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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