.0 0.053 0.894 263 251 4.6
a
Calculated at 95% condence interval.
Table 6
Results of kinetic study using modied Gompertz model.
Experiment Feed
composition
VS basis (%)
OLR g
VS/L
F/M ratio Temperature
(C)
Rm
a
(mL/g TCOD-d)
Lag phase
k
a
(days)
R
2
T
90
(days)
T
ef
(days)
Methane yield (45 days digestion time)
Measured
(mL/g TCOD)
Predicted
(mL/g TCOD)
Difference
(%)
Experiment I AW-100 2.5 0.5 36.5 8.9 5.5 0.947 31.0 25.5 242 236 2.5
SM-100 2.5 0.5 36.5 14.2 9.4 0.994 30.0 20.6 264 271 2.7
Experiment II SM-100 5.0 1.0 36.5 16.3 4.3 0.996 25.5 21.2 263 258 1.9
AW-33 5.0 1.0 36.5 9.8 10.1 0.995 41.5 31.4 249 246 1.2
AW-33 5.0 1.0 55.0 13.0 5.1 0.992 25.0 19.9 263 272 3.4
T
90
Time taken for 90% biogas production.
T
ef
Effective biogas production duration (T
90
k).
a
Calculated at 95% condence interval.
68 G.K. Kae, S.H. Kim/ Applied Energy 103 (2013) 6172
Fig. 3. Plot of measured and predicted methane yield with statistical indicators: (a) Experiment I and (b) Experiment II.
G.K. Kae, S.H. Kim/ Applied Energy 103 (2013) 6172 69
TCOD added for AW-33% under mesophilic and thermophilic con-
ditions, respectively (Table 4). Gonzlez-Fernndez et al. [40] re-
ported a methane yield of 246 mL/g COD added from SM, which
is similar to the results of our study. The H
2
S concentration in bio-
gas was higher for AW-33% than for SM-100% (Fig. 2d). The H
2
S
concentration in biogas produced from mixed feed (AW-33%)
was lower under thermophilic conditions than under mesophilic
conditions.
The initial and nal characteristics of the digester contents in
Experiment II are shown in Table 3. The nal TVFA and TVFA/TA ra-
tio in AW-33% digesters were higher under thermophilic condi-
tions than under mesophilic conditions. The nal NH
3
N
concentration increased in SM-100% but decreased in AW-33%.
The decrease in NH
3
N concentration may be due to the low nitro-
gen content in AW. The TCOD removal increased slightly with
mixed feed (AW-33%) compared to in SM only (Table 4). Similarly,
the BR was higher in mixed feed than SM only (Table 4).The reason
for this higher BR may be due to the higher quantity of readily
degradable compounds and higher organic content (VS/TS ratio)
in the AW.
3.4. Kinetic study results
Tables 5 and 6 summarise the results of a kinetic study using a
rst-order kinetic model and modied Gompertz model, respec-
tively. The kinetic constants were calculated for 45 days of diges-
tion time because the time needed for 90% biogas production
(T
90
) fell within the range of 2542 days (Table 6). The methane
production rate constant (K) for AW and SM was found to be al-
most identical under mesophilic conditions at an OLR of 2.5 g VS/
L and a F/M ratio of 0.5 (Table 5). The K value of mixed feed
(AW-33%) was increased by approximately 1.7 times under ther-
mophilic conditions compared to mesophilic conditions at an
OLR of 5.0 g VS/L and a F/M ratio of 1.0 (Table 5).
The effective biogas production period (T
ef
) was calculated by
subtracting the lag time (k) from T
90
(Table 6). The T
ef
value for
SM was found to be lower than that for AW at an OLR of 2.5 g
VS/L and a F/M ratio of 0.5 under mesophilic conditions. The T
ef
for mixed feed (AW-33%) at an OLR of 5.0 g VS/L was larger than
that for SM-100% under mesophilic conditions, but it decreased un-
der thermophilic conditions. One possible reason for the increased
T
ef
under mesophilic conditions could be the VFAs inhibition to
methanogens due to AWs rapid acidication and slow rate of
digestion. However, the rate of digestion is faster under thermo-
philic conditions, so the acidication of AW should have less of
an effect than under mesophilic conditions. The acidication of
AW during thermophilic digestion should also reduce ammonia
inhibition and further improve the methanogen activity. The pre-
dicted methane yield derived from the rst-order kinetic model
and modied Gompertz model are shown in Tables 5 and 6,
respectively. The difference between the predicted and measured
methane yields was higher in the rst-order kinetic model (4.6
18.1%) than in the modied Gompertz model (1.23.4%). Thus,
the modied Gompertz model was found to have the best t to
the substrates used. To evaluate the soundness of the model results
in the modied Gompertz model, the predicted values of methane
yield were plotted against the measured values, as shown in Fig. 3.
The statistical indicators (RMSE and R
2
) are also shown in Fig. 3.
The RMSE value fell within the range of 0.15630.4879 and the
R
2
value fell within the range of 0.95210.9971.
3.5. Performance of the continuous digester with a mixture of AW and
SM
The batch test results from Experiment I showed AW as poten-
tial substrate for biogas production, but there was a possibility of
VFA inhibition in the digester when using only AW. Similarly, using
AW-33% (AW:SM = 33:67,% VS basis) during Experiment II resulted
in inhibition during the start-up period (Fig. 2b and c), which sug-
gested that AW content greater than 33% disturbed the digestion
process at higher OLRs. Thus, based on the results of the batch test,
the apple waste content in the feed mixture started at 25% (by VS
basis) in the continuous test, after which the AW percentage was
increased to 33% and 50%. The results of the batch test showed that
biogas production from a mixture of SM and AW increased signif-
icantly under thermophilic conditions, but there was no signicant
difference in the methane yield between mesophilic and thermo-
philic temperatures. Thus, the continuous test was operated at
mesophilic temperature.
The operation and performance parameters of the continuously
fed single stage CSTR are summarised in Table 7. The continuous
test was conducted for 146 days and the characteristics of the
SM were different for different test periods, as shown in Table 1.
The digester was started with a mixture of AW and SM. The AW
content was xed at 25% (based on VS) for days 190. During the
start-up period, the OLR was kept at 1.0 g VS/L/d and thereafter in-
creased to 1.4 and 1.6 g VS/L/d at a constant HRT for 30 days (Ta-
ble 2). A biogas yield of 260317 mL/g TCOD added was obtained
with AW-25% (AW:SM = 25:75,% VS basis) at an OLR of 1.0 g VS/
L/d (days 149). The average methane content in the biogas fell
within the range of 76.376.4%, and the pH was between 7.76
and 7.85. The TVFA and TVFA/TA ratio in the digester were
66887155 mg/L and 0.5070.534, respectively. The BA concentra-
tion in the digester was within the range of 83058549 mg/L, the
digester operation was stable, and no inhibition was observed dur-
ing days 149. McCarty [25] proposed that a BA concentration in
the range of 25005000 mg/L was more desirable for anaerobic di-
gester operation. Similarly, Georgacakis et al. [41] reported that the
BA in a SM-fed digester should be greater than 6000 mg/L to main-
tain higher biogas production. When the OLR was increased to
1.4 g VS/L/d during days 5074 at the same AW-25% feed mixture,
the biogas yield dropped from 260 to 201 mL/g TCOD added, and
Table 7
Performance of continuous reactor with different feed mixture ratios at mesophilic temperature.
Feed composition
(%), VS basis
OLR (g VS/L/d) Days Biogas yield
(mL/g TCOD added)
Methane
content (%)
pH TVFA (mg/L) TA (mg/L) TVFA/TA ratio BA (mg/L)
AW-25 1.0 128 317(13) 76.3(0.7) 7.85(0.07) 6688(560) 13,297(789) 0.507(0.071) 8549
AW-25 1.0 2949 260(18) 76.4(1.4) 7.76(0.03) 7155(331) 13,385(160) 0.534(0.023) 8305
AW-25 1.4 5074 201(21) 7.37(0.03) 10,705(1134) 11,277(769) 0.954(0.118) 3676
AW-25 1.6 7590 197(28) 74(2.9) 7.56(0.07) 11,132(1039) 11,953(654) 0.936(0.119) 4049
AW-33 1.6 9198 182(8) 76.3(0.88) 7.82(0.091) 9310(1403) 14,146(626) 0.662(0.127) 7536
AW-33 1.6 99123 241(17) 78.7(0.72) 7.81(0.02) 8373(215) 16,580(148) 0.505(0.016) 10,635
AW-50
a
1.7 124146 109 44 7.13 14,656 11,975 1.224 1569
Values are expressed as mean (standard deviation).
a
Data of day 146.
70 G.K. Kae, S.H. Kim/ Applied Energy 103 (2013) 6172
the pH dropped from 7.76 to 7.37. Similarly, the TVFA increased
above 10,000 mg/L, and the TVFA/TA ratio reached up to 1.0. The
digester operation was still stable even though the gas yield de-
creased, and the TVFA accumulation and TVFA/TA ratio increased.
After day 75, the OLR was further increased to 1.6 g VS/L/d until
day 90. As a result, the biogas yield dropped slightly further and
the TVFA accumulation increased. However, the methane content
was maintained at 73.2%, and the pH (7.56) of the digester content
increased, showing that the methanogen acclimated to a higher
TVFA concentration. The bicarbonate alkalinity during days 75
90 (4049 mg/L) was higher than during days 5074 (3676 mg/L).
The increase in BA and pH with the increase in OLR from 1.4 to
1.6 g VS/L/d may have been due to use of SM with a higher TA con-
centration and pH during days 7590 than during days 5074 (Ta-
ble 1). During co-digestion of the AW with slaughterhouse waste,
Llaneza Coalla et al. [11] observed stable reactor conditions when
the VFA concentration was below 4000 mg/L, but inhibition to
methanogen was then observed when the VFA concentration was
increased to 7000 mg/L. Similarly, Ehimen et al. [42] observed
instability in an anaerobic digester when the TVFA concentration
was higher than 5000 mg/L during the co-digestion of microalgae
residues with glycerol. However, during anaerobic co-digestion of
Chinese cabbage silage with SM (25:75 VS basis), Kae and Kim
[43] observed stable digester operation for TVFA concentrations
of up to 10,000 mg/L whenever the TVFA/TA ratio was below 1.0.
After day 91, the AW content was increased from 25% to 33% at
constant OLR and HRT. The biogas yield at AW-33% (182 mL/g VS)
dropped slightly compared to that of AW-25% during days 9198.
The pH and methane content increased slightly, and the TVFA and
TVFA/TA ratio decreased slightly. The BA also increased from 6418
to 7536 mg/L. New SM with a high pH (7.87.85) and alkalinity
concentration (11,71312,100 mg/L) was used from day 99 on (Ta-
ble 1). The biogas yield increased from 182 to 241 mL/g TCOD
added (an increase of 28%) at the same feed mixture (AW-33%)
and OLR (1.6 g VS/L/d). The methane content also increased from
76.3% to 78.7%, and the TVFA and TVFA/TA ratio decreased further.
The TVFA/TA ratio (0.505) during days 99123 was almost the
same as that during days 128 (AW-25% at 1.0 g VS/L/d). The BA in-
creased from 7536 to 10,635 mg/L, which was a higher concentra-
tion than at any previous time in the experiments. Thus, the results
showed that SM with a lower TVFA and higher alkalinity concen-
tration allowed the digester to be operated stably with a higher
percentage of AW and OLR compared to SM with a lower alkalinity
concentration.
At day 124, the AW content was further increased to 50%, and
the OLR was xed at 1.7 g VS/L/d. The OLR was increased with an
increase in AW content to maintain constant HRT. The SM used
during this period was similar to that used during days 99123.
Gas production increased slightly (242262 mL/g TCOD added)
over the next week (days 125130) and then dropped regularly.
The TVFA concentration and TVFA/TA ratio increased regularly
and the TA, BA, pH, and methane content dropped accordingly.
Within 24 days (days 124146), the pH dropped from 7.81 to
7.13 and the methane content dropped from 78.7% to 44%. The
TVFA concentration increased from 8373 to 14,653 mg/L, the TA
decreased from 16,580 to 11,975 mg/L, and the TVFA/TA ratio in-
creased from 0.505 to 1.224 within those 24 days. Similarly, the
BA concentration decreased from 10,635 to 1569 (Table 7). Thus,
the process in the reactor was disturbed and heading towards fail-
ure. The digester operation was stopped on day 146.
The mixture of AW and SM showed a positive synergetic effect
on biogas production when the AW content in the feed was in-
creased from 25% to 33% (VS basis), whereas the further increase
in AW content from 33% to 50% had a negative synergetic effect
on the biogas production. The main reason for this negative syner-
getic effect was the rapid TVFA accumulation and drop in pH value.
Thus, the results of the continuous test suggested that for SM with
a TVFA concentration in the range of 13,37116,329 mg/L, the AW
content used the feed mixture could measure up to 2533% (VS ba-
sis) based on the alkalinity (TA) of the swine manure at an OLR of
1.01.6 g VS/L/d and a HRT of 30 days. Llaneza Coalla et al. [11] rec-
ommended less than 10% (TS basis) apple pulp as the optimum for
co-digestion with slaughterhouse waste.
4. Conclusions
Apple waste was anaerobically treated with swine manure in
both batch and continuous modes. The AW was found to be a po-
tential substrate for co-digestion with the SM for biogas produc-
tion. Biogas production in the batch test improved when using a
mixture of AW and SM (AW:SM = 33: 67,% VS basis) as opposed
to SM only. The biogas production from mixed feed was signi-
cantly higher under thermophilic conditions than under meso-
philic conditions, but there was no signicant difference in
methane production. The modied Gompertz model tted the
experimental results better than a rst-order kinetic model. The
results of the continuous tests showed positive synergetic effects
on biogas production when the AW content in the feed was in-
creased from 25% to 33% (VS basis) at an OLR of 1.6 g VS/L/d and
a HRT of 30 days, but a further increase in AW content from 33%
to 50% had a negative synergetic effect due to the rapid accumula-
tion of TVFA and the drop in pH.
Acknowledgements
This work was supported by research funds supported by the
Rural Development Administration (RDA), South Korea.
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