Beruflich Dokumente
Kultur Dokumente
a,b
Department of Chemical Engineering, University of Patras, Karatheodori 1 st., 26500 Patras, Greece
Institute of Chemical Engineering and High Temperature Chemical Processes, 26504 Patras, Greece
c
Department of Biology, University of Patras, 26500 Patras, Greece
Received 10 July 2006; received in revised form 26 November 2006; accepted 27 November 2006
Abstract
The present study focuses on the exploitation of sweet sorghum biomass as a source for hydrogen and methane. Fermentative hydrogen production from the sugars of sweet sorghum extract was investigated at dierent hydraulic retention times (HRT). The subsequent
methane production from the euent of the hydrogenogenic process and the methane potential of the remaining solids after the extraction process were assessed as well. The highest hydrogen production rate (2550 ml H2/d) was obtained at the HRT of 6 h while the highest yield of hydrogen produced per kg of sorghum biomass was achieved at the HRT of 12 h (10.4 l H2/kg sweet sorghum). It has been
proved that the euent from the hydrogenogenic reactor is an ideal substrate for methane production with approximately 29 l CH4/kg of
sweet sorghum. Anaerobic digestion of the solid residues after the extraction process yielded 78 l CH4/kg of sweet sorghum. This work
demonstrated that biohydrogen production can be very eciently coupled with a subsequent step of methane production and that sweet
sorghum could be an ideal substrate for a combined gaseous biofuels production.
2006 Elsevier Ltd. All rights reserved.
Keywords: Biofuels; Fermentation; Hydrogen; Methane; Sweet sorghum
1. Introduction
Renewable energy sources have received great interest
from the international community during the last decades.
Biomass is one of the oldest and the most promising energy
sources and includes organic and animal wastes, wastewater, energy crops, agricultural and industrial residues that
can be used for the production of biofuels. Nowadays, biomass provides approximately 14% of the total world-wide
energy needs (International Energy Agency, 1998) and rep*
Corresponding author. Address: Department of Chemical Engineering, University of Patras, Karatheodori 1 st., 26500 Patras, Greece.
Tel.: +30 2610997858; fax: +30 2610993070.
E-mail addresses: gavala@chemeng.upatras.gr, hng@biocentrum.
dtu.dk (H.N. Gavala).
0960-8524/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2006.11.048
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2. Experimental
2.1. Analytical methods
Determinations of soluble (after centrifugation at 3000
rpm for 10 min and ltration of the supernatant liquid)
chemical oxygen demand (COD), total (TSS) and volatile
(VSS) suspended solids and Kjendahl nitrogen were carried
out according to Standard Methods (APHA, 1975). For
total P determination, the persulfate digestion method
and the ascorbic acid method (APHA, 1975) were
employed. For the quantication of volatile fatty acids
(VFA) and ethanol (EtOH), 1 ml of sample acidied with
30 ll of 20% H2SO4 was analyzed on a gas chromatograph
(VARIAN CP-30), equipped with a ame ionization detector. The oven was programmed from 105 C to 160 C at a
rate of 15 C/min, and subsequently to 235 C (held for
3 min) at a rate of 20 C/min for VFA analysis and from
60 C (held for 1 min) to 230 C (held for 0.5 min) at a rate
of 45 C/min for ethanol analysis. Helium was used as the
carrier gas at 15 ml/min, the injector temperature was set at
175 C and the detector at 225 C and 200 C, for VFA and
ethanol determinations, respectively. The concentration of
lactic acid was measured on a liquid chromatograph (DIONEX DX300), equipped with an electron conductivity
detector and a Dionex IonPac column (AS11-HC, 4
250 mm Analytical). The eluent (sodium hydroxide solution) ow rate was 1.5 ml/min and the analysis was carried
out at 30 C. The produced gas composition in hydrogen
and methane was quantied with a gas chromatograph
(VARIAN STAR 3600) equipped with a thermal conductivity detector and a packed column with nitrogen as carrier gas. The injector, column and detector temperatures
were set at 70 C, 80 C and 180 C, respectively. The measurement of the produced gas volume was based on the displacement of acidied water. For the determination of
carbohydrates, a colored sugar derivative was produced
through the addition of L-tryptophan and sulfuric and
boric acids and subsequently measured colorimetrically at
520 nm (Joseson, 1983).
2.2. Feedstock
Fossil fuel equipments and agrochemicals (e.g. fertilizers
and pesticides) are usually used when applying conventional
farming methods and techniques for energy crops cultivation resulting to increased emissions of CO2 and nitrogen
oxides (Cook and Beyea, 2000). Therefore, alternative cultivation methods, such as organic or biological farming, need
to be used so that the cultivation of energy crops is emissions
neutral. The sweet sorghum biomass (Sorghum bicolor L.
Moench) used in the present study was produced in eld
experiments through biological farming techniques according to European Regulation EC 2092/91. The experiments
were conducted at the University of Patras experimental station (latitude 3825 0 N, longitude 218 0 E). Sweet sorghum
var. Keller seeds were sown at mid of May in plot rows
S S 0 S 0 S in eV t
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2000
200
-2
A 3 l active volume mesophilic (35 C) CSTR-type digester (CH4-CSTR) was started up using anaerobic sludge and
fed with the euent of the hydrogenogenic reactor. The
digester had the same structural characteristics with H2CSTR and was operated anaerobically at a hydraulic retention time of 20 days. The reactor was fed for 1 min every
8 h. It must be noted, however, that the hydrogenogenic
and the methanogenic reactor were not connected; the euent of the H2-CSTR was collected, homogenized and preserved at 20 C before use. The reactor performance
(biogas production and composition in CH4, pH, soluble
COD and VFA concentration) was monitored 34 times a
week and complete characterization of the reactor euent
was made when steady state was reached.
Sugar productivity (g m )
-2
tration when feeding started, namely the concentration measured at the end of each cycle, Q is the volumetric feeding
rate, V is the reactor volume and t is the duration of feeding.
2.24 g NaOH and 6.8025 g KH2PO4 per liter of sorghum
extract were added in order to maintain the pH of the
H2-CSTR at levels (4.75.5) allowing for hydrogen production. Also 2 g urea (NH2CONH2) per liter of sorghum
extract was added to make up for N deciency of the feed.
Gas and liquid samples were taken 1015 min before feeding started. The reactor performance (biogas production
and composition in H2, pH, carbohydrates, soluble COD,
ethanol, butanol, lactic acid and VFA concentration) was
monitored daily throughout the experimental period. Gas
samples were analyzed for methane daily, in order to monitor whether methane production was taking place. Complete characterization of the reactor euent was made
once a steady state was reached. Steady-state here meant
constant conditions between successive feeding cycles.
1500
150
1000
100
500
50
0
0
160 170 180 190 200 210 220 230 240 250 260 270 280 290
Julian days
Table 1
The main characteristics of sorghum extract
Characteristics
Value
pH
TSS (g/l)
VSS (g/l)
Total COD (g/l)
Soluble COD (g/l)
Soluble carbohydrates (g/l)
Total Kjendhal nitrogen (g/l)
Total phosphorus (g/l)
7.5 0.5
1.98 0.27
1.87 0.35
18.5 2.5
17.5 2.0
17.0 2.0
0.025
0.035
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Table 2
The characteristics of the H2-CSTR at steady state
HRT
(h)
pH
TSS
(g/l)
VSS
(g/l)
Glucose
(mg/l)
Eciency of glucose
consumption (%)
24
12
8
6
4
5.5
5.3
4.8
4.9
4.8
8.5
5.5
10.7
12.8
22.0
6.4
4.1
8.8
10.2
16.5
110 20
470 70
680 110
450 20
290 70
99.4
97.4
95.3
97.6
97.9
Table 3
Biogas and hydrogen production rates and hydrogen yields in the H2-CSTR at steady state accompanied by their standard deviation
HRT
(h)
Biogas composition
in H2 (%)
Biogas production
rate (ml/d)
Hydrogen production
rate (ml/d)
24
12
8
6
4
30.4 1.2
39.9 1.2
40.5 1.9
39.2 0.5
35.0 1.5
1490 130
4260 180
5160 120
6510 200
6180 400
410 40
1740 100
2070 120
2550 90
2180 150
0.37 0.02
0.86 0.04
0.75 0.05
0.70 0.02
0.41 0.02
4.9
10.4
8.4
7.6
4.3
Table 4
Hydrogen productivity of dierent mesophilic mixed cultures fed with sugar-based medium in continuous suspended growth systems
Study
Operating conditions
HRT
(h)
pH
VSS (mg/l)
% H2
l H2/l/d
mmol H2/mmol
glucose
6
6
6
12
8.5
155.5
416
416
109.45
150.11
5.5
5.7
6.2
6.8
6
780
1270
1670
1590
1060
64
43.1
42.6
64
22.9
4.6
15.9
8.0
4.4
4.8
2.1
1.7
1.4
2.6
1.4
8.5
150.11
1450
53.4
3.0
0.9
233
188.89
5.1
5.3
680
4140
42.2
39.9
4.4
3.6
1.6
0.9
6
12
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6
6000
5500
5000
mg products /L
4500
4000
3500
3000
2500
2000
1500
1000
500
0
24h
12h
8h
6h
4h
Heterofermentative pathway
C6 H12 O6 ! CH3 CHOHCOOH + CH3 CH2 OH + CO2
6
Bifidum pathway
2C6 H12 O6 ! 3CH3 COOH + 2CH3 CHOHCOOH
Ethanol production
C6 H12 O6 ! 2CH3 CH2 OH + 2CO2
A ow chart showing the dierent reaction pathways discussed in the present study is presented in Fig. 4. Based
on the above equations and on the metabolic products
measured the anticipated hydrogen production rate was
calculated in the H2-CSTR, i.e. 2 mmol of hydrogen per
1 mmol of acetic acid produced, 2 mmol of hydrogen per
1 mmol of butyric acid produced and minus 1 mmol of
hydrogen per 1 mmol of propionic acid produced. The proCOD - products
COD- calculated
18000
16000
COD (mg/L)
14000
12000
10000
8000
6000
4000
2000
0
24
12
8
HRT (h)
Fig. 3. COD measured (COD-products) and calculated at dierent steady states of H2-CSTR.
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GLUCOSE
(eq. 4)
C6H12O6 + 2H2 2CH3CH2COOH + 2H2O
GLYCERALDEYDE
PHOSPHATE
PROPIONIC ACID
[PYRUVIC ACID]
[ACETYL-CoA]
(eq. 8)
C6H12O6 2CH3CH2OH + 2CO2
ETHANOL
(eqs. 5, 6, 7)
(eq. 3)
C6H12O6 2CH3CHOHCOOH
C6H12O6 CH3CHOHCOOH + CH3CH2OH + CO2
2C6H12O6 2CH3CHOHCOOH + 3CH3COOH
C6H12O6
CH3CH2CH2COOH + 2CO2 + 2H2
BUTYRIC ACID
LACTIC ACID
H2 + CO2
(eq. 9)
3CH3CHOHCOOH
2CH3CH2COOH + CH3COOH + CO2 + H2O
(eq. 10)
(eq. 2)
C6H12O6 + 2H2O
2CH3COOH + 2CO2 + 4H2
PROPIONIC ACID +
ACETIC ACID
4H2 + 2CO2
CH3COOH + 2H2O
ACETIC ACID
9
10
Table 5
The main characteristics of the inuent of the CH4-CSTR
Characteristic
Value
pH
TSS (g/l)
VSS (g/l)
Soluble COD (g/l)
Soluble carbohydrates (g COD/l)
Volatile fatty acids (g COD/l)
4.7 0.5
1.9 0.1
1.5 0.1
15.9 1.5
0.9 0.3
12.2 2.0
Value
pH
Alkalinity, mg CaCO3/l
Biogas production (l/d)
% in CH4
Soluble COD (mg/l)
Acetic acid (mg/l)
Butyric acid (mg/l)
7.5 0.1
6650 50
1.14 0.12
64
560 170
50 10
40 5
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biogas
methane
1400
1200
1000
800
600
400
200
0
0
20
40
60
80
100
120
140
160
180
Time, d
with solids
control without
solids
40
CH4, ml
35
30
25
20
15
10
5
0
0
10
12
14
16
Time, d
Fig. 6. Methane production during the batch experiment for the determination of the methane potential of the solid fraction after the extraction
process.
Table 7
Production rate of acetic, propionic and butyric acids and the theoretically calculated hydrogen production rate compared with the experimentally
measured hydrogen production rate in the H2-CSTR
HRT
(h)
24
12
8
6
4
Acetic
acid
Propionic
acid
Butyric
acid
Experimentally
measured
19.93
30.98
86.99
68.27
95.36
4.04
3.34
1.70
2.05
4.91
26.87
65.66
93.52
127.68
186.38
89.55
189.94
359.31
389.85
558.56
53.73
131.31
187.03
255.35
372.76
18.35
77.59
92.37
113.75
97.37
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