Professional Documents
Culture Documents
com
a,b
Received 26 September 2006; received in revised form 11 December 2007; accepted 18 December 2007
Available online 8 February 2008
Abstract
The aim of the current study was to examine eects of daily temperature variations on the performance of anaerobic digesti
on. Forced
square-wave temperature variations (between 11 and 25, 15 and 28, and 19 and 32 C) were imposed on a bench-scale
digester using a
mixture of llamacowsheep manure in a semi-continuous process. The volumetric biogas production rate, methane yield,
and the volatile solid reductions were compared with the results obtained from anaerobic digestion (AD) at constant temperatures.
The forced cyclic variations of temperature caused large cyclic variations in the rate of gas production and the methane c
ontent. As
much as 9497% of the daily biogas was obtained in the 12 h half-cycle at high temperature. The values for volumetric biogas
production
rate and methane yield increased at higher temperatures. The average volumetric biogas production rate for cyclic operation
between 11
3
1
1
1
and 25 C was 0.22 L d L
with a yield of 0.07 m CH 4 kg
VS added (VSadd), whereas for operation between 15 a
nd 29 C the
3
1
1
1
volumetric biogas production rate increased by 25% (to 0.27 L d L with a yield of 0.08 m CH 4 kg VSadd). In the hig
hest temper3
1
ature region a further increase of 7% in biogas production was found and the methane yield was 0.089 m CH 4 kg
VSad
d.
The employed digester showed an immediate response when the temperature was elevated, which indicates a wellmaintained metabolic capacity of the methanogenic bacteria during the period of low temperature. Overall, periodic temperature variations app
ear to give
less decrease in process performance than a priori anticipated.
2007 Elsevier Ltd. All rights reserved.
Keywords: Anaerobic digestion; Temperature; Periodic operation; Manure
1. Introduction
the treated sludge (Robertson et al., 1975). The use o Anaerobic digestion is a temperature dependent process
,
f AD
which is normally operated at dened and constant tempe
is widely demonstrated in Asia with several million s
rmallatures. Nevertheless, situations exist in which reactors a
scale biogas plants in China and India (Khoiyan
re
gbam
subject to repeated sudden and abrupt changes of tempe
et al., 2004; Nazir, 1991).
rature. On farms, bioreactors may be subjected to temper
a*
Corresponding author. Tel.: +46 46 222 0862.
ture uctuations due to large variations in outd
E-mail address: Gunnar.Liden@chemeng.lth.se (G. Liden).
oor
temperature, especially in highland and northern climat
0960-8524/$ - see front matter 2007 Elsevier Ltd. All rights
es
reserved.
(Alvarez et al., 2006; Masse et al., 2003). The anae
doi:10.1016/j.biortech.2007.12.055
robic
digestion process is normally classied into three diere
nt
temperature ranges, namely psychrophilic (<20 C), mes
ophilic (2040 C) and thermophilic (>40 C) (ElMashad
et al., 2004). The microorganisms involved in anaero
bic
digestion are characterized by an optimal temperature
as
well as by an upper limit that would cause immediate dea
th
of the considered group of bacteria (Chen, 1983).
The anaerobic digestion of manure in convention
al
treatment tends to have high process stability. Howev
er,
R. Alvarez, G. Liden / Bioresource Technology 99 (2008) 72787284
7279
ature. The average highs during the day range from 15 Brazil). The samples were packed into 500 g polyeth
to
ylene
20 C and the average lows range from 15 to 3 C
bags and stored at 10 C in a freezer. The characteri
with
stics
an atmospheric pressure around 460500 mm Hg. T
of the various manures are given in Table 1.
he
Batches of equal volumes of the three manures (3
large variation in ambient temperature is likely to aect
3.3%
2. Methods
49.5 (3.2)
19.8 (1.1)
77
70.3 (2.2)
74.9 (1.6)
61
1.7 (0.1)
1.6 (0.2)
.6 (2.2)
Volatile solids (% of TS)
Llama, sheep and cow manure were collected fr .3 (5.6)
Total nitrogen (% of TS)
om
.1 (0.3)
farms in the Bolivian Altiplano (19 S latitude, 68 W lo Total organic carbon (% of TS)
n9 (4.1)
gitude). The manures were separately minced and pulv Total phosphorous (% of TS)
5 (0.1)
erized with a semi-industrial cutter (CUT-3, Metvi Total potassium (% of TS)
8 (0.5)
sa,
7280
2.2. Apparatus
29.5 (2.3)
26.5 (5.7)
18.
0.4 (0.1)
0.4 (0.1)
0.
1.5 (0.2)
0.7 (0.3)
1.
(60 rpm) was used for stirring and the stirrer drive jacket surrounding the reactor. The reactor was fed on
ce
shafts
a day at 30 days H RT regime and 6 0.1% w/w VS c
were inserted through a gas-tight bearing. The r
oneactor
tent. The content of the reactor was stirred for 15 min ev
was fed from a lateral port through a 50 mm I D ball v
ery
alve.
hour at 60 rpm.
The euent was drawn from the bottom of the r
The pH and the solid content of the slurry were analyse
eactor
d
through a 12.7 mm ball valve.
every 10 days. Biogas was collected in a separate 30 L pl
as2.3. Experimental procedure
tic bottle and the volume was measured once a day by d
isTwo kinds of experiments were conducted; anaer
placement of acidied water (pH = 2) at zero ga
obic
uge
digestion at constant temperatures (35, 25 and
pressure and ambient temperature. The volumes w
18 C),
ere
and anaerobic digestion during forced square-wave
recalculated to standard temperature and pressure (0
cycling
C,
of temperature. The low and high temperatures in the l
760
mm Hg).
atter
kind of experiments were 11 and 25, 15 and 29, and 1
2.3.2. Cyclic square-wave temperature experiments
9 and
After nishing the experiment described above at 18
32 C, respectively.
C,
the bench-scale digester was subjected to a daily squ
2.3.1. AD experiments at constant temperatures
The eect of temperature on digestion of llama arewave uctuation of temperature in order to study the e
cow
ect
sheep manure mixture was tested in the bench-scale
on the anaerobic digestion process. The reactor operated
reactor
at
with 9.3-L active volume described above. For the
temperature intervals 1125, 1529, and 1932 C succ
start-up
period (60 days at 35 C), the initial medium was pre essively for 60 days at each interval. The square-wave t
pared
emwith 5% llama manure, 11% cow manure, 4% sheep
perature uctuation consisted of 12 h at high temperatu
manre
ure, 64% tap water and 16% active slurry from a semi
followed by 12 h at low temperature. The reactor was co
-conntinuous digester working with llamacowsheep
trolled by a Pt sensor PLC-Software heater/cooler syste
manure at
m
25 C with H RT of 50 days (7.3% TS, 71% V
that changed the temperature of the slurry in the reac
S, and
tor
pH = 7.6). Llama, cow and sheep manure (33.3%
from low to high (or high to low) in less than 30 min.
VS/VS
The reactor was fed once a day at the beginning of the
of each) with a VS content of 6 0.1% w/w was fed
high
daily
temperature half-cycle. The H RT was 30 days and the
in an amount giving a H RT of 30 days.
loadAfter the start-up period the reactor temperature
3
1
ing rate was 2 kg VS m d with 6 (0.1)% w/w. The f
was
eedkept at the selected temperatures (60 days each of
stock was a mixture of llamacowsheep with 33.3% VS
35, 25
of
and 18 C in this order) by water circulating in the
each. The content of the reactor was stirred at intervals
water
of
5 min (on/o) all through the day at 60 rpm to improve t
he
heat transference and the control system. The pH, solid c
ontent, biogas volume and methane content were measur
ed
according to the procedure described above.
13
Biogasproduction(LL-1d-1)
12
9
6
7
5
11
10
9
4
Methanecontent(%)
Fig. 1. Schematic diagram of bench-scale digester: 1. vessel, 2. feed inlet, 3. euent valve, 4. motor, 5. agitation impeller, 6. pH probe, 7. Pt
100 electrode,
8. accumulation and measurement biogas system, 9. electro valves, 10. pumps, 11. thermostatic heater, 12. cooler, 13. pressostat.
R. Alvarez, G. Liden / Bioresource Technology 99 (2008) 72787284
7281
VSineffluent%(VS/w.w)
detector (TCD) and a Carboxen-1010 plot Cap until the weight change was less than 4%. Volatile
illary
solids
column 30 m 0.53 mm I D (Supelco, USA). The inje were determined by ignition of the residue produce
d in
ctor,
detector and oven temperatures were 130, 200, and 10TS analysis to constant weight in a mue furnace at a
tem0 C,
respectively. Helium served as the carrier gas at a pre perature of 550 C. TOC was determined by high temp
ssure
eraof 300 kPa.
ture combustion method (Method 5310 B). TKN
Total solids (TS), volatile solids (VS), pH, total org was
anic
measured using the semi-micro-Kjeldahl method (Meth
carbon (TOC), total Kjeldahl nitrogen (TKN), potass od
4500-Norg C), Potassium and Phosphorus were meas
ium
and phosphorus were determined according to stan ured
dard
by spectrophotometry (Method 3500-K and 45
methods (Clesceri et al., 2000). The total solids (TS 00-P,
) conrespectively).
tent was determined after heating (105 C for 1 h), co
oling,
3. Results
desiccating, and weighing procedures that were rep
eated
0.70
0.60
0.50
40
20
0.40
0.30
0.20
0
8
0.10
0.00
80
60
6
4
2
3.1. Anaerobic digestion at constant temperat tent in the biogas increased from 49.9% to 61.1% bet
ure
ween
35 and 18 C, which partly counteracted the decrease i
The fermentation of a mixture of lla
n volmacowsheep
manure was found to be quite stable with re umetric gas production rate. The volumetric methane
prospect to daily
duction rate was reduced from 2094 (at 35
biogas production, methane content and vo
C) to
latile solid in
1
(at 25 C) representing a reducti
euent. Once stabilized, the daily variation i 1676 ml CH 4 d
on
of
n digester performance (Fig. 2) at 35, 25, and 18 C w 20%. A further reduction of 47% (from 16
76 to
1
as less than 5%
894 ml CH 4 d ) was seen when the temperature
with respect to the variables above.
was
As to be expected, the volumetric biogas pr
reduced from 25 to 18 C. The methane yield followed
oduction rate
the
decreased as the temperature was lowered.
same pattern.
The reduction
from 35 to 25 C resulted in a reduction of 30
3.2. Anaerobic digestion with a forced cyclic temperatur
% in volumetric
biogas production rate, whereas the 7 C redue
variation
ction from 25
to 18 C caused a reduction of 51% (Table 2
). Clearly, the
anaerobic digestion is a process that is stron
gly dependent
on temperature. On the other hand, the meth
ane content in
the biogas increased at low temperature. The
methane conMethanecontent(%)
Temperature(oC)
Methanecontent(%)
10
20
30
40
50
60
ime (d)
Temperature(oC)
Biogasproduction(ml)
Table 2
Measured and calculated parameters from bench-scale reactor digesting mixture of llamacowsheep manure with square-wave
temperature uctuation
and dierent constant temperatures
Biogasproduction(ml)
Temperature OLR
range (C)
1125
1529
1932
18
25
35
2.0
2.0
2.0
2.0
2.0
2.1
H RT (d)
Reduction
of VS (%)
Methane
Volumetric biogas production rate
content (%) eld
1
1
(L d L )
Daily biogas Biogas at
low T (%) high T (%)
30
30
30
30
30
30
13.8
14.7
19.0
19.1
25.7
29.4
56 (2)
55 (2)
56 (3)
61(1)
56 (2)
49 (1)
(2.9)
(1.2)
(1.5)
(2.8)
(3.3)
(1.0)
0.2
0.3
0.3
0.2
0.3
0.5
2226 (155)
2738 (98)
2890 (32)
1464 (94)
2977 (124)
4198 (139)
3
3
6
0.069
0.084
0.089
0.048
0.092
0.109
3
(0.005)
(0.003)
(0.005)
(0.003)
(0.002)
(0.005)
1
(m kg VSadd)
97
97
94
Methane yi
s
i
v
e
l
y
f
which the t
emperature
was kept lo
w. For eac
h temperat
ure
40
30
20
10
0
6
12
18
24
30
36
42
30
36
42
Time (h)
45
0
12
18
24
48
Time (h)
inuence that the temperature exerts on the process.
Time-averaged steady-state results are summarize Fig. 4. Methane content in biogas (bar symbols) and temperature (
d in
Table 2. The values of methane content, productivity s)
during forced periodic variation of temperature (a) and at a
and
yield were based on an average of measurements xed
operating temperature of 25 C (b).
over a
10-day period after two retention times. In this study,
the
high temperature, which corresponded to 97% of the tot
measured pH-value was 7.2 0.5 throughout. On a
al
dayaveraged basis, the methane content in the gas was be production. When the temperature was reduced to 11
tween
C
55 and 56%. When the digester was working with f (about 2030 min cooling time) a drastic reduction in
orced
biooscillations between 11 and 25 C, most of the daily bi gas generation was observed, and in the following 12 hou
rs
ogas
1
production (2226 ml d ) was obtained during the 12 only 3% of the daily biogas production was obtained.
A
h of
1000
750
500
0
250
0
12
18
24
0
1000
3
36
42
48
750
ime (h)
500
250
12
18
24
30
36
42
48
similar pattern was observed in the ature (1 productivity for the experiment running at a constant te
digester working at
9 C) pe mtemperatures between 15 and 29 C. riod in t perature of 18 C (cf Table 2).
30
Volumetric biogas production rate and methane yiel
The digester working
he force d
between 19 and 32 C showed som d cyclin
20
both increased with temperature. The average volumet
ewhat higher activity
g experi ric
at the low temperature, and 6% of the
1
10
ment wo biogas production rate at 1125 C was 0.22 L d
daily biogas produc1
L
tion was obtained at 19 C (173 ml d rk3
1
0
1
ing betw (with a yield of 0.07 m CH 4 kg
VSadd). Increasing
), and the remaining
the
een
19
94% was produced at 32 C (2717 ml
1
and 32 temperature range to a low temperature of 15 C an
d ). In all the forced
cycling experiments it was clear tha C was d a
very mu high temperature of 29 C raised the volumetric bio
t the volumes of gas
obtained in the periods of low temperat ch lowergas
1
1
rate by 25%, to 0.27 L d L
than the production
ure (12 h) were very
3
1
(0.08 m CH 4 kg
VSadd). However, increasing the te
low. Interestingly, the productivity duri
mng the low temperTime (h)
perature further to a low and a high temperature of
19
Fig. 3. Gas production (bar symbols) and temperature (s) during f
and 32 C, respectively, gave only a further increased b
ioorced
1
1
production
of
7%
(to
0.29 L d L
periodic variation of temperature (a) and at a xed operating temper gas
ature
and
3
1
of 25 C (b).
0.09 m CH 4 kg
VSadd).
40
4. Discussion
ion
ations
The results obtained in the present study show
that
anaerobic digestion of manures from, e.g. llamas,
cows
and sheep in a semi-continuous process subject
to a
square-wave daily temperature uctuation may
operate in
a stable fashion, although with productivity changing
over
the 24 h cycle. Both the pH (7.2) in the euent a
nd the
methane content of the biogas (5556%) were stable,
which
is a sign of a well balanced biomethanation p
rocess
(Mountfort and Asher, 1978) with expectable biogas
volumes (Alvarez et al., 2006).
The square-wave temperature uctuation that
was
imposed on the digester resulted in an interesting b
ehaviour. In eect, the daily biogas volumes obtained
when
the digester was working at 1125 C and at 15
29 C
strong
magnication
of
the
cyclic
vari
than that of the digester working at the average te described above (Figs. 3a and 4a) with an imm
mperediate
ature 18 C in an isothermic process (Table 2). response to sudden increases of temperature and to ad
ded
These
results suggest that there are positive eects when substrate. At low temperature, on the other hand, the
biodigesters are subjected to periodic cyclic uctuations in gas production almost ceased. The suppression of ac
temidoperature. A digester working at 1932 C on the genic activity due to rapid temperature drops (to b
elow
other
hand had a volumetric biogas production ra 20 C) has been previously reported by Cha et al. (
te of
1997).
3
1
1
0.3 L d L
and a methane yield of 0.09 m CH In that study, the number of bacteria was slowly redu
1
ced,
4 kg
VSadd, numbers which are more similar to wha but the acidogens became temporarily inactive during
the
t was
obtained when the digester was working at a co period of low temperature.
nstant
The anaerobic fermentation process appears capable
25 C. Increased gas production associated with te of
an immediate response to sudden increases in tempera
mperature uctuations has been previously noticed by C ture
and to added substrate, which suggests that the meta
hayovan et al. (1988).
bolic
For a digester working at a constant tempe capacity of the methanogenic bacteria is well maintai
ned.
rature
(Fig. 3b), a daily cyclic uctuation in the rate of ga It appears that some components of the llamacow
sheep
s production was observed as a result of the feeding. D manure are rapidly converted to biogas (e.g. car
bohyuring
the rst hours after feeding, there was a clear incre drates), whereas the bulk of the materials is broken d
ase in
own
biogas production, which was followed by a declin more slowly (Hawkes and Young, 1980).
e. A
small variation in methane concentration in the ga 5. Conclusion
s was
observed as well (0.52.5% above the daily average).
A mixture of manures of llama, cow and sheep
was
However, the measurement of this variation was mask shown to be a suitable feedstock for biogas produ
ction
ed by
dilution in the gas space volume in the digester a on the Bolivian Altiplano. A methane content in the bio
gas
nd by
the collecting bottle. The variations due to the daily fee of 55% and a volumetric biogas production rate bet
ween
ding
1
1
were obtained at a H RT of 30
to the reactors are most likely a result from metabolic 0.2 and 0.3 L d L
days
variations, as has previously been reported by Mountfort for the conditions investigated. Daily square-wave c
yclic
and
Asher (1978), and others (Hawkes and Young, uctuations of temperature, designed to mimic uctuati
ons
1980;
of ambient temperatures on the Bolivian Altiplano, cau
Chayovan et al., 1988).
sed
large cyclic variations in the rate of gas production.
The
digester required an adaptation period between 20
and
40 days to reach the pseudo-steady-state with a longer
period required for the lower temperature region. Inter
est-
ingly, the biomethanation process responded immediate Bouskova, A., Dohanyos, M., Schmidt, J.E., Angelidaki, I.,
2005.
ly
Strategies for changing temperature from mesophilic to thermop
to the sudden increase in temperature. This suggests t hilic
hat
conditions in anaerobic CSTR reactors treating sewage sludge. Wa
activity of the methanogenic bacteria are well preser ter
Research 39, 14811488.
ved
Cha,
G.C., Chung, H.K., Chung, J.C., 1997. Suppression of acido
during the period at low temperature.
genic
activities due to rapid temperature drop in anaerobic dige
References
stion.
Biotechnology Letters 19 (5), 461464.
Ahn, J.H., Forster, C.F., 2002. The eect of temperature variations on t Chayovan, S., Gerrish, J.B., Eastman, J.A., 1988. Biogas production f
he
rom
performance of mesophilic and thermophilic anaerobic lters treating
dairy manure: the eects of temperature perturbations. Biolo
a simulated papermill wastewater. Process Biochemistry 37 (6), 58 gical
9
Wastes 25, 116.
594.
Chen, M., 1983. Adaptation of mesophilic anaerobic sewage ferm
Alvarez, R., Villca, S., Liden, G., 2006. Biogas production from llama entor
and
population to thermophilic temperatures. Applied and Environmen
cow manure at high altitude. Biomass and Bioenergy 30, 6675.
tal
Microbiology 45 (4), 12711276.
7284
R. Alvarez, G. Liden / Bioresource Technology 99 (2008) 72787284
Clesceri, L.S., Greeberg, A.E., Eaton, A.D., 2000. Standard MethodMasse, D.I., Masse, L., Croteau, F., 2003. The eect of temper
s for
ature
the Examination of Water and Wastewater, 20th ed. American P
uctuation on psychrophilic anaerobic sequencing batch react
ublic
or
Health Association (APHA), Washington DC, USA.
treating swine manure. Bioresource Technology 89, 5762.
El-Mashad, H.M., Zeeman, G., van Loon, W.K.P., Gerard, P. Mountfort, D.O., Asher, R.A., 1978. Changes in proportion of aceta
A.B.,
te
Lettinga, G., 2004. Eect of temperature and temperature uctu
and carbon dioxide used as methane precursors during the anaerobi
ation
c
on thermophilic anaerobic digestion of cattle manure. Biores
digestion of bovine waste. Applied and Environmental Microbiology
ource
35 (4), 648654.
Technology 95 (2), 191201.
Nazir, M., 1991. Biogas plants construction technology for rural are
Hawkes, F.R., Young, B.V., 1980. Design and operation of labora as.
toryBioresource technology 35, 283289.
scale anaerobic digesters: operating experience with poultry Peck, M.W., Skilton, J.M., Hawkes, F.R., Hawkes, D.L., 1985. Eect o
litter.
f
Agricultural Wastes 2, 119133.
temperature shock treatments on the digester stability of anaero
Khoiyangbam, R.S., Kumar, S., Jain, M.C., Gupta, N., Kuma bic
digester operated on separate cattle slurry. Water Research 20 (4), 45
r, A.,
Kumar, V., 2004. Methane emission from xed dome biogas plan 3
t in
462.
hilly and plain region of northern India. Bioresource Technology Robertson, A.M., Burnett, G.A., Hobson, P.N., Bouseld, S., Summers,
95,
S., 1975. Bioengineering aspects of anaerobic digestion of pigg
3539.
ery
wastes. In: Third International Symposium on Livestock Waste, 21
Man-chang, W., Ke-wei, S., Yong, Z., 2006. Inuence of temper
24
ature
uctuation on thermophilic anaerobic digestion of municipal org
April, Urbana-Champaign, IL .
anic
solid waste. Journal of Zhejiang University Science B 7 (3), 180
185.