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Biogas Production from Biological SludgeBiogas Production from Biological Sludge
D. J. LeeDepartment of Chemical EngineeringNational Taiwan University
Sludge?Sludge?EffluentInfluent
Secondarysettler
Primarysettler
Aeration tank
Recycled activated biomass
Primarysludge
Secondary sludge(waste activated sludge)
Flocculation
Thickener
Pretreatment
DigesterDewatering facility
ASM
Settling
Filtration
Biological Sludge Biological Sludge FlocFlocFloc is a common form of Floc is a common form of bioaggregates appearing in the bioaggregates appearing in the wastewater treatment process.wastewater treatment process.
•Irregular shape;
•Highly porous;
•Compressible and fragile;
•Inhomogeneous distribution
of internal mass.
Sludge Sludge FlocFloc
Frolund (1994)
•A group of symbiotic microorganisms “embedded” in the extracellular polymers
pH 5-6
pH 7-8
Biogas
Anaerobic digestionAnaerobic digestion
Organic monomers(sugar/ amino acids/ fatty acids)
Long chain VFA(C3/C4/i-C4/C5/C6)alcohol/methanol/lactate/formate/butanolacetone
H2/CO2 Acetate
Long chain VFA(C3/C4/i-C4/C5/C6)alcohol/methanol/lactate/formate/butanol/acetone
Acetogenic B.
Homoacetogenic B.
75%
35%
13% 17%
5% 20%Complex biopolymers(Carbohydrate/ protein/ lipids)
CH4/CO2/H2O
Hyd
roly
sis
Aci
doge
nesi
sA
cido
gene
sis
Ferm
enta
tive
bact
eria
10%
30%
Acetogenesis
Methanogenesis
Hydrogenophilic B.72%Acetoclastic B. 28%
△△GGOO′′StepStep
-207-135-922
2326126 442243
HHHCOCOOCHOHOHC +++→+ +−−
222326126 232)(23
HHHCOCOOCHCHOHOHC +++→+ +−−
2223236126 222243 HHOHCOCOOCHCOOCHCHOHC +++++→ +−−
OHCOOCHHHHCO
HHCOOCHOHCOOCHCH
HCOHHCOOCHOHCOOCHCH
HHCOOCHOHOHCHCH
2323
232223
323223
23223
442
222)(
33
2
+→++
++→+
+++→+
++→+
−+−
+−−
−+−−
+−
++
+−
+−
++→+
++→
+→+
+→+
++→+
+→+
424233
2243
243
242
224
2422
4396)(4
234
324
2344
24
NHCOCHOHNHCH
OHCOCHOHCH
COCHHCOOCH
COCHOHCO
OHCOCHHHCOO
OHCHHCO
Acetogenesis
Fermentation
+10+76+48
-105
-130-120-186
-33-309-666
Methanogenesis
StepStep-1946
-632-134
Denitrification
OHCONOHCON
OHCOONOHCNO
OHCONOOHCNO
22261262
22261262
22261263
661212
6648
661212
++→+
++→+
++→+−
−−
-152-48
-151+−−−−
−−−−
−+−
++→+
+→+
+→++
HHCOCOOCHSOCOOCHCH
HSHCOSOCOOCH
HSOHHSOH
332423
3243
2242
4434
2
44Sulphatereduction
PhasePhaseFermenting BacteriaFermenting Bacteria
pH=5.2~6.3pH=5.2~6.3YYXX=0.2g=0.2g--VS gVS g--CODCOD--11
FaculativeFaculative anaerobicanaerobic
AcedogenesisAcedogenesis and and MethadogenesisMethadogenesispH=6.8~7.2 pH=6.8~7.2 YYXX=0.03~0.05=0.03~0.05 gg--VSVS gg--CODCOD--11
Obligate anaerobicObligate anaerobicSyntrophicSyntrophic reaction reaction
Interspecies hydrogen transferInterspecies hydrogen transfer
Propionate and HPropionate and H22Propionate: account for over 30% of the electron flowPropionate: account for over 30% of the electron flow
Deterioration of propionate degradationDeterioration of propionate degradationDecrease in VFA removal efficiency Decrease in VFA removal efficiency
1/2CH3CH2OH+1/2H2O 1/2CH3COOH+H2
Log(H2)
△Go(W)
kCal
2
0
-2
-4
-6
-8
-10
-8 -7 -6 -5 -4 -3 -2 -1 0
Region for Propionate to CH4
Region for Ethanol to CH4
1/3CH3CH2COOH+2/3H2O1/3CH3COOH+1/3CO2+H2
1/2CH3COOH 1/2CH4+1/2CO2
H2+1/2CO2 1/2CH4+1/2H2O
McCarty, P.L. and Smith, D.P. Anaerobic wastewater treatmen[J]. Environ. Sci. Technol., 1986,20:1200-1206
Through enzymes
Enhanced HydrolysisEnhanced Hydrolysis
pH3
TT
pH11
FT
1 0 0 µ m
Na-salt
US
PrePre--hydrolysishydrolysisPrePre--hydrolysis of sludge is often applied hydrolysis of sludge is often applied in prior to the anaerobic digestion toin prior to the anaerobic digestion to::
Disintegrate the suspended particlesDisintegrate the suspended particlesDecompose the insoluble organic Decompose the insoluble organic moleculesmolecules..
Alkaline treatmentAlkaline treatment and and ultrasonicationultrasonicationwere reported as effective prewere reported as effective pre--hydrolytic treatments.hydrolytic treatments.
Enhancing Enhancing DigestionDigestion
Waste Activated Sludge Waste Activated Sludge Sampling from the recycled stream in Sampling from the recycled stream in the secondary treatment stage in St. the secondary treatment stage in St. MarysMarys sewage treatment plant in sewage treatment plant in Sydney, Australia.Sydney, Australia.pH = pH = 7.507.50TSS = 10,700 mg/L.TSS = 10,700 mg/L.ρρSS = 1,612 kg/m= 1,612 kg/m33. .
(a) (b)
Strains in innoculum K8: (a) bacillus; (b) cocci.
Time (day)0 10 20 30 40 90 100
Met
hane
pro
duct
ion
(g/k
g D
S)
0
100
200
300
OriginalFlocculated
OriginalFlocculated
Before sonication
After sonication Flocculation retardsDigestion; while UltrasonicationEnhances it.
Time (Day)0 10 20 30 40 90 100
ATP
con
tent
( µg/
L)
0
2
4
6
8
10
OriginalFlocculated
OriginalFlocculated
Before sonication
After sonication
Time (Day)0 10 20 30 40 90 100
OR
P (m
V)
-350
-300
-250
-200
OriginalFlocculated
OriginalFlocculated
Before sonication
After sonication
Time (Day)0 10 20 30 40 90 100
d f[4,3
] ( µ
m)
40
60
80
200
300
400
OriginalFlocculated
OriginalFlocculated
Before sonication
After sonication
Poordigestion
100 µm
Ori, 0 & 30 d
Floc, 0 & 30 d
Ori, 0 & 30 d
Floc, 0 & 30 d
Insufficient Challenge
Sonication time (min)
0 50 100
Flo
c si
ze ( µ
m)
0
50
100
0.11 Watt/ml
0.22 Watt/ml
0.33 Watt/ml
0.44 Watt/ml
0.11 W/cm3
0.22 W/cm3
0.33 W/cm3
0
7
14
21
28
0 2 4 6 8 10 12operation time (day)
CO
D (g
/L)
R1 leachate R2 leachate R3 leachate Rm effluent
0
20
40
60
80
0 2 4 6 8 10 12operation time (day)
0
20
40
60
80
100
CH
4 con
tent
(%)
R1/R2/R3 CH4 yield Rm CH4 yield Rm CH4 content
cum
ulat
ive
CH
4 yie
ld (L
)
0
3
6
9
12
15
18
0 2 4 6 8 10 12operation time (day)
TVFA
(g/L
)
R1 leachate R2 leachate R3 leachate Rm effluent
4.0
5.0
6.0
7.0
8.0
0 2 4 6 8 10 12operation time (day)
pH
R1 leachate R2 leachate R3 leachate Rm effluent
Full-Scale Landfill Site
Sustainable Landfill
Simulativerainfall
Fresh
layer
Column No.1
Leacahterecycling
Leacahterecycling
No. 2
Fresh
layer Pretreatment
No.3-5
Fresh
layer
Internal Circulation
Leachate
Gas sample
Leachate
Aerobic SBR
Ana UFB
Old
layer
(a)
0
20
40
60
80
0 5 10 15 20 25 30
week
COD(g/L)
column No.1
column No.2
column No.3
column No.4
column No.5
1.5
3.0
4.5
6.0
7.5
9.0
0 5 10 15 20 25 30
week
pH
column No.1
column No.2
column No.3column No.4
column No.5
Biogas production
0
20
40
60
80
100
0 5 10 15 20 25 30
week
CH4 concentration(%)
column No.1column No.2column No.3column No.4column No.5
天子岭Site in HangZhu
pH 5-6
pH 7-8
Hydrogen from wasteHydrogen from wasteHydrogen production by pure substance or mixture
molasses (Tanisho and Ishiwata, 1994)glucose (Kataoka et al., 1997; Lin and Chang, 1999) crystalline cellulose (Lay, 2001)peptone (Bai et al., 2001)starch (Lay, 2001)
Hydrogen production by concentrated wastewater(Bolliger et al., 1985 ; Liu et al., 1995 ; Ueno et al.,1996 ; Zhu et al., 1999)
Hydrogen production by solid wastemunicipal solid waste (Lay et al., 1999)bean curd manufacturing waste (Mizuno et al., 2000 )
Hydrogen production by biological sludge
???
MinMin--shengsheng SludgeSludge
Concentration of wet solids 10,000~12,000 mg/L
Concentration of dry solids 1,429 kg/m3
pH value 6.4
Neutron particle size 71.6 µm
Zeta potential -19.1 mV
TCOD 24,800 mg/L
SCOD 435 mg/L
alkalinity 325 mg/L
Elemental composition C 34.3%、H 5.3%、N 5.4%、O 55 %
63µm63µm63µm
63µm
TongTong--yiyi SludgeSludge
Concentration of wet solids 10,000 mg/L
Concentration of dry solids 1,450 kg/m3
pH value 6.7
Neutron particle size 59.7 µm
Zeta potential -24.7 mV
TCOD 16,000mg/L
SCOD 86.7 mg/L
alkalinity 410 mg/L
Elemental composition C 41.3%、H 6.6%、N 5.4%、O 46.7%
63µm63µm
Strains screening DNA sequencing
Finding optimal dealing parameters
Concentration Pretreatment methods Inhibitors Measuring time points
Continuous anaerobic experiments
Gas production Hydrogen productive substrates Composition analysis
Strains screening (1)Strains screening (1)
Screening
Strains screening (2)Strains screening (2)Add them individually
Test the ability of hydrogen production
M-B M-D M-F M-G
The ability of hydrogen production is about 0.65-1.11 H2/kg DS
Species identificationSpecies identification
Extract DNA PCR
F8R1510
purification
Continuous sequencing
GCGGGNGNGGTNCCTAACACATGCAAGTCGTAACANGGTATTCCACANCAGNGNGCTGGACGGACNNGNAACAGAGG…...
purification
sequencing
Compare to the gene library
DNA SequenceDNA Sequence
M-B M-D M-F M-G
Clostridium bifermentans
Clostridium bifermentans
Pretreatment flow chartPretreatment flow chart
Original sludge
Ultrasonication
Acidification
Pasteurization
Add BESA
Freeze-thaw treatment
BESA addingFiltrate
Original sludgeFiltrate
Ultrasonicated Filtrate
AcidifiedFiltrate
Pasteurized Filtrate
Freeze-thawedFiltrate
Sludge fermentation test Sludge fermentation test -- CODCODCOD0 – COD of original biosolidSCOD – Soluble COD
Time (hours)0 25 50 75 100
SCO
D/C
OD
0
0.0
0.2
0.4
0.6
0.8
1.0
Original SonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Min-sheng sludge
Time (hours)0 25 50 75 100
SCO
D/C
OD
0
0.0
0.2
0.4
0.6
0.8
1.0
Original SonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Tong-yi sludge
Sludge fermentation testSludge fermentation test ––Hydrogen production Hydrogen production
CODi – COD of the substrate before testing
Time (hours)0 25 50 75 100
Yiel
d of
hyd
roge
n(m
g/g-
CO
Di)
0
2
4
6
8
10
12
Original SonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Time (hours)0 25 50 75 100
Yiel
d of
hyd
roge
n(m
g/g-
CO
Di)
0
2
4
6
8
10
12
Original SonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
24hr 24hr8hr 8hr
Min-sheng sludge Tong-yi sludge
ludge fermentation testludge fermentation test ––methane productionmethane production
Time (hours)0 25 50 75 100
Yiel
d of
met
hane
(mg/
g-C
OD
i)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Original SonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Min-sheng sludge
Time (hours)0 25 50 75 100
Yiel
d of
met
hane
(mg/
g-C
OD
i)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Original SonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Tong-yi sludge
No CH4!!
Sludge fermentation testSludge fermentation test ––pH measuringpH measuring
Time (hours)0 25 50 75 100
pH
3
4
5
6
7
8
Original SonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Min-sheng sludge
6
5.5
Time (hours)0 25 50 75 100
pH
3
4
5
6
7
8
Original SonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Tong-yi sludge
6.5
5.5
Sludge fermentation test Sludge fermentation test -- ORPORP
Time (hours)0 25 50 75 100
OR
P(m
V)
-400
-300
-200
-100
0
Original SonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
-300
-350
Tong-yi sludge
Time (hours)0 25 50 75 100
OR
P(m
V)
-400
-300
-200
-100
0
Original SonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
-300
Min-sheng sludge
Sludge fermentation test Sludge fermentation test ––Zeta potentialZeta potential
Time (hours)0 25 50 75 100
Original SonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Time (hours)0 25 50 75 100
Zeta
pot
entia
l(mV
)
-40
-30
-20
-10
0
Original SonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
-12
-32
-18
-20
Min-sheng sludge Tong-yi sludge
Zeta
pot
entia
l(mV
)
-40
-30
-20
-10
0
Sludge fermentation test Sludge fermentation test ––Particle size distributionParticle size distribution
Time (hours)0 25 50 75 100
d f,avg
( µm
)
0
50
100
150
200
250
300
350
400
Original SonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Min-sheng sludge
70
35
Time (hours)0 25 50 75 100
d f,a
vg( µ
m)
0
200
400
600
800
1000
1200
Original SonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Tong-yi sludge
90
40
Filtrate fermentation test Filtrate fermentation test -- CODCOD
Time (hours)0 25 50 75 100
SCO
D/C
OD
0
0.0
0.2
0.4
0.6
0.8
1.0
OriginalSonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Min-sheng filtrate
Time (hours)0 25 50 75 100
SCO
D/C
OD
0
0.0
0.2
0.4
0.6
0.8
1.0
OriginalSonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Tong-yi filtrate
Filtrate fermentation test Filtrate fermentation test ––Hydrogen productionHydrogen production
Time (hours)0 25 50 75 100
Yiel
d of
hyd
roge
n(m
g/g-
CO
Di)
0
10
20
30
40
50
60
OriginalSonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Time (hours)0 25 50 75 100
Yiel
d of
hyd
roge
n(m
g/g-
CO
Di)
0
10
20
30
40
50
60
OriginalSonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
24hr8hr 8hr 24hr
Min-sheng filtrate Tong-yi filtrate
Filtrate fermentation test Filtrate fermentation test ––pH measuringpH measuring
Time (hours)0 25 50 75 100
pH
3
4
5
6
7
8
9
OriginalSonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Min-sheng filtrate
5.5
6
Time (hours)0 25 50 75 100
pH
3
4
5
6
7
8
9
OriginalSonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Tong-yi filtrate
6.8
6
Filtrate fermentation test Filtrate fermentation test ––ORPORP
Time (hours)0 25 50 75 100
OR
P(m
V)
-400
-300
-200
-100
0
100
OriginalSonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Tong-yi filtrate
-300
-360Time (hours)
0 25 50 75 100
OR
P(m
V)
-400
-300
-200
-100
0
100
OriginalSonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Min-sheng filtrate
-300
-350
Filtrate fermentation test Filtrate fermentation test ––Zeta potentialZeta potential
Time (hours)0 25 50 75 100
Zeta
pot
entia
l(mV
)
-40
-35
-30
-25
-20
-15
-10
-5
0
OriginalSonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
Time (hours)0 25 50 75 100
Zeta
pot
entia
l(mV
)
-40
-35
-30
-25
-20
-15
-10
-5
0
OriginalSonicatedAcidifiedPasteurizedFrozen/thawedBESA-inhibited
-15
-12
-24
-18
Min-sheng filtrate Tong-yi filtrate
Clostridium inoculum
0 8 16 24 32 40 48 72 96 120 144 168 192 216 240
Clostridium sp.
C-2
C-3
產氫不增不減 產氫氣 氫氣不增不減
SoSo……All pretreatments can assist hydrolysis of organic All pretreatments can assist hydrolysis of organic materials effectively. But not all of them help in producing materials effectively. But not all of them help in producing hydrogen.hydrogen.
The production of hydrogen increases markedly over 8The production of hydrogen increases markedly over 8--24 24 hr, and is consumed afterward. hr, and is consumed afterward.
FreezingFreezing--thawing, pasteurization, and acidification assist thawing, pasteurization, and acidification assist hydrogen production. But adding BESA and hydrogen production. But adding BESA and ultrasonicationultrasonication retard it. retard it. Hydrogen production reaction occurs in liquid phase, Hydrogen production reaction occurs in liquid phase, while the existence of sludge would in some sense while the existence of sludge would in some sense consumes the hydrogen.consumes the hydrogen.
CoCo--Production Production of Hof H22 and CHand CH44
Filter
HydrogenFermenter
MethaneDigester
Pre-treatment
Sludge
Filtrate
Cake CH4
H2
Twin Twin FermentorsFermentors
K8 K8 inoculuminoculum
0 8 16 24 32 40 48 72 96 120 144 168 192 216
產 氫 消耗氫氣
累積甲烷
240hr 厭氧消化
ClostridiumClostridium
K8
96hr 厭氧消化
K8
至240hr 厭氧消化
CoCo--ProductionProduction
yiel
d of
CH
4 (g
/kg
DS)
20
40
60
80
100
120
140
original sludgesludge+clostridiumfrozen/thawedacidifiedalkalized
Hyd
roge
n co
nten
t(g/k
g D
S)
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
sludgesludge+clofrozen/thawedacidifiedalkalized
H2 CH4
Time(hrs)0 100 200 300 400
0
Time(hrs)0 100 200 300 400
0.0
TCOD
Time(hrs)0 100 200 300 400
TCO
D(m
g/L)
6000
7000
8000
9000
10000
11000
12000sludgesludge+clofrozen/thawedacidifiedAlkalizednoodle
SCOD
Time(hrs)0 100 200 300 400
SCO
D(m
g/L)
0
2000
4000
6000
8000
10000
sludgesludge+clofrozen/thawedacidifiedalkalizednoodle
Time(hrs)0 100 200 300 400
NH
3-N
(ppm
)
0
50
100
150
200
250
300
original sludgesludge+clofreeze/thawed +cloacidified+cloalkalized+cloalkalized noodle+clo
frozen/thawed
Time(hrs)0 100 200 300 400
ppm
0
200
400
600
800
1000
1200
lactic acidacetic acidpropionic acidbutyric acid
Basified sludge
Time(hrs)0 100 200 300 400 500 600
ppm
0
200
400
600
800
1000
lactic acidacetic acidpropionic acidbutyric acid
sludge+clo
Time(hrs)0 100 200 300 400
ppm
0
200
400
600
800
1000
lactic acidacetic acidpropionic acidbutyric acid
Alkalized
Ori+clo
Fre/thaw
Acidified
Time(hrs)0 100 200 300 400
ppm
0
200
400
600
800
1000
1200
1400
1600
1800
2000
lactic acidacetic acidpropionic acidbutyric acid
Acidified original sludge
Time(hrs)0 100 200 300 400
ppm
0
100
200
300
400
lactic acidacetic acidpropionic acid
Original
K80 8 16 24 32 40 48 72 96 120 144 168 192 216
K8
Time(hrs)0 100 200 300 400 500
Met
hane
(g/k
g D
S)
0
1
2
3
4
Original
0 8 16 24 32 40 48 72 96 120 144 168 192 216
Original sludge
Time(hrs)0 100 200 300 400 500
Met
hane
(g/k
g D
S)
0
10
20
30
40
50
60
70
SUMMARY
pH 5-6
pH 7-8