Session 1

Anaerobic digestion of sewage sludge

Jaime L. Garca de las Heras

A - FUNDAMENTALS

The anaerobic process

The anaerobic process

A complex system
Simultaneous biochemical transformations by bacteria
Set of chemical compounds degraded by different groups
of microorganisms
Reactants => Products / metabolites
Substrates for other microorganisms
Some of them are inhibitors

=> Pool of microorganisms living in their substrates

A liquid environment where

physico-chemical transformations occur
physico-chemical variables affect the biochemical processes
4

Bacterial growth in a substrate

Substrate : S
Biomass (bacterial population) : X

Products
Substrate

GROWTH
Biomass

DECAY

Insoluble organics
Hydrolysis

Soluble organics

Acid formation
Volatile acids
H2
Methanogenesis
CH4
CO2
6

Stoichiometry

Mass balance
Chemical reactions* (100% mass)
Reactants => Products + Energy
aerobic
Glucose + O2 => CO2 + Energy
anaerobic
Glucose => Butirate + Propionate + Acetate + H2
Mass distribution
Substrate depleted=> Biomass growth + Energy*
8

Aerobic process
External electron acceptor (O2)

Anaerobic process
No external electron acceptor
CH3CH2COOH => CH3COOH + H2
Electrons

Scheme chemical reaction

Process

Electron acceptor
+

H in VFA

H+ + e- ==> H2
+1
0

Anaerobic oxidation of VFA

Electron donor
C in VFA and LCFA

C
==>
-2n/(2+n)

CH3COOH + e0

Anaerobic oxidation of VFA

10

Oxidation state of Carbon

Entalpy of reaction
Respiration quotient
Energy produced/Oxigen consumed
Theoretical COD
COD/VS ratio
Specific methane potential
Methane content (%) in biogas
11

Estados de oxidacin (1)

El estado de oxidacin (EO) de un elemento en un compuesto se mide

mediante el n de valencia o n de oxidacin (NO):
NO: n de electrones ganados por el elemento (elemento se reduce: EO
negativo) o perdidos (elemento se oxida: EO positivo) al pasar a formar parte
del compuesto /Babor pg 456/

En compuestos hidrogenados el EO del H es+1. En compuestos oxigenados el

EO del O es -2
N => NH3
N => NO3

N + 3 e- => N-3 ,
N => N+5 + 5 e-

EON = -3
EON = +5

En los compuestos orgnicos ... el EO de los elementos es fijo, salvo para el C

H+1,, O-2,, N-3,, P+5

Conocidos los EO de los elementos del compuesto, el estado de oxidacin del

C se obtiene por resta
Propionato C3H6O2 ,, EOC = - (6*1 2*2)/3 = - 2/3
12

Estados de oxidacin (2)

Theoretical Oxigen Demand (ThOD) es similar pero en peso de Oxgeno.
Ejemplo: Hidrgeno
Oxidado H0 => H+ + 1 eOxidante O 0 + 2 e- => O -2
-------------------------------------2 H0 + O 0 => H2O
Cada electrn cedido equivale a 8 g de ThOD demandados
ThOD del H0 = +8 g de ThOD / mol H
13

Theoretical Oxigen Demand

Element or charge Z
C
Carbon
H
Hydrogen
O
Oxygen
N
Nitrogen
P
Phosphorous
Negative charge
+
Positive charge

State of reference
CO2
H2O
HO2O
2
NH4+
PO43Zero charge
Zero charge

Equivalent ThOD
+ 32 g ThOD (mol C) -1
+8 g ThOD (mol H) -1
-16 g ThOD (mol O) -1
-24 g ThOD (mol N) -1
+40 g ThOD (mol P) -1
+8 g ThOD (mol (-)) -1
-8
g ThOD (mol (+)) -1
/Ref ASM3 IWA 2000/

Sulfur

SO4-2

+48 g ThOD/mol S

14

Calculation of Chemical Oxygen Demand ratio (1)

ThOD/VS

ThODcompuesto = (Mi ThODi)

Mi
ThOD
MW

moles del elemento i en el compuesto

i
ThOD del elemento i
Peso molecular del compuesto

COD/VS = ThODcompuesto/MW
15

Exercise
Calculation of Chemical Oxygen Demand ratio
(ThOD/VS) for Glucose (C6H12O6)

16

Calculation of Chemical Oxygen Demand ratio (2)

COD/VS

17

Calculation of Chemical Oxygen Demand ratio (3)

COD/VS
Cn Ha Ob Nd + x H2O => y CH4 + z CO2 + d NO3

CnHaOb + (...)O2 => (...)CO2 + (...) H2O

COD/VS = 8 (4n+a-2b) / (12n+a+16b)

CnHaObNd + (...)O2 => (...)CO2 + (...) H2O

COD/VS = 8 (4n+a-2b-3d) / (12n+a+16b+14d)
18

/Buswell/

Calculation of Specific Biological Methane Potential

(1) Theoretical BMP (Nl CH4/ gVS)
Cn Ha Ob + x H2O => y CH4 + z CO2

a + 2x = 4y
b + x = 2z
n=y+z

19

/Buswell/

Calculation of Specific Biological Methane Potential

(2) Theoretical BMP
Cn Ha Ob Nd + x H2O => y CH4 + z CO2 + d NH4
CnHaObNd + [n-(a/4)-(b/2)+(3d/4)] H2O =>
=> [n+(a/4)-(b/2)-(3d/4)]/2 CH4 + [n-(a/4)+(b/2)+(3d/4)]/2 CO2
%CH4 = 100 {[n+(a/4)-(b/2)-(3d/4)]/2 }/n
%CO2 = 100 {[n-(a/4)+(b/2)+(3d/4)]/2 }/n

20

Stoichiometric 0.35 Nm3CH4 / kg CODremoved

Buswell
C oxidation state
ThODCH4 = 132 + 48 = 64 gCOD/molCH4
1 mol 22,4 liters of gas
22,4 l gas / 64 g = 0,35 l CH4/g CODremoved

21

Exercise
CnHaObNd
Specific Biological Methane Potential
Th SBMP (Nl CH4/g VSrem) = 0.35COD/VS*
%CH4
Buswell => 100 {[n+(a/4)-(b/2)-(3d/4)]/2 }/ n
from ThOD* =>COD/VS MW/64 1/n 100 ??

22

23

Name

Sugars
Formula C6H12O6
COD / VS 1,07
C ox. st. 0,00
ThSBMP

Amnoacids
x
C4H6.1O1.2N
1,53
-0,18

0.37

0.53

LCFatty acids
C16O2H32
2,88
-1,75
1.01

Nm3/kg VS
=0.35 COD/VS
24

Calculation of biogas potential %CH4

25

More oxidation degree (state) Less COD

0,5

C oxidation state

0,0
0,0
-0,5

0,5

1,0

1,5

2,0

2,5

3,0

3,5

Carbohidrates
Proteins

-1,0

Fats

-1,5

y = -1,064x + 1,1867
R2 = 0,8996

-2,0
COD / VS

26

Mayor grado (estado) de oxidacin del C Less methane content in biogas

Porcentaje de metano en el biogas

80

Lipids
Fatty Acids

70

Valerate

Butyrate
Biomass

60

Propionate

% CH4

50

Waste*

Acetate

Proteins/Aminoacids
Carbohydrates

Sugars

40

30

20

10

0
-2

-1.5

-1

-0.5

Estado de Oxidacin del Carbono

27

% CH4 en el biogs vs relacin DQO/SV

Lipids

Porcentaje de metano en el biogas

Sugars

% CH4

40

30

Fatty Acids

Valerate

Propionate

Butyrate

50

Proteins/Aminoacids
Waste*

60

Carbohydrates

Acetate

70

Biomass

80

20

10

0
1

1.2

1.4

1.6

1.8

2
ThOD/SV

2.2

2.4

2.6

2.8

28

Produccin de metano vs relacin DQO/SV

29

Reaction kinetics

30

Kinetic expressions
Disintegration First order in Xcomposites
Hydrolysys First order in particulate polymers
The others:

Km Monod Activation Inhibition Xbiomass

Monod: S/(Ks+S)
Activation: So/(Ko+So)
Inhibition: Ki/(Ki+Si)

(Valerate, butirate
Km Monod Competition)

Decay First order in Biomass

31

Factors affecting kinetics

Temperature
pH
Inhibition

32

experimental

(r at T) / (Optimum r)

1.2

0.8

0.6

0.4

0.2

0
0

10

20

30

40

50

Temperature ( C)

33

Influence of Temperature on Km, Ks, Kdecay

/van Lier 1997/

34

Arrhenius + decrease
rT mesfila (To=308)
rT=rTo*e**C(T-T0)
10

Traditional Arrhenius

rT = ro e

C ( T To )

rT

6
4
2
0
0

10

20

30

40

50

T-273

rT = rop K (Top T)
Tmax T
rT = rop
Tmax Top

for T<Top

(2.21)

for T>Top

(2.22)

Tmax: Temperature at which there is no microbial growth

Top: Temperature of optimum growth
K: Coefficient
rop: Optimum reaction rate (at Top)

rT vs T
(T<Top; T>Top)

35

(van Lier et al., 1997)

km (T ) = km ( 35C ) e 0.01(T 308.15) + km ( 55C ) e 0.01(T 328.15)

2

km (T)

k m (55C)

k m (35C)

20

25

30

35

40

45

50

55

60

65

70

Temperatura (C)

36

Influence of pH
Factor to correct reaction rate
1,2

I=

1 + 2 10 0.5( pH LL pH UL )
1 + 10 ( pH pH UL ) + 10 ( pH LL pH )

pHUL = 7,5
pHLL = 6,5

0,8

0,6

0,4

0,2

0
5

5,5

6,5

7,5

8,5

37

Specific growth rate ( )

Influence of inhibition

= max

Inhibitor concentration = I1

1
(1 +

Ks
I
) (1 +
)
S
Ki

Substrate concentration
Non Competitive - Constant concentration of Inhibitor
38

Ao 2 =

S o2
K A,o 2 + S o 2

Anh 4 =

Ahpo 4 =
Aco 2

S nh 4
K A, nh 4 + S nh 4

Activacin por oxgeno

Activacin por nitrgeno inorgnico

S hpo 4
K A, hpo 4 + S hpo 4

S co 2
=
K A,co 2 + S co 2

Activacin por fsforo inorgnico

Activacin por carbono inorgnico

39

I o2 =

K I ,o 2
K I ,o 2 + S o 2

I h 2, fa =
I h 2,c 4 =

I h 2, pro =
I nh 3 =

Inhibicin por oxgeno

K I , h 2, fa

Inhibicin por hidrgeno de la acetognesis

de los cidos grasos

K I , h 2, fa + S h 2
K I , h 2,c 4

Inhibicin por hidrgeno de la acetognesis

de los cidos valrico y butrico

K I , h 2,c 4 + S h 2

K I , h 2, pro
K I , h 2, pro + S h 2

Inhibicin por hidrgeno de la acetognesis

del cido propinico

K I , nh 3
K I , nh 3 + S nh 3

I pH , aa =

I pH , ac =
I pH , h 2 =

Inhibicin por amoniaco

K I , h , aa

Inhibicin por pH de las transformaciones

de acidognesis y acetognesis

Inhibicin por pH de la metanognesis

acetoclstica

K I , h , aa + S h +
2

K I , h , ac

K I , h , ac + S h +
2

K I ,h,h 2

K I ,h,h 2 + S h +
2

Inhibicin por pH de la metanognesis

hidrogenfila
40

Physicochemical processes

41

Gas absorption/desorption.
Acid/Base
Precipitation

42

Importance
The acid-base systems
Buffer capacity => process stability
Inhibition due to
pH (prediction of H+)
free form of acids (VFA) = f(pH)
soluble gas in liquid phase: soluble free NH3 = f(pH)

Transfer from gas state to liquid state

Gas flow (CO2)
Partial Alkalinity (HCO3)
43

Most common acid / base pairs in A.D.

Acid

Base + H+

CO2
NH4
HAc
HPro
HBu
HVa

HCO3- + H+
NH3 + H+
Ac- + H+
Pro- + H+
Bu- + H+
Va- + H+
44

Acidity constant

Three main acid-base pairs (buffer systems)

NH4+ / NH3
CO2 / HCO3 HVFA / VFA-

pKa = 9.3
pKa = 6.3
pKa = 4.8

(SCO2 liq >> SH2CO3)

45

Algebraic expressions as a function of pH

Ka = Sbase SH+ / Sacid

Acid

Base + H+

CO2
NH4
HAc
HPro
HBu
HVa

HCO3- + H+ Sacid + Sbase = Stotal

__________________________________
NH3 + H+
Ac- + H+
Sacid = Stotal SH+ / (Ka + SH+)
Pro- + H+
Bu- + H+
Sbase = Stotal Ka / (Ka + SH+)
Va- + H+
46

% NH3 & % NH4 VS pH

100

80

60

40

20

0
6

6,5

7,5

8,5

9,5

pH

% NH3

% NH4

47

% HCO3 & % CO2 VS pH

100

80

60

40

20

0
4

4,5

5,5

6,5

7,5

pH

%HCO3

%CO2

48

% ac - & % HAC VS pH

100

80

60

40

20

0
3

3,5

4,5

5,5

6,5

pH

% ac -

HAC

49

% NH3 & % NH4 VS pH

100

80

60

40

20

0
6

6,5

7,5

8,5

9,5

pH

% NH3

% NH4

% HCO3 & % CO2 VS pH

100

80

60

40

20

0
4

4,5

5,5

6,5

7,5

6,5

pH

% a c - & % HAC VS pH
%HCO3

%CO2

100

80

60

40

20

0
3

3,5

4,5

5,5

pH

% ac -

HAC

50

Acid/Base dynamic equilibrium

NH4 +

R1

NH3 + H+

R2

dSNH4+/dt=R2-R1
R1=K1SNH4+
R2=K2SNH3SH

51

Liquid to Gas transfer

If dilute soluble gas concentration (Sliq,i), Henry law applies for

equilibrium
Liquid => gas transfer : two film theory

T,i = k L a(Sliq,i - K H p gas,i )

T,i: Specific mass transfer rate of gas i (Kg or Kmole/m3d)
KLa = (D/d) * (A/V) :Volumetric mass transfer coefficient (d-1)
Overall mass transfer coefficient (D/d)
Specific transfer area (A/V)

GAS

LIQUID

Sliq,i : Soluble gas i concentration in the bulk liquid

KH : Henry constant (Mbar-1)
pgas,i : Partial pressure of gas i
52

B REACTOR DESING

53

TYPE OF REACTORS

54

Reactor types
CSTR
Batch
Plug flow
Contact

55

Completely (Continuous)
Stirred Tank Reactor - CSTR

Contact Reactor

Continuous
Complete mix
Concentration change instantly
Uniform concentration

56

Anaerobic Filter

Upflow sludge reactor

57

Upflow Anaerobic Sludge Bed

Reactor - UASB

Anaerobic Hybrid Reactor

58

CSTR Anaerobic Digester

59

DESING CRITERIA

60

Nomenclature
HRT
Hydraulic retention time
Tiempo de retencin hidrulico
Volumetric loading
HRT = VR/Q0 (days)

OLR
BV,COD
Organic loading rate
Carga orgnica volumtrica
Velocidad de carga orgnica
Organic loading
Organic volumetric loading

Qo: Influent flow rate (m3/d)

So: Influent substrate concentration
(kgS/m3)
VR: Reactor volume (m3)
XBH: Biomass concentration
(kgBH/m3)

OLR = Q0S0/VR (Kg Substrate/m3day)

61

Nomenclature
F/M
BX,COD
Food to microorganism ratio
Carga msica (fangos activos)
Sludge loading
F/M = Q0S0/VRXBH (Kg Substrate/Kg Biomassday)
SRT
Sludge retention time
Cell retention time
Tiempo de retencin celular
Sludge age

Qo: Influent flow rate (m3/d)

So: Influent substrate concentration
(kgS/m3)
VR: Reactor volume (m3)
XBH: Biomass concentration
(kgBH/m3)

SRT = VRXBH/QwXBw (days)

62

Relationships
OLR (ds/dt)utilizatoin
FM K = Km S/(ks+S)

63

Desing criteria for CSTR

HRT criteria
HRTdesign = VR/Qo
Qo
<= Data
HRTdesig <= Experience
<= Result
VR

OLR criteria
OLRdesign = QoSo/VR

Qo
So
OLRdesign
VR

<= Data
<= Data
<= Experience
<= Result

64

Simple model
Insoluble organics
Hydrolysis

K1

Soluble organics

Acid formation

K2

Volatile acids
H2
K3

Methanogenesis
CH4
CO2

65

A) Hydrolysis as limiting step

if

K1 << (K2, K3)

=> Efficiency hydrolysis = f(HRT)

=> Total methanification of solubilized matter
Mass balance in Xc:
Xc = Xco/(K1 HRT + 1)
Efficiency = K1 HRT / (K1 HRT + 1)
HRT = f(efficiency )

66

B) Bacterial wash-out at low HRT

and

HRT < HRTcritical

=> Bacterial wash-out

Mass balance in XBH:
HRTcritical = 1/(m Kdecay)

67

C REACTOR OPERATION

68

Performance parameters
Organic matter removal

Solubilization efficiency
Removal of particulate organic matter (%)
VSS
Particulate COD
(Total) Organic matter removal efficiency (%)
VS
Total COD (COD)*
Methanification* = %COD transformed in CH4
Specific Methane production
Nm3/kg VS fed (related to OM removal efficiency)
Stoichiometry Nm3CH4/kg COD removed
(Acidification = CH4 + VFA produced in %)
69

Performance parameters
Effluent quality

Dissolved COD
VFA
Soluble hydrolized organics (su, aa, lcfa)
(Dissolved TOC)
Ammonia
Phosphorous

70

Performance ratios

COD/VS ratio
%CH4 in the biogas

Alkalilnity
AI/AP,, AI/AT

Carbon oxidation state

BuswelCOD-SV.ppt

Acid/base systems
Buffer capacity

71

Parameters of digester stability

Parameters of stability

Acetate
Propionate
VFA Intermediate Alcalinity
Partial Alcalinity
AI/AT
AI/AP..................
%CH4
pH

Early warning
parameters

<= H2 conc. in biogas

<= CO conc. in biogas ??

72

Total Alk

Volatile acids
ppm H2

VFA/Total alkalinity

%CH4
ppm CO ??
%CO2
pH

73

74