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Production of Methane From Sugar Beet Silage Without Manure Addition by A Single-Stage Anaerobic Digestion Process
Production of Methane From Sugar Beet Silage Without Manure Addition by A Single-Stage Anaerobic Digestion Process
Available at www.sciencedirect.com
http://www.elsevier.com/locate/biombioe
B. Demirel, P. Scherer
Lifetec Process Engineering, Faculty of Life Sciences, Hamburg University of Applied Sciences, Lohbrügger Kirchstrasse 65,
21033 Hamburg, Germany
Article history: Single-stage continuous anaerobic conversion of sugar beet silage without manure to
Received 23 July 2007 methane was investigated in this experimental work, using a laboratory-scale mesophilic
Received in revised form anaerobic biogas digester. The sugar beet silage had an extreme low pH of 3.3. The reactor
10 September 2007 was operated in a hydraulic retention time (HRT) range of between 95 and 15 days, and an
Accepted 15 September 2007 organic loading rate (OLR) range of between 0.937 and 6.33 g1 VS l1 d1. The highest
Available online 23 October 2007 specific gas production rate (spec. GPR) of 0.72 l g VS1 d1 could be obtained at 25 days of
HRT, with an average methane content of about 63%, at a pH of around 6.8. Since sugar beet
Keywords:
silage without the leaves is a poor substrate, in terms of the availability of the nutrients and
Anaerobic digestion
the buffering capacity, external supplementation of nitrogen and buffering agents has to be
Biogas
regularly performed, in order to achieve a stable and an efficient process. Sodium or
Biomass
potassium hydrogen carbonate addition seemed to function best in our case, among the
Methane
other agents used, to provide adequate buffering capacity and to keep the digester pH
Renewable energy
stable during the operation. Use of a new harvest (a new charge of substrate) also affected
Sugar beet
the spec. GPR values significantly.
& 2007 Elsevier Ltd. All rights reserved.
price was decreased by the EU in 2006, and now many farmers 2.2. Substrate
are looking for an alternative use.
Sugar beet silage (without the leaves) was used as the mono-
substrate. The general characteristics of the sugar beet silage
are given in Table 1. More data about the characteristics of the
2. Materials and methods sugar beet silage can also be found elsewhere [14]. Two
harvests of sugar beet silage were used during the entire
2.1. Description of the reactor system experimental work, and both harvests were obtained from
Soltau, Germany. Parallel analyses were carried out for
A laboratory-scale, single-stage continuous digester was used determination of each parameter. The substrate was stored
in this experimental work. The schematic configuration of the at 4 1C until further use. Since sugar beet silage is a poor
anaerobic biogas reactor is given in Fig. 1. The description of substrate, in terms of nitrogen (N), phosphorus (P) and
the reactor was previously reported [13]. The reactor was buffering capacity, nitrogen was regularly provided to the
inoculated with 1/3 of sewage sludge, 1/3 of swine manure feed by external addition of ammonium hydrogen carbonate
and 1/3 of a compost suspension (without solids). Tempera- (NH4HCO3) or ammonium chloride (NH4Cl), while sodium
ture was kept at 41–42 1C during the entire operation. The hydrogen carbonate (NaHCO3), potassium hydrogen carbo-
reactor was fed once a day, manually. Biogas production was nate (KHCO3), potassium hydroxide (KOH) or sodium carbo-
measured daily, using a Milligascounters type MGC10 (Ritter, nate (Na2CO3) were used as buffering agents to provide
Bochum, Germany). Methane (CH4) and carbon dioxide (CO2) alkalinity and to keep the reactor pH stable. Stock solutions
compositions (v/v) were measured online, using infrared of minerals were also prepared and added to the substrate,
sensors (BlueSens Gaz Analyzer, Herten, Germany). Tempera- to provide phosphate (5.2 mM, Na and K salts), calcium
ture, pH and redox potential (ORP) were also continuously (Ca, 1 mM), magnesium (Mg, 2 mM), zinc (Zn, 10 mM), manganese
measured online. (Mn, 2 mM), copper (Cu, 2 mM), wolfram (W, 1 mM), cobalt
(Co, 5 mM), nickel (Ni, 10 mM), selenium (Se, 0.4 mM), molybdenum
(Mo, 2 mM) and sulphur (S, 0.5 mM). All chemicals were reagent
grade, obtained from commercial sources (Merck, Darmstadt,
Feed Germany).
pH
7.0
average of 53%. However, towards the end of period 1b the 3000
reactor pH started to decline, to 6.3–6.4, due to low buffering
pH
capacity of sugar beet silage (after reactor day 1500). No
1500 6.5
external addition of buffering agents was carried out at 38
days of HRT. In order to maintain a stable reactor pH, without
addition of any external buffering agents, HRT was increased
0 6.0
from 38 to 95 days, in the second period (2b). However, in spite
0 20 40 60 80 100 120
of a high HRT of 95 days, the digester pH still remained in a
HRT (days)
range of between 6.3 and 6.4. Therefore, ammonium hydro-
gen carbonate addition was started, in order to increase both Fig. 3 – Values of pH and alkalinity at different hydraulic
the buffering capacity and the ammonium (NH+4 ) content of retention time (HRT) levels during mesophilic anaerobic
the reactor. The ammonium content and the buffering digestion of sugar beet silage (for the old and new harvests
capacity (total alkalinity) of the reactor ranged from 150 to there exist two different steady-state conditions at 25 days
215 mg l1, and 1176 to 1478 mg CaCO3 l1, respectively, before of HRT; no alkalinity data are available for operation at 38
days of HRT).
Table 2 – A summary of the observed operational and environmental conditions for anaerobic digestion of sugar beet
silage
Period HRT Reactor Feeding spec. GPR OLR VSS reactor Temp. Redoxa
(days) days (mL) (l g VS1 d1) (g VS l1 d1) (%) (1C) (mV)
a
Corrected redox potential (ORP) values by 230 mV reference electrode are reported here.
b
Substrate charge 1.
c
Substrate charge 2.
ARTICLE IN PRESS
206 BIOMASS AND BIOENERGY 32 (2008) 203 – 209
external supplementation began. After external supply was tively, with a pH of about 6.9. These low levels of spec. and vol.
started, the reactor pH gradually increased, from 6.3 and 6.4, GPR could be attributed to a relatively high HRT employed
to 6.75, in about 2 weeks, and the steady-state conditions during this period of reactor operation. The methane content
could then be attained. At 95 days of HRT, the spec. GPR and of digester biogas ranged between 49% and 58%, with an
vol. GPR levels were 0.4 l g1 VS d1 and 0.37 l l1 d1, respec- average of 53%. Alkalinity ranged between 2548 and
5145 mg CaCO3 l1, while the ammonium concentration var-
ied from 678 to 1380 mg l1. Change in HRT affected both
1400 specific and volumetric GPR values adversely. However,
Change of substrate charge at HRT of 25 days
variation in HRT did not provide a more stable reactor pH,
1200 without the supplementation effect of the buffering agents.
Addition of NH4HCO3 obviously provided a stable reactor pH,
Concentration (mg l-1)
1000
with a high amount of buffering capacity, but seemed to have
800 no profound effect on increased biogas production rate.
SCh-2 SCh-1 SCh-1
In the following period (3b), HRT was decreased from 95 to
600 50 days. At steady-state conditions at 50 days of HRT, the
spec. GPR and vol. GPR levels of 0.53 l g1 VS d1 and
400 Ammonium 0.944 l l1 d1 were obtained, respectively, with a pH of 7.1
Phosphate
(on average). The methane content of digester biogas varied
200 between 50% and 58%, with an average of 54%. The alkalinity
ranged from 3440 to 4743 mg CaCO3 l1, while the ammonium
0
concentration varied between 1087 and 1320 mg l1. HRT
20 40 60 80 100
variation only had a slight effect on spec. GPR. Besides, the
HRT (days)
methane content also remained almost the same. In the
Fig. 4 – Concentrations of ammonium (NH+4) and phosphate following run (4b), HRT was further adjusted from 50 to 25
(PO3
4 ) in a mesophilic anaerobic biogas reactor during the days. During steady-state conditions, the spec. and vol. GPR
entire operation with sugar beet silage without manure levels were 0.49 l g1 VS d1 and 1.743 l l1 d1, respectively,
addition using substrate charges SCh-1 and SCh-2. with an average reactor pH of 7.27. The methane content of
digester biogas varied between 51% and 61% (57% on average),
and the alkalinity ranged from 5250 to 6825 mg CaCO3 l1.
Table 3 – A comparison of reactor output with substrate
During this period, NH4HCO3 addition was reduced, due to
charge 1 and 2, both at 25 days of HRT operation
high ammonium concentrations (between 2060 and
2674 mg l1). Change in HRT from 50 to 25 days seemed to
Parameter Substrate Substrate affect only spec. GPR slightly. These steady-state data at 25
charge 1 charge 2
days of HRT were obtained during use of the substrate charge
Spec. GPR (l g1 VS d1) 0.49 0.72 1 (Table 2). However, during the steady-state operation at 25
Vol. GPR (l l1 d1) 1.743 2.863 days of HRT, we had to use a new charge of substrate (a new
Methane (CH4) 51–61 58–67 harvest-substrate charge 2), because the old charge of
content (%) substrate ran out (reactor day 1695). Eventually, the reactor
pH 7.27 6.79
1.25 7.5
80
spec.GPR (l gVS-1d-1)
Methane
1.00 7.0
60
pH
0.75 6.5
40
spec. GPR
0.50 6.0
20
0.25 5.5
pH
0.00 5.0 0
1800 1810 1820 1830 1840 1850 1860
Reactor operation (days)
Fig. 5 – Spec. GPR, pH and methane values before (during steady-state conditions at 25 days of HRT before reactor day 1860)
and during the failure period (on reactor day 1860 at 15 days of HRT).
ARTICLE IN PRESS
BIOMASS AND BIOENERGY 32 (2008) 203 – 209 207
output was obviously affected by this variation. During the and a higher methane content in digester biogas produced
operation with the new charge of substrate at 25 days of HRT (Table 3).
(period 4c), external addition of NH4HCO3 was ceased (Fig. 4). Higher ammonium concentrations between 2060 and
In order to provide adequate buffering capacity and a stable 2674 mg NH+4 l1 due to external addition during substrate
reactor pH, sodium carbonate, calcium carbonate and potas- charge 1 feeding caused free ammonia (NH3) concentrations
sium hydroxide were used. However, calcium carbonate ranging between 464 and 593 mg l1. During substrate charge
addition caused excessive foam formation in the digester, 2 feeding, lower ammonium concentrations could be main-
which led to clogging of gas outline and condensate trap. tained in the reactor, ranging from 77 to 505 mg l1, causing
Sodium carbonate was also avoided later, since sodium ions even lower NH3 concentrations between 109 and 17 mg l1.
could have a positive effect on methanogenesis [17,18]. The formula reported by Gallert and Winter was used to
The spec. and vol. GPR levels were 0.72 l g1 VS d1 and calculate NH3 concentrations from measured NH+4 concentra-
2.863 l l1 d1, respectively, with an average reactor pH of 6.79, tions [19]. Previously, stable anaerobic digestion of swine
at steady state for 25 days of HRT, using substrate charge 2, manure has been reported for ammonia concentrations at
with KOH addition. The methane content of digester biogas 6000 mg N l1, and inhibition of the biogas process occurred at
varied between 58% and 67% (63% on average), and the a free ammonia concentration of approximately 1100 mg N l1
alkalinity ranged from 1580 to 2975 mg CaCO3 l1. The [20]. Furthermore, it was recently reported that the optimum
ammonium concentration also varied between 77 and growth conditions for Methanosaeta concilii, which is the most
505 mg l1. A slightly higher OLR was used with substrate ammonia-sensitive methanogen, were in the range of
charge 2, because it had a higher VS content than that of 250–1100 mg NH+4 l1 [21]. Therefore, it was unlikely to con-
substrate charge 1. The new charge of substrate used clude that high ammonium or free ammonia concentrations
provided higher specific and volumetric gas production rates, had an adverse effect on anaerobic digestion of sugar beet
silage.
In the following period (5c), HRT was decreased from 25 to
15 days (reactor day 1850). No external ammonium supply
12000 was used at 15 days of HRT, in order to find out the minimum
VFA concentration(mg l-1)
Total VFA
amount of ammonium concentration required for anaerobic
10000 HAC
HPRO
conversion of sugar beet silage to methane. It was earlier
8000 HISOBUT reported that the ammonia concentration had to be kept in
6000 HBUT excess of at least 40–70 mg N l1, to prevent reduction of
HISOVAL bacterial activity [22]. KOH was still used to control digester
4000 HVAL pH. Within 10 days, the ammonium concentration in the
2000 reactor depleted, and in spite of pH control by KOH, the
reactor pH declined to 5.5 (on reactor day 1860). The spec.
0
GPR, pH and methane values before (during steady-state
1800 1820 1840 1860 1880 1900 1920
conditions at 25 days of HRT, before reactor day 1860) and
Reactor operation (days)
during the failure period (on reactor day 1860 at 15 days
Fig. 6 – Concentrations of VFA during failure at 15 days of of HRT) are displayed in Fig. 5. The concentrations and
HRT and the following recovery periods during anaerobic
digestion of sugar beet silage.
*Three-fold experiments were carried out at 37 1C; incubation time was 26 days [23].
**SBS ¼ sugar beet silage.
ARTICLE IN PRESS
208 BIOMASS AND BIOENERGY 32 (2008) 203 – 209
Reference
This study
recovery periods are also shown in Fig. 6. The maximum
[10]
[11]
[12]
[8]
[9]
concentrations of acetic (HAC) and propionic (HPRO) acids
were determined to be 6238 and 3514 mg l1, respectively (Fig.
6). Even an alkalinity level of 2900 mg CaCO3 l1 could not
prevent decrease of pH, when the bacterial activity was
Methane
58-61%
inhibited. In order to recover the activity of the reactor at
71.9%
70%
63%
–
–
operation day 1861, HRT was firstly adjusted from 15 to 100
days. Then, it was further adjusted to 75, 50 and 25 days.
During this recovery phase, firstly NH4HCO3, and then KOH
were used to provide N and buffering capacity. After stable
0.31–0.36 m3 kg1 VSadded
0.36–0.41 l CH4 g1 d1
15 days again.
591-670 l kg1
0.74 m kg VS
Gas yield
17.5–24.6 l d1
(Table 4). The methods for these batch tests at HAW Hamburg
have been previously reported [23].
At steady-state conditions at 15 days of HRT, the specific
and volumetric GPR levels were determined to be only
0.6–1.2 days
17 days
20 days
25 days
0.53 l g1 VS d1 and 3.357 l l1 d1, respectively, with an aver-
HRT
1 kg VS m
Meso
Meso
Single-phase
Single-phase
Single-phase
Two-phaseb
Two-phase
4. Conclusions
Process
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