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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 effects of daily temperature variations on the performance of anaerobic digestion. 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 llama–cow–sheep manure in a semi-continuous process. The volumetric biogas production rate, methane yield, and the vol-
atile 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 content. As
much as 94–97% 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
and 25 °C was 0.22 L d 1 L 1 with a yield of 0.07 m3 CH4 kg 1 VS added (VSadd), whereas for operation between 15 and 29 °C the
volumetric biogas production rate increased by 25% (to 0.27 L d 1 L 1 with a yield of 0.08 m3 CH4 kg 1 VSadd). In the highest temper-
ature region a further increase of 7% in biogas production was found and the methane yield was 0.089 m3 CH4 kg 1 VSadd.
The employed digester showed an immediate response when the temperature was elevated, which indicates a well-maintained meta-
bolic capacity of the methanogenic bacteria during the period of low temperature. Overall, periodic temperature variations appear to give
less decrease in process performance than a priori anticipated.
Ó 2007 Elsevier Ltd. All rights reserved.
0960-8524/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2007.12.055
R. Alvarez, G. Lidén / Bioresource Technology 99 (2008) 7278–7284 7279
sudden environmental changes, e.g. dramatic increases or ature. The average highs during the day range from 15 to
drops in temperature, may cause severe disturbance in all 20 °C and the average lows range from 15 to 3 °C with
parameters of the process, and the overall adaptation to an atmospheric pressure around 460–500 mm Hg. The
new stable operation requires a long period of time (Bousk- large variation in ambient temperature is likely to affect –
ova et al., 2005; Cha et al., 1997). The extent of the distur- to some extent – the operating temperature of low-cost sim-
bance has been related to the magnitude of the temperature ple anaerobic digestors. This effect of daily temperature
variation (El-Mashad et al., 2004). The effect of increasing fluctuations on the anaerobic digestion process has rarely
or decreasing temperatures followed by re-establishment of been investigated.
the initial temperature has been assessed in some previous The aim of the current work was to assess the effect of
studies. These studies show that a decrease in temperature daily temperature variations on the semi-continuous anaer-
typically causes lower chemical oxygen demand (COD) obic digestion of manures from the Bolivian Altiplano
removal efficiencies, lower biogas production, and the using an experimental model system with forced tempera-
accumulation of volatile fatty acids (VFA). Anaerobic ture variation. The daily temperature variations were sim-
digestors were in one previous study reported to recover ulated by a forced square-wave oscillation of the reactor
their efficiencies fully after the temperature had been read- temperature of an anaerobic digester, which used a mixture
justed (Ahn and Forster, 2002). In another study, different of llama, cow and sheep manure as feedstock. The perfor-
recovery methods were tested after the temperature in mance of the digester was analysed with respect to volu-
digesters operating at steady state had been lowered. Rais- metric biogas production rate, methane yield and volatile
ing the temperature in a single day gave only a transient solid reduction in the substrate.
effect and steady state was re-established within eight days.
However, a slow increase in temperature led to more dele- 2. Methods
terious effect on the digester stability (Peck et al., 1985).
Digesters working with imposed daily cyclic tempera- 2.1. Feedstock and preparation
ture fluctuation have been the subject of only a few studies
– with different purposes: Man-chang et al., 2006 simulated Llama, sheep and cow manure were collected from
the heating failure of a thermophilic anaerobic digester fed farms in the Bolivian Altiplano (19° S latitude, 68° W lon-
with municipal organic solid wastes by rapidly decreasing gitude). The manures were separately minced and pulver-
the temperature and then re-establishing the optimal tem- ized with a semi-industrial cutter (CUT-3, Metvisa,
perature. The effect of temperature fluctuations between Brazil). The samples were packed into 500 g polyethylene
10 and 20 °C on a psychrophilic anaerobic sequencing bags and stored at 10 °C in a freezer. The characteristics
batch reactor treating swine manure has also been evalu- of the various manures are given in Table 1.
ated. Results suggest that the performance of anaerobic Batches of equal volumes of the three manures (33.3%
sequencing batch reactors (ASBRs) will deteriorate signifi- (VS/VS) each) were prepared with llama manure (5.7%
cantly if the operating temperature is decreased from 20 to by weight), cow manure (13.4% by weight), and sheep man-
10 °C. However, the ASBRs will remain stable and it will ure (4.2% by weight). Each batch was diluted with tap
recover at 20 °C (Massé et al., 2003). In another study, water (76.6%) to obtain the desired solid content (6% of
the gas production dynamics was investigated using a lab- VS w/w). The slurry was homogenized in a domestic elec-
oratory scale digester fed daily with dairy manure that was tric blender (Hamilton Beach 908, Hamilton Beach Com-
operated at a constant temperature, as well as with a pro- mercial, USA) and fractionated (with a volume defined
grammed temperature fluctuation of 3.3 °C about a mean by the value of the desired hydraulic residence time,
of 35.8 °C. The data suggested that it would be possible HRT = 30 days). The samples were packed into polyethyl-
to manipulate gas production by heating and cooling the ene bags and stored in a freezer. The samples for each day
content of the digester. Thus it may be possible to reduce were withdrawn from the freezer and allowed to thaw
gas storage volume by matching the production to a vary- overnight.
ing energy demand (Chayovan et al., 1988).
In highlands, such as the Bolivian Altiplano, where the
livestock is composed mainly of llamas, cows and sheep Table 1
Characteristics of fresh undiluted manure used in experiments at 18, 25,
(currently more than 1.8, 0.6, and 6.2 million animals,
35 °C and temperature fluctuation
respectively), the use of the manure from these animals in
Analysis Llama Cow Sheep
anaerobic digestion could satisfy the energy demands for
manure manure manure
cooking and lighting (especially in remote rural areas)
Total solids (% w.w) 49.5 (3.2) 19.8 (1.1) 77.6 (2.2)
and reduce the use of firewood and the deforestation that
Volatile solids (% of TS) 70.3 (2.2) 74.9 (1.6) 61.3 (5.6)
goes with it. However, the extreme environmental condi- Total nitrogen (% of TS) 1.7 (0.1) 1.6 (0.2) 1.1 (0.3)
tions constitute a limiting factor for the biomethanation Total organic carbon (% of TS) 29.5 (2.3) 26.5 (5.7) 18.9 (4.1)
process. The Bolivian Altiplano has an average elevation Total phosphorous (% of TS) 0.4 (0.1) 0.4 (0.1) 0.5 (0.1)
of nearly 4000 m, it is swept by strong, cold winds, and Total potassium (% of TS) 1.5 (0.2) 0.7 (0.3) 1.8 (0.5)
has an arid, chilly climate, with large differences in temper- Standard deviation from five samples in parentheses.
7280 R. Alvarez, G. Lidén / Bioresource Technology 99 (2008) 7278–7284
2.2. Apparatus jacket surrounding the reactor. The reactor was fed once
a day at 30 days HRT regime and 6 ± 0.1% w/w VS con-
A bench-scale bioreactor made of stainless steel with a tent. The content of the reactor was stirred for 15 min every
total capacity of 15 L and a liquid volume of 9.3 L was hour at 60 rpm.
used (Fig. 1). The digester had a built-in cooling and heat- The pH and the solid content of the slurry were analysed
ing system for temperature control. The jacketed cylindri- every 10 days. Biogas was collected in a separate 30 L plas-
cal vessel was equipped with a flanged top, to which a tic bottle and the volume was measured once a day by dis-
flange plate with a gas outlet port was fitted. This allowed placement of acidified water (pH = 2) at zero gauge
gas collection and measure of pressure. An impeller pressure and ambient temperature. The volumes were
(60 rpm) was used for stirring and the stirrer drive shafts recalculated to standard temperature and pressure (0 °C,
were inserted through a gas-tight bearing. The reactor 760 mm Hg).
was fed from a lateral port through a 50 mm ID ball valve.
The effluent was drawn from the bottom of the reactor 2.3.2. Cyclic square-wave temperature experiments
through a 12.7 mm ball valve. After finishing the experiment described above at 18 °C,
the bench-scale digester was subjected to a daily square-
2.3. Experimental procedure wave fluctuation of temperature in order to study the effect
on the anaerobic digestion process. The reactor operated at
Two kinds of experiments were conducted; anaerobic temperature intervals 11–25, 15–29, and 19–32 °C succes-
digestion at constant temperatures (35, 25 and 18 °C), sively for 60 days at each interval. The square-wave tem-
and anaerobic digestion during forced square-wave cycling perature fluctuation consisted of 12 h at high temperature
of temperature. The low and high temperatures in the latter followed by 12 h at low temperature. The reactor was con-
kind of experiments were 11 and 25, 15 and 29, and 19 and trolled by a Pt sensor PLC-Software heater/cooler system
32 °C, respectively. that changed the temperature of the slurry in the reactor
from low to high (or high to low) in less than 30 min.
2.3.1. AD experiments at constant temperatures The reactor was fed once a day at the beginning of the high
The effect of temperature on digestion of llama–cow– temperature half-cycle. The HRT was 30 days and the load-
sheep manure mixture was tested in the bench-scale reactor ing rate was 2 kg VS m 3 d 1 with 6 (±0.1)% w/w. The feed-
with 9.3-L active volume described above. For the start-up stock was a mixture of llama–cow–sheep with 33.3% VS of
period (60 days at 35 °C), the initial medium was prepared each. The content of the reactor was stirred at intervals of
with 5% llama manure, 11% cow manure, 4% sheep man- 5 min (on/off) all through the day at 60 rpm to improve the
ure, 64% tap water and 16% active slurry from a semi-con- heat transference and the control system. The pH, solid con-
tinuous digester working with llama–cow–sheep manure at tent, biogas volume and methane content were measured
25 °C with HRT of 50 days (7.3% TS, 71% VS, and according to the procedure described above.
pH = 7.6). Llama, cow and sheep manure (33.3% VS/VS
of each) with a VS content of 6 ± 0.1% w/w was fed daily 2.4. Analytical methods
in an amount giving a HRT of 30 days.
After the start-up period the reactor temperature was Methane and carbon dioxide concentrations in the biogas
kept at the selected temperatures (60 days each of 35, 25 were determined with a gas chromatograph (Shimadzu
and 18 °C in this order) by water circulating in the water Model GC14B, Japan) equipped with a thermal conductivity
13 8
12
9
6 1 2
7
11 5
10 9
4 3
Fig. 1. Schematic diagram of bench-scale digester: 1. vessel, 2. feed inlet, 3. effluent 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. Lidén / Bioresource Technology 99 (2008) 7278–7284 7281
detector (TCD) and a Carboxen-1010 plot Capillary until the weight change was less than 4%. Volatile solids
column 30 m 0.53 mm ID (Supelco, USA). The injector, were determined by ignition of the residue produced in
detector and oven temperatures were 130, 200, and 100 °C, TS analysis to constant weight in a muffle furnace at a tem-
respectively. Helium served as the carrier gas at a pressure perature of 550 °C. TOC was determined by high tempera-
of 300 kPa. ture combustion method (Method 5310 B). TKN was
Total solids (TS), volatile solids (VS), pH, total organic measured using the semi-micro-Kjeldahl method (Method
carbon (TOC), total Kjeldahl nitrogen (TKN), potassium 4500-Norg C), Potassium and Phosphorus were measured
and phosphorus were determined according to standard by spectrophotometry (Method 3500-K and 4500-P,
methods (Clesceri et al., 2000). The total solids (TS) con- respectively).
tent was determined after heating (105 °C for 1 h), cooling,
desiccating, and weighing procedures that were repeated 3. Results
0.70
a
0.60
The fermentation of a mixture of llama–cow–sheep
0.50
manure was found to be quite stable with respect to daily
0.40 biogas production, methane content and volatile solid in
0.30 effluent. Once stabilized, the daily variation in digester per-
0.20 formance (Fig. 2) at 35, 25, and 18 °C was less than 5%
0.10 with respect to the variables above.
0.00
As to be expected, the volumetric biogas production rate
decreased as the temperature was lowered. The reduction
80 from 35 to 25 °C resulted in a reduction of 30% in volumetric
b
Methane content (%)
8
c duction rate was reduced from 2094 (at 35 °C) to
6 1676 ml CH4 d 1 (at 25 °C) representing a reduction of
20%. A further reduction of 47% (from 1676 to
4 894 ml CH4 d 1) was seen when the temperature was
reduced from 25 to 18 °C. The methane yield followed the
2
same pattern.
0
0 10 20 30 40 50 60 3.2. Anaerobic digestion with a forced cyclic temperature
Time (d) variation
Fig. 2. Daily biogas production (a), methane content (b) and VS in
effluent (c) at different temperatures: 18 °C (), 25 °C (h) and 35 °C (N) A square-wave temperature variation was imposed on
from anaerobic digestion of llama–cow–sheep manure mixtures. the bench-scale digester in order to experimentally investi-
Table 2
Measured and calculated parameters from bench-scale reactor digesting mixture of llama–cow–sheep manure with square-wave temperature fluctuation
and different constant temperatures
Temperature OLR Digester Reduction Methane Volumetric biogas production rate Methane yield
range (°C) (kg VS m3 d 1) HRT (d) of VS (%) content (%) (L d 1
L 1) Daily biogas Biogas at Biogas at (m3 kg 1 VSadd)
(ml d 1) low T (%) high T (%)
11–25 2.0 30 13.8 (2.9) 56 (2) 0.2 2226 (155) 3 97 0.069 (0.005)
15–29 2.0 30 14.7 (1.2) 55 (2) 0.3 2738 (98) 3 97 0.084 (0.003)
19–32 2.0 30 19.0 (1.5) 56 (3) 0.3 2890 (32) 6 94 0.089 (0.005)
18 2.0 30 19.1 (2.8) 61(1) 0.2 1464 (94) 0.048 (0.003)
25 2.0 30 25.7 (3.3) 56 (2) 0.3 2977 (124) 0.092 (0.002)
35 2.1 30 29.4 (1.0) 49 (1) 0.5 4198 (139) 0.109 (0.005)
Standard deviation from 10 consecutive days in parentheses.
7282 R. Alvarez, G. Lidén / Bioresource Technology 99 (2008) 7278–7284
Temperature (oC)
between 11 and 25, 15 and 29, and 19 and 32 °C succes- 65 30
sively for 60 days at each interval. The variation imposed
was a square-wave, in which the temperature was main- 60 20
tained at the high level for 12 h followed by 12 h during
which the temperature was kept low. For each temperature 55 10
interval the digester required an adaptation period of
between 20 and 40 days to reach the pseudo-steady-state 50 0
0 6 12 18 24 30 36 42 48
(i.e. when the measured response during one cycle looks
Time (h)
the same as the subsequent ones). A longer adaptation per-
iod was required for the cycling experiments conducted at 65
lower temperatures. b
750 30
at the low temperature, and 6% of the daily biogas produc-
tion was obtained at 19 °C (173 ml d 1), and the remaining
500 20
94% was produced at 32 °C (2717 ml d 1). In all the forced
250
cycling experiments it was clear that the volumes of gas
10
obtained in the periods of low temperature (12 h) were very
0
low. Interestingly, the productivity during the low temper-
0
0 6 12 18 24 30 36 42 48 ature (19 °C) period in the forced cycling experiment work-
Time (h) ing between 19 and 32 °C was very much lower than the
productivity for the experiment running at a constant tem-
1000
b perature of 18 °C (cf Table 2).
Biogas production (ml)
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