2013

1 2 1 1 2*
1.
2.
*kslee@ctust.edu.tw
NSC 101-2221-E-166-004 & NSC 102-2622-E-035-007

CSTR (continuous flow stireed tank reactor,)

(81000 ppm)(0-50 ppm)
20 g COD/L
(hydraulic retention time, HRT) 6 h
300 ppm H2S
1000 ppm H2S
25 ppm H2S 50 ppm H2S
280-807 ppm H2S HRT
4 hH2S 2-183 ppm HRT H2S
CSTR

[1]
[2]
(sulfate-reducing
bacteria, SRB)

2.1.1

95-100 [3] 1

2.1.2
20 g COD/L (17.8125 g/L)

Endo [4]
(g/L) NH4HCO3 5.24; K2HPO4 0.125;
CaCl2H2O 0.10; MgCl26H2O 0.10; MnSO4
6H2O 0.015; FeSO47H2O 0.025; CuSO45H2O
0.005; CoCl25H2O 0.000125 pH
NaHCO3

2.1.3
1.31 L CSTR
(continuous flow stirred tank reactor)

37.5pH 5.75 HRT

(hydraulic retention time) 6 h
(Gas
meter)

2.2
2.2.1
(gas chromatograph,

2013

SHIMAPZU GC-14B)
(thermal
conductivity detector, TCD)(carrier gas)
170C
160C 160C
(gas chromatograph,
SHIMAPZU GC-8A)
(flame ionization
detector, FID)(carrier gas)
150C 150C
150C
2.2.2
(SHIMADZU LC-10AT
Liquid Chromatograph)
(soluble microbial product, SMP)
(refractive index
detector, RID) (column)
COREGEL 87H3(mobile phase)
0.005N H2SO4 35 0.6
mL/min
2.2.3
(volatile suspended solid,
VSS)(APHA, 1997)
-(phenol-sulfuric
acid method)
Turbidimetric Method(Standard Methods,
1996)Iodometric Method
(Standard Methods, 1996)
Methylene Blue Method Standard
Methods, 1996

3.1
8
1003005001000 ppm SO42-
1
1000 ppm
300 ppm

8 ppm
HPR (H2 production rate,
HPR) H2 yield (HY) HPE (overall H2
production efficiency, HPE) 46.4%

0.782 mol/L/d3.92 mol H2/mol sucrose

46.9% ( 1)
100 ppm
HPRHY
HPE 43.2%0.742 mol/L/d3.66 mol
H2/mol sucrose 44.5% ( 1)
300
ppm 1
85.5 ppm

SO42-+2(CH2O)+2H+H2S+2CO2+2H2O

(1)

HPRHY
HPE 43.8%0.715 mol/L/d3.58 mol
H2/mol sucrose 42.9% ( 1)
3

(ppm)
8
100
300
300
500
500
1000
(day 33-34)
1000
(day 34-42)
1000
(dat 45-50)

H2S

(/)
X
X
X
O
X
O
O

(ppm)
2
77
210
196
365
275
880

(ppm)
6
23
90
104
135
225
120

911

89

821

179

500 ppm
317.8
ppm
300 ppm

1000 ppm

74.1 ppm 3
500 ppm 225

2013

50

800

40

600

30
2SO4 conc (ppm)
H2 conc (%)

200

HPR (mol/L/d)

10
0
300

0.8
0.6

200

0.4

HPR (mol/L/d)
H2S conc. (ppm)

0.2
0.0

100
0

6
pH

20

H2S conc. (ppm)

SO4

2-

400

-200

-400

ORP (mV)

conc. (ppm)

60
1000

H2 content in biogas (%)

ppm 1000 ppm

120 ppm
500 ppm
8

HPRHY HPE 39.6%0.549

mol/L/d2.77 mol H2/mol sucrose 32.9%
( 1)

Biomass (g VSS/L)

-600

ORP
100

80

60

40

20
Biomass
substrate utilization (%) 0

0
0

10

20

30

40

Substrate utilization (%)

pH
3

50

Time (day)

1
1000 ppm
(8 ppm)
30%Lin Chen[5]
500 1500 ppm
18 ppm 81.4 62.5%

Ethanoligenens harbinense
[6,7]
(1000
ppm)(67.3%)

(44.3%)( 2)
3.2

(0
ppm)HPRHY
HPE 47.5%0.807 mol/L/d4.06 mol
H2/mol sucrose 48.4% ( 4)

25 ppm
93-364 ppm

50 ppm
280-807
ppm
12
10%

HPRHY HPE 47.3%

0.760 mol/L/d3.76 mol H2/mol sucrose
46.0% ( 4)

HRT (wash out)

[8] HRT ()

HRT
(substrate
concentration)
(organic loading rate, OLR) HRT
4 h 13.3 g COD/L
OLR 3.33 g COD/L/h 2
HRT 4 h
807 ppm 84 ppm
10% H2S 7062 ppm
HRT
HPRHY HPE
0.719 mol/L/d3.46 mol H2/mol sucrose

2013

50

80

40

60

30
40

20
2SO4 conc (ppm)
10
H2 conc (%)

20
0

0
800

0.8
600

0.6
0.4

400

HPR (mol/L/d)
H2S conc. (ppm)

0.2

200

0.0

6
pH

H2S conc. (ppm)

HPR (mol/L/d)

60

-200

-400

ORP (mV)

conc. (ppm)
2SO3

HRT 4 h

HRT 6 h

100

H2 content in biogas (%)

43.7% ( 4) 6%
90%
HRT

Biomass (g VSS/L)

-600

ORP
100

80

60

40

20
Biomass
substrate utilization (%) 0

0
0

10

20

30

40

Substrate utilization (%)

pH
3

50

Time (day)

300 ppm

1000 ppm

(8 ppm) 70%
25 ppm
50 ppm
807 ppm HRT
90%

NSC101-2221-E-166-004 & NSC 102-2622-E035-007)

1. 2013

2. 2004

3. Lin CY, Chang RC. 1999. Hydrogen

production during the anaerobic acidogenic
conversion of glucose . J Chem Technol
Biotechnol 74: 498-500.
4. Endo G, Noike T, Matsumoto J. 1982.
Characteristics of cellulose and glucose
decomposition in acidogenic phase of
anaerobic digestion. Proc Soc Civ Engrs
325: 61-68.
5. Chiu-Yue Lin, Hong-Pin Chen.
2006.
Sulfate effect on fermentative hydrogen
production
using
anaerobic
mixed
microflora.
International
Journal
of
Hydrogen Energy 31 953-960
6. Liying Xu, Nanqi Ren, Xingzu Wang,
Yongfeng
Jia.
2008.
Biohydrogen
production by Ethanoligenens harbinense
B49: Nutrient optimization. International
Journal of Hydrogen Energy Volume 33,
Issue 23, : 69626967.
7. Guo Jun Xie, Liu Bing Feng, Nan Qi Ren,
Jie Ding, Chong Liu, De Feng Xing, Guo
Wan Qian, Hong Yu Ren. 2010. Control
strategies for hydrogen production through
co-culture of Ethanoligenens harbinense
B49 and immobilized Rhodopseudomonas
faecalis RLD-53. International Journal of
Hydrogen Energy Volume 35, Issue 5,
March 2010, Pages 19291935.
8.
2007
54169-106
9. Lin CY, Chang RC. 1999. Hydrogen
production during the anaerobic acidogenic
conversion of glucose . J Chem Technol
Biotechnol 74: 498-500.
10. 2013

2013

1
2-

SO

HS
2

Cb
(g VSS/L)

HPR
(mol/L/d)

CH2
(%)

X
(%)

H2 Yield
(mol H2/mol
sucrose)
3.920.09
3.660.11
3.580.37
4.120.39
3.800.20

HPE
(%)

(ppm)
(ppm)
8
ND
3.160.48
0.7820.016
46.41.0
96.10.9
46.90.8
100
ND
3.890.18
0.7420.027
43.20.9
97.30.5
44.51.3
300
85-ND
2.780.32
0.7150.081
43.81.4
96.24.1
42.94.2
500
318-ND
3.270.64
0.7870.070
47.41.2
91.84.9
47.24.1
1000
74-ND
2.040.95
0.7560.160
44.72.0
96.43.3
45.44.4
(day 33-42)
1000
ND
2.230.32
0.5490.020
39.61.2
95.12.1
2.770.16
32.91.5
(dat 45-50)
Cb: biomass concentration; HPR: H2 production rate; CH2: H2 content in biogas; X: substrate utilization efficiency; HY: H2 yield; HPE: over all H2 production efficiency; HPE =
(HPR)/((24/HRT*(ToSu/180)*4)); ND: not detectable

2
2-

SO4
(ppm)

SMP
(mg COD/L)

VFA
(mg COD/L)

EtOH
(mg
COD/L)
1.80.2
1.20.9
3.00.2
1.70.1
3.50.7

BuOH
(mg
COD/L)
ND
ND
ND
ND
ND

HLa
(mg
COD/L)
6.85.0
3.60.2
8.21.8
8.50.4
6.20.8

HFo
(mg
COD/L)
ND
ND
ND
ND
ND

HAc
(mg
COD/L)
21.71.0
24.30.3
18.60.7
20.81.3
19.90.8

HPr
(mg
COD/L)
2.40.4
1.10.1
2.80.2
1.80.1
3.00.4

HBu
(mg
COD/L)
67.34.3
69.81.1
67.41.6
62.71.1
67.31.0

HVa
(mg
COD/L)
ND
ND
ND
ND
ND

8
104721360
95441114
100
11615459
9544418
300
11733630
104201459
500
10190612
9569562
11217720
11021681
1000
(day 33-42)
110951112
8032839
21.20.6
ND
6.20.9
25.00.8
2.30.2
44.61.1
1000
ND
ND
(dat 45-50)
SMP: soluble microbial products (mg COD/L) ;TVFA (total volatile fatty acid, mg COD/L) = HFo+HAc + HPr + HBu+HVa ; EtOH: ethanol; EtOH: ethanol;BuOH: buthanol;
HLa: lactate; HFo:Formic acid;HAc: acetic acid; HPr: propionic acid; HBu: butyric acid;HVa: Valeric acid; ND: not detectable

2013

4
2-

SO

(ppm)
0
25
50
50

HRT
(h)
6
6
6
4

OLR
(g COD
/L/h)
3.33
3.33
3.33
3.33

HS
(ppm)

Cb
(g VSS/L)

HPR
(mol/L/d)

CH2
(%)

X
(%)

ND
216100
422145
7062

2.320.33
2.640.28
2.490.21
1.820.27

0.8070.067
0.8430.063
0.7600.069
0.7190.048

47.51.10
46.91.42
47.32.57
46.32.37

95.73.40
98.21.01
97.82.08
99.00.05

H2 Yield
(mol H2/mol
sucrose)
4.060.27
4.110.32
3.760.27
3.490.24

HPE
(%)

HPr
(mg
COD/L)
1.80.2
1.80.1
1.70.1
3.10.4

HBu
(mg
COD/L)
69.40.8
70.31.0
69.61.3
67.11.6

48.44.14
50.63.73
46.04.13
43.72.92

5
2-

SO3
(ppm)

HRT
(h)

0
25
50
50

6
6
6
4

OLR
(g COD
/L/h)
3.33
3.33
3.33
3.33

SMP
(mg COD/L)

VFA
(mg COD/L)

9648881
9941239
10660746
6926370

8986854
9318328
9908585
6500394

EtOH
(mg
COD/L)
2.70.3
2.20.3
2.90.7
3.50.5

BuOH
(mg
COD/L)
ND
ND
ND
ND

HLa
(mg
COD/L)
4.20.9
4.11.2
4.10.8
2.70.7

HFo
(mg
COD/L)
ND
ND
ND
ND

HAc
(mg
COD/L)
21.90.6
21.60.4
21.80.2
23.60.6

HVa
(mg
COD/L)
ND
ND
ND
ND